GIO TRNH

HA HC PHN TCH

2004

GII THIU V MN HC

V tr, ngha, vai tr mn hc Mn hc Ho hc phn tch l mt trong nhng kin thc c bn ban u trong cc mn hc lin quan n vic phn tch cc sn phm du kh. Mn hc ny s cung cp cho cc hc vin cc kin thc c bn ca Ngnh phn tch ha hc, t hc vin s t hnh thnh cc k nng s dng cc dng c trong phng th nghim phn tch c th phn tch c cc ch tiu trong sn phm ca du kh phn c s, cng nh vn dng sng to cc kin thc c hc hiu v tm ti khc phc trong cc th nghim tng t ca thc t. Ngoi ra, mn hc cng rn luyn cho hc vin nhng thc v thi quen qua cc bi thc hnh, luyn tp trong tng giai an Mc tiu ca mn hc Hc xong mn hc ny, hc vin cn phi: 1. Nm vng cc khi nim c bn v ha phn tch. 2. 3. 4. Phn tch nh tnh. Phn tch nh lng. Hiu bit cc nh lut ha hc.

5. Thc hin phn tch cc loi cht khc nhau. Mc tiu thc hin ca mn hc Khi hon thnh mn hc ny, hc vin c kh nng: 1. M t cc khi nim c bn v phn tch nh 1

tnh v nh lng. 2. Phn tch cc ion theo: + 3. Phn tch nh tnh. + Phn tch nh lng. Phn tch cc loi cht khc nhau.

Thc hin cc th nghim lm trong PTN ha phn tch ca trng. Ni dung chnh ca mn hc Bi 1: Khi nim c bn.(h thng phn tch nh tnh) Bi 2: Phn tch nh tnh Cation nhm 1 Bi 3: Phn tch nh tnh Cation nhm 2 Bi 4: Phn tch nh tnh Cation nhm 3 Bi 5: Phn tch khi lng. (phn tch nh lng khi lng) Bi 6: Phn tch th tch Bi 7: Phn tch nh lng acid baz Bi 8: Phn tch nh lng oxy ho kh Bi 9: Phn tch nh lng to phc Bi 10: Phn tch nh lng to ta

CC HNH THC HOT NG HC TP CHNH TRONG MN HC

Hc trn lp v: + + + + + Cc cn bng trong dung dch Phn tch nh tnh cc cation cc nhm 1,2,3 Phn tch nh lng theo phng php khi lng Phn tch nh lng theo cc phng php th tch Cc phng php tnh sai s ca php chun

T nghin cu ti liu lin quan n Phn tch c s. Theo di vic hng dn gii cc bi tp Lm cc bi tp v cc cn bng trong cc h dung dch, cc bi tp v xc nh hm lng cc mu cht Tnh ton cc bi ton sai s trong cc bo co v hm lng c tnh ton Tho lun v xy dng cc cng thc tnh ton, cc h thng phn tch nh tnh Tham gia cc bi kim tra nh gi cht lng hc tp. Tham gia cc bi thc hnh ti phng th nghim 3

YU CU V NH GI HON THNH MN HC

V kin thc Vn dng c cc kin thc c hc xc nh c cc phng php phn tch cho ph hp vi mt s mu thc. Xy dng c ng nh phn v th ca chng Xc nh c cc ch th tng ng cho php chun Vn dng c cc l thuyt v cn bng trong dung dch xc nh c cc yu t nh hng n dung dch Vn dng tt cc cng thc phn tch tnh

ton c hm lng cc cht phn tch V k nng Thnh tho cc thao tc s dng cc thit b, dng c phn tch trong phng th nghim Tnh ton c sai s trong qu trnh phn tch Tnh ton thun thc cc bi ton v xc nh hm lng cc dung dch phn tch. H thng ho c cc cch nh tnh cc ion trong dung dch Thc hin tt cc bi th nghim ca mn hc

Xc nh c hm lng cc mu cht ban u V thi 4 Nghim tc trong thc tp khi thc hin cc bi

th nghim phn tch trong phng th nghim Lun ch ng trong vic xc nh p dng cc phng php phn tch ng vin, nhc nh cc ng nghip thc hin ng thao tc k thut c hc.

BI 1. CC KHI NIM C BN M bi: HPT 1

Gii thiu tin hnh phn tch c cc mu dung dch nc, cn phi nm vng mt cch c h thng cc kin thc v dung dch, cc khi nim lin quan trong ho phn tch Mc tiu thc hin Hc xong bi ny hc vin s c kh nng:
1. 2. 3. 4. 5.

M t s in ly trong dung dch. M t tch s ion ca nc - pH ca dung dch. M t pH trong cc h acid - baz. Nm vng cc khi nim v ho tan, tch s tan.

Nm vng cc khi nim c bn v phc cht. 6. M t phn ng thy phn. Ni dung chnh 1. 2. 3. S in ly trong dung dch. Tch s ion ca nc - pH ca dung dch. pH trong cc h acid - baz.

. Khi nim v ho tan, tch s tan. 5. Khi nim c bn v phc cht. 6. Phn ng thy phn 1. 1. S in ly trong dung dch 1.1.1. Khi nim in ly Dung dch l mt h ng th gm 2 hay nhiu cht m thnh phn ca n c th thay i trong gii hn rng. Gm 3 loi dung dch: dung dch kh, dung dch lng, dung 6

dch rn. Dung dch kh l hn hp ca hai hay nhiu cht kh (nh khng kh). Trong iu kin bnh thng do tng tc gia cc phn t kh qu nh nn dung dch kh gn nh l hn hp c hc. Nhng khi iu kin thay i vi p sut cao, s ho tan ca cc cht kh ging nh s ho tan ca cc cht lng, v lc ny chng c lc tng tc ng k. Dung dch lng l dung dch c to thnh t nhng cht c kh nng ho tan trong dung mi lng. Dung dch rn l nhng tinh th c to thnh do s ho tan ca cc cht kh, lng, rn trong dung mi cht rn. Xt trong h dung dch lng, khi cho cht tan vo trong dung mi lng, lun xy ra 2 qu trnh: qu trnh chuyn pha ph v cu trc cht tan thnh cc ion, phn t hay nguyn t, ri khuych tn vo trong dung mi (y l qu trnh vt l, thu nhit) + qu trnh sonvat ho tng tc hnh thnh gia cc phn t chuyn pha vi cc phn t dung mi (y l qu trnh ho hc, pht nhit ) " S in ly l qu trnh phn ly cc cht tan thnh nhng ion mang in tch tri du, cc cht trong trng thi nng chy hay trong dung dch, c kh nng phn ly thnh nhng ion mang in tch tri du, lm cho h c kh nng dn c in, gi l cht in ly " 7

D tc dng ca dng in, cc ion dng s di chuyn v pha in cc m (catod) nn gi l cation, cn cc ion m s di chuyn v in cc dng (anod) nn gi l anion. Cc ion c tnh cht khc hon ton so vi cc nguyn t cng loi nguyn t (chng hn, ion H+ c tnh chua, gy chua, lm qu tm ha , nhng nguyn t H th khng c tnh cht ny) Phn loi: cht in ly gm hai loi: Cht in ly mnh: l cht in ly c kh nng phn ly hon ton, c biu th bng du ( ) Cht in ly yu: l cht in ly khng c kh nng phn ly hon ton, c biu th bng du

( ) V d: dung dch HCl, NaCl... l nhng dung dch cht in ly mnh c biu th trong dung dch nc l: HCl H+ + ClNaCl Na+ + Cl-

Cn nhng dung dch FeCl 2 , Cu(OH)2... l nhng dung dch cht in ly yu n rt yu, c biu th trong dung dch nc l: FeCl2 Fe2+ + Cl-

Cu(OH)2 Cu2+ + 2 OH- v.v... Mt iu cn lu l: nhng ion c minh ha bng cc phng trnh in ly trong cc qu trnh in ly, l nhng ion sonvat ch khng phi l nhng ion t do (cch vit trnh by trn l cch biu th s sonvat ho c vit gin lc ri)

1.1.2. Hng s phn ly dung dch 1.1.2.1. Khi nim Trong dung dch in ly lun c mt cn bng ng c xc lp cho qu trnh n ly cht tan, chng hn cho cht tan AmBn tan trong nc, th qu trnh ho tan lun bao gm hai qu trnh phn ly cht tan AmBn thnh cc ion sonvat v qu trnh kt hp cc ion ny thnh phn t AmBn. Sau mt thi gian, cc vn tc ca 2 qu trnh ny bng nhau th dung dch s t ti qu trnh cn bng AmBn m A+n + n B-m
[ A n ]m .[B m ]n = cn [ Am Bn ]

Khi hng s cn bng KCB

c gi l hng s in ly hay hng s phn ly A mBn. y l mt i lng c trng cho cht in ly ho tan trong mt dung mi nht nh. V d: i vi acid phn ly mt nc nh CH3COOH l: CH3COOH CH3COO- + H+ Th hng s phn ly (hay cn gi l hng s acid): KCB =
[ H ].[CH 3 OO ] = 1,82. 10 - 5 . [CH 3 COOH ]

i vi acid phn ly hai nc nh H2CO3 : mi nc phn ly c mt hng s tng ng H2CO3 KCB = HCO3H+ + HCO3[ H ].[HCO3 ] = 0 - 6,35 . [ H 2 CO3 ]

H+ + CO329

KCB =

[ H ].[CO3 ] [ HCO3 ]

= 10 - 10,33 .

Khi nim v mnh ca mt acid hay mt baz cng c th c xc nh da trn hng s phn ly ca cht : KCB ca phng trnh in ly acid cng ln th tnh acid cng mnh (hay ngc li i vi baz). Lc , KCB cn c gi l hng s acid K a (hay i vi baz l hng s baz Kb) Hng s in ly ca mt cht in ly rt ph thuc vo bn cht ca dung mi ho tan n. Vic thm mt dung mi khc c thm in mi nh hn nc (chng hn Dioxan c = 2,2 so vi nc l 80,4) vo dung dch cht in ly s lm gim hng s K ny (khi cho Dioxan vo dung dch acid acetic th pK a = 4,75 tng ln pKa = 10,52, tc hng s in ly b gim i gn 1 triu ln), kt qa cht tan s kh tan hn. ( tin vic tnh ton, thng s dng pK a = - lg Ka v pKb = - lg Kb, vi pKa + pKb = 14) 1.1.2.2. Hng s bn v khng bn Cc qu trnh in ly trong dung dch cht in ly c xc nh nh lng theo hng s in ly K CB, cn gi l hng s phn ly hay hng s khng bn (KPl) Chng hn
CH3COOH CH3COO- + H+ c KCB = KPl = 1,82.10 5.

Cn cc qu trnh kt hp ion trong dung dch cht in ly c xc nh nh lng theo hng s kt hp, cn gi l hng s bn . Chng hn: 10

CH3COO- + H+

CH3COOH

KCB =

= 10 + 4,74 .

Nh th trong mt dung dch cht in ly lun c KPl. = 1. (Thng hng s bn c s dng cho cc qu trnh phn ly ca cc phc) V d: Tnh nng cc ion ti cn bng trong phn ng gia thuc th HmR vi ion kim loi solvat M theo phng trnh sau: M(OH)i + q. HmR M(OH)i (Hm-nR)q + q.n.H (1) ( n gin cc phng trnh phc khng ghi in tch) Khi h tn ti hai hnh thc cn bng l cn bng ca ion kim loi vi nc v thuc th vi nc. Kho st phn ng gia ion kim loi vi nc Cc phn ng to phc ca M vi hydroxo: M + H2O MOH + H2O
2

MOH + H M(OH)2 + H

1 2

[MOH] =

[M] h-1
1

[M(OH)2] =

[M] h

-2

.............................................................................................
M(OH)i-1 + H2O [M(OH)i ] =
1 2... i

M(OH)i + H [M] h
-i

Theo nh lut bo ton nng ban u, ta c: CM = [M] + [MOH] + [M(OH)2 ] +....+[M(OH)i ] + CK [M] = v [M(OH)i ] =
1
1h 1 1

1 1

CM 2h

CK ...

... i h

CM 2h

CK ...

2 ... i h

...
i

l biu thc tnh nng ion solvat ca M ti thi 11

im cn xt. Kho st phn ng ca thuc th HmR Phng trnh phn ly ca thuc th Hm+1R K0 K1 ..
Hm-(n-1)R Hm-nR + H Kn [Hm+nR]=[HmR].h-n.k1 k2...kn

HmR + H Hm-1R + H

[Hm+1R] = [HmR].h.k0-1 HmR [Hm-1R] = [HmR].h-1.k1

.....................................................................................

Theo nh lut bo tan nng ban u: [HmR]=

CH m R qCK 1 h1K 0
1

K1h

K1K 2 h

... K1K 2 ...K n h

CH m R qCK

K1 K 2 ...K n hn

Nn nng ti thi im ang xt: [Hm-nR] = Hng s bn (1) : Kp =

1 h1K 0
1

K1h

K1K 2 h

... K1K 2 ...K n h

ca phc M(OH)i (Hm-nR)q

[ H ]q.n .[M (OH )i .(H m n R) q ] [ M (OH )i ].[H m R]q

V hng s khng bn: KKB =

KKB=

[ M (OH )i ].[H m n R]q [ M (OH )i .(H m n R) q ]

[ M (OH )i ].(CH m R qCK ) q
1 1 2

CK (1 h1 K 0

K1h

K1 K 2 h

... K1 K 2 ...K n h n ) q

K1 K 2 ...K n q ) hn

t: 12

B=

[ M (OH )i ].(CH m R qCK ) q CK (1 h1 K 0

1

K1h

K1 K 2 h

... K1 K 2 ...K n h n ) q

Th: KKB= B. (

K1 K 2 ...K n q ) l biu thc tnh KCB hay hn

ca phc. V d: Tnh nng ca cu t (CH 3COO- ) trong dung dch phn ly CH3COOH. (HS p dng cng thc trn tnh c: = 10 - 4,74 ). 1.1.3. in ly 1.1.3.1. nh ngha L t s gia nng cht in ly b phn ly vi nng cht in ly em vo ho tan. Cng thc c tnh l: =
n n0

Trong : n l s mol ca cht in ly b phn ly n0 l s mol ca cht in ly em vo ho tan i lng l i lng khng c th nguyn, n thng c biu din bng %, v gi tr ny nm trong gii hn [0, 1] = 0 lng cht tan b vo khng phn ly hon ton ( l nhng cht in ly yu n rt yu, nh cc cht kh, cht kt ta khng tanv.v...) = 1 lng cht in ly b vo tan hon tan ( l nhng cht in ly mnh) 0< <1 cht in ly yu (CH3COOH 0,1M) = 0,0135, ngha l 13

Chng hn:

trong 100 phn t CH3COOH ch c 1,35 phn t CH3COOH b phn ly thnh ion, cn 98,65 phn t CH3COOH khng b phn ly. Ni cch khc, khi ho tan CH3COOH vo dung mi nc th trong dung dch to thnh c 3 cu t b solvat l CH3COO-, H+, CH3COOH. 1.1.3.2. Mi quan h gia in ly ly KPl Thit lp mi quan h gia (AmBn ) C : Qu trnh phn ly: AmBn Nng ban u: C Nng cn bng: C - x Vi =
x C
M

v hng s phn

v K trong dung dch m A+n + 0 m. x n B-m 0 n. x

(m.x) n .( n.x) m . C x

x = C. .Th: K(A) =

Phng php gii ng: t biu thc trn, chuyn thnh phng trnh i s, ri gii tm hay K Phng php gii gn ng: Nu khi chuyn biu thc sang phng trnh ton hc bc hai tr ln v gi s c C >> x (thng ch chp nhn vi gi tr x nh hn 100 ln so vi C) th

c th chp nhn c C - x C (tc b qua x trong mu s), biu thc quan h s l: Ka = mn. nm. x(n + m). (Thng vi i lng [H +] = x trong qu trnh phn ly ca dung dch acid c t l h) V d: Tnh hng s phn ly ca CH3COOH 0,1M c = 1,35% 14

Qu trnh phn ly: CH3COOH Nng ban u: 0,1 Nng cn bng: 0,1 - x Vi =
x 0,1

CH3COO0 m. x

+ H+ 0 n. x

x = 0,1. K(A) = K(A) =

= 0,00135

x2 0,1 x

(0,00135 ) 2 = 1,85.10-5. 0,1 0,00135

V d: Thit lp mi quan h gia th in cc E v K trong dung dch oxy ho kh (ox1 + kh2) Qu trnh kh : ox1 + n e kh1 (E1) Qa trnh oxy ho: kh2 - m e ox2 Qa trnh oxy ho kh: m ox1 + n kh2 n ox2 Nn: E1 = E01 + E2 = E02 +
ox1 0,059 lg kh1 n
ox1 0,059 lg kh1 m ox1 0,059 0,059 lg ] - [E02 + lg kh1 n m

(E2) m kh1 +

E = E1 - E2 = [E01 +
ox1 ] kh1

Khi phn ng t trng thi cn bng th E = 0, qua bin i ta c: lgKCB =

m.n 0,059

E0 .

15

1.2. Tch s ion ca nc pH ca dung dch 1.2.1. Khi nim v acid baz 1.2.1.1. Theo Arrhenius Acid l cht khi phn ly to thnh cc ion hydro, v baz l cht khi phn ly to thnh cc ion hydroxyt. Chng hn: HCl khi phn ly cho ion H+ nn HCl c coi l acid ; hay NaOH khi phn ly cho ion OH - th c coi l baz Tuy nhin, l htuyt ny ch ng tng i trong mt s t cc trng hp c trong thc t. Hin nay cc khi nim acid - baz ch c s dng i vi cc dung dch nc v tr thnh khng thun tin khi chuyn sang dung dch trong cc dung mi khc: Khi nghin cu nhng dung dch khng nc ca cc acid v baz th trong cc dung dch acid khng to ra cc ion H+ v baz th khng to ra cc ion OH-. V d: Khi ho tan HCl trong NH 3 lng, s xy ra phn ng nhng HCl khng to thnh cc ion hydroxoni H3O+ : HCl + NH3 xem l acid NH4+ + Cl- , nhng HCl vn c

V d: Trong dung dch benzen d dng xy ra phn ng trung ho HCl bi NH3 to thnh mui: HCl + NH3 NH4Cl, nhng phn ng ny khng km theo s to thnh nc. Do trong dung dch benzen khi trung ho acid bng baz khng xy ra phn ng tng tc gia ion H+ vi ion OHCc v d trn nu ra mt vi im mu thun vi l thuyt Arrhenius 16

1.2.1.2. Theo thuyt proton (cn gi l thuyt Bronsted)

Acid l cht c kh nng nhng proton (proton l cc ion hydro khng b hydrat ho), baz l cht c kh nng nhn proton. Nh vy khi nim acid vn ging nh trc l trong cht acid c hydro v c kh nng nhng proton ca n, cn khi nim baz khng gn lin vi ion hydroxyl. Do khi nim v baz c m rng: bt k cht no c kh nng nhn proton u l baz. Bn cht theo thuyt ny coi qu trnh phn ng acid vi baz l qu trnh chuyn proton t acid sang baz, tng t nh bn cht qu trnh oxy ho kh l chuyn electron t cht kh sang cht oxy ho. Thc nghim chng t, khng th c proton t do trong dung dch. Do phn ng tch hoc kt hp proton khng xy ra mt cch c lp, m bao gi cng c km theo s chuyn proton t acid ny sang mt baz khc. Nh vy trong dung dch lun tn ti hai qu trnh cho v nhn proton ca cc acid v baz: acid(1) H+ + baz(1) H+ + baz (2) acid(2) V d: HCl + acid(1) H2O baz(2) Cl+ baz(1) H3O+ acid(2)

Trong phn ng trn, c hai cp acid - baz tham gia tng tc (cp acid - baz lin hp), v c gi l nhng cht proton phn. Trong thuyt proton, coi dung mi nh l hp phn 17

ca cc proton phn. V th acid c chia lm cc loi: Acid trung ho v in nh HCl H+ + ClH2SO4 Acid anion nh H SO4H2PO4H+ 2 H+ + SO42 H+ + SO42 + HPO42-

Acid cation nh H3O+ H+ + H2O NH4+ H+ + NH3

Cc cation hydrat ho ca hydro v kim loi cng nh cc cation phc aque u c xem l acid cation, nh: [Al(H2O)6]3+ H+ + [Al(H2O)5 OH]2+ Tng t baz c chia lm hai nhm chnh l: baz trung ho v in (nh H2O, NH3 , C6H5NH2 ...), v baz anion (nh Cl-, Br-, NO3-...) Nhiu cht ng vai tr va ca acid v va ca baz, chng l nhng cht lng tnh, nh nc, NH 3, v mt s dung mi proton phn l nhng cht lng tnh V d: Khi phn ly, nc hay amoniac a ra proton vo dung dch v th hin tnh acid: H2O H+ + OH- v NH3 H+ + NH2Nhng ng thi H2O v NH3 li c th nhn H+, th hin tnh baz: H2O + H+ H3O+ v NH3 + H+ NH4+

Qu trnh ion ha ca chnh dung mi cng ch c th xy ra khi n c tnh cht lng tnh, chng hn s ion 18

ho nc: H2O + H2O H3O+ + OHNc l mt dung mi tng i mnh, n c i lc i vi proton tng i ln (7,9eV), do khi ho tan cc acid mnh (HClO4, H2SO4, HNO3...) vo nc, cn bng proton phn gia acid v nc thc t hon ton chuyn sang phi, iu ph hp vi s ion ho hon ton ca cc acid trong dung dch. Khi thay th nc bng dung mi c i lc rt nh i vi proton, nh CH3COCH3 hoc C6H5NO2, th mi acid mnh trong dung dch nc (khng k HClO4, v H2SO4 ) s tr thnh cc acid mnh va. Nhng tnh cht tng t nh cng xy ra tri ngc i vi cc dung mi baz, v d, trong NH 3 lng, NH3 c i lc rt ln i vi proton (9,3eV) s lm nhiu acid yu tr thnh acid kh mnh, c phn ly gn bng phn ly ca HNO3 trong dung dch nc. Ghi nhn tng qut: Mt phn ng acid - baz bao gm hai na phn ng l nhng v nhn proton. Acid (1) H+ + baz (1) ( K1 ) H+ + baz (2) acid (2) (K2- ) Acid (1) + baz (2) acid (2) + baz(1) (K = K1 . K2- ) Cc hng s K1 v K2 c trng cho kh nng nhng proton ca cc acid (1) v (2). Gi tr K gip gii thch mnh ca acid (1) khng nhng ph thuc vo kh nng c th nhng hay nhn proton m cn ph thuc vo kh nng nhn proton ca baz hay dung mi 19

baz (2) 1.2.1.3. Theo thuyt Lewis Acid l nhng cht c kh nng nhn cp electron Baz l nhng cht c kh nng cho cp electron Chng hn: NH3 c gi l baz v trong phn t ca chng c nguyn t N cn cp electron t do, c kh nng cho cp electron vi H+ hay vi cht F3B. NH3 + H+ NH4+ NH3 + F3B F3B - NH3 Thuyt ny c phm vi ng dng kh cao v tnh khi qut ca n rng ln. Trong chng mc ca gio trnh ny, chng ta khng nghin cu su v l thuyt ca Lewis. Tt c cc acid ca Ahrrnius, Bronsted u l nhng acid nh ca Lewis, v baz cng vy, ngoi ra thuyt Lewis cn gii thch c cc trng hp khc m cc thuyt Arrhnius, Bronsted cha gii thch c hon chnh nh phn ng xy ra gia NH3 vi F3B. 1.2.1.4. Dung dch mui Mui l nhm cc hp cht ho hc dng tinh th c cu to ion, c to thnh khi acid tc dng vi baz. Tan trong nc th phn ly thnh cation kim loi (hoc amoni) v anion gc acid (i khi c ion H + hoc OH-) Mt s mui b nc phn hu sinh ra acid v baz tng ng. Mui c chia thnh 5 loi: Mui trung ho: l mui trong cng thc cu to khng cha cc nhm H+ hoc OH-. Nh: NaCl, Na2SO4, MgCl2... Mui acid: l mui trong cng thc cu to cn

20

cha cc nhm H+, nh l NaHSO4, Na2HPO4... Mui baz: l mui trong cng thc cu to cha cc nhm OH-, nh MgOHCl, Cu2 (OH)2 CO3, Cu(OH)2 ,...

Mui kp: l mui trong cng thc cu to cha cc nhm nguyn t lm phi t cho a kim loi, nh: KCr(SO4)2. 12 H2O, mui Mohr (NH4)2SO4.FeSO4.7 H2O, mui Seignette KOOC (CHOH)2 COONa.4 H2O...

Mui hn tp: l mui trong cng thc cu to cha a tp cc nhm nguyn t anion gc acid, nh: CaCl(OCl)...

Dung dch mui l dung dch c cc cation kim loi (hay NH4+ ) v anion gc acid, b solvat ho trong dung mi tng ng (thng thng dung mi l H 2O, th cc ion c gi l cc ion hydrat ho) Mt cch ghi nhn khc th dung dch nc mui l dung dch thu phn ca cht mui tan c trong nc. V d: dung dch nc mui CuCl2 l: CuCl2 + H2O (CuOH)+ + 2 Cl- + H+ (khi nim dung dch nc l ch cc dung dch dng dung mi l nc) 1.2.2. pH ca nc Nc l mt dung mi lng tnh: 2 H2O H3O+ + OH-. Khi mt cht c tnh cht acid vo nc th n s nhng proton cho nc v ngc li khi cho mt baz 21

vo nc th n s nhn proton ca nc. V d: Khi cho HCl vo nc th s c qu trnh: HCl + H2O H3O+ + ClAcid HCl l mt acid mnh, v n nhng hon ton proton cho H2O v c bao nhiu phn t HCl cho vo nc th s c mt lng tng ng ion H 3O+ gii phng ra. n gin c th ghi phn ng trn dng rt gn: HCl H+ + ClV d: Trong dung dch acid acetic: CH3COOH + H2O CH3COO- + H3O+ y l mt acid yu, v ch mt phn acid nhng proton, hay ni cch khc ch mt phn ion H 3O+ c gii phng ra. n gin c th vit phn ng trn dng rt gn l: CH3COOH CH3COO- + H+ V d: Khi cho NaOH vo nc: 2 H2O H3O+ + OHSau : NaOH + H3O+ Na+ + 2 H2O Qu trnh ny gii thch NaOH l mt baz mnh, v ton b lng NaOH c trong dung dch u nhn proton ca H2O, ng thi qu trnh trn li gii phng ra mt lng tng ng ion OH-. n gin c th ghi gn l : NaOH Na+ + OHQu trnh phn ly ca nc c th vit l: H2O H+ + OHKhi p dng nh lut tc dng khi lng: K (H2O) = 22
[ H ].[OH ] [ H 2 O]

Trong nc nguyn cht th [H 2O] K

1, nn

(H+ ).(OH - ) = W (1.1)

W c gi l tch s ion ca nc, n ph thuc vo nhit : pW = -lgW Bng 1.1. Bng cc gi tr pW cc nhit tng ng
t0C 0 5 10 15 pW 14,943 14,734 14,535, 14,346 t0C 20 22 25 30 pW 14,167 14,00 13,996 13,833 t0C 35 40 50 60 pW 13,680 13,535 13,262 13,017 t0C 70 80 90 100 pW 12,80 12,60 12,42 12,26

Bin i (1.1) bng logarit c: pH + pOH = pW, vi pH = - lg(H+ ) v pOH = -lg(OH - ) Trong nc nguyn cht cng nh trong cc dung dch trung tnh, lun c: ([H+] = ([OH-]) Nn pH = pOH = 1/2 pW (chng hn 22 0C th pH = pOH = 7) V trong dung dch acid th ([H +]) > ([OH-]): pH < pOH pH < 1/2 pW (hay 22 0C th pH <7 v pOH > 7), vi dung dch baz th ([H+]) < ([OH-]): pH > pOH pW (hay 22 C th pH > 7 v pOH < 7). 1.3. pH trong cc h acid baz 1.3.1. iu kin proton Nng proton trong dung dch trng thi cn 23
0

pH>1/2

bng l tng nng ion proton m cc cht trng thi so snh (c quy c l mc khng) gii phng ra tr i tng nng proton m cc cht trng thi so snh thu vo t ti cn bng. (Trng thi so snh c th l trng thi gi nh mt iu kin v nhit d no hay l l trng thi ban u). y chnh l nh lut bo ton proton c p dng cho h acid - baz. V d: Vit iu kin proton ca dung dch hn hp gm NaOH C1M v Na3PO4 C2M Gii: Chn mc khng l NaOH, Na3PO4 , H2O Cc qu trnh in ly xy ra H2O H+ + OHNa3PO4 NaOH + H+ PO43- + H+ PO43- + 2 H+ 3 Na+ + PO43Na+ + H2O HPO42H2PO4-

PO43- + 3 H+ H3PO4 Trong h c mt qu trnh cho proton ca H2O v bn qu trnh nhn proton, nn iu kin ca proton l:
[H+ ] = [OH - ] - ([Na+ ] + [HPO42- ] + 2 [H2PO4- ] + 3 [ H3PO4 ])

= [OH - ] - C1 - [HPO42- ] - 2 [H2PO4- ] - 3 [ H3PO4 ]) (1.2) C th tm c iu kin proton thng qua nh lut bo ton nng v bo ton in tch, chng hn vi v d trn: H2O H+ + OH Na3PO4 3 Na+ + PO4324

Th:

NaOH Na+ + OH [H+ ] + [Na+ ] = [OH - ] + [PO43- ] [Na+ ] = C1 + 3 C2

C2 = [PO43- ]+ [HPO42- ] + [H2PO4- ] + [ H3PO4 ] Kt hp cc phng trnh li cng c kt qa (1.2) V d: Vit iu kin proton ca dung dch CH3COONa C1M v CH3COOH C2M. Chn mc khng l H2O v CH3COOH, th cc qu trnh phn ly c trong dung dch: CH3COONa CH3COO- + Na+ CH3COOH CH3COO- + H+ H2 O H+ + OH Khi iu kin proton l: [H+] = [OH-] + [CH3COO- ] - C1 = [OH-]+ C2 C1 Chn mc khng l H2O v CH3COO- th cc qu trnh trong dung dch CH3COO- + Na+ CH3COONa CH3COO- + H+ H2O CH3COOH H+ + OH -

Khi iu kin proton l: [H+ ] = [OH - ] - ( [CH3COOH ] - C2) = [OH - ] + C2 - [CH3COOH] = [OH-]+ C2 C1 1.3.2. pH trong cc h acid - baz n chc 1.3.2.1. Kho st trong h n acid - baz mnh V d: Tnh th tch ca acid HClO4 0,001M cn phi ly iu ch 1 L dung dch acid ny c pH = 6,2. Gi 25

s acid ny c xem l acid mnh phn ly hon ton. Gii: Cc qu trnh xy ra trong dung dch: H2O H+ + OH HClO4 H+ + ClO4iu kin proton l: [H+ ] = [OH - ] + [ClO4- ] Gi C l nng dung dch HClO4 c pH = 6,2 Ta c: nng HClO4 = nng ClO4- = C nn (1.3) hW -C=0 h
14 6, 2

(1.3)

sau khi pha

C = 10-6,2 -

10 10

= 6,15.10-7 M

6,15 .10 -7 .1000 Vy th tch cn tm l: = 0,615 mL 0,001

1.3.2.2. Kho st trong h n acid yu - baz mnh hoc acid mnh - baz yu Trong cc h ny, dung dch lun c hai cn bng l ca nc v ca acid yu phn ly ra proton hay baz yu nhn proton: H2O H+ + OH (1) + Acid yu: CH3COOH CH3COO + H (2) Hay baz yu: NH3 + H+ NH4+ (3) Cc acid, baz yu phn ly ph thuc vo nng ban u v hng s phn ly K (trong dung dch nc mc nh 22 0C n 25 0C c W = 10 - 14 ), nn mun so snh kh nng phn ly ca cc acid yu hay baz vi nc th dng tch s ion ca nc. n gin trong 26

vic tnh ton, nu [H+] (ca acid) >>> [H+] (ca nc) th c th b qua s phn ly [H+] ca nc v ch tnh [H +] trn s phn ly ca dung dch acid. V cng tng t l lun nh trn cho baz. V d: Tnh pH trong dung dch CH3COOH 0,001M bit Ka=1,8.10-5 Trong dung dch c qu trnh: CH3COOH CH3COO- + H+ H2O H+ + OH Ta c K(A) =
[ H ].[CH 3COO ] h2 = 0,001 h [CH 3COOH ]

(K) (W)

h2 + 1,8.10-5 h - 0,001.1,8..10-5 = 0 pH = 3,89

h = 1,26.10-4

(Theo phng php gn ng, tc nu xem 0,001 - h 0,001 th phng trnh vit li l: h=
C.K =

0,001.1,8.10

= 1,34.10-4

[H+ ] = 10-3,87 pH = 3,87 Nhn thy cch tnh khng cho sai s ln, c th chp nhn trong qu trnh gii n gin ) V d: Tnh pH trong dung dch NH 310-2 M, bit K(NH4+) = 5,7.10-10 Trong dung dch c qu trnh: H2O H+ + OH - (W) NH3 + H+ Nn: NH3 + H2O NH4+ (K- )

NH4+ + OH - (W. K-1 ) 27

Nng ban u: 0,01 Nng phn ng :W/h Nng cn bng: 0,01 - W/h Ta c:W.K- =

0 W/h W/h

0 W/h W/h

(W / h) 2 . Vic gii phng trnh ny 0,01 W / h

kh phc tp, c th coi W/h<<C, th dng phng php gii gn ng, ta c: W = h2.K-.0,01 h=
W -11 K = 2,38.10 0,01

pH= 10,62

1.3.2.3. Kho st trong h n acid - baz yu V d: Tnh s mol NaCN cn c cho vo 1 L dung dch HCN 0,1M nhm thu c dung dch c pH = 7,3, bit K(A) = 4,8.10-10. Gii: Cc qu trnh phn ly: H2 O H+ + OH - (W) NaCN Na+ + CNHCN H+ + CN- (K = 4,8.10-10) Gi x l s mol ca NaCN cn tm pha vo trong 1 L dung dch HCN, th x cng l nng ca NaCN ly, ta c: HCN Nng ban u: 0,1 Nng phn ng : h Nng cn bng: 0,1 - h Nn: K(A) =
h( x h) 0,1 h

H+ + CN- (K(A)) 0 h h x h x+h

h2 + (x + K) h - 0,1.K = 0

Theo dung dch thu c c pH = 7,3 nn [H+ ] = 10-7,3, thay vo phng trnh c: 28

(10-7,3)2 + (x + 4,8.10-17,3). 10-7,3 - 4,8.10-11 = 0 x = 9,57.10-4 M Vy lng mol m mui NaCN cn dng l 9,57.10-4 (mol) 1.3.2.4. Kho st trong h hn hp acid - baz yu V d: Tnh pH khi pha trn dung dch HCl 0,001M vi dung dch CH3COOH 0,1M, bit Ka (CH3COOH) = 1,8.10-5. Gii: Qu trnh phn ly:
CH3COOH CH3COO- + H+ (K= 1,8.10-5)

Nng ban u: 0,1 Nng phn ng: h Nng cn bng: 0,1 - h Nn: K(A) =
h(0,001 h) 0,1 h

0 h h

0,001 h 0,001 + h

h2 + (0,001 + 1,8.10-5) h - 1,8.10-6 = 0 (1.4) h = 9,2595.10-4 [H+] = 9,2595.10-4 + 0,001 = 1,92595. 10 3 pH = 2,715 Nhn xt Nu coi s phn ly ca CH3COOH l khng ng k, v y l mt acid yu, th pH dung dch pha trn nu ch tnh cho dung dch HCl, c [H +] = 0,001M pH = 3. y l mt gi tr c th xem l gn ng vi tnh ton c th trn. Nh th, s pha trn hn hp cc acid, c th tnh theo cch gn ng l ch ly pH theo acid mnh. Tuy nhin nhn xt trn ch ng trong trng hp nng ca acid mnh khng long lm. Chng hn v 29

d trn, nu ly nng dung dch HCl<10 -5M, nh l 10 8

M, th phng trnh (1.4) trn s c h thay i ln. Do trong hn hp cc acid, nng acid mnh thp qu thng khong gp 100 ln - th trong qu trnh tnh ton gi tr pH mi b nh hng ca nng acid yu. V d: Tnh pH khi pha trn dung dch CH3COOH 0,01M vi dung dch HCN 0,2M, bit K a ca mi acid ln lt l 1,8.10-5 v 4,8.10-10. Gii: Cch gn ng Cc qu trnh xy ra: CH3COOH CH3COO- + H+ (K1=1,8.10-5) HCN H+ + CN(K2 = 4,8.10-10) Gi hi = [H+]i tng ng ca dung dch acid c Ki. Ta nhn thy: h1 = v Nn h1 > h2 acid CH3COOH l acid mnh hn acid HCN Nh vy nhn c kt qu: h1 >> h2. Do vic tnh pH ca dung dch pha trn ch nn tin hnh trn dung dch acid mnh nht l CH3COOH: pH = -lg h1 = 3,37. Cch gii chnh xc Kho st qu trnh phn ly ca acid HCN c s pha trn vi CH3COOH: HCN Nng ban u: 0,2 Nng phn ng: h 30 H+ + CN- (K=4,8.10 - 10) 0 h h2 =
-4 C1 K1 = 4,24.10 -6 C2 K 2 = 9,79.10

4,24.10-4 h

Nng cn bng: 0,2 - h 4,24.10-4+h h Nn: h2 + (4,24.10-4 + 4,8.10-10) h - 0,92.10-10 = 0 h = 2,17.10-7 [H+] = 4,24.10-4+h = 4,24.10-4+ 2,17.10-7 = 4,24217. 10-4 pH = 3,37 (iu ny ng vi kho st h dung dch trn trong thc nghim: pH o c trong thc nghim l 3,368) Nhn xt: Khi tnh pH trong dung dch hn hp cc acid (hay baz) phi so snh (h) ca tng dung dch cho, vic tnh pH ca dung dch pha trn cng h l tnh theo pH ca acid mnh nht. 1.3.3. H a acid - baz C th coi cc a acid nh l hn hp ca nhu n acid. Trong a s trng hp, nht l i vi cc acid v c, th s phn ly ca cc a acid xy ra mnh nht nc th nht, v sau gim dn cc nc sau, ngha l cc hng s phn ly thng sp xp gim dn theo th t K1 > K2 >... iu ny d hiu v mt phn t khng mang in mt proton d dng hn mt anion, v anion c mt in tch li mt proton d dng hn mt anion c 2 in tch v.v... Theo Pauling: Cc hng s phn ly ca th t cc nc, gim dn theo t l cch l 10-5 C th biu din cng thc tng qut ca cc 31

oxyacid di dng (HO)nXOm : khi m cng tng th kh nng acid cng mnh Vi acid a chc m hai nc phn ly gn nhau c gi tr cch nhau rt xa: gp 104 ln th c th coi s phn ly nc ng trc l ng vai tr quyt nh hn nc phn ly ng sau v c th tnh nng ion hydro da vo cn bng phn ly nc ng trc ny. Vi acid a chc m cc nc gn nhau hoc khng cch nhau nhiu lm th phi tnh chnh xc da trn cc qu trnh, cc phng trnh ton hc, phi thit lp cc biu thc tnh nng cc cu t trong dung dch da trn s t hp thng thng cc nh lut tc dng khi lng v nh lut bo ton nng . V d: Trong dung dch acid H2A CM c hai qu trnh phn ly: H2A H+ + HA- c K1 =
[ H ].[HA ] [ H 2 A]

[H2A] = K11-. [H+ ]. [HA- ] HAH+ + A2- c K2 =

[ H ].[A 2 ] [ HA ]

[HA- ] = K21-. [H+ ]. [A2- ]. Theo nh lut bo ton nng : (H2A)= C = [ H2A] + [HA- ] + [ A2-] C = K11-.K21-[A2-][H+]2+ K21- [A2- ] [H+ ] + [A2- ] [A2- ] = C.
1 K 1 .K 2 .h
1 1 2

K 2 .h 1

32

Do : v

[HA- ] = C.

K 1 .h K 1 .h K 1 K 2

[H2A] = C.

h2

h2 K1 .h K1 K 2
hn ... K1 K 2 ...K n 1 .h K1 K 2 ...K n

Trong trng hp tng qut vi acid HnA: [HnA] = C.

h n K1 .h n 1 K1 K 2 h n
2

[Hn-1A-] = C.

h n K1 .h n 1 K1 K 2 h n
h
n

K1 h n 1 ... K1 K 2 ...K n 1 .h K1 K 2 ...K n

n 2

.......... [An-] = C.
K 1 .h
n 1

K 1 K 2 ... K n K1 K 2 h ... K 1 K 2 ... K n 1 .h

K 1 K 2 ... K n

V d: Tnh pH ca dung dch H4A 0,1M Cc qu trnh phn ly: H4A H3A H2A2HA3V K1 H+ + H3A - K1 = 10-2 (1.6) H+ + H2A2- K2 = 10-2,67 (1.7) H+ + HA3- K3 = 10-6,20 H+ + A4- K4 = 10-10,30 K2 >> K3 >> K4, nn khi tnh phi k n hai

cn bng (1.6) v (1.7) v khng cn tnh cc cn bng K3, K4, nn theo nh lut trung ho v in [H+ ] = [OH - ] + [H3 A- ] + 2[H2 A2- ] h - W/h - C.
K 1 .h 2 K 1 K 2 =0 h K 1 .h K 1 K 2
2

V dung dch c mi trng acid nn: h >> W/h, bin i c: h3 + K1 h2 + K1 (K2 - C) h - 2 K1 K2 C = 0 h3 + 10-2 h2 - 9,8 10-4 h - 4,28 10-6 = 0 33

Gii theo phng php gn ng Newton: h = 2,94 10-2 pH = 1,53 [Nu ch tnh theo cn bng (1.6) th: h = 2,7 10-2 v pH = 1,57] Tng t vi h a baz, cch tnh ton u nh nhau. V d: Tnh pH ca dung dch Na2CO3 0,1M Gii: Qu trnh phn ly: Na2CO3 CO32H2O + H+ 2 Na+ + CO32H+ + OH HCO3(K2-1 = 1010,38 )

HCO3- + H+ H2CO3 (K1-1 = 106,36 ) V K2-1 >> K1-1 nn tnh theo qu trnh: CO32H2O + H+ H+ + OH HCO3HCO3- + OH - (W.K21-) 0 x 0 x

CO32- + H2O Nng ban u : 0,1 Nng cn bng:0,1 - x (x =[OH-]) Ta c: W K21- =

x2 0,1 x

x = 10-2,34 h = 10-11,66 pH = 11,66

Nhn xt chung: Vi cc h a acid hay baz, nu cc nc phn ly sau qu b, th c th xem xt pH ca dung dch theo nc 1. 34

1.4. Khi nim v ho tan, tch s tan 1.4.1. tan (S) V mt l thuyt, mi cht u c kh nng tan c trong cc dung mi tng thch. Tuy nhin trong thc t, mi cht ch c kh nng tan trong mt mi trng nht nh, mt nhit nht nh, vi nng nht nh, nh: cht ny c th tan c trong nc nhng cht khc li ch tan trong xng du v.v... c trng cho kh nng tan ca cc cht trong nhng mi trng thch hp ng vi iu kin tng ng, a ra khi nim v ho tan hay tan, c k hiu l S. Chng hn, khi ho tan mui n trong 100gam nc nhit 25 0C th ch lm tan ti a 36g NaCl, nu tip tc cho thm lng NaCl vo th lng mui cho thm ny s khng tan c na. Nu tip tc un nng ln 80 0 C th c th ho tan thm 25 gam NaCl na. (c k hiu l SNaCl(250C) = 36 v SNaCl(800C) = 56) Dung dch khng th ho tan thm ti nhit ang th nghim, gi l dung dch bo ho ti nhit . tan (S) l lng cht tan tan trong 100 gam nc to thnh dung dch bo ho ti nhit ang xt Mi quan h gia nng phn trm C% vi tan S: Tnh C% ca dung dch (A) c tan (S) ti nhit t xc nh. Ti nhit (t) xc nh, c S gam cht tan trong 100 gam nc khi lng dung dch bo ho l (100 + S), 35

nn: C% =
S .100 (%) S 100
D.S .1000 M (100 S )

Mi quan h gia nng mol/ L CM vi tan S: CM = 1.4.2. Tch s tan (T) Khi nghin cu phn tch nh tnh thng hay ni n phn ng lm xut hin kt ta v ho tan kt ta v dng n thut ng tch s tan. Chng hn, cho BaSO 4 vo mt cc nc, qu trnh ho tan bt u: cc ion Ba2+ v SO42 cu to nn lp b mt ca mng tinh th BaSO4 s ht cc phn t lng cc ca nc, tng tc vi chng v s bt u chuyn vo dung dch di dng cc ion hydrat ho. Cc ion hydrat ho, s tu vo mc nng lng tch lu c m va chm vo b mt cc tinh th ca kt ta v chu sc ht ca cc ion tri du vi n, v mt mc no , chng s b kh nc v to thnh kt ta. Nh vy qu trnh ho tan l qu trnh thun nghch km theo qu trnh to kt ta: BaSO4 Ba2+ + SO42(dng kt ta -cht rn) (dng ion -cht tan) y l mt qu trnh cn bng ng. Khi t ti trng thi cn bng, nng cc ion hydrat ho trong dung dch ngng tng cn kt ta cn li ca tng rn th ngng gim, thu c dung dch bo ho. c im ca cc qu trnh xy ra trong mt h d th, s va chm gia cc ion cht tan v cc tinh th kt ta ch xy ra trn b mt ca tng ch khng phi trn ton b cht phn ng. 36

Theo nh lut tc dng khi lng th vn tc ho tan cht rn (V1) t l thun vi b mt cht rn (p), tc l: V1 = k1. p Khi cn bng c thit lp v nhit khng i, c th coi i lng b mt tng rn l khng i v bng 1. Khi c th tha nhn V 1 = k1, tc l vn tc ho tan ch ph thuc vo bn cht ca cht in ly c ho tan. Vn tc kt ta cc ion trn b mt tinh th s t l vi b mt tng rn, vi nng v vn tc di chuyn ca cc ion trong dung dch. Bi v b mt tng rn bng 1 nn vn tc kt ta V 2 c xc nh bi nng v vn tc chuyn ng ca cc ion, tc l c xc nh bi hot (a) ca cc ion. Do : v2 = K2. a(Ba2+ ). a( SO42-). Khi cn bng c thit lp, vn tc kt ta bng vn tc ho tan v1 = v2, nn: K2.a(Ba2+ ). a( SO42-) = K1
K1 = a(Ba2+ ). a( SO42-), K2

T l trn c k hiu l T (BaSO4) = a(Ba2+). a( SO42 ) v gi l tch s tan, v nhit khng i th T l mt i lng khng i, c trng cho mi cht in ly. i vi cht in ly c lng cu t ln hn 2 th T l tch s hot ca tt c cc ion c trong dung dch vi lu tha l h s tng ng. M hot c xc nh cng thc: a(M) = [M]. f(M), trong [M] l nng mol/L ca cht in ly M v f(M) h s hot ca M. 37

Trong cc trng hp cc cht M t tan hoc khng tan ti iu kin nhit xc nh, nng mol ca cc ion m chng phn ly ra trong dung dch bo ho qu nh, nn c th coi lc ion v hot tnh ho hc ca cc ion khng c s thay i ng k no, v c th chp nhn c f(M) = 1. Vi cht kt ta (M) l AmBn th cng thc tch s tan: Tt (AmBn) = [An+ ]m. [Bm- ]n. (Xem ph lc cui gio trnh v tch s tan mt s hp cht) 1.4.3. iu kin kt ta, kt ta hon ton, ho tan kt ta Da vo nng cc cht tc dng, v dng tch s tan tnh kh nng to thnh kt ta v ho tan kt ta khi thc hin phn ng trao i, cng nh tnh mc kt ta hon ton cc ion xc nh. Tuy nhin s xut hin kt ta s ph thuc vo tch s hot ca cc ion c trong dung dch, nu nh tch ny ln hn T th kt ta s to thnh, nhng nu chng b hn T th kt ta li khng c to ra. V d: Trong dung dch bo ho AgCl c [Ag+ ]. [Cl- ] = T (AgCl) Nn nu trong dung dch no li c: [Ag+]b. [Cl-]b > T (AgCl) s xy ra s to kt ta ca AgCl. Nhng [Ag+]b. [Cl-]b < T (AgCl) s khng to kt ta ca AgCl. V d: Xc nh iu kin v a v b khi trn (CH3COO)2 Pb vi dung dch KCl c nng mol/L tng ng ln lt l 2a v 2b, vi cng mt th tch, th xut hin kt ta. 38

Gii: V nguyn tc khi pha trn cc cht ny c phn ng to kt ta PbCl2 theo phn ng: (CH3COO)2 Pb + 2 KCl = 2 CH3COOK + PbCl2 Thc t vi nng cc cht cho th tu vo nng cc cht tng tc m c hay khng c kt ta. Nng cc ion sau khi pha trn l: [Pb2+ ] = a (iong/L) v [Cl- ] = b (iong/L ) [Pb2+ ]. [Cl- ] = ab (iong/L) M: T ( PbCl2 ) = 1,6.10-5. Do : Nu ab > 1,6.10-5 th dung dch to ra qu bo ho, s pha trn c kt ta Nu ab < 1,6.10-5 th dung dch to ra cha ti bo ho, s pha trn khng c kt ta. Nu ab = 1,6.10-5 th dung dch t n bo ho 1.4.4. Cc quan h khi s dng (T) 1.4.4.1. Quan h gia tch s tan (T) v tan (S) Phng trnh phn ly ca cht (M): AmBn Nng ban u: C0 Nng phn ng: x m An+ + n Bm0 m.x 0 n.x nx

Nng cn bng: C0 - x mx Nu (M) tan trong nc nhit (t) th

[An+ ] = (m.S) m v [Bm- ] = (n.S)n Khi : T (M) = (m.S) m . (n.S) n = m m . n n. S m + n

39

1.4.4.2. Quan h gia tch s tan (T) v hng s cn bng (K) Trong phn ng to ta: m An+ + n BmAB + BmAB2 + BmABn - 1 + BmABn + A
n+ n+

AmBn

(KCB =

) (KCB =
2 3 1

C cc cn bng n: An+ + BmAB2 AB3 ABn A2Bn

AB (KCB = (KCB = (KCB = (KCB =

) ) )

...................................................
n 2')

A2Bn + A A3Bn (KCB = 3') ..................................................... Am - 1 Bn + An+ KCB =

I

AmBn
2..... n. 2

(KCB = '..... n'

m')

1.

V trong cn bng chuyn pha: AmBn (dung dch ) Nn: Tt (AmBn ) =

1 I.
II

AmBn (rn) ( = [An+ ]m. [Bm- ]n

II

V d: Trnh by cch tm tch s tan cho BaSO4 ti nhit phng th nghim. Gi s cc dung dch pha trn u c D = 1 g/mL Gii : Ho tan 1 lng BaSO 4 n khng tan trong nc ct to thnh dung dch bo ho nhit phng th nghim (t 0C) Ht 100mL dung dch ny lm bay hi hon ton. Tin hnh cn xc nh lng rn sau khi c cn (mg)
khi lng nc c trong dung dch bo ho l 100 -m (g)

40

 tan ca BaSO4 l S =

m .100 100 m

[BaSO4] = Phng trnh phn ly ca BaSO4 : BaSO4 Ba2+ + SO4210.m M

10.m M

Do : [BaSO4] = [Ba2+ ] = [SO42- ] = T (BaSO4 ) = ( Vy tch s tan BaSO4: (

10.m 2 ) M

10.m 2 ) . M

1.4.5. Cc yu t nh hng n s to kt ta (iu kin ho tan cht kt ta) 1.4.5.1. pH: tan ca nhiu cht kt ta c ngha quan trng trong dung dch phn tch nh lng, ph thuc trc ht vo nng ion hydro trong dung dch. Trong phn t ca nhng kt ta cha hoc anion c tnh baz hoc cation c tnh acid hoc lng tnh. Chng hn, tan ca florua canxi tng ln khi acid ho, hay Bimut Iodua gim tan khi pH gim. Trong dung dch bo ho BiI3 c cn bng sau: BiI3 Bi3+ + 3 I Bi3+ + H2O BiOH 2+ + H3O+ R rng khc vi tan ca canxiflorua, tan ca bismutiodua gim khi tng acid. Trong thc t phn tch thng cn phi kt ta nng ion H+ xc nh cho sn, th cn phi tnh tan 41

trong nhng iu kin . V d: Tnh tan ca CaC2O4 trong dung dch c [H ] = 10 -4 mol/L, bit rng acid H2C2O4 l acid hai chc,
+

c K1 = 10 - 1,25;K2=10- 4,27 v tch s tan ca CaC2O4 = 2,3.10 -9. Gii: Trong dung dch c: CaC2O4 Ca2+ + C2O42-

V acid H2C2O4 l mt acid yu, nhng ion oxalat lin kt mt phn vi ion hydro trong mi trng to acid bt buc l pH = 4 (do [H+]= 10 -4 mol/L) C2O42- + H3O+ HC2O4- + H2O HC2O4- + H3O+ H2C2O4 + H2O Mui CaC2O4 l mt hp cht ion, nng ca n bng nng ca ion Ca 2+ v cng bng nng cn bng nhng dng khc nhau ca ion C2O42Nn: S = [Ca2+ ] = [C2O42- ] + [HC2O4- ] + [H2C2O4 ] M cho cc gi tr: K1 = 10 - 1,25 ;K2 = 10 - 4,27, do : K2 =
[ H ].[C 2 O4 ] [ HC 2 O4 ]
10 4 [C 2 O4 ] ]= = 1,862.[ C2O42- ] 4 , 27 10
2

[HC2O4K1 =

[ H ].[HC 2 O4 ] [ H 2 C 2 O4 ]

10 4.1,862.[C2O4 ] = 10 -1,25 [ H 2C2O4 ]

[H2C2O4 ] = 0,0033. [C2O42- ] Nn:

[Ca ] = [C2O42-] + 1,862 [C2O42-] + 0,0033 [C2O42-] = 2,8653 [C2O42- ]
2+

42

[C2O42- ] =

[Ca 2 ] 2,8653

Thay vo biu thc tnh T : T = [Ca2+ ]. [C2O42- ] = 2,3. 10 -9 Vy tan l: S = 8,1.10 -5. 1.4.5.2. Nng cht in ly [Ca2+ ] = 8,1.10 -5 M

Bng thc nghim xc nh c rng, kt ta thng tan trong dung dch cht in ly nhiu hn trong nc (tt nhin iu kin cht in ly khng cha ion cng tn vi kt ta). l do: 1) Hiu ng nng cht in ly ph thuc nhiu vo in tch ca cc ht tham gia vo cn bng. Nu cc ht trung ho in th hng s cn bng bin i t, nhng in tch ca cc ht tham gia phn ng hoc sn phm ca phn ng cng ln th hiu ng cng tr nn r rt. V d: Khi thm lng va phi KNO3 vo dung dch bo ho AgCl (r) v BaSO4 (r), th trong hai cn bng: AgCl Ag+ + ClBaSO4 Ba2+ + SO42C cn bng sau chuyn dch sang phi mnh hn cn bng trc 2) nh hng ca cht in ly trong mt khong rng nng thc t khng ph thuc vo bn cht ca n m ch ph thuc vo thng s nng ion ca dung dch qua lc ion 43

Cng thc lc ion :

m1 Z 1
2

m2 Z 2 2

m3 Z 3 ...

Nu lc ion

< 0,1, cht in ly khng ph thuc vo

bn cht ion v c xc nh ch bng lc ion, nhng nu 0,1 th iu ny khng cn ng na. Lc ion cng ln th h s hot ca n cng ln, m hng s phn ly khng i nn nng cht in ly thay i, lm nh hng n tan ca kt ta. 1.4.5.3. S to phc tan ca kt ta c th bin i nhiu khi c mt mt s cht to phc tan vi anion v cation kt ta. Nh s kt ta ca nhm bng baz khng bao gi hon ton khi c mt ion florua, mc d tan ca Al(OH)3 cc nh. Phc florua nhm kh bn cn tr s xut hin nh lng ca Al3+ trong dung dch: Al(OH)3 Al3+ + 3 OH Al3+ + 6 FAlF6 3- . Nh vy ion F- cnh tranh mnh hn OH- phn ng vi Al3+ , v nng F- cng ln th tan ca Al(OH)3 cng ln, tc Al(OH)3 d b tan ra hn. Nu bit hng s bn ca phc, c th tnh tan ca kt ta khi c mt thuc th to phc. Khi nhng bin php c s dng tng t nh nhng phng php khc. V d: Tnh tan ca AgBr trong dung dch NH3 0,1M Cc qu trnh cn bng: AgBr 44 Ag+ + Br-

Ag+ + NH3 Ag(NH3 )+ + NH3 NH3 + H2O

Ag(NH3 )+ [Ag(NH3 )2]+ NH4+ + OH -

nh lut bo ton nng : [Br- ] = [Ag+ ]+ [Ag(NH3 )+ ] + [Ag(NH3 )2]+. Ta c: T(AgBr) = [Ag+ ]. [Br-] = 5,2.10-13 K1 = K2 =
[ AgNH3 ] = 2.103 [ Ag ].[NH 3 ]
[ Ag( NH 3 ) 2 ] [ AgNH 3 ].[NH 3 ]

= 6,9.103

K1.K2 = K(B) =

[ Ag( NH 3 ) 2 ] = 1,38.107 2 [ Ag ].[NH 3 ]

[ NH 4 ].[OH ] = 1,76.10-5 [ NH 3 ]

V Nng ban u l 0,1M, nn: 0,1 = [NH4+ ]+ [NH3 ] + [Ag(NH3 )+ ] + 2[Ag(NH3 )2+] Ngoi ra trong tng tc ca NH 3 vi H2O, c mi ion NH4+ xut hin l c mt ion OH- c to thnh, nn: [OH-] = [NH4+ ] Phng trnh trung ho v in:
[NH4+ ]+ [Ag+ ] + [Ag(NH3 )+ ] + 2[Ag(NH3 )2]+ = [Br- ] + [OH - ]

Gi s: [NH4 ]nh hn rt nhiu cc thnh phn khc ca phng trnh, v gi tr hng s baz ca
+

NH3 kh nh [Ag(NH3)2]+ >> [Ag NH3]+ v [Ag+], v gi tr hng s cn bng ca cc phng trnh K1 v K2 45

Nn c: [Br-]

[Ag(NH3)2]+ v

[NH3] 0,1- 2 [Ag(NH3)2]+ [NH3]= 0,1- 2 [Br-] Do : K1.K2 =

[ Ag( NH 3 ) 2 ] [ Ag ].[NH 3 ]2

1.4.5.4. Cn bng cnh tranh Mt cht kt ta c to thnh c xem nh l mt cht in ly t tan trng thi bo ho ti nhit xc nh. Khi s thay i mt lng cht khc trong h, s xut hin nhng cn bng mi v nhng cn bng ny s lm thay i trng thi n nh hnh thnh nn mt trng thi n nh khc. V d: Trong dung dch bo ho: Mg(OH)2 Mg2+ + 2 OH - th: T( Mg(OH)2 ) = [Mg2+ ]. [OH - ]2 Nu thm acid HCl chng hn vo dung dch ny th: HCl + H2O Cl- + H3O+ Cc ion H3O+ s phn ng vi ion OH- trong dung dch Mg(OH)2 lm cho [OH- ] b gim xung: H3O+ + OH2 H2O Cn bng b chuyn dch sang phi, ngha l Mg(OH)2 b ho tan. Hay ni cch khc, mun ho tan Mg(OH)2 phi thm vo dung dch cha n mt cht c kh nng kt hp vi mt trong cc ion ca Mg(OH) 2 lm cho [Mg2+ ]. [OH- ]2 lun nh hn tch s tan T ca n. 1.4.5.5. Mt s yu t ph khc Nhit : Phn ln cc cht rn khi tan hp th nhit. V th, khi tng nhit thng lm tng 46

kh nng tan ca kt ta v tch s tan tng ng ca phn ln cht t tan tng ln. Dung mi: tan ca phn ln cc cht v c trong hn hp nc vi cc dung mi hu c nh hn r rt vi nc tinh khit. Nhng d kin v tan ca CaSO 4 c dn ra bng sau l in hnh i vi nh hng loi ny Bng 1.2. Quan h nng v tan Nng ca ru etylic % theo khi lng 0 6,2 13,6 23,8 33,0 41,0 tan ca CaSO4 trong 100g dung mi 0,208 0,100 0,044 0,014 0,0052 0,0029

Tc to kt ta: phn ng to kt ta thng xy ra chm, t ti trng thi cn bng i khi ln n vi gi. y cng l mt thun li cho nh ho hc khi mun phn chia cc phn ng theo di. Chng hn c th tch Ca2+ ra khi Mg2+ bng cch kt ta oxalat mc d c hai cation u to c kt ta vi anion ny v chng cng c tan nh nhau, nhng do tc to kt ta Mg2+ vi anion C2O42- chm hn rt nhiu so vi Ca2+ . V th lc ngay 47

CaC2O4 th thc t kt ta thu c khng c ln MgC2O4. 1.4.6. L thuyt v s kt tinh, s to ta C ch ca qu trnh to kt ta c xem xt bi kh nhiu kin khc ngc nhau. c mt cch nhn hp l, hy chn cch gii thch da trn nhng quan st thc nghim, sau mi xem xt n l thuyt gii thch chng. 1.4.6.1. Nghin cu thc nghim qu trnh kt ta C th xem thi k tip xc ko di t lc trn thuc th n khi xut hin kt ta nhn thy c l giai on ng ch nht. Thi gian ny thng rt khc nhau: thi gian cho kt ta BaSO 4 xut hin tng i di th kt ta AgCl li rt ngn. H thc Nielsen: ng so snh nhng thi k tip xc ca nhng kt ta khc nhau v xc nh chng theo h thc sau: t1. C 0n = k (t1 l thi k tip xc - C 0n l nng ban u ngay sau khi pha trn cc cht - k, n l nhng hng s thc nghim) Gi tr n ca cc cht kt ta AgCl, Ag2CrO4 , CaF2, CaC2O4 , v KClO4 ln lt l: 5 - 4 - 7 - 9 - 3,3 - 2,6. Cn BaSO4 th c gi tr n thay i nhiu. Cn theo Johnson v O' Rourke, dn in trong thi k tip xc hu nh khng thay i do , trong thi gian ny ch mt phn cht tan dng cp ion hoc nhng lin hp ion ln hn m thi. Theo Lamer v Dinegar, chng hn trong trng hp 48

iu ch ion SO42 ng:

trong dung dch ng th theo phn

S2O82- + 2 S2O322 SO42- + S4O62Khi c mt ion Ba2+, dung dch to thnh mc qu bo ho xc nh khng sinh ra kt ta trong khong thi gian tng i di so vi chnh dung dch nhng c iu ch bng cch trn trc tip cc thuc th. V th c th kt lun rng kt ta ch c th xut hin khi qu bo ho t mc xc nh. Mt cng trnh khc, Collins v Leineweber nu ra gi tr mc qu bo ho chun ph thuc vo tinh khit ca thuc th. Khi kt tinh li nhiu ln v lc cc dung dch thuc th, thu c gi tr mc qu bo ho chun l 32. Cc tc gi ny kt lun, trong trng hp ny khng to thnh cc trung tm kt tinh ng th v s kt tinh bt u trn nhng trung tm l, c th l lu hynh tn ti trong dung dch thiosunfat l trung tm kt tinh. Khi lm sch bnh kt ta mt cch cn thn bng cc x l hi trong thi gian di, lng tinh th BaSO4 trn mt n v th tch gim i 10 ln v c th trn 10 ln, do nhng iu kin bnh thng, phn ln trung tm kt tinh c to SO 42 trn b mt thnh bnh thu tinh. Ngoi ra rt c nhiu bng chng ng tin cy v s to thnh cc trung tm kt tinh, cng nh s gm lng ng thi tng kch thc ht kt ta c to thnh. Von Weimarn hon thnh cng trnh nghin cu v s ph thuc kch thc v lng ht kt ta vo nng 49

cht kt ta: o kch thc tinh th BaSO4 bng cch trn nhanh nhng dung dch BaSCN vi dung dch MnSO 4 c nng phn t bng nhau. long 10
- 4

M, ni

chung kt ta khng xut hin. Khi tng nng trong gii hn t 10 - 4 n 10 - 3 M, th kt ta c to thnh. Ban u l nhng cht "v nh hnh", sau chuyn t t thnh nhng tinh th hon chnh trong 6 thng. Kch thc ca nhng tinh th cui cng gim i khi nng ban u tng. S tng kch thc ht cng vi s tng nng c tm thy vi cc cht kt ta Ag2CrO4, AgSCN v nikendimetylGlioximat... Khc vi BaSO4, AgCl kt ta nhanh ngay c trong cc dung dch qu bo ho khng ln. S kt ta ca AgCl hay AgBr l do s tch cp cc ht keo, ch khng phi l nhng tinh th ring bit nh BaSO4. 1.4.6.2. L thuyt c in v s to thnh trung tm kt tinh Hp phn nhng ht nh ca kt ta c quyt nh bi tc tng i ca 2 qu trnh: 1. Qu trnh to thnh cc trung tm kt tinh. 2. Qu trnh ln ln ca cc trung trm kt tinh. Theo Ostwald, dung dch qu bo ho c th l gi bn nn vn trng thi ng th lu v hn. Cho n khi cho vo mui thch hp vi cc trung tm kt tinh, th dung dch c kh nng t kt tinh (dung dch qu bo ho vt qua gii hn gi bn mt gi tr xc nh). Da trn nhng quan im , s to thnh kt ta c gii thch nh sau: nu t nhit t 0C ban u tng 50

dn nng cht b kt ta th khi n im gii hn C trn ng cong th kt ta khng hnh thnh c. Nu ng vi im C, khng thm thuc th, th nng ca n b h thp n im tng i B trn ng cong tan. Thm thuc th tip tc cng khng dn n s to thnh cc trung tm kt tinh mi nu nng lc khng t ti im gii hn C. Do kt ta to thnh khi phi l ht tng i ln v ng nht v kch thc. Nu do thm thuc th kt ta nhanh hoc do khuy khng nhanh, nng im mt lc no vt qu im C th trong qu trnh kt ta nhng trung tm kt tinh mi c th c to thnh v do s ht tng ng thi kch thc v ng nht ca chng gim. Nu nhng ng cong tan v siu tan kh gn nhau th hon ton chc chn rng kh c th thu c kt ta ng nht. 1.4.6.3. L thuyt Beckerr - Doring Becker v Doring xem xt qu trnh to thnh cc trung tm ngng t khi chuyn t mt cht trng thi hi v trng thi lng di quan im nhit ng hc v ng hc. Qu trnh ny bao hm mt lot cc phn ng bc lng phn t dn ti s to thnh cc tp hp v cc tp hp ny cng trong thi gian c th t lm gim kch thc ca mnh do mt i nhng phn t ring bit. T y tn s to thnh cc trung tm ngng t chnh l tc to thnh cc trung tm ngng t c kch thc chun khi cc tp hp phn t va chm mnh vi cc phn t ring bit. Khi nhng trung tm ngng t c 51

kch thc chun pht trin nhanh v to thnh nhng git trong lc nng tng ng vi trng thi dng thp hn nhiu so vi nng ca n cn phi c tng ng vi trng thi cn bng nu xy ra. Tc to thnh cc trung tm ngng t ph thuc nhiu vo nng v do ph thuc vo bo ho chun. Kch thc chun ca trung tm ngng t cht lng th hin gn nh ng nht i vi cc cht khc nhau, khong 50 - 100 phn t. Tuy vy l thuyt ny cha th m t c s tc ng ca sc cng b mt n s bin i cong ca ht. 1.4.6.4. L thuyt Christiansen - Nielsen Christiansen - Nielsen a ra l thuyt to thnh trung tm kt tinh trn c s gii thch thi gian ca thi k cng hng. V thi k ny lin quan chc ch n bc phn ng to thnh cc trung tm kt tinh. Tng t nh Becker v Doring, cc tp hp ion c to thnh nh cc phn ng lng phn t cho ti khi to thnh trung tm c kch thc chun ri sau cc trung tm kt tinh s t pht trin. Nhng v thi k cng hng l hm s c bc khng cao (t 3 n 9) ca nng nn dn n cc trung tm kt tinh ch bao gm mt s tng i khng ln cc ion. Thc ra, theo Johnson, ch cui thi k cng hng mi cn ch n s ln ln ca cc ht, cn trong sut thi k cng hng cn ch ti s to thnh trung tm kt tinh, cng nh s pht trin ca chng. Tng s cc trung tm kt tinh khi kt ta t cc dung dch long khng phi t l thn vi nng ca chng, 52

m tc to thnh trung tm kt tinh t l thun vi nng theo bc 4 v tr thnh hng nh trong sut thi k cng hng. Thi gian ca thi k cng hng t l nghch vi gi tr nng theo bc 4. Nh vy c th gii thch s ht hng nh trong kt ta quan st trong thc nghim: s ion trong cc trung tm kt tinh chun ca BaSO4, Ag2CrO4, CaF2 l 8, 6, 9. Tuy nhin Turnbull khng nht tr trong cc quan im trn ca Christiansen - Nielsen, ng cho rng s ln ln ca trung tm kt tinh c th l do bt u t nhng trung tm l, v a ra dn chng: thng nhng got nh ca cht lng hoc ca dung dch nc c th chm ng ng k so vi lng ln chnh xc ca cht lng y. Hin tng ny xy ra l do t c kh nng c d ch l mt trung tm l trong mt git cht lng. Chc chn l trn c s nghin cu ng cong dn in trong thi k ln ln ca tinh th cng c th rt ra nhng kt lun r rng v c ch kt tinh. C hai l thuyt ging nhau ch, trong sut qu trnh ca thi k cng hng, s ln ln ca cc mm ban u chm chp v ch cui giai on ny cc ion t do mi tch khi dung dch. 1.5. Khi nim c bn v phc cht 1.5.1. Khi nim Trong dung dch cc phc cht c hnh thnh do s kt hp gia hai hoc nhiu dng n gin hn c kh nng tn ti c lp. S to phc c th xy ra khng ch gia hai ion tch in ngc du m c th xy ra gia 53

proton, cation kim loi, vi cc cht cho electron tch in m, trung ha in hoc ngay c vi ion tch in dng. Chng hn: H+ + NH3 Ag+ + NH3 NH4+ [AgNH3 ]+

[AgNH3 ]+ + NH3 [Ag(NH3 )2]+ H+ + NH2- CH2 CH2 -NH3+ NH3+- CH2 CH2 - NH3+ Cng tng t nh vy, cc phc cht c th hnh thnh do s kt hp gia anion vi cht nhn electron l cation, phn t trung ha in, hoc anion. Chng hn s to phc gia Hg2+ v Cl- : Cl- + Hg2+ Cl- + Hg Cl+ Cl- + HgCl2 Hg Cl+ HgCl2 HgCl3-

Cl- + HgCl3HgCl4-2 Tng qut nu hai dng A v B cng tn ti trong dung dch th chng c th tng tc nhau to thnh mt hoc mt s phc cht c cng thc chung AmBn (m > 1; n 0) Trong cc dung dch long thng ch gp cc phc mt nhn: m = 1 v n 1; A c gi l nhm trung tm ca phc ABn v B c gi l phi t. A c th l ion kim loi n gin hoc l mt ion phc tp nh VO 2+, hoc l mt phc rt bn nh [Co(NH 3)6]2+.... S phi t lin hp vi nhm trung tm thay i rt khc nhau ty thuc bn cht ca ion trung tm,ca phi t v quan h nng gia chng. Thng thng khi nng ca phi t gp rt nhiu ln nng ca ion trung tm s to 54

thnh phc vi s phi t cc i. Phc cht mt nhn ( ABn )c chia thnh 2 nhm: Nhm 1: cc acid Bronsted, trong cc ion hydro ng vai tr phi t v lin hp vi nhm trung tm khng mang in hoc mang in m. Cn bng thuc loi ny l cn bng acid - baz. Nhm 2: Cc phc cht kim loi, k ccc cp ion c hnh thnh do s kt hp nhm trung tm l ion kim loi vi cc phi t trung ha in hoc tch in m. Cc phi t c th l n phi, nu phn t ca cht ny ch cha mt nguyn t c kh nng tham gia lin kt cho nhn. Ngc li, nu phn t ca phi t c nhiu nguyn t c kh nng cho electron th n c th chim ng thi nhiu phi t chung quanh ion trung tm, c gi l phi t a phi. Chng hn cc ion halozenua, amoniac l nhng phi t n phi, v mi ion hoc phn t ca chng ch chim mt phi v chung quanh nhn. in tch ion phc bng tng i s in tch ca nhm trung tm v cc phi t. Nhiu ion n gin khng c tnh cht g r rt, nhng khi chuyn thnh phc thch hp th chng li c nhng tnh cht rt c trng v c th s dng nhn ra ion . Chng hn ion Cu2+ c mu xanh nht v khng th nhn ra c khi nng thp. Nhng khi chuyn thnh phc amin [Cu(NH 3)4]+2 th n c mu xanh xm, pht hin c d dng hn. Nhiu phc c tan nh v c mu c trng c s dng xc nh nh tnh v nh lng cc vi lng 55

ion kim loi. Chng hn dimetylglyoxim to c phc mu vi ion Ni2+ v cho php tm ra ion ny vi nhy rt cao, v chn lc kh ln (c th tm ra ion ny khi c mt ca nhiu ion kim loi khc) 1.5.2. Cc tnh ton v cn bng phc v ng dng ca phc trong ho phn tch Vic tnh tan cn bng to phc trong dung dch thng rt phc tp. V cc qu trnh to phc thng xy ra tng nc vi chnh lch ca cc hng s gia cc nc l khng xa nhau lm, v cng vi s to phc th lun c cc qu trnh ph xy ra theo cng, lm lch i tnh chnh xc trong phng php chun to phc. Cn xt nhng kh nng tnh tan gn ng n gin cc qu trnh ny, nhng vn khng c sai lch nhiu 1.5.2.1. Tnh nng cn bng cc ion trong phn ng to phc V d: Tnh nng cc ion trong dung dch Fe(ClO4)3 0,1M v KSCN 0,01M v HClO4 0,1M Gii: Trong dung dch c s phn ly: Fe(ClO4)3 KSCN HClO4 Fe3+ + 3 ClO4K+ + SCNH+ + ClO4-

V dung dch trong mi trng acid nn b qua s to phc hydroxo ca Fe3+: Fe3+ + H2O (FeOH)2+ + H+ K =10-2,17
Nng ban u: 0,1 0 h h 0,1 h 0,1 + h Nng phn ng: h Nng cn bng: 0,1 - h

56

Nn: K =

h.( 0,1 h) (0,1 h)

2+

h = [(FeOH)

]=

10

2 ,17

.10
1

10

= 6,76.10-3.

iu ny c ngha nng ion phc (FeOH)2+ ch chim t l 6,76% so vi tng nng Fe3+, nn c th b qua s to phc ca ion Fe3+ny. Cc qu trnh to phc: Fe3+ + SCNFeSCN 2+ K1 = 10 3,03 FeSCN 2+ + SCNFe(SCN)2+ K2 = 10 1,94 Fe(SCN)2+ + SCNFe(SCN)3 1,4 K3 = 10 Fe(SCN)3 + SCNK4 = 10 0,8 Fe(SCN)4- + SCNFe(SCN)4Fe(SCN)5-2

K5 = 10 0,02 V nng Fe3+ >> nng SCN- v K1 > K2 > K3 > K4 > K5, nn coi nh K1 l qu trnh chnh trong dung dch: Fe3+ + SCNFeSCN 2+ K1 = 103,03 Nng ban u: 0,1 Nng phn ng: 0,01-x Nng cn bng: 0,09 + x Nn: K1 =
0,01 x (0,09 x) x

0,01 0,01-x x

0 0,01-x 0,01 - x

x = [ SCN- ] = 1,04. 10-4 ;

[ FeSCN 2+ ] = 9,9.10-3 ; [Fe3+ ] = 9,01. 10-2 Thc ra vic tnh tan theo phng php ng cho 57

thy nng ion phc Fe(SCN)2+ chim t l bng 1/ 10 nng phc FeSCN2+ , v nng ion FeSCN2+ va tnh c thc t bng tng nng tt c cc dng phc Fe(SCN)3 c trong dung dch. 1.5.2.2. Anh hng ca pH n s to phc pH c nh hng trc tip n qu trnh proton ha ca cc phi t l baz yu, v ti qu trnh to phc hydroxo ca cc ion kim loi trung tm. Do nng cc ion kim loi v cc phi t thay i theo pH, nn to phc cng thay i theo. Cc qu trnh to phc gia ion kim loi A v phi t B nh sau: To phc hydroxo ca ion kim loi: A + H2O AOH + H+
+ 1 2

A + 2H2O A(OH)2 + 2H ............................................ A + mH2O A(OH)m + m H+

+ Proton ho cc phi t B l cc baz yu: B + H+ BH Kn1BH + H+ BH2 .............................................. BHn - 1 + H+ BHn To phc gia A v B: Kn - 11K11-

A + B AB ( ) Trong trng hp to phc tng nc th pH khng nhng nh hng ti to phc ni chung m cn nh hng n quan h nh lng gia cc phc ring r. Thng thng nu trong h c d phi t th pH thp, 58

phc bc thp c hnh thnh nhiu hn, cn pH cao, phc c s phi t ln li c hnh thnh tt hn V d: Tnh pH i vi s to phc gia ion Pb 2+ v CH3COOGii: Cc qu trnh trong dung dch: Pb2+ + CH3COOCH3COO- + H+ Pb2+ + CH3COONn pH =
pK 2 p

PbOH+ + H+ CH3COOH Pb CH3COO+ =

6,18 4,74 = 5,46 2

= 10-6,18 K11- = 10-4,74 = 10 2,52

V d: Tnh nng ca cc dng phc khc nhau trong dung dch cha AgNO3 0,01M v NH3 1M pH = 4 v pH = 9 Gii Cc qu trnh xy ra trong h: AgNO3 Ag+ + NO3[AgNH3 ]+ [Ag(NH3 )2]+ AgOH+ + H+
1= 2=

Ag+ + NH3 Ag+ + 2 NH3 Ag+ + H2O H2O

2,09.10 1,86.10
-11,7

3 7

(1) (2) (3) (4)

= 10 W

H+ + OH -

NH3 + H+ NH4+ K11-= 1,8.109 = (5) ( gii bi ton n gin hn th dng phng php gii gn ng) pH = 4: mi trng acid yu, nn (5) xy ra mnh v phn ln NH3 d s tn ti di dng ion NH 4+. Mt khc v nng ban u NH 3 >> Ag+ nn c th coi nng NH3 1. 59

NH3 + H+ Nng ban u: 1 0 Nng cn bng: x 10 -4

NH4+ K11-= 1,8.109 0 1-x

(5)

Do : x = [ NH3 ] = 5,5 10 -6 Theo nh lut bo ton nng ban u ca ion Ag + :

C Ag = C1 = [Ag+ ] + [AgOH+ ] + [AgNH3 ]+ + [Ag(NH3 )2]+ (4.1)

trong : C1 = m. (1 +

h -1 +

a+

a2 )

vi a = [NH3] = 5,5 10 -6; C1 = 0,01; h= 10 -4 ; Tnh c m = [Ag+ ] = 9,89. 10 -3 iong/L Theo nh lut bo ton nng ban u ca ion NH3:
C NH 3 = C2 = [NH3 ]+ [NH4+ ] + [AgNH3 ]+ + 2 [Ag(NH3 )2]+

trong : C2 = a + . a. h + Theo (1) v (2):

1.m.a

2.m.

a2

a = 5,6. 10 -6.

[NH3] = 5,5. 10 -6 ; [Ag+] = 9,89. 10 -3 ; [AgNH3]+ = 1,15. 10 -4;

[Ag(NH3 )2]+ =6. 10 -6 Vy: pH = 4, s to phc gia Ag+ v NH3 xy khng ln v ch yu l phc amoniacat [AgNH 3 ]+. pH = 9: mi trng baz yu, nn c th c s to phc hydroxo ca ion Ag + (3) v qu trnh prton ho (5):
NH3 + H+ Nng ban u: 1 0 Nng cn bng: 1 - x 10 -9
Ag+ + H2O

NH4+ 0 x

K11-= 1,8.109 (5)

Do : x = 0,643; [ NH3 ] = 0,357.

AgOH+ + H+
= 10
-11,7

(3)

Nng ban u: 0,01 Nng cn bng: 0,01 - y

10 -9

Do : y = [AgOH+ ] = 10 -4,7 << C Ag 60

Nh vy to pH = 9, s to phc hydroxo ca ion Ag vn khng ng k, cn s prton ho ca NH 3 phi ch , v [ NH3 ] = 0,357 >> C Ag (0,01).
+

Coi nh [NH3 ] = a = 0,357. Kt qa l : [NH3 ] = 0,35; [Ag+ ] = 4,38. 10 -9 ; [AgNH3 ]+ = 3,2. 10 -6 ; [Ag(NH3 )2]+ = 9,89. 10 -6 Vy ti pH = 9, ton b ion Ag+ chuyn ho thnh phc iamin 1.5.2.3. S phn hy phc cht Trong thc t khi tin hnh phn ng vi mt ion kim loi tn ti di dng phc th phi phn hu n, bng cch: Chuyn mt trong cc ion ca phc thnh mt hp cht khc t phn ly hn, v d acid, baz yu hoc mt phc khc bn hn. Chng hn phn hu cc phc amin, th cho tc dng vi acid d, y amoniac trong phc s tc dng vi ion hydro chuyn thnh ion amoni. Hoc khi nh KCN vo dung dch phc ng amoniacat [Cu(NH3)4]2+ mu xanh m th dung dch s mt ngay v ion Cu2+ do phc amin phn ly ra tc dng ngay vi ion CN- chuyn thnh Cu(CN)42+ khng mu bn. Nu mt trong cc ion ca phc c tnh oxy ho kh th c th phn hu phc bng mt tc nhn oxy ha kh thch hp Chuyn mt trong cc cu t ca phc thnh 61

hp cht t tan. Chng hn khi nh dung dch Na2S vo dung dch cha phc [Cd(NH 3)4]2+ th s c kt ta CdS t tan, mu vng xut hin 1.5.3. Khi nim v s to phc vi thuc th hu c Cc thuc th hu c l dn xut ca amoniac c tnh cht to phc gn nh amoniac, c dng iu chnh pH, lm cht che. Cc cht thng dng l Pyrydin, Pycolin... cc cht ny c tnh baz yu hn NH 3 rt nhiu. Cng nh amoniac, chng to c cc phc bn vi nhiu kim loi, chng hn Ag+; Cd2+ ; Ni2+ ; Co2+ v.v...phn ng to phc y khng y cc ion hydro ra nhng ph thuc vo pH Cc thuc th hu c ngy nay c s dng rng ri trong phn tch, bi v nhy v tnh chn lc cao ca chng i vi nhiu ion kim loi. a s cc thuc th hu c dng trong phn tch cng l nhng cht in ly yu, v do phn ng gia chng vi cc ion kim loi cng l cc phn ng thuc loi ion. ACID ETYLEN DIAMIN TETRA ACETIC (EDTA) cn c gi l Complexon II hay ChelatonII. L mt acid 4 chc, c k hiu l H4Y.

L mt acid 4 chc, c phn ly theo 4 nc vi hng s phn ly ln lt l: p K1 = 2 ; p K2 = 2,67 ; p K3 = 7,23 ; p K4 = 12,30 Thuc th ny c kh nng to phc kh bn vi hu ht cc ion kim loi theo t l 1: 1 62

EDTA c s dng kh ph bin trong Ha phn tch lm cht che, chun cc ion kim loi. Cn dng n di dng mui Na2H2Y (Complexon III hay trilonB)

2 METYL PYRYDIN: C6H7N - trong nc c phn ng baz C6H7N + H2O C6H7N H+ + OH -. c dng phn tch nhm 4 - PYCOLIN: CH3 C5H4 N - trong nc cng c tnh baz RODAMIN: C3H3ONS2. c dng phn tch nhm 1 DIMETYL GLYOXIM: C4H8O2N2. c dng phn tch nhm 5. L mt acid yu, c k hiu Hdim c K = 8. 10 -12 . Thuc th ny to phc vi cc ion Ni 2+; Pd2+, v to phc mu tan trong nc vi ion Fe 2+ TIONALIT: C12H11ONS. c dng phn tch nhm 4 v 5. 1.5.3.1. Thuc th to phc ni vi cc ion kim loi Cc hp cht ni phc l nhng hp cht trong phn t c mt hoc nhiu vng cha ion kim loi. Trong phn t thuc th phi c t nht hai nhm nh chc gn nhau c kh nng tham gia phn ng vi ion kim loi to thnh vng. Trong a s cc trng hp, mt trong hai nhm 63

nh chc c cha hydro linh ng v khi tng tc vi ion kim loi th kim loi s thay th hydro. Lin kt y l lin kt in ha tr. Nhm nh chc ny thng c gi l nhm to mui. Cc nhm c cha hydro thng gp l nhm hydroxyl -OH ; cacboxyl -COOH ; sunfonic SO3H ; oxim = N-OH ; amin bc mt - NH2 ; amin bc hai - NHR ; asonic -AsO3H2 v.v... Nhm nh chc th hai thng cha cc nguyn t c tha t nht mt cp electron t do, v d, O,S,N. Khi lin kt vi ion kim loi th nguyn t ny ng vai tr cht cho v ion kim loi ng vai tr cht nhn v cp electron c dng chung cho c hai. Lin kt ny c gi l lin kt phi tr v thng c biu din bng mi tn (hoc ng chm). Cc nhm nh chc ny c gi l cc nhm to lin kt phi tr, thng gp l: = O; - OH; -Ndb ; = N-OH; = S; -S- v.v... V d: 8-oxyquinolin c hai nhm -OH v -N. Nhm OH l nhm to mui v nhm - N = to lin kt phi tr:

V d: DimetylGlyoxim khi tham gia phn ng to phc th nhm - OH trong mt nhm oxim ng vai tr nhm to mui, cn nguyn t N trong nhm oxim th hai th to lin kt phi tr:

64

Trong phn ng ny, ion Ni 2+ c hai in tch dng tc dng vi hai phn t DimetylGlyoxim to thnh hp cht trung ha c vng nm cnh. Ch rng, mt s thuc th hu c cng to phc cng vi ion kim loi, nhng c hai nhm nh chc u cng to lin kt phi tr, hoc cng c lin kt in ha tr. V d: O -phenantriolin c 2 nhm amin bc ba cng to lin kt phi tr vi ion kim loi. Hay nh Pyrocatesin c 2 nhm hydroxyt c hydro linh ng v u c kh nng thay th bi ion kim loi

O - phenantrolin c lin kt phi tr vi ion kim loi

Pyrocatesin b ion kim loi thay th 2 nhm hydroxyl

1.5.3.2. ng dng phc ni trong phn tch a s cc hp cht ni phc trung ha v in, u rt t tan trong nc v d tan trong dung mi hu c. iu ny cho php s dng cc thuc th hu c lm kt ta cc lng "vt" kim loi v sau "gom gp" chng li bng dung mi hu c tch chng ra khi dung dch. 65

Mt s cc phc c mu c trng c chn trong ng dng phn tch. Mu sc ny ph thuc vo bn cht ion kim loi v thuc th. i vi cc thuc th khng c ni i lin hp th ch c cc hp cht ni phc gia thuc th vi cc ion sinh mu mi c mu, chng hn, cc aminoacetic, pyrocatesinat, dithiocacbanat Cu, Fe..) Cn i vi cc thuc th c ni i lin hp c lin quan n vng cng, th s to ra phc mu vi cc cation kim loi, k c cc ion khng sinh mu, chng hn, dithizon v cc hp cht ni phc vi ion kim loi c cu to ni i lin hp

Nn chnh bn thn thuc th c mu xanh ve v cc phc cht ca thuc th ny vi ngay chnh cc kim loi khng sinh mu nh Zn, Cd u c mu da cam m. Mt c tnh c gi tr phn tch khc ca cc hp cht ni phc l bn ln. bn ca phc ph thuc nhiu yu t nh bn cht ca ion kim loi v trng thi ha tr ca n, bn cht ca nguyn t cho electron ca thuc th tham gia trc tip vo phn ng to phc, baz ca thuc th, cu to khng gian ca phc. c bit s vng v s lng cc nguyn t trong vng, s lng cc lin kt i trong vng v.v... c nh hng ln n bn ca phc. Trong iu kin nh nhau khi tng s vng th bn ca phc tng ln. Cc phc c vng 5 hoc 6 cnh th rt bn v rt hay gp. Mt s thuc th c chn lc kh cao, ngha l chng c kh nng nh 66

hng vo v tr no ca ion kim loi nht nh. Chng hn, dimetylGlyoxim ch to hp cht kh tan vi Ni 2+ ; Cd2+ ; Fe2+. Tuy vy s ln cc thuc th to c hp cht ni phc vi nhiu ion kim loi, chng hn, oxyquinonlin phn ng vi nhiu ion kim loi c kh nng to c hydroxyt kh tan, dithizon to c hp cht ni phc vi nhiu ion kim loi cho sunfat kh tan. Trong thc t tng chn lc ca thuc th, phi c cc yu t sau: Lm vic pH thch hp nht i vi phn ng cho Che cc ion cn tr nh cc cht to phc ph. S dng vic chit chn lc nh cc dung mi khng trn ln vi nc. Dng cc thuc th oxy ha kh chuyn ion cn tr tr thnh cc ion khng tc dng vi thuc th cho

Cc phc to c phc mu phi tho mn quy lut sau: Khng th xut hin phn ng mu gia ion kim loi khng c tc dng mang mu vi thuc th khng mu. Phn ng ca cc nguyn t c mu ring vi cc cht mu hu c nhy hn nhng km la chn hn so vi phn ng mu gia cc ion ny vi thuc th khng mu. ca phc ph thuc mc ion ca lin kt kim loi vi phi t.
max

67

Khi cation kim loi to phc mu vi thuc th hu c dng acid th cc i hp th mu ca phc chuyn v pha sng di so vi hp th

dng phn t Nu s to phc xy ra mt mc tng i, l do nhm mch nhnh ca thuc thu v do trng thi lin hp ca n t b ng chm. Do vy mu ca phc v thuc th t

khc nhau. 1. 6. Phn ng thy phn 1.6.1. Khi nim s thu phn Cc cht in ly acid hay baz khi ho tan trong dung mi nc u to dung dch c phn ng acid hay kim tng ng. Tuy nhin cng c nhng cht in ly l mui khi tan trong nc cng cho cc phn ng tng t. Chng hn khi xt s ho tan (CH 3COO)2 Ba:
(CH3COO)2 Ba + 2 H2O Ba2+ + 2 CH3COO- + 2 OH[Ba(H2O)n]2+ + 2 CH3COOH + 2 OH-

hay:
(CH3COO)2 Ba + (n + 2) H2O

S to thnh cht in ly yu CH 3COOH lm cn bng n ly trong nc b ph hu: trong dung dch xut hin [OH-] solvat d, lm cho dung dch c phn ng kim. Phn ng tng tc gia nhng ion ca mui v nhng ion ca H+ v OH- gi l s thu phn. Trong cc phn ng ny, cc ion H+ v OH- ch c tch t li trong dung dch, chng lm chm li qu trnh dch chuyn t tri sang phi, chng khng xy ra phn ng ti cng, m cui cng cn bng ng c 68

thit lp: phn ng thu phn l phn ng trung ho, chng hn: CH3COO- + H2O CH3COOH + OH(thu phn ) AlCl3 + 6 H2O Al2S3 + 6 H2O (trung ho) Al(OH)3 + 3 H2O + 3 Cl-. 2 Al(OH)3 + 3 H2S

(dung dch acid mnh) (dung dch acid yu) NaAlO3 + H2O Na+ + HAlO2 + OH(dung dch kim mnh) Vy phn ng thu phn l phn ng tng tc gia nhng cht khc nhau (mui, hydrua, cc hp cht oxy, halozen v thioanhydric) vi nhng ion ca nc, km theo s ph hu cn bng in ly ca nc v lm thay i pH ca dung dch (k c s thay i mu sc ca dung dch ) V d: kho st s thu phn ca mui NH 4Cl Trong dung dch c s in ly: NH4Cl Trong dung mi mc: NH4+ + H2O Nn: NH4Cl + H2O NH3 + H3O+ NH3 + Cl- + H3O+ NH4+ + Cl-

V th dung dch thu c sau khi ha tan mui NH4Cl trong nc l dung dch c tnh acid (v cha ion H3O+ ; khong pH < 7), dung dch khng c mu V d: Kho st s thy phn ca dung dch mui CuSO 4 Trong dung dch c s in ly: Nn: CuSO4 2+ Cu + H2O Cu2+ + SO42(CuOH) + + H+ 69

CuSO4 + H2O

(CuOH) + + SO42- + H+

V th dung dch thu c khi ha tan cht rn mu trng CuSO4 vo nc c mu xanh (v cha ion (CuOH)+ ), dung dch c tnh acid (v c cha ion H+) Kt lun chung: Khi thy phn mui tan s thu c dung dch c pH ty thuc vo mnh ca gc acid v baz ca mui . Khi nim dung dch c xc nh: Dung dch acid l dung dch c cha ion H + Dung dch baz l dung dch c cha ion OH-

Dung dch mui l dung dch c cha cc cation kim loi (hay NH4+ ) v anion gc acid. Hydroxyt l cc hp cht c cha nhm lin kt - OH ng dng ca phn ng thu phn Cc mui amoni ca cacbonat, sunfat hay mui natri ca acetat, cacbonat, mui ca cc baz hu c yu... u b thu phn to nhng dung dch c pH xc nh. Nn c th dng nc kt ta cc hydroxyt ca chng Trong phn tch, cc phn ng thu phn cc mui amoni to thnh cc amoniac t do c s dng pht hin gc amoni, nht l khi chng c un nng vi kim Vic tch cc ion Crom v nhm da trn s

phn hu thu phn cromit khi un si to kt ta Cr(OH)3 v.v... 1.6.2. Phn ng trao i L phn ng ha hc trong khng c s thay i 70

s oxy ha ca cc cht trc v sau phn ng. iu kin c phn ng trao i (nh lut Betthorlet): phn ng xy ra khi c s to thnh cht kt ta hoc cht bay hi, hoc cht in ly yu. V d: AgNO3 + HCl KCl + H2SO4 ? ?
(phn ng xy ra v sn phm thu c c cht kt ta AgCl) (phn ng khng xy ra v sn phm khng tha nh lut Bertholet)

NH4Cl + Ca(OH)2 HCl + KOH ?

(phn ng xy ra v c s to thnh cht bay hi NH3 ) (phn ng xy ra v c s to thnh cht in ly yu H 2O) Cch vit phng trnh phn ng trao i thu gn Vit phng trnh phn ng dng phn t Chuyn phng trnh v dng ion (cc cht kt ta, cht rn, cht bay hi, cht kh hoc H2O

vn gi nguyn dng phn t) Rt gn hai v nhng ion ging nhau, v chuyn H+ thnh H3O+ V d: Vit phng trnh phn ng trao i khi pha trn ZnCl2 vo dung dch NaOH. Phng trnh phn t: ZnCl2 + 2 NaOH Phng trnh rt gn: Zn2+ + 2 OHZn(OH)2 1.6.3. Hydroxyt lng tnh Hydroxyt lng tnh l hydroxyt va c tnh acid va 71 Zn(OH)2 + 2 NaCl

c tnh baz, chng hn Al(OH)3, Cr(OH)3, Zn(OH)2, Sn(OH)2, Be(OH2, Pb(OH)2... Chng hn vi Al(OH)3: Al(OH)3 Al(OH)3 Zn(OH)2 + 3 H+ + OH+ 2 H+ Al3+ + 3 H2O ( AlO2 )- + 2 H2O Zn2+ + 2 H2 O

Hay vi Zn(OH)2: Zn(OH)2 + 2 OHZnO22- + 2 H2O Hng s in ly ca cc hydroxyt lng tnh: Xt cn bng ng: Be(OH)2 (dung dch) Trong : 2 H+ + BeO22Be(OH)2 (dng ta) Be(OH)2 Be2+ + 2 OH-

(dng acid) (dng ta) (dng baz) K : 10 - 30 10 - 18 Theo cc cng trnh nghin cu ca L.P. Adamovich, th qu trnh in ly ca Be(OH)2 l: Khong pH
Be(OH)2 BeOH + H
+ +

K
5.10-14 2.10 - 9
4.10 - 9

5,4

6,2 5,4
5,4

Be(OH)2 + BeOH+ 2 Be(OH)2 + BeOH+

[Be2 (OH)2 ]2+ + OH- 5,1 [Be3 (OH)3 ]3+ + OH- 5,1

[Be2 (OH)2 ]2+ [Be3 (OH)3 ]3+

2 Be2+ + 2 OH3 Be2+ + 3OH-

3,8 3,8

5,1 5,1

4,9.10- 22 4,4.10- 34

Nh vy qu trnh phn ly ny cng c c trng bng mt hng s phn ly Tnh cht ny c ng dng nh tnh mt s cc cation to c cc hydroxyt khng tan trong nc 72

bng cch cho mt lng d kim natri hoc kali tc dng vi cc cation, khi cc hydroxyt ny s c tch ra khi hn hp dng ta. Sau nu trong c hydroxyt lng tnh th li lm tan chng trong dung dch kim (nh tch Fe3+ ra khi Al3+) Hng s in ly dng acid ca hydroxyt lng tnh tng theo s tng in tch ca cc ion to thnh chng, do mun lm tng tan ca nhng hydroxyt kh tan trong nc m nhng hydroxyt cha ion c kh nng b oxy ho, th hy oxy ho ion ny. Chng hn, nu cho hn hp ca Fe(OH) 3 v Cr(OH)3 th di tc dng ca hydroperoxyt hoc cc cht oxy ho khc trong mi trng kim, Cr3+ s b oxy ho n Cr6+ to thnh CrO4
2-

d dng chuyn vo dung dch.

Vic so snh cc hng s phn ly ca hydroxyt lng tnh mt gi tr pH, c th ch ra c tnh cht acid hay baz no ca n tri hn V d: Hydroxyt Pb(OH)2 Al(OH)3 In(OH)3 Ga(OH)3 As(OH)3 K (dng baz) 9,6. 10 - 4 8. 10 - 25. 1,3. 10 - 34. 1,6. 10 - 11. 1. 10 - 14. K (dng acid) 2. 10 - 16. 4. 10 - 13. 1. 10 - 16. 5. 10 - 11. 5,7. 10 10

Nh th c th thy c Pb(OH) 2 c tnh baz th hin r hn tnh acid trong cc dung dch nc.

73

Bi tp 1. Tnh hng s cn bng ca dung dch sau: 1.1. Dung dch NH3 0,1M c = 1,35% 1.2. Dung dch CCl3COOH 10 3 M c = 54% 2. Tnh nng [H+] ca cc dung dch sau: 2.1. Dung dch HCl 5.10 4 M 2.2. Dung dch CH3COONa 10 2 M (c pKa= 4,75) 3. Tnh nng [H+] khi pha trn cc dung dch sau: 3.1. Dung dch CH3COOH 0,1M v dung dch CH3COONa 0,2M 3.2. 100mL dung dch CH3COOH 0,1M v 50mL dung dch CH3COONa 0,2M 3.3. Dung dch NH3 0,1M + dung dch NH4Cl 0,2M 3.4. 50mL dung dch NH3 0,1M + 100mLdung dch NH4Cl 0,2M

74

BI 2. PHN TCH NH TNH CATION NHM 1 M bi: HPT 2

Gii thiu Vic xc nh cc ion trong dung dch nc l mt trong nhng cng vic cn c ca ngh phn tch. Cc ion trong dung dch s c phn chia theo cc nhm thun li cho vic tch chng ra khi dung dch nc Mc tiu thc hin Hc xong bi ny hc vin s c kh nng: 1. M t cc h thng phn tch. 2. M t cch lm th nghim phn tch. 3. Phn tch nh tnh nhm. 4. Xc nh cc cht sau phn tch. Ni dung chnh 1. Cc h thng phn tch. 2. Phn tch nh tnh nhm 1. 2. 1. H thng phn tch 2.1.1. H thng phn tch nh tnh Phn tch nh tnh cc cation theo cc nhm phng php phn tch, tu thuc vo thuc th s dng, gm 3 h thng c bn l: 2.1.1.1. H thng phn tch sunfua cc cation tan ca cc sunfua, clorua v cacbonat l c s ca h thng ny. Theo h thng ny, cc cation c chia lm 5 nhm phn tch (trong quyn Cc c s ho hc phn tch ca A. P. Kreskov trnh by y h thng phn tch ny) 75

Nhm 1 gm cc cation kim loi kim v NH4+, Mg2+ Nhm 2 gm cc cation kim loi kim th (Ba2, Sr2+, Ca2+). Nhm ny b kt ta bi thuc th nhm - amoni cacbonat trong dung dch m amoniac di dng cc cacbonat khng tan trong nc. Nhm 2 khng b kt ta bi amoni sunfua v H2S

Nhm 3 gm hai phn nhm l phn nhm ca Al3+, Cr3+ v phn nhm ca Mn2+, Fe2+, Fe3+, Ni2+, Co2+, Zn2+. Nhm ny khng b kt ta bng H2S di dng sunfua t dung dch acid. Nhm 4 gm Cu2+, Cd2+, Hg2+, Bi3+, As3+, As5+, Sb5+, Sb3+, Sn2+, Sn4+. Nhm ny b kt ta bi H2S di dng cc sunfua trong mi trng acid pH = 0,5. Cc sunfua ca chng thc t khng tan trong nc v trong cc dung dch acid v c long. Thuc th chng l H2S trong HCl. Nhm 5 gm Ag+, Hg22+, Pb2+. Cc clorua ca nhm ny khng tan trong nc v trong cc

acid long. Thuc th ca nhm l HCl 2N 2.1.1.2. H thng phn tch acid - baz H thng ny chia cation thnh 6 nhm: + Nhm 1 gm cc cation kim loi kim v NH4+. Cc clorua, sunfat v hydroxyt ca chng u tan trong nc. Chng khng c thuc th nhm. Cc hp cht c mt nhm ny u c th tan to thnh dung dch. 76

Nhm 2 gm Ag+, Hg22+, Pb2+. Cc clorua ca nhm ny khng tan trong nc v trong cc acid long. Thuc th ca nhm l HCl 2N Nhm 3 gm Ba2+, Sr2+, Ca2+, Pb2+. Sunfat ca chng khng tan trong nc v trong cc dung dch acid. Thuc th ca nhm l H2SO4 2N Nhm 4 gm Al3+, Cr3+, Zn2+, As3+, As5+, Sb3+, Sn2+, Sn4+. Cc hydroxyt ca chng u lng tnh tan trong dung dch kim d. Thuc th thng dng l NaOH 4N v KOH 4N d. Nhm 5 gm Mg2+, Mn2+, Fe2+, Fe3+, Bi3+, Sb5+, Sb3+. Cc hydroxyt ca chng u khng tan trong dung dch kim d. Thuc th thng dng l dung dch NH3 25% d. Nhm 6 gm Cu2+, Cd2+, Hg2+, Co2+, Ni2+. Cc hydroxyt chng to ra cc amoniacat tan. Thuc th l dung dch NH3 25% d.

u im ca h thng ny l s dng c nhng tnh cht c bn ca cc nguyn t: quan h ca chng vi cc acid, baz, tnh lng tnh ca cc hydroxyt v kh nng to phc ca cc nguyn t. V nhc im ca h thng ny l cn gii hn v s lng cc cation, cc tnh cht ca cc hydroxyt ca cc cation nhm 4 v 5 cha c nghin cu k, cng nh cc iu kin tch, to kt ta ca chng. 2.1.1.3. H thng phn tch photphat - amoniac H thng ny chia cc cation thnh 5 nhm phn tch. 77

Nhm 1 gm cc cation kim loi kim v NH4+. Khng c thuc th c trng cho nhm Nhm 2 gm Ba2+, Sr2+, Ca2+, Mg2+, Fe2+, Fe3+, Al3+, Cr3+, Mn2+, Bi3+. Nhm ny b kt ta bi thuc th nhm - amoni hydro phophat

(NH4)2HPO4 trong dung dch amoniac c. Nhm 3 gm Cu2+, Cd2+, Hg2+, Co2+, Ni2+, Zn2+. Cc phophat ca chng tan trong dung dch amoniac to thnh cc amoniacat )6]2+. [Me(NH3

Nhm 4 gm:As3+, As5+, Sb5+, Sb3+, Sn2+, Sn4+. Cc ion thic v antimon khi un nng vi HNO 3 th to thnh kt ta khng tan l acid metastanic v acid metaantimon (H 2SnO3, HSbO3). Cc hp cht asen (III) khi un nng vi HNO3 th b oxy ho thnh H3AsO4 Nhm 5 gm Ag+, Hg22+, Pb2+ b kt ta bi acid

HCl di dng cc clorua t tan. 2.1.2. Phn tch nh tnh cc anion Phn tch nh tnh l mt mt trong cng tc phn tch, c nhim v xc nh thnh phn phn t ca cht hoc thnh phn phn t ca cc cht trong hn hp, hoc cc ion c trong dung dch. Thng c tin hnh bng cc phng php nh phng php ho hc (dng phn ng ho hc chuyn cht cha bit thnh cc cht mi c tnh cht c trng, ri mi xc nh cht cn tm), phng php vt l, phng php ho l (da vo l tnh v ho tnh ca cc cht, phng php ny ch yu dng my nn chnh xc cao v cho kt qu nhanh) 78

Cc nhm anion c phn lm 3 nhm: Nhm I: gm cc anion Cl-, Br-, I-, SCN-, S2O3 2-. Nhm II: gm cc anion SO 42-, PO43-, C2O42-, CO32-, BO2Nhm III: gm cc anion NO3-, NO2-, CH3COO-. 2.1.2.1. Phn tch nh tnh nhm anion I 2.1.2.1.1. c tnh ca nhm Anion nhm I gm cc ion Cl-, Br-, I-, SCN-, S2O3 2. Thuc th c dng l AgNO3, Ba(NO3)2,

dung dch S2O3 2-. Cc anion nhm I khi tc dng vi AgNO3 s to c kt ta mui bc. Kt ta ny tng i bn, khng tan trong cc dung dch acid, ngay c vi dung dch HNO 3 2N. Cc anion nhm I khng to kt ta vi Ba(NO3)2 tr dung dch S2O32- m c. Cc phn ng xy ra: Ag+ + ClAg+ + BrAg+ + IAg+ + SCNAgCl AgBr AgI AgSCN (trng chuyn en) (vng nht) (vng ng nh) (trng)

Ag+ + S2O3 2Ag2 S2O3 (trng chuyn en) 2.1.2.1.2. Tnh cht ca cc anion ca nhm I Vi ion ClDng thuc th KMnO 4 trong mi trng acid H2SO4 hoc MnO2 trong mi trng H2SO4 hay K2Cr2O7: 10 Cl- + 2 KMnO4 + 8 H2SO4 5 Cl2 + K2SO4 + 2 MnSO4 + 5 SO42- + 8 H2O 79

Kh Cl2 thot ra c xc nh bng s ho xanh giy tm hn hp anilin v orthoToludin hoc lm xanh giy tm hn hp KI v h tinh bt. Gii thch: Th oxy ha tiu chun ca cp oxy ha kh lin hp l Cl2/2Cl- = 1,36 (v), cho nn Cl- l cht kh rt yu. N ch b oxy ha bi cc cht oxy ha mnh nh MnO 4-, S2O82-, PbO2, MnO2.. 10Cl- + 2MnO4- + 16H+ = 5Cl2 + 2Mn2+ + 8H2O 4Cl- + MnO2 + 4H+ = 2Cl2 + Mn2+ + 2H2O 4Cl- + PbO2 + 4H+ = 2Cl2 + Pb2+ + 2H2O K thut phn tch Cho khong 0,01(g) tinh th KMnO4 (hoc MnO2 hoc PbO2) vo trong mt ng nghim, pha trn ng nghim, gn ming ng, gi mt mu giy lc tm dung dch KI / H tinh bt. Nh dung dch HCl c vo tinh th KMnO4 (cn cn thn trnh nh nhm vo giy lc). Ming giy s xut hin mu xanh ca I 2 c trong h tinh bt. Dng thuc th Hg 2(NO3)2: to kt ta trng Hg2Cl2 (trng) khng tan Dng thuc th Pb(NO3)2: to kt ta trng PbCl2 (trng) khng tan Dng thuc th AgNO3: to kt ta mu trng em ra ngoi nh sng ho thnh mu en: Cl+ Ag+ = AgCl (trng) tm thy ti thiu l 1gam Cl -, pha long gii hn l 1: 105 Kt ta AgCl tan trong NH 4OH, KCN, Na2S2O3, 80

HCl c v c trong (NH4)2CO3 10%: AgCl + NH4OH = [Ag(NH3)2}+ + Cl- + 2H2O AgCl + 2CN + [Ag(CN)2]+ + ClAgCl + 2HCl = H2[AgCl3] Dng thuc th K2Cr2O7 / H2SO4 c: Trn mt lng mui clorua (KCl hoc NaCl) rn vi K2Cr2O7 theo t l 2: 1, tm t hn hp ny bng H2SO4 c, ri un nng nh th s c hi mu nu CrO 2Cl2 bay ra. Hi CrO2Cl2 ha tan trong kim s to thnh dung dch cromat mu vng: K2Cr2O7 + 4KCl + 3H2SO4 = 2CrO2Cl2 + 2K2SO4 + 3H2O CrO2Cl2 + 2NaOH = Na2CrO4 + 2HCl Cc ion Br- v I- khng gy cn tr v chng khng to thnh cc hp cht tng t. Br- v I- tc dng vi H2SO4 c to thnh Br2 v I2, nhng khi tc dng vi kim th chng to thnh dung dch khng mu: Br2 + 2OH- = Br- + BrO- + H2O I2 + 2OH- = I- + IO- + H2O Vi ion BrDng thuc th AgNO3: to kt ta vng nht (nh mu trng ng) Br- + Ag+ = AgBr mu vng nht AgBr khng tan trong HNO3, (NH4)2CO3 nhng tan trong NH4OH, KCN v Na2S2O3: AgBr + 2NH4OH = [Ag(NH3)2]+ + Br- + H2O AgBr + 2CN= [Ag(CN)2]- + Br81

AgBr + 2S2O32- = [Ag(S2O3)2]3- + BrDng thuc th KMnO 4 trong mi trng acid H2SO4 hoc MnO2 trong mi trng H2SO 4 m c hay K2Cr2O7:
2Br
-

+ MnO2 + 2 H2SO4

Br2 + MnSO4 + SO42- + 2 H2O

Br2 to ra trong dung dch c s un nng nh s thot ra ngoi v c xc nh bng s lm hng giy tm Florescein C20H12O5 do to thnh Dosin c mu hng rt c trng (nu Br2 c hay d th mu hng ny bin mt) hoc bng dung dch clorofom, th hi Br2 ho tan trong dung dch lm dung dch c mu vng nu. Cc ion I- v NO3- cng cho cc phn ng tng t, nn l nhng ion gy cn tr cho vic thc hin phn ng. K thut phn tch Cho 1 git dung dch mu cha Br- vo ng nghim + 3 git CH3COOH 2N + 0,01(g) PbO2. y ng nghim bng giy lc c tm dung dch Fluoretxein, sau vi giy giy s xut hin mu hng c trng ca Dosin. Cc cht oxy ha khc nh K2S2O8, HNO3 c cng tc dng vi Br- v gii phng ra Br2 tng t nh trn: 2Br- + S2O82- + 8H+ = Br2 + 2SO2 + 4H2O 6Br- + 2HNO3 + 6H+ = 3Br2 + 2NO + 4H2O Dng thuc th ch acetat (CH3COO)2Pb hay hn hp PbO2 trong dung dch acetat ; xut hin kt ta PbBr2 mu trng (ch nu lng Br 2 sinh ra d th lm kt ta ny tan do to phc [PbBr4 ] 2-. 82

2 Br- + PbO2 + 4 H+ 2 Br- + Pb(CH3COO)2

Br2

+ Pb2+ + 2 H2O

PbBr2 mu trng + 2CH3COO-

PbBr2 tan trong kim, trong amoni axetat v KBr d: PbBr2 + 2KBr = K2[PbBr4] Ch Ion Br- tn ti trong dung dch acid l mt cht kh Dng thuc th Cl2: 2Br- + Cl2 = Br2 + 2ClBr2 to thnh tan nhiu trong cc dung mi hu c nh C6H5, CS2, CHCl3... Cc cht kh mnh nh SO32-... s b Br2 oxy ha gy tr ngi cho phn ng. K thut phn tch Cho khong 3 git dung dch mu c cha Br - vo ng nghim + 3 git H2SO4 2N + 0,5mL dung dch Benzen. Nh tng git nc Clo (khng lm xao ng dung dch), th trn b mt dung dch xut hin mu vng rm. Nu tip tc nh nc Clo, th mu vng ny bin mt do to hp cht khng mu BrCl. Dng thuc th K2Cr2O7 / H+: 6Br- + Cr2O72- + 14H+ = 3Br2 + 2Cr3+ + 7H2O K thut phn tch Cho 3 git dung dch mu c cha Br- vo ng nghim + 5 git dung dch H 2SO4 2N + 0,5 mL Benzen. Nh t t dung dch K 2Cr2O7 vo v lc cn thn, dung dch s xut hin mu vng rm ca Br-. Tch lp dung dch benzen, ri nh vo ng nghim dung dch KI, th 83

dung dch s xut hin mu tm do Br 2 y I2 thot ra. Dng thuc th KBrO3 / H+: 5Br- + BrO3- + 6H+ = 3Br2 + 3H2O Phn ng ny c gi tr trong phn tch nh lng. Vi ion IDng thuc th AgNO3: to kt ta vng nht I + Ag+ = AgI AgI khng tan trong HNO3 v NH4OH (khc vi AgCl v AgBr), nhng tan trong KCN v to thnh phc K[Ag(CN)2] Dng thuc th KMnO4 hay K2Cr2O7 trong mi trng acid H2SO4 trng H2SO4 :
2I- + MnO2 + 2 H2SO4

hoc MnO2 trong mi

I2 + MnSO4 + SO42- + 2 H2O

Cr2O72- + 6I- + 14H+ = 2Cr3+ + 3I2 + 7H2O 2MnO4- + 10I- + 16H+ = 2Mn2+ + 5I2 + 8H2O

Hi I2 bay ra c xc nh khi lm xanh giy h tinh bt Dng thuc th Fe2(SO4)3 c trng cho IBr- v Cl- khng phn ng v

2 I- + Fe2(SO4)3 I2 + 2 FeSO4 + SO42Nu thm H3PO4 vo th phn ng s xy ra theo chiu hon ton ngc li. Dng thuc th ch acetat (CH3COO)2Pb to kt ta PbI2 mu vng ng nh 2I- + (CH3COO)2Pb 84 2I- + HgCl2 PbI2 (vng) + CH3COODng thuc th HgCl2: to kt ta HgI2 mu HgI-2 (vng) + 2 Cl-

Ch Ion I- tn ti trong dung dch acid l mt cht kh v HgI2 tan c trong thuc th d: HgI2 + 2I- = [HgI4]2Dung dch mui K2[HgI4] trong mi trng kim gi l thuc th Netle, dng tm ion NH 4+. Dng thuc th CuSO 4: to CuI dung dch cha I2 mu nu sm: 3Cu2+ + 4I- = 2CuI + I2 I2 + SO32- + H2O = 2I- + SO42- + 2H+ Dng thuc th KNO 2 (hoc NaNO2) trong mi trng acid: 2I- + 2NO2 + 4H+ = I2 + 2NO + 2H2O K thut phn tch Cho vo ng nghim 3 git dung dch mu c cha I + 3 git dung dch H2SO4 2N + 3git h tinh bt + 2 git dung dch KNO2 . Dung dch s xut hin mu xanh tm. Dng thuc th nc Clo: 2I- + Cl2 = I2 + 2ClClo d s lm mt mu ca I2 v: I2 + 5Cl2 + 6H2O = 2HIO + 10HCl Dng thuc th H2SO4 c v HNO3 c: 6KI + 8HNO3 = 3I2 + 2NO + 6KNO3 + 4H2O 10KI + 7 H2SO4 = 5I2 + SO2 + H2S + 5 K2SO4 + 6H2O Vi ion SCN Dng thuc th Ag+: SCN- + Ag+ = AgSCN trng AgSCN khng tan trong cc acid v c long, nhng tan trong NH4OH, KCN v SCN- d, 85 mu trng v

Na2S2O3 AgSCN + 2NH4OH = [Ag(NH3)2]SCN + 2H2O AgSCN + 2CN- = [Ag(CN)2}- + SCNAgSCN + 2SCN- = [Ag(SCN)3]2Dng thuc th FeCl3 to dung dch phc mu c trng SCN - + FeCl3 Hay vit l: Khi Fe3+ + SCN- = [Fe(SCN)]2+ d SCN- th to thnh [Fe(SCN)2]+, Fe(SCN)3 (dung dch mu )

[Fe(SCN)3] Dng thuc th Co(NO3)2: to dung dch mu xanh SCN - + Co(NO3)2 [Co(SCN)4] 2- + 2 NO3Phc ny rt khng bn, b phn hy ngay. gi c phc ny, phi thm axetn vo dung dch hay dng ru isoamylic chic phc. Lc , lp ru chit s c mu xanh (xem phn phn ng ion Co2+) Dng thuc th Hg(NO3)2: Hg(SCN)2 + 2SCN- = Hg(SCN)2 mu trng Kt ta ny tan trong KSCN d: Hg(SCN)2 + 2SCN- = [Hg(SCN)4]2Nu cho ion Co2+ tc dng ln dung dch va thu c th s c kt ta tinh th mu xanh thm: Co2+ + [Hg(SCN)3]2- = Co[Hg(SCN)4] 86 Dng thuc th CuSO4:

2 SCN- + Cu2+ = Cu(SCN)2

en

Nu thm Cu2+ vo dung dch SCN- c cha H2SO3 v H2SO4 long th s c CuSCN kt ta mu trng:
2Cu2+ + 2 SCN- + SO32- + H2O = 2CuSCN + SO42- + 2H+

CuSCN khng tan trong H2SO4 long. em ly tm ly CuSCN ri thm vo kt ta mt vi git dung dch FeCl3 th dung dch s c mu mu, v: 2CuSCN + 2Fe3+ = 2[FeSCN]2+ + 2Cu2+ Dng thuc th HNO3, H2SO4:
3SCN + 13NO3- + 10H+ = 3CO2 + 3SO42- + 16NO + 5H2O KSCN- + 2H2SO4 + H2O = KHSO4 + NH4HSO4 + CO

Dng thuc th Zn (Al hoc Mg) / H +:

SCN- + ZnO + 3H+ H2S +HCN + Zn2+ H2S thot ra c th nhn c d dng bng giy tm mui ch hay mui antimon. Dng thuc th ClO- / OH-: 3ClO- + 2SCN- + 6OH- = 2CO32- + N2 + 3H2O Vi ion S2O3 2- (anion thiosunfat) Dng thuc th I2 long: 2S2O32- + I2 Ion S2O322 I- + S4O6 2(anion tetrathiosunfat) b oxi ha n tetrathionat (S4O6)2-

ng thi n kh I 2 n I-, do , n lm mt mu dung dch I2. Phn ng ny xy ra rt nh hng nn c dng trong phn tch th tch. Dng thuc th FeCl 3: to dung dch mu tm 87

Fe2(S2O3)3 tan, mt lc dung dch ny b mt mu do s chuyn ho Fe3+ thnh Fe2+ 2 S2O3 2- + FeCl3 [Fe (S2O3)2] - + 3 Cl2Fe3+ + 2 S2O32- = 2Fe2+ + S4O62Dng thuc th KMnO4 trong mi trng acid H2SO4 hoc MnO2 trong mi trng H2SO 4 m c hay K2Cr2O7, ion S2O32- lm mt mu tm ca dung dch KMnO 4 hay mu da cam ca K2Cr2O7 S2O3 2- + 2 H+ 5SO2 + 2KMnO4 + 2H2O H2S2O3 SO2 + S + H2O K2SO4 + 2MnSO4 + 2H2SO4

Dng thuc th BaCl2 : to ta trng Ba2+ + S2O32- = BaS2O3 BaS2O3 d to thnh dung dch qu bo ha, cho nn thu c kt ta, cn dng a thy tinh c vo thnh ng nghim, th tinh th BaS2O3 xut hin Kt ta BaS2O3 d tan trong cc acid v c long. Ion Sr2+ khng kt ta c vi S2O32- (khc vi SO32-)

Dng thuc th AgNO3:to kt ta trng 2Ag+ + S2O32- = Ag2S2O3 Kt ta trng Ag2S2O3 sinh ra bin thnh mu vng ri nu v cui cng thnh en v to thnh Ag2S: Ag2S2O3 + H2O = Ag2S Ag2S2O3 tan trong Na2S2O3 d: + H2SO4

88

3Na2S2O3+Ag2S2O3 = 2Na3[Ag(S2O3)2] Dng thuc th l acid v c hong: lm dung dch b vn c S2O32- + 2H+ = H2S2O3 = SO2 + S + H2O Dng thuc th CuSO4: 2Cu2+ + 2S2O32- = S4O62- + 2Cu+ Ion Cu+ sinh ra s tc dng vi S2O32- d to thnh ion phc [CuS2O3]. Khi un si, ion phc ny b phn hy, to thnh kt ta sunfua ng (I) mu en:

2[CuS2O3]- + 2H2O = Cu2S + S

+ 2SO42- + 4H+

2.1.2.1.3. Phn tch h thng anion nhm 1

89

Hnh 2.1. S phn tch dung dch anion nhm I 2.1.2.2. Phn tch nh tnh nhm Anion II 2.1.2.2.1. c tnh ca nhm Anion nhm II gm cc ion SO42-, PO43-, C2O42-, CO32-, BO2Thuc th chung ca nhm: AgNO3, Ba(NO3)2, S2O3 2-. Cc anion nhm II khi tc dng vi AgNO3 s to c cc mui kt ta. Cc kt ta ny tan trong dung dch HNO3 2N, tr Ag2SO4 khng tan. Cc anion nhm II to mui Ba2+ tan trong dung dch HNO 3 2N tr BaSO4 khng tan Cc phn ng xy ra: Ba2+ + SO42Ba2+ + PO43Ba Ba
2+

BaSO4 Ba C2O4 Ba(BO2 )2 Ag2SO4 Ag3PO4 Ag2C2O4

(trng) (trng) (trng) (trng) (trng) (trng) (trng)

Ba3 (PO4 )2

+ C2O4 + BO2-

2-

2+

Ag+ + SO42Ag+ + PO43Ag+ + C2O42+

Ag + AgBO2 (nu en ca Ag2O) 2.1.2.2.2. Cc anion trong nhm II Vi ion SO32Dng thuc th BaCl2: Ba2+ + SO32- = BaSO3 mu trng BaSO3 tan trong acid long (khc vi BaSO4): BaSO3 + 2HCl = BaCl2 + SO2 + H2O 90

BO2-

Sr2+ cng cho kt ta vi SO32- (nhng khng cho kt ta vi S2O32-) Dng thuc th AgNO3: 2Ag+ + SO32- = Ag2SO3 mu trng

Ag2SO3 tan trong HNO3 long, NH4OH v Na2SO3 d: Ag2SO3 + 2HNO3 = AgNO3 + SO2 + H2O Ag2SO3 + 4NH4OH = [Ag(NH3)2}2SO3 + 4H2O Ag2SO3 + 3Na2SO3 = 2Na3[Ag(SO3)2} Dng thuc th acid v c long: SO32- + 2H+ = H2SO3 SO2 + H2O SO2 bay ra dn qua dung dch nc vi trong s lm c v lm mt mu dung dch KMnO 4 long. K thut phn tch Cho 3 git dung dch mu c cha SO 32 vo ng nghim + 3 git HCl 2N + 3 git KMnO4, ri y kn bng nt cao su c ng nha ng sn dung dch KMnO 4. Tin hnh un nh y ng nghim trong ni cch thu th mu hng ca KMnO4 trong ng nghim s bin mt. Dng thuc th: Br2, I2, KMnO4 SO32- + I2 + H2O = SO42- + 2I- + 2H+

5SO32- + 2MnO4- + 6H+ = 5SO42- + 2Mn2+ + 3H2O Dng thuc th Zn / HCl: SO32- + 3Zno + 6H+ = H2S + 3Zn2+ + 3H2O H2S sinh ra c th pht hin bng phn ng vi ion Pb2+ . Cc ion S2- v S2O32- cn tr phn ng ny. K thut phn tch 91

Cho 3 git dung dch mu c cha SO 32 + 1 mu Zn + 12 mL dung dch HCl 2N, ri y kn ng nghim bng ming giy lc c tm (CH3COO)2Pb. un nh ng nghim trong ni cch thy. Giy lc s chuyn sang mu en ca PbS Dng thuc th malachit: Ion SO32- lm mt mu ca dung dch thuc th xanh malachit. ti thiu tm thy l 1 gam SO32-; pha long ti hn vi t l l 1: 5.104 Cc ion S2-, ClO-, ClO4-, IO4-, IO3-, SCN- v C2O42- cn tr phn ng K thut phn tch Cho mt git dung dch thuc th xanh Malachit 0,0025% ln mt knh ng h + 3 git dung dch mu c cha SO32 . Mu thuc th s bin mt. Vi ion SO42Phn ng Woblers: trong mi trng KMnO 4, ion SO42- to kt ta BaSO4 mu trng (nhng do tnh hp th ca kt ta ny i vi mu tm hng ca KMnO4, nn trng kt ta c mu tm hng) Dng thuc th H 2O2 trong mi trng acid HCl kh mu tm hng ca KMnO4, to kt ta BaSO4 vn cn mu tm hng. Nhn bit c SO42Dng thuc th BaCl2: Ba2+ + SO42- = BaSO4 trng BaSO4 khng tan trong HCl, HNO3 92

Dng thuc th AgNO 3: Ch to thnh kt ta Ag2SO4 khi nng ca ion sunfat trong dung dch m c. Khi pha long bng nc, n li

tan. Kt ta rdizonat bari mu khng tan trong HCl, nhng khi tc dng vi dung dch c cha ion SO 42-, kt ta s mt mu , v to thnh BaSO4 t tan hn. K thut phn tch Cho 3 git dung dch BaCl 2 2N + 1 git thuc th Rodizonat Natri 1%, giylc c mu . Nh tip vo 1 git dung dch mu c cha SO 42 , th mu bin mt Dng thuc th BaCl2 khi c mt KMnO4: BaSO4 v KMnO4 ng hnh, nn KMnO4 i vo mng li tinh th ca BaSO 4. V vy kt ta c mu tm. Nu nh vo dung dch H 2O2 3% th dung dch s mt mu, nhng ion MnO4- trong mng li tinh th khng b kh, do kt ta vn c mu tm. K thut phn tch Cho 3 git dung dch mu c cha SO42 + 3 git KMnO4 bo ho, lc u. Dng ng nh git ht ra nh ln t giy lc, sau nh tip vo 1 git dung dch BaCl2 0,05N. em sy kh t giy lc (ch khng c t giy b vng hay chy en), nh ln 3 git dung dch H2SO4 1N, mu xanh tm ca KMnO4 vn khng b thay i Vi ion PO4393

Dng thuc th BaCl 2:to kt ta BaHPO4 mu trng Ba2+ + HPO42- = BaHPO4 .

BaHPO4 tan trong cc acid HCl, HNO3; HCOOH. Khi un nng chuyn thnh photphat bari: 3BaHPO4 = Ba3(PO4)2 Ag3PO4 3Ag+ + HPO42- = 3Ag3PO4 + H+ Kt ta Ag3PO4 tan trong cc acid v c v trong NH4OH: Ag3PO4 + 3HNO3 = 3AgNO3 + H3PO4 Ag3PO4 + 9NH4OH = 3[Ag(NH3)2]OH + (NH4)3PO4 + 6H2O Dng thuc th FeCl3 / CH3COO-: to ta vng FePO4 HPO42- + Fe3+ + CH3COO- = FePO4 + CH3COOH FePO4 khng tan trong CH 3COOH nhng tan trong HCl v HNO3 long. Dng thuc th Bi(NO3)3: to ta trng BiPO4 HPO42- + Bi3+ = BiPO4 + H+ Kt ta ny khng tan trong HNO3 long 2HPO4-

+ H3PO4

Dng thuc th AgNO3: to ta mu vng

Dng thuc th Pb(PO4)2

Pb(CH3COO)2: to ta trng
+ 4CH3COO- + 2CH3COOH

+ 3Pb(CH3COO)2 = Pb(PO4)2

Kt ta Pb(PO4)2 khng tan trong axetic, tan trong cc acid v c long. Dng thuc th (MgCl2 + NH4OH + NH4Cl): to tinh th trng 94

HPO42- + Mg2+ + NH4OH

PO43- + Mg2+ + NH3 + H2O

MgNH4PO4
Mg NH4PO4

+ 2H2O
+ OH -

Kt ta ny khng tan trong NH 4OH, tan trong cc axit. Dng thuc th (NH4)2MoO4 / HNO3: to ta vng (NH4)2MoO4
3NH4+ + PO43- + 12MoO42- + 24H+ [(NH4)3]PMo12O40 + 12H2O

hoc cng c th vit:

H3PO4 + 12(NH4)2MoO4 + 21HNO3 (NH4)3H4[P(Mo2O7)6 + 21NH4NO3 + 10H2O

hoc: PO43- + 12 (NH4)2Mo O4 + 24 HNO3 21 NH4+ + (NH4)3[PMo12O40 ] (vng) + 24 NO3- + 2 H2O Kt ta amoniphotphomolypat c mu vng; n tan trong kim v amomiac, nhng khng tan trong acid nitric. K thut phn tch Cho 3 git dung dch (NH 4)2MoO4 vo ng nghim, ri nh tng git dung dch HNO 3 c n khi kt ta trng sinh ra b tan ht, th nh tip vo 3 git dung dch mu c cha PO 43-, th s xut hin mu vng hoc dung dch mu vng Nu dng cht kh nh benzidin, SnCl 2, Fe2+, acid ascobic kh acid photphomolypic mi to thnh th s c mu xanh c trng gi l xanh molip en. Cch thc hin phn ng: nh 3 git dung dch amoni molipat ln ming giy lc loi khng tn, sy tht kh, sau nh tip ln y 1 git dung dch kho st + 1 95

git dung dch benzidin + 1 git dung dch axteat ri h ln ming l ng amoniac c. Nu c ion PO43- trong dung dch kho st th s xut hin vt mu xanh. Cc ion AsO43- v SiO32- gy cn tr cho vic thc hin phn ng v chng cng cho phn ng tng t. C th loi tr nh hng ca cc ion ny bng cch thm acid tactric vo dung dch. Khi , acid tactric s to phc vi mlipen; nhng phc ny km bn hn phc ca acid phophomolipdic, song bn hn phc ca asen v silicmlipic. Do , khi c mt acid tatric th ch c acid photpho molipic c to thnh v cc ion AsO 43-, SiO32- khng h gy nh hng. K thut phn tch Nh mt git dung dch amonimolipat c ln acid tactric v mt git dung dch kho st ln ming giy lc loi khng tn, sy tht kh. Sau , nh tip mt git dung dch axetac benzidin ln ming l ng amoniac c. Nu c ion PO43- s to thnh vt xanh. Vi ion C2O42Dng thuc th CaCl 2: to kt ta CaC2O4 mu trng CaCl2 + C2O42CaC2O4 + 2 ClDng thuc th KMnO4 trong mi trng acid H2SO4 : ion C2O42- lm mt mu tm ca dung dch KMnO4 5C2O42- + 2 KMnO4 + 8 H2SO4 10 CO2 + K2SO4 + MnSO4 + 5 SO42- + 8 H2O 96

Vi ion CO32Dung dch CO32- lm hng phenolphtalein Dng thuc th BaCl2: to ta trng Ba2+ + CO32- = BaCO3 Kt ta ny tan trong cc acid v c v c trong acid axetic Dng thuc th AgNO3: to ta trng 2Ag+ + CO32- = Ag2CO3 Kt ta Ag2CO3 s ha en khi lu v c bit nhanh khi un nng v n b phn hy thnh Ag2O: Ag2CO3 + H2O = Ag2O + H2CO3 Ag2CO3 tan trong HNO3 v trong NH4OH: Ag2CO3 + 4NH3 = 2[Ag(NH3)2]+ + CO32Dng thuc th dung dch acid long: Cc acid v c long v acid axetic tc dng vi CO32- cho kh CO2 bay ra: CO32- + 2H+ H2CO3 H2O + CO2 Kh CO2 bay ra c th nhn c bng dung dch vi nc vi trong, v CO2 lm c nc vi trong do to thnh CaCO3 kt ta: CO2 + Ca(OH)2 CaCO3 + H2 O Nu lng CO2 bay ra qu nhiu th kt ta CaCO3 li b tan v to thnh hidro cacbonat: CO2 + CaCO3 + H2O Ca(HCO3)2 Cc ion SO32- v S2O32- khi tc dng vi acid long cng to thnh kh SO2 v n cng lm c nc vi trong nh kh CO 2: SO2 + Ca(OH)2 CaSO3 + H2O 97

Bi vy, khi tm CO32- bng phn ng trn, nu trong dung dch c ln ion SO32- v S2O32- th trc ht cn thm vo dung dch vi git K2Cr2O7 hay H2O2 v un si. lu trong khng kh oxy ha chng thnh SO42-: SO32- + Cr2O72- + 8H+ = 3SO42- + 2Cr3+ + 4H2O K thut phn tch Cho 3 git dung dch mu c cha CO 32- vo ng nghim + 3 git dung dch HCl 2N. y nhanh ng nghim bng nt cao su c ng nha lun bn trong cha sn mt lng nh nc vi trong (cn thn kim tra v nh nhng trong thao tc). em un nh ng nghim trn ni cch thu. Phn nc trong ng nha s ho c Dng thuc th HgCl2 to kt ta mu vng nu, sau chuyn sang mu nu: CO32- + HgCl2 Vi ion BO2Dng thuc th CH3OH trong mi trng acid H2SO4 m c: hi borat metylic thot ra chy vi ngn la mu xanh lc BO2- + H+ + H2O H3BO3 + 3 CH3COOH H3BO3 (CH3)3BO3 + 3 H2O HgCO3 + 2 Cl-

98

2.1.2.2.3. Phn tch nh tnh h thng anion nhm II

Hnh 2.2. S phn tch dung dch anion nhm II 2.1.2.3. Phn tch nh tnh Anion nhm III 2.1.2.3.1. c tnh ca nhm Anion nhm III gm cc ion: NO3-, NO2-, CH3COO-. Thuc th chung cha nhm l AgNO3, Ba(NO3)2, dung dch S2O32-. Cc anion nhm III khng to kt ta vi AgNO3 , Ba(NO3)2, nhng li c th to kt ta vi dung dch NO 2- m 99

c hay dung dch CH 3COO- m c, cc kt ta ny tan trong dung dch HNO3 2N. Cc phn ng xy ra: NO2- + Ag+ CH3COO- + Ag+ AgNO2 (trng) (trng) CH3COOAg

2.1.2.3.2. Cc anion trong nhm III Vi ion NO3Dng thuc th FeSO4 trong mi trng H2SO 4 m c: ion NO3- trong mi trng H2SO4 s b phn hu to thnh NO v Fe 2+ s kt hp vi NO to phc [FeNO] 2+ mu en
NO3- + FeSO4 + H2SO4 [FeNO] 2+ + 2 SO42- + H2O

Ion NO2- cng cho phn ng tng t cc anion Cl-, Br-, Fe(CN)64-, SCN- CrO42-, SO32-, S2O32-, SO42- gy cn tr cho phn ng. K thut phn tch Cho 6 git dung dch FeSO4 vo ng nghim + 1 mL dung dch mu c cha NO 3-, lc k dung dch. Nh cn thn tng git dung dch H2SO4 m c (khng dung dch b xo mnh). S xut hin mt vnh nu ngay ch tip gip ca hai dung dch (nu lm khng kho lo s khng xut hin c vnh ai ny) Dng thuc th H2SO4 m c un nng vi v bo ng (c th dng vi cc kim loi Al, Zn): ion NO3- b oxy ho bi H+ v SO42 ca acid H2SO4. Sau chnh n li oxy ho Cu to kh NO2 mu nu: NO3- + H2SO4 100 SO42- + HNO3

Cu + 2H+ + NO3-

Cu2+ + NO2

+ H2O

Dng thuc th dung dch kim vi Al (kim loi): cho dung dch kim vo dung dch HNO 3 thm ming Al vo ri un nng. Kh NH3 bay ra lm xanh giy qu. NO3- + 8 |H| NH3 + OH - + 2 H2O

Vi ion NO2Dng thuc th KMnO4 trong mi trng acid H2SO4 (hoc MnO2 trong mi trng H2SO 4 m c hay K2Cr2O7 ) NO2- lm mt mu tm ca dung dch KMnO4: 5 NO2- + 2 KMnO4 + 3 H2SO4 5 NO3- + 2MnSO4 + 2 K2SO4 + 3 H2O Dng thuc th H2SO4: to kh mu nu 2NO2- + 2H+ = NO + NO2 + H2O Khi tc dung vi H2SO4 c th phn ng xy ra mnh lit hn. Dng thuc th dung dch KI / H+: 2NO2- + 2I+ + 4H+ = I2 + 2NO + H2O Phn ng ny c th thc hin theo phng php nh git. Cc cht oxi ha gy cn tr cho phn ng. K thut phn tch Nh 1 git h tinh bt ln ming giy lc + 1 git dung dch CH3COOH 2N + 1 git dung dch KI 0,1N + 1 git dung dch mu c cha NO 2-. Giy s xut hin cc vt xanh hay vng nc mu xanh Dng thuc th FeSO4 / H+: to kh NO v phc 101

khng bn FeNO2+ c mu nu sm. Ion NO 3cng cho phn ng tng t (xem cch thc hin phn ng trong mc nitrat). Dng thuc th hn hp acid sunfanilic [C6H4 (NH2)(SO3H)] v naphtlamin (C10H7N2) to hp cht azo mu : C6H4 (NH2)(SO3H) + NaNO2 + 2CH3COOH C6H4 (N=N-OOCH3)(SO3H) + CH3COONa + 2H2O C6H4 (N=N-OOCH3)(SO3H) + C10H7H2 C6H4 (N2C10H6NH2)(SO3H) + CH3COOH Phn ng ny rt nhy d lng NO 2- rt nh, nn c s dng nhiu trong phn tch nh tnh. K thut phn tch Cho 3 mL dung dch thuc th (gm dung dch acid sunfanilic trong CH3COOH theo s ho tan 0,5g acid ny vi 100mL dung dch CH3COOH 10%) vo ng nghim + 5mL dung dch mu c cha NO2-. un ng nghim n 80 0C ri cho vo 1 mL dung dch naphtylamin, dung dch s c mu . Dng thuc th kim loi kim, nhm, Mg / OH-: NO2- + 2Al + OH- + H2O = NH3 + 2AlO2-. Phn ng xy ra vi ion NO 3-: NO3- + 4Zn + 7OH- + 6H2O = NH3 + 4NH3 + Zn(OH)42Vi ion CH3COODng thuc th H2SO4 bng phng php ui acid:c mi dm bay ra: CH3COO- + H2SO4 102 CH3COOH + HSO4-

Dng thuc th felling: ion CH3COO- to phc mu ca Fe3+ khi pha long un nng, b thu phn thnh mui ta mu nu
[Fe(OH)3 (CH3COO- )6] + + 2H+

6CH3COO- + 3 Fe3+ + 2H2O

(phc mu ) [Fe(OH)3 (CH3COO- )6] + + 3 H2O 3[Fe(OH)2CH3COO] + 3 CH3COOH (kt ta mu nu)

Dng thuc th AgNO 3: trong dung dch CH3COO- m c, to kt ta trng CH3COOAg. Ag+ + CH3COOCH3COOAg Kt ta ny tan trong dung dch HNO3 v NH3.

Dng thuc th C2H5OH hay ru amylic trong H2SO4: to ester c mi c trng K thut phn tch Ly 3 git dung dch mu + 5 git ru + 1mL dung dch H2SO4 m c, un nng thch hp, thy thot ra mi du chui 2.2. Phn tch nh tnh cation nhm 1 2.2.1. c tnh chung Nhm 1 cation gm: Ag ; Hg22+ ; Pb2+, cc nguyn t ny nm trong cc nhm khc nhau ca h thng tun hon. Chng c hoc 18 electron lp ngoi cng hoc (18 + 2) electron 2 lp ngoi cng, l nguyn nhn ti sao chng li tc dng ging nhau i vi cc ion halozenua. 103

2. 2. 2. Thuc th chung ca cation nhm 1 2. 2. 2. 1. Dng thuc th l HCl To cc hp cht kt ta kh tan trong nc v trong cc acid long AgNO3 + HCl AgCl + HNO3 + 2 HNO3 + 2 HNO3 Hg2Cl2 Pb(NO3 )2 + 2 HCl Hg2(NO3 )2 + 2 HCl PbCl2

Cc kt ta ca AgCl, Hg2Cl2 v PbCl2 c tan trong nc khng ging nhau. 2. 2. 2. 2. Dng thuc th KI hay KBr Dung dch ny phn ng vi cc cation Ag +, Pb2+ v Hg2- to thnh nhng kt ta tinh th c mu c trng: Ag+ + I- = AgI Ag + Br = AgBr
2+ +

mu vng mu vng nht

Hg2 + 2I = Hg2I2 mu xanh lc Pb2+ + 2I = PbI2 mu vng 2. 2. 2. 3. Dng thuc th H2SO4 long H2SO4 long v cc mui sunfat tan s phn ng vi cc cation nhm 1 vi mc khc nhau. Cc cation Ag + v Hg22+ mun to kt ta vi ion SO42- th nng ca chng trong dung dch phi tng i ln so vi Pb 2+ to kt ta PbSO4 - tan PbSO4 l 0,00015 mol/ L. Pb2+ + SO42- = PbSO4 (trng tinh th) 2. 2. 2. 4. Dng thuc th NaOH hay KOH Cc cation nhm I s phn ng vi thuc th to thnh cc hirxit kt ta mu trng AgOH, Hg2(OH)2, Pb(OH)2 nhng tnh cht ca cc hirxit ny c khc nhau. AgOH v Hg2(OH)2 rt khng bn, b phn hy ngay 104

sau khi to thnh v cho ra cc oxit tng ng Ag 2O, Hg2O, cn Pb(OH)2 th li tan trong kim d. Ag+ + OH = Ag(OH) mu trng mu AgOH b phn hy rt nhanh. 2 AgOH = Ag2O

en +H2O Ag2O khng tan trong kim d, nhng d tan trong HNO3, NH4OH v b nh sng phn hy thnh Ag kim loi. 2. 2. 2. 5. Dng thuc th l dung dch NH3 Dung dch NH3 phn ng vi cc cation nhm I hon ton khc nhau 2Ag+ + 2 NH4OH = Ag2O + NH4 + H2O, Kt ta Ag2O tan trong thuc th d: Ag2O + 2 NH4OH = 2[Ag(NH4)2]OH + 3H2O Cc mui thy ngn tc dng vi dung dch NH 3 to thnh kt ta mecuamoni trng v Hg kim loi dng bt mu en 2Hg2(NO3)2 + 4NH3 + H2O = (NH2Hg2O)NH3 = 2Hg0 + 3NH4NO3 Amonic tc dng vi Pb2+ to thnh kt ta mui baz khng tan trong thuc th d: Pb(NO3)2 + NH4OH = PbOHNO3 + NH4NO3 2. 2. 2. 6. Dng thuc th Na2CO3 hay K2CO3 Cc cation nhm I s phn ng vi thuc th to kt ta bc cacbonat, ch cacbonat baz; thy ngn cacbonat khng bn b phn hy thnh HgO v Hg: 2Ag+ + CO32- = Ag2CO3 2Pb2+ + CO32- + 2OH- = Pb2(OH)2CO3 Hg2 + CO32- = Hg2CO3 105

Nhng Hg2CO3 khng bn b phn hy ngay: HgO + Hg + CO2 2. 2. 2. 7. Dng thuc th K2CrO4 Cc cation nhm I to thnh nhng kt ta c mu sc v tnh cht khc nhau: 2Ag + CrO42- = Ag2CrO4 mu nu Phn ng ny tin hnh trong mi trng trung tnh (pH = 7). V: Trong mi trng kim s tch kt ta en Ag2O. Trong mi trng amniac kt ta khng to thnh do Ag+ s i vo phc [Ag(NH3)]2+. Trong mi trng acid, chng hn, acid axetic s to thnh kt ta bc icromat (Ag2Cr2O7), trong mi trng acid mnh kt ta khng to thnh do cn bng: CrO42- + H+ HCrO4 Hg22+ + CrO42HgCrO4 mu (Kt ta ny kh tan trong acid nitric) Pb2+ + CrO42- = PbCrO4
2+

mu vng

2Pb + + H2O = 2PbCrO4 + 2H+ 2. 2. 2. 8. Dng thuc th l dung dch H2S: Trong mi trng acid long, H2S phn ng vicc cation nhm 1 to thnh cc kt ta sunfua, c bit Hg22+ trc ht t oxi ha- kh thnh Hg2+ v Hg0, ri sau Hg2+ mi phn ng vi S2- to thnh HgS. Hg2+ + H2S = HgS 106 + Hg0 en + 2H+

Cr2O72-

2Ag + S2- = Ag2S Ag2S khng tan trong NH 4OH, KCN, Na2S2O3 nhng tan trong HNO3long nng: 3Ag2S + 2NO3- + 8H+ = 6Ag+ +2NO + 3S + 4H2O Cn: Pb2+ + H2S = PbS + 2H+ Phn ng ny tng i nhy nn thng dng tm ch. Lng ti thiu tm thy ch l 2gama ch, long ti hn l 1: 3.10-5 PbS khng tan trong HCl, H 2SO4 nhng tan trong HNO3long khi nng. Trong HNO3c, PbS cng tan nhng ng thi S2- b xi ha thnh SO 42-, do c kt ta PbSO4 3PbS + 8 HNO3 = 3PbSO4 2. 2. 2. 9. Dng thuc th Na2SO3 + 8NO + 4 H2O

Cc cation nhm I phn ng vi thuc th trong mi trng trung tnh u cho kt ta: kt ta dn dn chuyn thnh kt ta sunfat mu en: 2Ag+ +S2O32- = Ag2S2O3 mu trng Ag2S2O3 tan trong thuc th d: Ag2S2O3 + 3S2O32- = 2[Ag(S2O3)2]3un nng hoc acid ha dung dch th phc ny b phn hy to thnh Ag2S:
2[Ag(S2O3)]3- + H2O = Ag2S 2[Ag(S2O3)]3- + 4H+ = Ag2S + SO42- + 2H+ + 3S2O32+ SO42- +3SO2 + 3S0 + 2H2O

Vi Hg22+ tc dng vi Na2S2O3 trong mi trng acid cng cho HgS, Hg0 v S kt ta: Hg22+ + 2S2O22- = HgS + Hg0 +S + 2SO32107

Pb2+ + S2O32- = PbS2O3

trng

Kt ta ny cng tan trong thuc th d to thnh anion phc [Pb(S2O3)]4- v phc cht ny cng b acid phn hy khi un nng: PbS2O3 + 2S2O32- = [Pb(S2O3)]4[Pb(S2O3)]4- + 2H+ = PbS + 2S + 2SO2 + SO42- + H2O 2. 2. 2. 10. Dng thuc th Na2HPO4 Cc cation nhm 1 phn ng vi thuc th trong mi trng trung tnh to cc kt ta photpht: 3Ag+ + HPO42- = Ag3PO4 Ag3PO4 tan trong HNO3 v NH4OH: Ag3PO4 + 6 NH4OH = 3 [Ag(NH3)2]+ + PO43- + 6 H2O 3Pb2+ + 2HPO42- = Pb3(PO4)2 + 2H+ mu trng Pb3(PO4)2 + 9OH- = 3HPbO2- + 2PO43- + 3H2O (vng ti)+ H+

108

2.2.3. Phn tch h thng cation nhm 1

Hnh 2.3. S phn tch dung dch cation nhm I

109

THC HNH PHN TCH NH TNH CATION NHM 1

BI THC HNH NH TNH CATION NHM 1: Ag+, Pb2+, Hg22+ I. 1. CHUN B Dng c 6 ng trung 1 2. Kp nghim 1 n Ha cht cn 1 Pipet 5mL HNO3 6N HCl 6N NH4OH 2N NaOH 2N CH3COOH 2N K2CrO4 5% KCN 0,1N KI 0,1N HCl 2N L Cu I. NH TNH Ag+ (dung dch mu pha t dung dch KBr 0,1N Na2S2O3 0,1N NaHPO4 0,1N K4[Fe(CN)6] 0,1N KSCN 0,1N NaOH 5N HCl 0,1N Na2SO4 0,1N (NH4)2MoO4 0,1N nghim ng 1 Pipet 10mL 1 Cn phn tch 3 ng nh git

AgNO3 0,1N) Th nghim 1 Ly 5 git dung dch mu+ 3 git HCl 6N. Quan st hin tng

110

CU HI

Ly tm ly ta. Thm tng git NaOH 2N vo ta. Quan st hin tng. Thm vi git HNO3 6N vo. Quan st hin tng

1. 2.

Hy vit cc phng trnh phn ng xy ra? C th dung dch HCl bng dung dch NaCl c

c khng? Gii thch? Th nghim 2 Ly 5 git dung dch mu+ tng git NaOH 2N hoc CH3COOH 2N (ty theo mi trng ca dung dch u) chnh v pH = 7. Thm 5 git dung dch K2CrO4 5% Quan st hin tng CU HI Gn ly kt ta thm tng git NaOH 2N vo ta gn ly nc. Quan st hin tng
Ti sao phi chnh pH ca dung dch mu pH = 7? Vit cc phng trnh phn ng xy ra?

1. 2.
-

Th nhim 3 Ly 5 git dung dch mu cho vo ng nghim trung + 2git KI 0,1N. Quan st hin tng. Ly 5 git dung dch mu cho vo ng nghim khc + 2git KBr 0,1N. Quan st hin tng. Gn ly kt ta hai ng nghim trn, nh vo c 2 ng cha kt ta 5 git NH 4OH 2N. So snh hin tng hai ng nghim. Lm li th nghim v thay NH 4OH bng dung dch KCN 0,1N quan st hin tng. 111

CU HI

Lm li th nghim v thay NH 4OH bng dung dch Na2S2O3 0,1N quan st hin tng.

1. 2.

Vit cc phng trnh phn ng xy ra trong cc th nghim?.

So snh kh nng tan ca c 2 kt ta trong NH4OH v trong Na2S2O3? Th nghim 4 Ly 5 git dung dch mu cho vo ng nghin trung. Thm tng git NaOH 2N. Quan st hin tng Gn ly kt ta + thm tng git NH4OH 2N. Quan st hin tng. Lm li th nghim, nhng thay NH 4OH bng HNO3 6N. Quan st hin tng. CU HI 1. 2. Vit cc phng trnh phn ng xy ra? Sn phm ca dung dch Ag + vi NaOH va tan c trong dung dch NH 3, va tan trong dung dch HNO3 nn chng c phi l hp cht lng tnh khng? Th nghim 5 Ly 5 git dung dch mu cho vo ng nghim trung + cho tng git Na2HPO4 0,1N. Quan st hin tng. Gn ly kt ta + tng git NH4OH 2N. Quan st hin tng.

CU HI 112

1. 2.

Vit cc phng trnh phn ng v gii thch? Nu thay dung dch NH4OH bng dung dch NaOH 2N th c thay i hin tng khng?

Gii thch Th nghim 6 Ly 5 git dung dch mu cho vo ng nghin trung + cho tng git K4[Fe(CN)6] 0,1N. Quan st hin tng Gn kt ta + 5 git NH 4OH 2N un si. Quan st hin tng Vit cc phng trnh phn ng v gii thch? Nu thay dung dch NH 4OH bng dung dch NaOH 2N th c thay i hin tng khng? Gii thch Th nghim 7 CU HI Vit cc phng trnh phn ng v gii thch? D on kh nng to ta ca Ag + vi dung dch CN- v SCN- ? III. NH TNH Pb2+ (dung dch mu pha t dung dch Pb(CHCOO)2 0,1N) 1. 2. Th nghim 1 Ly 2 git dung dch mu+ 2 3 git NaOH 2N 113 Ly 5 git dung dch mu + 2git KSCN 0,1N. Quan st hin tng Tip tc cho tng git KSCN n d. Quan st hin tng

CU HI 1. 2.

xut hin ta mu trng CU HI 1. 2. Vit cc phng trnh phn ng v gii thch? Nu thay NaOH bng dung dch NH 4OH th c thay i hin tng khng? Th nghim 2 Ly 5 git dung dch mu+ 5 git dung dch CH3COOH 2N + 5 git dung dch K 2CrO4 5%. Quan st hin tng Tip tc thm 5 git NaOH 2N + un nng, quan st hin tng. Gn kt ta + tng git NaOH 2N n d. Quan st hin tng.

CU HI

1. Vit phng trnh phn ng xy ra? 2. Nu tc dng ca CH3COOH trong phn ng? Th nghim 3 CU HI 1. 2. 3. Vit phng trnh phn ng xy ra? C th dung dch HCl bng dung dch g m khng lm thay i hin tng xy ra? Ly 5 git dung dch mu + 5 git dung dch HCl 6N. Quan st hin tng Tip tc cho thm 5 git H2O + un nng. Quan st hin tng.

Dng HCl m c th c thay i hin tng khng? Gii thch? Th nghim 4 114 Ly 5 git dung dch mu + 2 git dung dch KI

CU HI

0,1N. Quan st hin tng Tip tc cho thm lng d thuc th. Quan st hin tng Lm li th nghim nhng khng cho d thuc th m un si dung dch. Quan st hin tng.

Vit phng trnh phn ng xy ra? Gii thch C ch ca 2 hin tng 2 ng ny nh th no? Th nghim 5 1. 2. CU HI 1. 2. Vit phng trnh phn ng? Nu thay H2SO4 m c bng dung dch NaOH Ly 5 git dung dch mu + 3git Na2SO4 0,1N. Quan st hin tng Gn ly kt ta + 5 git H2SO4 m c. Quan st hin tng.

th c thay i hin tng khng? Gii thch? Th nghim 6 Ly 5 git dung dch mu cho vo ng nghim trung + 2 git (NH4)2MoO4 0,1N. Quan st hin tng CU HI 1. Vit phng trnh phn ng v gii thch hin tng? IV. NH TNH Hg22+ ( dung dch mu pha t dung dch Hg2(NO3)2 0,1N)

115

Th nghim 1 CU HI 1. 2. 3. Vit phng trnh phn ng? Hin tng g xy ra khi cho NH3 2N vo kt ta? Gii thch? Hin tng g xy ra khi cho HNO 3 2N vo kt Ly 3 git dung dch u + 3 git dung dch HCl 2N. Quan st hin tng Thm vo kt ta 5 git NH3 2N. Quan st hin tng Thm tip 5 git HNO3 . tng. dch HNO3 2N. Quan st hin

Lp li th nghim nhng thay NH 3 bng dung Quan st hin tng.

ta? Gii thch? Th nghim 2 CU HI 1. 2. Vit phng trnh phn ng? Mu sc? Khi tip tc thm dung dch KI ti d th hin tng thay i nh th no? Gii thch? Th nghim 3 116 Ly 5 git dung dch mu cho vo ng nghim Thm 5 git NaOH 2N. Quan st hin tng Gn ly kt ta +5 HNO 3. Quan st hin tng. Ly 3 git dung dch u + tng git dung dch KI 0,1N. Quan st hin tng Tip tc thm dung dch KI 0,1N, va thm va lc. Quan st hin tng.

CU HI 1. 2. Vit phng trnh phn ng? Mu sc? Khi thm dung dch HNO 3 th hin tng thay

i nh th no? Gii thch? Th nghim 4 Ly 5 git dung dch mu cho vo ng nghim Thm 3 git NH4OH 2N Quan st hin tng. CU HI 1. Vit phng trnh phn ng? Gii thch hin tng? Th nghim 5 Ly 5 git dung dch mu cho vo ng nghim Thm 3 git K2CrO4 5%. Quan st kt ta. CU HI Vit phng trnh phn ng? Gii thch hin tng? Th nghim 6 1. CU HI Vit phng trnh phn ng? Gii thch hin tng? V. NH TNH H THNG HN HP Th nghim 1. Dung dch mu l hn hp gm: Ag+ v Pb2+ c pha vi nng 0,1 1N. Ly 10 git dung dch mu+ 117 Ly 5 git dung dch mu cho vo ng nghim Cho thm mt ming Cu nh. Quan st hin tng.

tng git dung dch HCl 6N n khi ngng kt ta, ly tm tht k, thu c dung dch lc (L1) v kt ta (T1). Ra T1 bng nc ct v nhp nc ra vo (L1) tm cc Cation nhm khc. Chia (T1) thnh 2 phn: Phn 1: (T1) + 2mL nc ct, un cch thu khong 5 pht, hi ngui, ly tm ngay v nhanh chng gn phn dch lc qua ng nghim khc, cho vo ng nghim ny 5git dung dch KI 2N hoc dung dch K2CrO4 5%, thy c kt ta vng, chng t c Ion Pb2+. Phn 2: (T1) + 5 git NH3 2N ta tan thnh dung dch (D1.2). Thm tng git HNO3 2N vo (D1.2), thy c kt ta trng xut hin, chng t c Cation Ag+. CU HI 1. Lp s phn tch h thng Cation nhm 1? 2. Vit phng trnh cc phn ng? BI TP 1. Tnh th tch nc ct cn pha vo: 1.1. 100mL dung dch HCl 20% (d= 1,1g/mL) thu c dung dch c nng 5% 1.2. 100g dung dch H2SO4 20% (d= 1,12g/mL) thu c dung dch c nng 5% 1.3. 100g dung dch NH3 2M (c d = 1,14g/mL) thu c dung dch c nng 1,5M 2. pha c dung dch m loi: 2.1. m acid th phi pha theo t l nh th no v th tch gia V1(mL) dung dch CH3COOH C1M vi V2 (mL) ddch CH3COONa C2M ? 118

2.2. m baz th phi pha theo t l nh th no v th tch gia V1(mL) dung dch NH3 C1M vi V2 (mL) dung dch NH4Cl C2M?

119

BI 3. PHN TCH NH TNH CATION NHM 2 M bi: HPT 3

Gii thiu Ngoi dung dch cha cc ion kim loi nhm 1, dung dch cha cc ion kim loi kim th cng c pht hin d dng. Mc tiu thc hin Hc xong bi ny hc vin s c kh nng: 1. M t cc tnh cht ca cation nhm 2. 2. 3. Phn tch nh tnh cc ion trong nhm 2. Thc hin cc th nghim lm trong PTN phn tch ca trng. Ni dung chnh 1. 2. 3. 4. Tnh cht chung ca cation nhm 2. Thuc th ca cc ion trong nhm 2. Ha cht phn tch ion nhm 2. Phn tch cc ion trong nhm 2.

5. Xc nh cc cht sau phn tch. 3.1. c tnh chung ca cation nhm 2 Nhm 2 cation gm: Ca2+, Sr2+, Ba2+ l nhng nguyn t thuc nhm hai trong h thng tun hon, chng c y s electron lp ngoi l 8, l c s chng c nhng tnh cht inh tnh gn ging nhau. Hot tnh ho hc ca chng tng t Ca n Ba. Cc ion ca chng trong dung dch nc u khng ging nhau. 3.2. Thuc th chung ca cation nhm 2 3.2.1. Dng thuc th H2SO4 long v cc mui sunfat To tinh th mu trng 120

Ba2+ + H2SO4 = BaSO4 Sr2+ + H2SO4 = SrSO4

+ 2H+ + 2H+

Ca2+ + H2SO4 = CaSO4 + 2H+ Tt c cc kt ta BaSO4, SrSO4 v CaSO4 khng tan trong acid v trong kim. tan ca chng trong nc l: BaSO4 S (g/L) 0,0025 Tt 1,1.10 -10 Cc mui sunfat to thnh, SrSO4 CaSO4 0,097 2,0 -7 3.10 2.10-4 trong thc t khng tan,

nhng v tch s tan ca CaSO 4 l 9,1 10 - 6 nn vic kt ta ion Ca2+ bng H2SO4 long xy ra khng hon tan. V th khi lm "mt" Ca2+ trong phn tch cn phi thc hin phn ng kim tra cc ion Ca 2+ sau khi lm kt ta cc cation nhm ny bng thuc th ca nhm hoc lm kt ta cc cation nhm ny bng hn hp acid H2SO4 vi etanol. Sau khi tch cc cation nhm I, cc cation kim loi kim th (Ba2+,Sr2+,Ca2+) v ion Pb2+ (kt ta nhm I cha ht) cho cho phn ng vi thuc th H 2SO4 long tch cc cation nhm II ra khi cc cation khc di dng kt ta sunfat. Nhng kt ta sunfat ca cc cation nhm ny li khng tan trong cc acid cng nh kim. V vy tch v nhn bit tng ion ca nhm ny, phi chuyn chng thnh dng kt ta ccbonat d ha tan trong cc axit, chuyn chng vo dung dch. Da vo nhng tnh cht ha hc khc nhau ca tng ion tch v nhn bit 121

chng bng cc phn ng c trng. 3.2.2. Dng thuc th Na2CO3 (hoc K 2CO3, (NH4)2CO3 ) To kt ta tinh th mu trng. Na2CO3 + MeCl2 = MeCO3 + 2 NaCl (Me2+ l cc cation kim loi nhm II) Kt ta ny t tan trong nc, nhng tan trong cc acid HCl, HNO3 v CH3COOH.
BaCO3 + 2HCl = BaCl4 + H2O + CO2 SrCO3 +2HNO3 = Sr(NO3)2 + H2O +CO2 CaCO3 + 2CH3COOH = Ca(CH3COO)2 + H2O + CO2

tan ca cc kt ta BaCO3, SrCO3 v CaCO3 trong nc xp x nh nhau (6,9. 10-6 mol/L; Tt CaCO3 = 4,8.10-9) 3.2.3. Dng thuc th K2CrO4 to ta vi ion Ba2+ v Sr2+ To kt ta tinh th mu vng BaCrO 4, SrCrO4 t tan trong nc ( tan ca chng l S (BaCrO4 ) = 1,55.10-5 gmol/L; S (SrCrO4 )= 4,0.10-4 gmol/L). Ba2+ + CrO42- = BaCrO4 Sr2+ + CrO42- = SrCrO4 Nu un nng dung dch trc khi thm thuc th th s thu c kt ta c tinh th ln d lc. Ca2+ khng to c kt ta vi K2CrO4 v cromat canxi tan nhiu trong nc (S CaCrO4 = 1,15 gmol/L) 3.2.4. Dng thuc th (NH4)2C2O4 to kt ta oxalat tinh th mu trng Me2+ + (NH4)2C2O4 = MeC2O4 + 2NH4+ MeC2O4 tan trong cc acid HCl, HNO3, ring BaC2O4 122

v SrC2O4 tan c c trong acid axetic, nhng CaC 2O 4 th khng tan. 3.2. 5. Dng thuc th Na2HPO4 to thnh kt ta mu trng Me2+ + Na2HPO4 = MeHPO4 +2Na+ Kt ta MeHPO4 tan trong cc acid HCl, HNO3 v c trong CH3COOH. Mui phtphat cng to thnh kt ta vi hu ht cc cation kim loi nhm II. 3.2.6. Dng thuc th NaOH (KOH) c to Me(OH)2 kt ta tan ca hydroxit cc kim loi kim th tng i ln ( S Ba(OH)2 = 0,190g mol/L; S Ca(OH)2 = 0,0179 g mol/L) c bit l khi c mt ion NH4+, cho nn phn ng ny khng c s dng trong phn tch. 3.2. 7. Th mu la: y l phn ng kh c trng ca nhn ra cc cation nhm II. K thut phn tch Dng a thu tinh gn sn si dy bch kim sch, chm vo tinh th mui kim loi kim th, ri em t trn ngn la khng mu, mu ngn la s b thay i tu theo ion c trong mu mui: mui can xi c mu gch ; mui strnti s c mu cacmin; mui bari s c mu vng lc. 3.3. Ho cht phn tch nhm 2 3.3.1. Vi ion Ba2+ Dng thuc th dung dch K 2CrO4: to kt ta mu vng BaCrO4. Kt ta ny khng tan trong 123

dung dch NaOH Dng thuc th Wohlers: Trong mi trng KMnO4, ion Ba2+ tc dng vi dung dch H2SO 4 2M to kt ta BaSO4 mu trng, tuy nhin thc t ch thy kt ta mu tm hng trong dung dch. l do kt ta ny c tnh hp th mu ca dung dch thuc tm KMnO 4. Khi dng H2O 2 kh mu tm ca dung dch KMnO 4 th mu hng ca BaSO4 hp th vn gi nguyn 3.3.2. Vi ion Ca2+ Dng thuc th (NH4)2C2O4 to kt ta mu trng ca CaC2O4. Kt ta ny khng tan trong dung dch CH3COOH. Ch rng cc ion Ba 2+ v Pb2+ cng to c kt ta mu trng vi ion oxalat C2O42-, nn khi dng thuc th ny tm ion Ca2+ th phi loi cc ion Ba 2+ v Pb2+ ra trc Phn tch h thng nhm 2 Cation Bng 3.1 Xy dng quy trnh h thng phn tch cation nhm 2 1. Thm CH3COOH v CrO42- vo dung dch th, tch ly tm. Kim tra s kt ta hon ton ca Ba2+ 2.Kt 3. Nc ly tm (I) cha cc cation Sr 2+, ta (I) l Ca2+, CrO42BaCrO4 4. Lm kt ta cc cation Sr2+, Ca2+ bng Na2CO3 (pH > 10)

124

5. Ra kt ta (II)SrCO3, CaCO3 bng nc v ho tan trong CH3COOH. 7. Nc ly tm (III): (CH3COO)2Sr v (CH3COO)2Ca. Tm cc cation Sr2+ bng dung dch bo ho CaSO4 khi un nng v tch Sr2+ bng (NH4)2SO4 8. Kt ta (III) l SrSO4. Kim tra Sr2+ trn ngn la, trc cn chuyn n thnh cc hp cht d bay hi.

6. Nc ly tm (II) khng nghin cu 9. Nc ly tm (IV): Ca2+, (NH4)2SO4 d. Tm cation Ca2+ bng (NH4)2C2O
4

Xy dng quy trnh h thng phn tch cation nhm 2:(dng nhnh cy)

125

Hnh 3.1. S phn tch dung dch cation nhm II

THC HNH PHN TCH NH TNH CATION NHM II

BI THC HNH I. 1. NH TNH CATION NHM II: Ca2+, Ba2+, Sr2+ CHUN B Dng c 6 ng nghim trung 1 Kp ng nghim 3 ng nh git 1 Pipet 5mL 1 Pipet 10mL 1 Cn phn tch

126

2.

Ha cht CH3COOH,H2SO4,HCl u 2N K2CrO4 5% Na2HPO4 0,1N K4[Fe(CN)6] bo ha CaSO4 bo ha (NH4)2C2O4 0,1N Ru etylic (NH4)2CO3 0,1N m pH = 9 CH3CO ONa 2N

II. NH TNH Ca2+ Th nghim 1

Ly 5 git dung dch mu+ 5 git dung dch CH3COOH 2N (dng giy pH iu chnh pH ca dung dch < 7) + 5 git dung dch (NH4)2C2O4 0,1N + un nng. Quan st hin tng. CU HI 1. Vit phng trnh phn ng gii thch hin tng? Nu vai tr ca CH3COOH v vic phi un nng trong phn ng? Nu thay CH3COOH bng dung dch NH 3 0,05N

2.

th c thay i g khng? Th nghim 2 Ly 5 git dung dch mu+ 5 git H2SO4 6N + 2 git ru Etylic Quan st hin tng. CU HI 1. Vit phng trnh phn ng v gii thch vai tr ca C2H5OH trong phn ng? 127

Th nhim 3 Ly 5 git dung dch mu + 5 git (NH4)2CO 3 0,1N. Quan st hin tng Gn ly kt ta + tng git HCl 2N. Quan st hin tng. CU HI 1. 2. Vit phng trnh phn ng? Khi thay HCl bng H 2SO4 th hin tng c thay

i khng? Th nhim 4 Ly 5 git dung dch mu + 5 git dung dch m pH = 9 (pha t NH4Cl + NH3). un nng + 3 git K4[Fe(CN)6] bo ha mi pha. Quan st hin tng. CU HI 1. 2. 3. Vit phng trnh phn ng. Ti sao li s dng dung dch m pH = 9?

Thuc th K4Fe(CN)6 c c dng nhn bit Ca2+ trong hn hp dung dch Cation nhm 2 khng? Th nhim 5 Ly 5 git dung dch mu + 2 git NaOH 0,1N (cho vo tht nh nhng trnh gy kt ta) + Thm 1 git thuc th Murexit 1%. Quan st hin tng. CU HI 1. 2. 128 Vit cc phng trnh phn ng v gii thch? Nu vai tr ca NaOH trong phn ng?

III.

NH TNH Ba2+ (mu c pha t dung dch BaCl 2

0,1N) Th nghim 1 Ly 5 git dung dch mu+ 5 git dung dch H2SO4 2N. Quan st hin tng Thm 1 git HCl + 3 git HNO3 m c. Quan st kt ta. CU HI 1. 2. Vit phng trnh phn ng? C th thay dung dch H 2SO4 bng cht c gc

SO42- th hin tng c thay i khng? Gii thch Th nghim 2 Ly 5 git dung dch mu+ 5 git dung dch CH3COOH 2N + Thm 5 git dung dch K2CrO 4 5% + un nh. Quan st hin tng CU HI 1. 2. Vit phng trnh phn ng? V nu vai tr ca CH3COOH trong phn ng? Ion Sr2+, Ca2+ c gy cn tr cho phn ng ny

khng? Gii thch Th nghim 3 Ly 5 git dung dch mu cho vo ng nghim trung + cho thm 3 git dung dch (NH4)2CO 3 0,1N. Quan st hin tng - Gn ly kt ta + tng git HCl 2N. Quan st hin tng. CU HI 1. Vit cc phng trnh phn ng v gii thch? 129

2.

Nu thay dung dch HCl bng cch sc kh CO 2

vo dung dch th c lm thay i hin tng khng? Th nghim 4 Ly 5 git dung dch mu cho vo ng nghim + thm 3 git dung dch (NH 4)2C2O4 0,1N. Quan st hin tng. Gn ly kt ta + 3 git HCl 2N. Quan st hin tng. CU HI 1. Vit phng trnh phn ng gii thch? Th nghim 5 Ly 5 git dung dch mu cho vo ng nghim + thm 3 git dung dch Na 2HPO4 0,1N. Quan st hin tng Gn ly kt ta + 3 git HCl 2N. Quan st hin tng. Lp li th nghim trn nhng thay HCl bng dung dch CH3COOH 2N. Quan st hin tng. CU HI 1. 2. Vit phng trnh phn ng xy ra? Cc Ion Sr2+, Ca2+ c gy nh hng cho phn ng ny hay khng? IV. NH TNH Sr2+ (dung dch mu pha t dung dch SrCl2 0,1N) Th nghim 1 Ly 5 git dung dch mucho vo ng nghim + thm 5 git dung dch H 2SO4 2N Quan st hin 130

tng CU HI 1. Vit phng trnh phn ng xy ra? Th nghim 2 Ly 5 git dung dch mu+ 5 git dung dch CH3COOH + thm 5 git dung dch K 2CrO4 5%, un nh. Quan st hin tng Gn ly kt ta + 5 git CH3COONa 2N. Quan st hin tng. CU HI 1. 2. Vit phng trnh phn ng xy ra? Hy kt lun g v s khc bit gia Sr2+, Ba2+

trong phn ng vi K2CrO4. Th nghim 3 Ly 5 git dung dch mu cho vo ng nghim + 5 git (NH4)2CO3 0,1N + un nng. Quan st hin tng Gn ly kt ta + HCl 2N. Quan st hin tng Lp li th nghim nhng thay HCl bng CH3COOH 2N. Quan st hin tng. CU HI 1. Vit phng trnh phn ng xy ra? Th nghim 4 Ly vo ng nghim 5 git dung dch nc thch cao (dung dch CaSO 4 bo ha) + thm tng git dung dch mu. yn mt thi gian. Quan st hin tng. CU HI 131

V. 1.

1. Vit phng trnh phn ng xy ra? NH TNH H THNG HN HP nh tnh hn hp nhm 2 cation

Dung dch mu l hn hp Ca 2+, Ba2+, Sr2+ c pha vi nng 0,1-1N Ly 5 git dung dch muvo ng nghim + 5 git dung dch CH3COOH, un nh, thm tng git K2CrO4 10% kt ta vng (BaCrO4, v tch s tan ca SrCrO4, CaCrO4, BaCrO4 ln lt l: 4,44 - 3,15 - 9,93 ) chng t c Ba2+ Ly tm ly dung dch chia lm 2 phn: Phn 1 + 5 git dung dch (NH 4)2 SO4 bo ho. un cch thy 7 8 pht xut hin ta trng ca SrSO4. Li tm b kt ta thm vo dung dch 5 git (NH4)2 C2O4 0,5M th c kt ta trng CaC2O4 khng tan trong CH 3COOH Chng t c Ca2+ Phn 2 + 5 git CaSO4 bo ho 2. kt ta trng xut hin. Chng t c Sr2+ nh tnh hn hp 2 nhm Cation 1 v 2 Dng dung dch mul hn hp cc ion Ag+, Pb2+, Ca2+, Ba2+, Sr2+ c pha vi nng t 0,1N 1N Ly 10 git dung dch mu+ tng git dung dch HCl 6N n khi ngng kt ta, ly tm tht k, thu c dung dch lc (L1) v kt ta (T1). Phn ta (T1) c x l pht hin cc Cation nhm 1. Phn dung dch lc (L1) c x l pht hin 132

cation nhm 2. Phn ta (T1) c chia thnh 2 phn: Phn 1: (T1) + 2mL nc ct, un cch thu khong 5 pht, hi ngui, ly tm ngay v nhanh chng gn phn dch lc qua ng nghim khc, cho vo ng nghim ny 5 git dung dch KI 2N hoc dung dch K2CrO4 5%, thy c kt ta vng, chng t c ion Pb2+. Phn 2: (T1) + 5 git NH3 2N ta tan thnh dung dch (D1.2). Thm tng git HNO3 2N vo (D1.2), thy c kt ta trng xut hin, chng t c Cation Ag+. Phn dung dch lc (L1) Thm 3 git ru Etylic + tng git H2SO4 6N cho n khi ta c to ra hon ton (th thm 1 git H 2SO4 na). Li tm, thu c ta, gn cn thn (ng mt ta). Cho 7 8 git Na2CO3 bo ha vo ta (T2) chuyn thnh ta Cacbonat (khi cho Na2CO 3 bo ha vo nh ly a thu tinh khuy cho ta tan ra, em li tm. Lp li thao tc trn t nht 3 ln (nh gn ta cn thn). Cui cng ho tan ta trong CH 3COOH 2N (thm tng git dung dch acid ta phi tan ht). un si dung dch ri thm 2 3 git K2Cr2O7 10% (1N) cho n khi dung dch c kt ta vng chng 133 t c Ba2+ (Ghi ch: Nu c ln Pb 2+ th cng c

ta PbCrO4 vng. Nhng ta ny s tan trong NaOH 2N) Li tm b ht ta BaCrO4, gi ly dung dch lc (c mu hng da cam) + 5 git dung dch (NH4) 2 SO4 bo ho. un cch thy 7 8 pht, ta xut hin chng t c Sr2+ Li tm b kt ta thm vo dung dch 5 git (NH4)2 CrO4 0,5M th c kt ta trng khng tan trong CH3COOH CU HI 1. 2. BI TP 1. Lp s phn tch h thng hn hp Cation nhm 1 v 2? Vit phng trnh cc phn ng? chng t c Ca2+

Khi trn 100mL dung dch Pb(NO3)2 104M vi 400mL dung dch Na2SO4104M th c kt ta to thnh khng ? Bit tch s tan (T) ca PbSO4=10 7,8. Bin lun cc gi tr a v b khi pha V1mL dung dch BaCl2 nng 2a (M) vi V2 mL dung dch H2SO4 nng 2b(M) th: 2.1. Dung dch thu c khng c ta BaSO 4 hnh thnh 2.2. Dung dch thu c c ta BaSO4 to ra

2.

134

BI 4. PHN TCH NH TNH CATION NHM 3 M bi: HPT 4

Gii thiu Tip tc vic kho st nh tnh cc ion kim loi nhm 1, 2 l cc ion kim loi lng tnh cng c nh tnh d dng theo ng k thut phn tch. Mc tiu thc hin Hc xong bi ny hc vin s c kh nng: 1. M t cc tnh cht chung ca cation nhm 3. 2. M t tnh cht cc ion trong nhm. 3. Phn tch cc ion trong nhm 3. Ni dung chnh 1. 2. 3. Tnh cht ca cation nhm 3. Thuc th chung ca cc ion trong nhm. Ha cht phn tch ion nhm.

4. Cch phn tch nh tnh 4. 1. c tnh chung ca cation nhm: Cation nhm 3 gm Al3+, Zn2+, Cr3+ tng ng vi nhng nguyn t l nhng kim loi lng tnh, khi tc dng vi dung dch kim to thnh cc hydroxyt lng tnh kt ta. Cc kt ta ny tan trong dung dch kim c d. Nhm ng pha u chu k III ca h thng tun hon, c lp st lp ngoi cng v lp ngoi cng khi bo ho gm 8 electron. Cc nguyn t khc c sp xp phn gia ca chu k ln th t, chng c s in tip cc electron vo lp th 3 t 8 n 18 electron. 135

Crm l nguyn t chuyn tip. N ng na chu k 4, cui hng chn v c mt s tnh cht khc vi tt c cc cation cn li ca nhm ny. N biu hin kh nng to phc. Hydroxyt hydrat ho ca crom c nhng tnh cht rt gn vi hydroxyt hydrat ho ca nhm Km c sp xp na th hai ca chu k ln th 4 v c lp st lp ngoi l 18 electron. Nhm v km c s oxy ho khng i, cn cc nguyn t cn li trong nhm c s oxy ho thay i tu theo mi trng, vo nhit ... 4.2. Thuc th chung ca cation nhm 4.2. 1. Dng dung dch KOH hay NaOH d Phn ng to ra cc hydroxyt kt ta. Cc hydroxyt ca nhm c tnh cht lng tnh, tc l chng va c kh nng phn ly trong nc theo kiu acid li va c kh nng phn ly theo kiu baz. Hin tng phn ly phc tp ny cng c quan st ng thi vi khuynh hng tch phn t nc. Me 3+ + 3 OH -

Me(OH)3

H2O + H+ + MeO2

Trong phn th nht tng ng vi s phn ly Zn(OH)2 trong dung dch, cn phn cui ph hp vi s phn ly ca Al(OH)3, Cr(OH)3. Acid buc s phn ly ca hydroxyt theo kiu acid v kt hp vi ion OH- thnh cc phn t nc, thc t t phn ly. Do cn bng s chuyn v pha phi. Al(OH)3 + 3 HCl Al(OH)3 136 + 3H
+

AlCl3 + 3 H2O Al3+ + 3 H2O

Kim mnh buc s phn ly ca hydroxyt theo

kiu baz v ng thi kt hp vi ion H+ to thnh nc: H2CrO3 + NaOH NaCrO2 + 2 H2O Cc Cromit v aluminat bn vng khi no c mt ca mt lng d hydroxyt. a s mui ca cc cation nhm 4 ( mc ny hay mc khc) u b thu phn, chng hn: Sn 2+ + 2 H2O Al2(CO3)3 + 3 H2O
2ZnCO3 + 2 H2O

Sn(OH)2 + 2 H+ 2 Al(OH)3 + 3 CO2

(ZnOH)2CO3 + CO2 + H2O

Cc hydroxyt NaOH, KOH cng vi cc cation nhm 3 to ra cc hydroxyt khng tan trong thuc th d: Cr3+ + 3 NaOH Cr(OH)3 + NaOH Cr(OH)3 + 3 Na + NaCrO2 + 2 H2O

Tnh cht chung ca cc cation nhm III l chng u to thnh cc mui tan trong mi trng kim d, th d: Al3+ + 4OH = AlO2- + 2H2O Zn2+ + 4OH = ZnO22- + 2H2O Da trn tnh cht ny c th tch cc cation nhm III ra khi nhm khc bng kim d. Tuy nhin, cng cn nhn xt ngay rng ion cromit (CrO2-) thng kt hp vi cc cation nh Mg2+, Mn2+, Fe3+, Zn2+ to thnh nhng kt ta kh tan Mg(CrO 2)2, Zn(CrO2)2, Mn(CrO2)2 v vy tch Cr 3+ cng vi nhm III, thng dng kim d v c mt H2O2 oxi ha Cr3+ v CrO423Cr3+ + 3H2O2 + 10OH = 2CrO42- + 8H2O Chnh v vy cho nn thuc th tch nhm III l NaOH (hoc KOH) d v H2O2. 137

4.2. 2. Dng thuc th dung dch NH3 Amni hidrxit (NH4OH) tc dng vi cc cation nhm III to thnh cc hidrxit khng tan, nhng ring Zn2+ khi dung dch NH3 d s lm kt ta ny v c ion ny chuyn thnh phc amoniacat tan Zn(NH3)22+ Al3+ + 3NH4OH = Al(OH)3 + 3NH4+ Al(OH)3 + NH4OH = AlO2- + NH4+ + 2H2O Al(OH)3 kt ta hon ton khi dung dch c pH Sn
2+

+ 2NH4OH = Sn(OH)2

+ 2NH4

Sn4+ + 4NH4OH = Sn(OH)4

+ 4NH4+

Cr3+ + 3NH4OH = Cr(OH)3 + 3NH4+ Cr(OH)3 tan mt t trong NH 4OH d, khi c mt NH4Cl to thnh mui kp CrCl3.NH3 mu tm Zn(OH)2 tan trong NH3 d, nht l khi trong dung dch c ln mui amni, to thnh ion phc km amniacat Zn(NH3)42+: Zn(OH)2 + 2NH4OH + 2NH4+ = [Zn(NH3)4]2+ + 4H2O 4.2. 3. Dng Natri hoc kali cacbonat (Na2CO3 hay K2CO3) To thnh kt ta hidroxit, ring vi ion Zn2+ to thnh mui cacbonat baz c thnh phn ph thuc nng dung dch v nhit : 2AlCl3 + 3Na2CO3 + 3H2O = 2Al(OH)3 + 6 NaCl + 3CO2 Cr2(SO4)3+ 3Na2CO3+3H2O= 2Cr(OH)3 +3Na2SO4 + 3CO2 SnCl4 + 2Na2CO3 + H2O = Sn(OH)2 + 2NaCl + CO2 3SnCl4+3Na2CO3 + H2O = Zn3(OH)2(CO3)2 + 6 NaCl + CO2 Tt c kt ta trn u tan trong kim d, ring mui 138

cacbonat baz ca km tan c c trong amoniac v trong mui amoni. 4.2. 4. Dng thuc th inatrihidr phtphat To thnh mui phtphat kh tan: AlCl3 + 2Na2HPO4 = AlPO4 + 3NaCl + NaH2PO4 keo mu trng CrCl3 + 2Na2HPO4 = CrPO4 + 3naCl + NaH2PO4 mu lc
3ZnCl4 + 4Na2HPO4 = Zn3(PO4)2 + 6NaCl + NaH2PO4

Ring Sn

2+

to thnh hidroxit:

3SnCl4 + 4NaHPO4 = Sn3(PO4)2 + 6NaCl + 2NaHPO4 Sau Sn3(PO4)2 tc dng hon ton vi H2O: Sn3(PO4)2 + 6H2O = 3Sn(OH)2 +2H3PO4 4.2. 5. Dng thuc th H2S (hoc dung dch nc H2S) Ion Al3+ v Cr3+ trong mi trng trung tnh hoc amoniac th ch to thnh Al(OH)3 v Cr(OH)3 ch khng to thnh sunfua nhm v crm c bi v: 2NH4OH + H2S = (NH4)2S + 2H2O Al2(SO4)3 + 3(NH4)2S = Al2S3 + 3(NH4)2SO4 V ngay tc khc Al2S3 + 6H2O = 2Al(OH)3 + 3H2S i vi ion Cr3+ phn ng cng xy ra tng t 4.2. 6. Dng thuc th dung dch S2Ion Zn+2 trong mi trng trung tnh, kim yu hoc c mt mui axetac natri th tc dng vi H2O hay (NH4)2S to thnh kt ta sunfua km mu trng: ZnCl4 + H2S = ZnS + 2HCl HCl + CH3COONa = NaCl + CH3COOH 139

Hay ZnCl2 + H2S + 2CH3COONa = ZnS + 2NaCl + 2CH3COOH ZnS lkt ta v nh hnh mu trng, tan trong cc acid v c nhng khng tan trong acid axetic NaOH: ZnS + 2H+ = Zn2+ + H2S Khong phn ng thch hp nht kt ta ZnS l1,5 3. tha mn iu kin , mun kt ta hon ton ZnS thng tin hnh trong mi trng fomiat c pH = 2. Ion Sn4+ v Sn2+ trong mi trng HCl tc dng vi H2S to thnh cc sunfua kh tan: SnCl4 + 2Cl- = [SnCl4]2SnCl42- + H2S = SnS Cn: SnCl4 + 2Cl- = [SnCl6]2SnCl62- + 2H2S = SnS2 mu vng ti + 6Cl + 4H+ 4.3. Phn tch cc ion trong nhm 4.3.1. Vi ion Al3+ Dng thuc Aurintricacboxylic, th c aluminon (cn gi l acid cng thc phn t l (mu scla) + 4Cl- + 2H+

C22H11O9(NH4)3, l cht bt mu nu, d tan trong nc to dung dch mu c phn ng trung tnh, t tan trong ru etylic ngay c khi c un nng, v khng tan trong aceton Trong trong mi trng CH3COOH hoc dung dch m acetat: to kt ta l mt phc ni mu hng m. Tu theo hm lng ca ion Al 3+ trong dung dch s c mu hoc dung dch mu . Phn ng ny rt nhy, dng trong nh tnh pht hin ion Al 3+ v trong phn 140

tch o mu nh lng nhm. Tuy nhin Aluninon cng cho phn ng tng t vi cc mui ca Ba, Ca, Sr, La, Ra, Be. Cs, Nd, Zr, Th, Hf, Cr, In, Ga, Fe, Er nhng vi cc tr s pH khc nhau. Aluninon to kt ta trng vi cc cation ca Sb, Bi, Pb, Hg, Ti, H2SiO3. Dng thuc th dung dch (NH3 + NH4Cl): to kt ta Al(OH)3 mu trng keo tan trong dung dch acid cng nh tan trong dung dch baz, nhng khng tan trong dung dch NH3 v dung dch mui amonium Dng thuc th dung dch Alizarin S (C14H7O7SNa. H2O) v cc dn xut ca n u cho phn ng mu c trng vi ion Al 3+ nn c dng nh tnh v nh lng nhm. N dng hnh kim mu da cam vng hoc bt mu vng da cam. Tan trong nc v ru etylic khi un nng, khng tan trong cc dung mi hu c nh benzen, etxng, clorofom, v tu vo mi trng m cho mu tng ng: trong acid c mu vng, khi c baz th chuyn sang mu xanh, nhng trong dung dch NH4OH, th n li c mu tm Khi cho alizarin d S tc dng vi ion Al 3+ trong mi trng NH4OH, nh t t CH3COOH long cho n mt mu tm, ri tip tc nh thm lng CH3COOH, th to mui ni phc mu dng kt ta hay dung dch. 4.3.2. Vi ion Zn2+ Dng thuc th (NH 4)2 [Hg(SCN )4 ] (amoni tetrathioxy-anat thy ngn (II)) trong dung dch m 141

CH3COO - to kt ta mu trng Zn[Hg(SCN )4 ] . Ion Cu2+ cng tc dng c vi (NH4)2[Hg(SCN)4] to thnh kt ta mui phc Cu[Hg(SCN)4 ] mu lc. Nu trong dung dch c mt ng thi c hai ion Zn 2+ v Cu2+ th chng s cng tc dng vi (NH4)2[hg(SCN)4] to thnh kt ta mu Zn[Hg(SCN)4].Cu[Hg(SCN)4] tm c thnh phn l

Nu thay ion Cu2+ bng ion Co2+ th s c kt ta tinh th mu lc Zn2+ + Co2+ + 2(Hg(SCN)4)2 = Zn[Hg(SCN)4].Co[Hg(SCN)4] Dng thuc th K3[Fe(CN)6]: to kt ta mu vng hung Zn3[Fe(CN)6]2 Dng thuc th K4[Fe(CN)6]: to kt ta mu trng K2Zn3[Fe(CN)6]2 Dng thuc th dung dch Montequi A v dung dch CoCl2 0,1% trong dung dch CH 3COO - : to kt ta mu ca: ZnCo[Hg(SCN )4 ]2 . 4.3.3. Vi ion Cr3+ Dng thuc th H2O2 trong mi trng kim oxy ho Cr3+ (mu xanh lc) thnh Cr6+ (CrO42- hay Cr2O72 c mu vng hay da cam). Sau tm ion Cr 6+ dng CrO4 2bng cc thuc th (AgNO 3 hay (CH3COO)2Pb hay BaCl2). Phn ng oxi ha Cr 3+ n CrO42- c tin hnh trong mi trng kim bng cc cht oxi ha khc H 2O2 nh Cl2, Br2, PbO2 hoc trong mi trng acid S2O22-, BiO Nu cho H2O2 tc dng vi cc ion CrO42 hay Cr2O72trong mi trng acid th s to thnh acid pecromic H2CrO6 (hay peoxit crm CrO c mu xanh tm) 142

Cr2O72- + 4H2O2 + 2H+ = 2H2CrO6 + 3H2O H2O2 + 2e + 2H+ = 2H2O Cr2O72 + 8e + 5H2O = 2H2CrO6 + 6H+ Axit pecromic rt khng bn trong nc n phn hy rt nhanh to thnh ion Cr3+ c mu lc v oxi: H2CrO6 = CrO5H2O 4CrO5 + 12H+ = 4Cr3+ + 7O2 + 6H2O Nhng chit n ln lp ru th n s t phn hy chm i, mu xanh tm gi c lu hn v c th nhn bit c. y l phn ng c bit dng nhn bit crm. Tuy nhin, khi dng phn ng ny cn lu c bit n th t thm cc thuc th nu khng s khng thu c kt qu. CrO42- v Cr2O72- l cc cht oxi ha mnh, c th dng cc cht kh kh v Cr3+ chng hn khi cho chng tc dng vi KI trong mi trng acid: Cr2O72- + 6I- + 14H+ 2Cr3+ (mu nu) + 7H2O + I2 Nu nh dn dung dch natri thiosunfat vo th mu nu ca dung dch s bin mt v c phn ng: 2S2O32- + I2 = S4O62- + 2IV khi dung dch c mu lc ca ion Cr 3+ Hoc phn ng vi Fe2+ trong mi trng acid: Cr2O72- + 6Fe2+ + 14H+ = 2Cr3+ + 6Fe3+ + 7H2O Dng thuc th H2S hay S2 trong mi trng acid: Cr2O72 + 3S2- + 14H+ = 2Cr3+ + 3S + 7H2O 4.3.4. Phn tch h thng Cation nhm 3

143

Bng 4.1 Xy dng quy trnh h thng phn tch Cation nhm 3 1. Thm dung dch NH3 v H2O vo dung dch th, un nng, ly tm 2. Kt ta (I) l Al(OH)3 c x l bng HCl v xc nh Al3+ bng alizarin hoc aluminon Xy dng h thng phn tch cation nhm 3 theo dng nhnh cy 3. Nc ly tm (I) gm CrO42-, [Zn(NH3 )4]2+, c trung ho bng CH3COOH, thm dung dch Na2CO3, v quay ly tm (hoc lc) 4. Kt ta (II) ho tan l (ZnOH)2CO3 trong CH3COOH v xc nh Zn2+ bng dithizon hay vi tinh th nghim 5. Nc ly tm (II) l CrO2-4 c tm di dng CrO5

Hnh 4.1. S phn tch dung dch cation nhm III 144

THC HNH PHN TCH NH TNH CATION NHM III

BI THC HNH NH TNH CATION NHM III: Al3+, Cr3+, Zn2+ I. 1. CHUN B Dng c 6 ng trung 1 n cn 2. 3 ng Ha cht nh git CH3COOH 2N Na2HPO4 0,1N K4[Fe(CN)6] 0.1N HCl 6N H2SO4 6N Ru amylic DD pH = 5 (pha t CH3COOH + CH3COONa) I. NH TNH Al3+ Th nghim 1 Ly 5 git dung dch mucho vo ng nghim trung + 3 git dung dch NH3 6N ri un nng. Quan st hin tng Tip tc cho 3 git dung dch NaOH 5N, lc u dung dch. Quan st hin tng 145 NH3 6N NH4Cl bo ha Aluminon 0,1% H2O2 5% H2SO4 1N AgNO3 0,1 nghim 1 Pipet 5mL 1 Pipet 10mL 1 Cn phn tch

1 Kp ng nghim

Thm tng git NH4Cl bo ha+ un si. Quan st hin tng. CU HI 1. 2. Vit cc phng trnh phn ng xy ra trong th nghim? Ti sao phi un si dung dch lc cho NH4Cl?

Gii thch? Th nghim 2 Ly 5 git dung dch mucho vo ng nghim + 3 git dung dch NH 3 6N + 3 git Alizarin + un si k. Quan st hin tng ngui. Cho vo 3 git CH 3COOH 2N. Quan st hin tng. CU HI Vit cc phng trnh phn ng xy ra trong th nghim ? Th nghim 3 1. Ly 5 git dung dch mu cho vo ng nghim + 4 git dung dch m actat pH= 5.5 + 3 git dung dch Aluminon 0.1%. Quan st hin tng. CU HI 1. Vit cc phng trnh phn ng xy ra trong th nghim? 2. Nhng yu t no c th nh hng n phn ng ny? II. NH TNH Cr3+ (dung dch mu pha t dung dch CrCl3 0,1N) Th nghim 1 146

Ly 5 git dung dch mu+ 3 git dung dch NaOH 5N + 5 git H2O2 5% + un nh. Quan st hin tng Tip tc thm 3 git H2O2 5% + 0.5mL ru amilic, lc u + thm tng git H2SO4 6N va thm va lc. Quan st hin tng. CU HI Vit cc phng trnh phn ng xy ra trong th nghim? 2. Gii thch s c mu lp ru? Th nghim 2 1. Ly 5 git dung dch mucho vo ng nghim + 3 git dung dch Na 2HPO4 0,1N. Quan st hin tng. Thm 5 git CH3COOH 2N + lc nh. Quan st hin tng. CU HI 1. 2. 3. Vit cc phng trnh phn ng xy ra trong th nghim? Phn ng ny c iu kin g khng? Nu thay CH3COOH bng dung dch NaOH th

c thay i hin tng khng? Th nghim 3 Ly 5 git dung dch mu vo ng nghim + 5 git H2O2 5% + 3 git NaOH 5N + un nh + 5 git H2SO4 1N vo dung dch trn + 3 git AgNO3 0.1N vo. Quan st hin tng. CU HI 147

1. 2.

Vit cc phng trnh phn ng xy ra trong th nghim? Nhng yu t no s nh hng n phn

ng? IV. NH TNH Zn2+ (dd mu pha t dung dch ZnCl 2 0,1N) Th nghim 1 Ly 3 git dung dch mucho vo ng nghm + 3 git dung dch HCl 6N + 1 git K4[Fe(CN)6] 0,1N. Quan st hin tng. CU HI 1. 2. Vit cc phng trnh phn ng xy ra trong th nghim? Cho bit cc yu t nh hng tc ng n

phn ng. Th nghim 2 Ly 5 git dung dch mucho vo ng nghim + 5 git dung dch (NH 4)2Hg(SCN)4] 0,1N (cn gi l thuc th Montequi A). Quan st hin tng. CU HI 1. Vit cc phng trnh phn ng xy ra trong th nghim? V. TCH CC CATION NHM 3 1. Phn tch h thng cation nhm 3 Dng dung dch mul hn hp cc ion: Al 3+, Zn2+, Cr3+c pha vi nng t 0,1N 1N Ly 10 git dung dch mu+ tng git dung dch NH3 c n d, em ly tm, thu c dung dch lc v ta mu trng. 148

Phn dung dch lc em chia lm hai phn: Phn 1 + 5git H2O2 5% + 3mL ru Amilic + 5 git H2SO4 c, tht nh v kho dch ru s c mu xanh tm ion Cr3+ Phn 2 + tng git dung dch Na 2S cho n khi xut hin ta trng Chng t c ion Zn2+ Phn ta trng + tng git HCl n tan hon ton (kim tra pH dung dch c mi trng kim yu). Thm vo dung dch 3 git Alizarin, un nh, xut hin ta mu da cam hoc nc sm Chng t c ion Al3+ 2. Phn tch hn hp h thng Cation cc nhm 1, 2, 3: Dng dung dch mul hn hp cc Ion Ag+, Pb2+, Ca2+, Ba2+, Sr2+, Al3+, Zn2+, Cr3+ c pha vi nng t 0,1N 1N Ly 10 git dung dch mu+ tng git dung dch HCl 6N n khi ngng kt ta, ly tm tht k, thu c dung dch lc (L1) v kt ta (T1). Phn ta (T1) c x l pht hin cc Cation nhm 1. Phn dung dch lc (L1) c x l pht hin Cation nhm 2 v 3. Phn ta (T1) c chia thnh 2 phn: Phn 1: (T1) + 2mL nc ct, un cch thu khong 5 pht, hi ngui, ly tm ngay v nhanh chng gn phn dch lc qua ng nghim 149 phn dung Chng t c

khc, cho vo ng nghim ny 5 git dung dch KI 2N hoc dung dch K2CrO4 5%, thy c kt ta vng, chng t c Ion Pb2+. Phn 2: (T1) + 5 git NH3 2N ta tan thnh dung dch (D1.2). Thm tng git HNO3 2N vo (D1.2), thy c kt ta trng xut hin, chng t c Cation Ag+. Phn dung dch lc (L1) Thm 3 git ru Etylic + tng git H2SO4 6N cho n khi ngng to ta (th thm 1 git H2SO4 na). Li tm, thu c ta (T2) v dung dch lc (L2) Phn ta (T2) c x l pht hin cc cation nhm 2. Phn dung dch lc (L2) c x l pht hin cation nhm 3. Phn ta (T2) Cho 7 8 git Na2CO3 bo ha vo ta (T2) chuyn thnh ta Cacbonat (khi cho Na2CO 3 bo ha vo nh ly a thu tinh khuy cho ta tan ra, em li tm. Lp li thao tc trn t nht 3 ln (Ch : gn ta cn thn). Cui cng ho tan ta trong CH3COOH 2N (thm tng git dung dch acid ta phi tan ht). un si dung dch ri thm 2 3 git K2Cr2O7 10% (1N) cho n khi dung dch c kt ta vng
2+ 2+

chng

t c Ba (Nu c ln Pb th cng c ta PbCrO4 vng. Nhng ta ny s tan trong NaOH 2N) 150

Li tm b ht ta BaCrO 4, gi ly dung dch lc (c mu hng da cam) + 5 git dung dch (NH 4)2 SO4 bo ho. un cch thy 7 8 pht, ta xut hin chng t c Sr2+ Li tm b kt ta thm vo dung dch 5 git (NH4)2 CrO4 0,5M th c kt ta trng khng tan trong CH3COOH Phn dung dch lc (L2) chng t c Ca2+

em c gn cn ui ru Etylic d, ngui + 2mL dung dch NaOH 10% + 10 git H2O2 6%, lc trn u, un si k, ngui, ly tm tht k, gn cn thn phn dung dch qua mt ng nghim khc, ra kt ta 2 ln bng nc ct, nhp nc ra vo ng nghim ng dung dch (L3). Dung dch 3 + 10 git NH4Cl bo ha, un si k, ngui, ly tm, gn cn thn phn dung dch trong qua ng nghim khc, ra kt ta 2 ln bng nc ct, nhp nc ra vo ng nghim thu c dung dch lc (L3.1) v ta (T3.1) Phn ta (T3.1) c x l pht hin Al 3+ Phn dung dch lc (L3.1) c x l pht hin Zn v Cr3+ Phn ta (T3.1) Nh tng git HCl 2N vo ta cho n khi ta tan ht + tng git NH3 6N (dng giy pH kim tra n mi trng kim yu) + 3 git Alizarin, un si, xut hin kt ta da cam chng t c cation Al3+. Phn dung dch lc (L3.1) 151
2+

em (L3.1) chia lm 2 phn: (Cation Crom III tn ti dng Cromat, Cation Km II dng phc Moniacat) Phn 1: thm vo 5 git H2O2 5% + 0.5mL ru Amilic, lc u, thm tng git H2SO4 6N, va thm va lc, lp ru s c mu xanh thm chng t c Cr3+ Phn 2: thm vo 5 git dung dch (NH4)2[Hg(SCN)4], phn ng to mui ni phc kt ta mu trng CU HI 1. 2. BI TP 1. Lp s phn tch h thng hn hp cc Cation nhm 1, 2, v 3? Vit phng trnh cc phn ng? chng t c Zn2+

Khi cho dung dch Cu2+ 10 -2 M vo dung dch EDTA 10 -2 M, th nng Cu2+ ti cn bng l bao nhiu? Bit rng ion Cu2+ c kh nng kt hp vi EDTA to phc bn (hng s bn = 10 18,8 ), v phc ny khng b nh hng bi cc ion H + hoc OH-. Ngoi ra Cu2+ cn c kh nng to phc vi OH- theo 4 phng trnh kt hp, cn EDTA l mt dung dch acid a chc phn ly 4 nc. Dung dch to thnh sau khi pha trn c pH = 6, v cc gi tr hng s cho trc l: Hng s bn 4 nc to phc Cu2+ vi OH- ln lt l 10 7 ; 10 6,68 ; 10 3,32 ; 10 1,5 Hng s bn 4 nc to EDTA t Y4- ln lt l

152

3.

9,1.10 10 ; 1,85.10 6; 4,76.10 2 ; 103 Pha trn cng mt th tch dung dch Hg2+ 10 4 M vi dung dch EDTA 10 4M, th c th to c phc Hg-EDTA khng ? Tnh nng Hg 2+ ti thi im cn bng sau pha trn. Bit rng dung dch to thnh sau khi pha trn c pH = 10, v ion Hg2+ c kh nng kt hp vi EDTA to phc bn (hng s bn = 1021,8), v phc ny khng b nh hng bi cc ion H+ hoc OH-. Ngoi ra Hg2+ cn c kh nng to phc vi OH- theo 3 phng trnh kt hp, cn EDTA l mt dung dch acid a chc phn ly 4 nc. Cc gi tr hng s cho trc l: Hng s bn tng cng 6 nc to phc Hg2+ vi OH- ln lt l 10 10,3 ; 1021,7 ; 0 ; 0 ; 0 ; 10 21,2. Hng s bn 4 nc to EDTA t Y4- ln lt l 9,1.10 10 ; 1,85.10 6; 4,76.102 ; 103

153

BI 5. PHN TCH KHI LNG M bi: HPT 5

Gii thiu Hm lng cc cu t c trong mu cht phn tch c th c xc nh bng php phn tch khi lng, l mt phng php da trn php o v khi lng ca cc cht t dng mu ban u n cc dng c nung, sy m chng c lin quan n thnh phn cu t cn phn tch. y l mt phng php c p dng rng ri v c kt qa tng i tht Mc tiu thc hin Hc xong bi ny hc vin s c kh nng: 1. M t c s ca phng php khi lng. 2. M t cc bc tin hnh phn tch khi lng. 3. Cch phn tch theo khi lng. Ni dung chnh 1. 2. 3. C s v nguyn tc tin hnh ca phng php khi lng. Cc bc tin hnh phn tch. K thut thc hin trong phn tch khi lng.

4. nh lng mt s mu th 5.1. C s v nguyn tc ca phng php khi lng Phn tch khi lng da trn php o khi lng ca hp cht c thnh phn bit, lin quan v mt ho hc vi cu t cn xc nh. C hai nhm cc phng php phn tch khi lng l nhm cc phng php kt ta v nhm cc phng php chng ct. Trong nhm 154

cc phng php kt ta, cu t cn xc nh tham gia vo phn ng ho hc vi thuc th, to thnh sn phm t tan, sau lc v thc hin nhng ng tc cn thit khc v cui cng cn kt ta rn c thnh phn ho hc bit. Trong nhm cc phng php chng ct, cu t cn xc nh c tch ra khi mu dng kh. Trong trng hp ny, php phn tch hoc l da trn php xc nh khi lng cht c ct ra, hoc l da trn php xc nh cht cn li. Trong hai nhm ny, thng c dng nhm phng php kt ta. Phng php phn tch khi lng bng nhm phng php kt ta, bao gm hai php o thc nghim: cn mu (A) c cha cu t (x) v cn sn phm (B) c cha cu t (x) bit thnh phn ho hc, thu c t mu qua php phn tch khi lng. Trn c s nhng d kin , bng nhng php tnh, tnh c hm lng theo phn trm ca cu t (x) cn xc nh. Cch tt nht l khng o trc tip khi lng A m cn tch v cn cht B, ri dng h s chuyn tnh khi lng A tng ng trong khi lng kt ta. V d: C bao nhiu gam Cl cha trong 0,2040(g) kt ta AgCl ? Gii: Ta c: 2. s mol ca AgCl = s mol ca Cl Vy: khi lng Cl = 0,2040.
35,45 = 0,0505(g) 143 ,3

V d: Khi lng AlCl 3 tng ng vi 0,2040(g) AgCl l 155

bao nhiu ? Gii: Ta c 1 phn t AlCl3 to c 3 phn t AgCl 3s mol ca AlCl3 = s mol ca AgCl Do : khi lng AlCl3 = 0,2040.
m AlCl3 3.m AgCl

= 0,2040.

133 ,3 3.143 ,3

= 0,0633 (g) V d: Cn m1 (g) cht (A) cha cu t (x) ri ho tan thnh dung dch bng V1 (mL) nc ct. Ht V2(mL) t dung dch ny, phn tch theo phng php khi lng th c m2(g) cht (B) c thnh phn xc nh cha (x) theo phng trnh chuyn ho: a A b B. Tnh hm lng % (x) c trong mu (A) ban u. Gii: T phng trnh chuyn i c h s chuyn i: K=
a.M A bM B

Th hm lng (x) c xc nh l: %(x) = K.

m 2 V1 . . 100 m1 V 2

Tng qut: Hm lng cu t (x) khi chuyn i t dng mu A thnh dng cn B (theo phng trnh chuyn ho: a A b B) sau khi c pha long (nh mc) n ln V 1, V2 ,...Vn ri trch ra m ln V'1, V'2,...V'm, th: % (x) = K. F.
m2 . 100 m1

156

Trong : H s chuyn i K=
n

a.M A bM B

Vi

H s pha lang F =

i:1 m

Vj
j:1

m1 v m2 l khi lng ca dng mu A v dng cn B V d: Cn 0,35(g) mt lng mui cha Na2SO4 ri nh mc thnh 25omL dung dch. Ht 50(mL) t dung dch ny, phn tch theo phng php khi lng th c 0,0405(g) BaSO4. Tnh hm lng % SO42 trong mu mui cha Na2SO4 ban u. Gii: Phn ng chuyn i: Na2SO4 H s chuyn i: K =
.M Na 2 SO4 .M BaSO4

BaSO4 (t l 1: 1) =
142 = 1,64 233

Vy hm lng % SO42- =

0,0405 .250 .1,64.100% 0,35 .50

= 94,88%. 5.2. Cc bc tin hnh v k thut phn tch khi lng 5.2.1. Cc bc tin hnh C th thc hin phng php khi lng theo 3 bc sau: Pha ch cc dung dch chun. Tin hnh th nghim 157

Cn o cht rn thu c, v x l kt qu.

Thng nhng kt qa phn tch khi lng bao gm nhng d liu ca hai php o hoc i khi ca hai dy php o: lng ban u ca mu v lng hp phn cn xc nh trong mu. V d, c th o khi lng, th tch, cng sng, hp th nh sng, cng pht hunh quang, in lng. Nhng nhng php o ch l mt phn ca phng php nh lng thng thng. Hon ton khng km phn quan trng l nhng giai on chun b trc, nhng giai on ny nng nhc lu di hn v nh hng trc tip n php o. V th cn tin hnh cn thn theo cc bc ngh sau y. Cc bc c th l: Chn mu: nh gi ng thnh phn, phn nh ng tnh cht ca ton b cht cn phn tch, th vic chn mu l giai on khng th thiu. Chng hn, vi mt lng cht cn nh gi l mt contener cha 25 tn qung bc i n tho thun gi c hp l gia ngi bn v ngi mua, trc ht phi xc nh c hm lng bc. V qung khng ng nht, hm lng bc trong cc phn khng ging nhau, m thc t ch c th phn tch trn c s mt lng bc l 1gam. Thnh phn ca n i din cho thnh phn ca 25 tn qung, tc l khang 2.270.000 gam qung hng ho. R rng vic la chn lc ny khng cn l vn n gin na. Ni mt cch khc, chn mu c khi lng 1gam v tin cy l thnh phn ca n 158

i din cho 2.300.000gam nguyn liu t n c ly ra, i hi phi x l s b ton b nguyn liu. Cn phi p dng cc phng php ly mu ph hp cho tng i tng mu mt cch cn thn v chnh xc. Chun b mu phn tch: Cn phi nghin v trn u m bo tnh ng nht ca mu. i khi cn phi loi tr m hp th ra khi cht rn bng cch phn tch mu sy kh. o mu Ho tan mu: Mu thng c em ho tan thnh dung dch trc khi tin hnh th nghim, v th, nu dng c mt dung mi thch hp m lm tan ho ton cc loi mu l mt iu l tng Tch hn hp cn tr: cn tin hnh nghin cu nhng s phn tch tch hp phn cn quan tm khi cc cht l c trong nguyn liu th v c th nh hng n php o trc tip cn xc nh gi l cht cn tr. Tch c cc cht cn tr trc khi tin hnh th nghim l nhim v quan trng trong ho phn tch. Giai on kt thc php phn tch: Vit bo co, tng trnh php phn tch 5.2.2. K thut 5.2.2.1. nhy ca phng php Phng php ny khng th dng thit b o xc nh c nhy, nu cn vi lng cn nh (vi 159

microgam) th sai s c th c n vi chc %, cn cn vi lng cn ln th c th h thp sai st n vi chc ngn %. Phn ln l do kh nng tch c cc kt ta v kh nng lc c chng. nhy ca phng php ph thuc phn ln giai on ny. V th phng php thng c dng phn tch cc cht c nng cn xc nh cao hn 0,1% 5.2.2.2. chnh xc ca phng php Tnh phc tp ca phng php sai s gn vi tan, s cng kt v s khc nhau trong thnh phn ho hc ca sn phm cui cng: mi mt yu t trong nhng yu t u ph thuc vo thnh phn ca mu. V d: st trong mu khng cha cc ion kim loi nng c th xc nh d dng bng phng php khi lng vi sai s khng hn mt vi chc %, nhng khi c mt cc cation ho tr 2 nh km, niken, ng... th sai s s ln hn nhiu hoc phi tn nhiu cng sc ngn nga s cng kt cc ion ny S hao ht (mt i) mt lng ion cn xc nh trong phng php ny do tan cng ph thuc vo thnh phn mu. Trong h nhiu cu t, xc sut to phc ca cht cn xc nh v ca cu t ca mu cng tng ln, ngoi ra lm sch kt ta phi cn mt th tch ln cht lng ra nn c th dn ti s mt mt ln do tan. Khi phn tch nhng mu n gin vi hm lng cht cn xc nh ln hn 1%, chnh xc ca phn tch khi lng t khi vt chnh xc ca cc phng php khc. Do sai s trong trng hp ny c th gim xung 160

n 0,1

0,2%. Khi tng tnh phc tp ca thnh phn

mu, tt nhin sai s tng ln hoc l phi tn thi gian khc phc. Trong trng hp ny chnh xc ca phng php khi lng c th t ra khng tt hn, thm ch cn xu hn chnh xc ca nhng phng php phn tch khc. 5.2.2.3. ng dng ca phng php Phng php ny c nghin cu cho phn ln cc anion v cation v c v c cho cc hp cht trung ho nh nc, ioxyt lu hunh, kh CO2, I2. C mt lot cc hp cht hu c cng d dng xc nh bng phng php khi lng, v d nh xc nh lactoza trong sn phm sa, salisilat trong dc phm, phenolphtalein trong thuc s, nicotin trong ho cht c, Cholesterin trong huyt thanh v benzalehid trong dch chit qu hnh nhn. Phng php khi lng l mt trong nhng phng php phn tch c s dng rng ri nht. 5.2.2.4. K thut phn tch Khi lng nh phn Phng php khi lng ny kh quan trng trong php phn tch kim loi, hp kim, t nham thch Bn cht phn tch nh lng l mt phng php phn tch da trn s o chnh xc khi lng ca cht cn phn tch hoc ca thnh phn n c tch ra trng thi tinh khit ha hc, hoc di dng hp cht thch hp C 3 phng php: 161

1.

Phng php tch: Cu t cn xc nh tch ra t cht phn tch di dng t do, cn bng cn phn tch, v d nh lng vng v ng trong hp kim, theo nguyn tc: Hn hp + dung dch cng thy vng ra sy cn. tan + H2O2 lc kh ion vng thnh nguyn t kim loi

2.

Phng php kt ta: kt ta cu t cn xc nh bng phng php ha hc di dng hp cht t tan c thnh phn xc nh, v d kt ta BaSO4. Phng php ct: ct mt cch nh lng cu t cn xc nh di dng hp cht bay hi. + Ct trc tip: cu t bay hi c hp th bng cht hp th c bit, xc nh khi lng cht bay hi.

3.

Ct gin tip: xc nh cht cn li sau khi lm bay hi. Phng php ny c chnh xc cao, dng xc nh cc hm lng kim loi, qung. Nhng phng php i hi thi gian thc hin kh lu. Nguyn tc Cn lng mu cht cn nh lng, ha tan thnh dung dch. Kt ta cht cn phn tch di dng hp cht bn. Da vo khi lng cht kt ta, tnh hm lng cht cn phn tch. 1. Ly mu trung bnh: 162

Mu trung bnh phi t c mc ch l lng mu khng ln, nhng trong hm lng ca tt c cu t cn nh lng phi bng hm lng ca chng c trong tt c khi lng cht cn phn tch 2. Yu t nh hng n s kt ta han ton, phn ng han ton khi dng kt ta cn li ( dng tan) bng chnh xc ca cn phn tch Dng cn: Dng kt ta sau khi sy kh hoc cn gi l dng cn. Dng cn phi c cng thc xc nh c thnh phn khng i t khi sy hoc nung n sau khi cn (khng ht m v khng b phn hy). Nu dng cn c trong hp cht c khang phn t lng cng ln th kh nng chnh xc cng cao, chng hn, xc nh hm lng Cr 3+ th dng Cr3+ trong dng BaCrO4 (M = 253,3) s chnh xc hn Cr 3+ 4. trong dng Cr2O3 (M = 152) Yu t kt ta: nng dung dch sau khi ha tan mu phi khang 0,1M. Lng cht thuc th phi ln hn 1,5 ln cht kt ta. Nc ra ty thuc vo tnh cht ca kt ta thng l dung dch lang mui amoni. Kt ta phi c sy kh trc khi nung, sau khi nung phi vo bnh ht m trc khi cn trnh sai s v khi lng cn 5.3. Sai s v x l sai s Trong qu trnh phn tch lun xut hin cc sai s 163

3.

do yu t ch quan hay khch quan cng nh ch quan, nn i hi nhiu n lc sng to v c trc gic. Nhng kt qa phn tch c hon thnh vi tin cy cha bit s khng c gi tr khoa hc v ngc li, nhng kt qa khng chnh xc cng c th rt quan trng nu c th xc nh c gii hn sai s vi tin cy cao. V khng c mt phng php no tng qut, chnh xc nh gi cho kt qu thc nghim, nn x l kt qa thng l mt vic rt phc tp so vi vic thu c kt qu Trong phn ny s cp n nhng loi sai s ny sinh khi thc hnh phn tch nh hng x l chng. 5.3.1. Mt s cng thc ton hc Trung bnh ( x ): l thng s php chia tng kt qa ca nhng php o ring bit (xi ) cho (n) s ln o mu. Cng thc: x = n

xi =
i :1

x1

x 2 ...xn1 n

Trung v (xt ): l trung bnh cng ca cp s trung tm dy cc php o: Cng thc: xt = =

xn / 2
Xn 2
1

xn 2

2/2

(vi n l s chn)

(vi n l s l)

lch trung bnh ( ): l hiu s gia gi tr ln o i (xi ) vi x Cng thc: = | x - xi |

164

Sai s tuyt i (E): l hiu s gia gi tr ln o i (xi) vi trung v Cng thc: E = xi - xt. Gi tr E c th dng

hoc m Sai s tng i (Et ): l t s gia sai s tuyt i E vi trung v xt. Cng thc:
E .100 xt

5.3.2. Phn loi sai s 5.3.2.1. Sai s h thng Sai s c bit: xut hin do s cu th hoc do khuyt tt ca ngi phn tch, chng hn do vn chuyn mu khng ng cch, ngi phn tch b m mu khng nhn nh chnh xc mu sc v.v...Do vy cn khc phc bng cch lm vic nghim tc, cn thn. Thng nh phn tch cn t rn cho mnh thi quen kim tra cc loi ch s thit b, lun ghi chp nht k v cn thn cc php tnh. V khuyt tt th nh phn tch trnh c bng cch chn cho mnh phng php ng, trong nhng iu kin bit trc. Sai s thit b: xut hin do thit b khng han thin, hoc l do nh hng ca mi trng ln thit b, chng hn, khi nhit ca cc dng c ny s dng khc nhiu vi nhit chun ha. C th loi tr sai s ny bng cch chun ha dng c nh mc nhit tng ng, hay phi 165

thng xuyn kim tra thit b nh k vi thi gian ch s Sai s phng php: xut hin do s sai lch ca tnh cht thuc th hoc phn ng dng lm c s cho php xc nh khi tiu chun l tng. Nguyn nhn ca nhng sai lch ny c th l tc phn ng nh, phn ng xy ra khng han ton, s khng bn ca cc cht no , s khng c trng ca thuc th v cc phn ng ph cn tr qu trnh xc nh. 5.3.2.2. Sai s ngu nhin l nhng sai s xut hin do nhng sai s khng th bit trc c, v cng khng th kim tra c ca php o nhng sai s, l nguyn nhn ca s tn mn kt qa khi o lp li Chng hn xt nh hng ca sai s ngu nhin trong ng tc chun ha pipet. y l mt thao tc tng i n gin, bao gm vic xc nh khi lng nc (vi chnh xc n miligam) chy ra t pipet theo bng sau: Bng 5.1. S liu trong thc nghim chun ha pipet STT Th tch (mL) 1 2 3 4 166 9,991 9,986 9,973 9,983 9 10 11 12 STT Th tch (mL) 9,988 9,976 9,980 9,973 17 18 19 20 STT Th tch (mL) 9,978 9,980 9,976 9,986

5 6 7 8

9,980 9,988 9,993 9,970

13 14 15 16

9,970 9,988 9,980 9,986

21 22 23 24

9,986 9,983 9,978 9,988

Th tch trung bnh : 9,982 mL lch trung bnh : 0,0054 mL Bin dao ng : 9,993 - 9,970 = 0,023mL lch tiu chun : 0,0065mL C th gii thch s khng trng lp kt qu ca nhng php o c km theo nhiu sai s khng bit c, gy ra do s khng trng lp ca nhng iu kin khng c kim tra ca thc nghim. Hiu ng tng cng ca nhng sai s cng l mt i lng ngu nhin. Thng cc sai s b tr nhau, nn tc dng ca chng l cc tiu. Nhng i khi cng cng hp vi nhau cho sai s dng hoc m kh ln R rng l ngay c mt ng tc n gin nh chun ha pipet cng km theo nhiu bin i khng ln khng kim tra c, chng hn c th l sai s do mt nh phn tch khi kim tra mc cht lng trong pipet, hay sai s do s dao ng trong thi gian dc ht nc t pipet, hay sai s do s bin i ca gc nghing khi nc chy, s dao ng ca nhit ph thuc vo cch cm pipet v.v.... Mc d khng vch r nhng nh hng ca mi sai s, nhng trong s nhng sai s cng c th din t hiu ng tng cng ca chng di dng sai s ngu nhin phn nh qua s phn tn s liu quanh gi tr trung bnh. 167

Khc vi sai s h thng, sai s ngu nhin khng th loi tr khi php o. Nn nh phn tch khng c b nh hng ca chng, cng nh khng c coi chng l nh. Chc chn l c th cng nhn rng gi tr trung bnh ca 24 ln o th tch bng 1 trn gn vi th tch tht hn bt k mt gi tr o no. Nu gi thit rng ch o c 2 ln v gi tr thu c trng vi kt qu STN 1 v 7, th gi tr trung bnh l 9,992 th lch vi kt qa trung bnh cho 24 ln o l 0,010mL. V lch trung bnh 2 ln ny so vi 24 ln l 0,001mL. Kt qa ny s gy sai lm cho nh phn tch khi lc quan cho mnh ng. Tht ra trong thc t, nu tin hnh STN ln n 1000 ln th c 2 - 3 trng hp, gi tr trung bnh l 9,984, tc lch 0,002mL so vi 24 ln v 0,008mL so vi 2 ln, v hn 100 trng hp lch i 0,010mL, v hn 200 trng hp lch i 0,100mL bt chp mi bin php phng nga ca nh phn tch. phn tch nhng sai s nh nh hng nh th no n kt qa ca nhng php o song song, gi s c 4 sai s trong sai s ngu nhin v quy c chng c c trng bng xc sut xut hin nh nhau v c th nh hng n kt qu cui cng ca php o gy nn sai s dng hoc m, c xc nh bng i lng U, l ng nht i vi tt c 4 sai s .

168

Bng 5.2. T hp c th c t 4 loi sai s ny dn n sai s ngu nhin T hp sai s + U1 + U2+ U3+ U4 - U1 + U2+ U3+ U4 + U1 U2+ U3+ U4 + U1 + U2- U3+ U4 + U1 + U2+ U3U4 - U1 - U2+ U3+ U4 - U1 + U2U3+ U4 - U1 + U2+ U3U4 0 6 - U1 + U2U3- U4 + U1 - U2U3- U4 - U1 - U2U3- U4 169 - 4U 1 - U1 - U2+ U3- U4 + 2U 4 + U1 U2+ U3U4 + U1 + U2- U3U4 - U1 - U2U3+ U4 - 2U 4 i lng SSNN + 4U Tn s tng i 1 T hp sai s + U1 - U2U3+ U4 i lng SSNN Tn s tn g i 6

Nh vy t l tn s sai s l 6: 4: 1, n phn nh xc sut sai s ca mi vng Cng vy khi xt vi nhng php o vi s lng sai s ln hn (10 sai s hay thm ch s rt ln sai s) th cng cho kt qa s xut hin sai s khng c xc sut ln nht, cn sai s cc i li c tn s nh nht.

Hnh 5.1 Sai s ngu nhin vi 4 sai s v sai s ngu nhin vi 10 sai s Dng phng php tnh ca Gause xy dng ng cong khng nht thit phi c s ng nht ca nhng sai s ring bit, th ng cong Gause c nhng c trng sau: Tn s xut hin sai s ngu nhin khng l cc i Gi tr sai s i xng qua cc i, ngha l xc sut xut hin sai s m v dng bng nhau Xc sut xut hin gim dn gi tr sai s ngu nhin ca php phn tch ha hc s tin ti rt gn vi ng cong phn b Gause.

170

Hnh 5.2. Hnh dng ca ng cong phn b Gause Trc tung l tn s xut hin ca sai s ngu nhin Trc honh l gi tr ca i lng sai s ngu nhin Hnh dng th Gause l gn ging vi ng cong Parabol c nh cc i l sai s khng. 5.3.3. Phng php thng k 5.3.3.1. Khi nim c bn Thng k cho php m t tan hc nhng qu trnh ngu nhin, chng hn nh nh hng ca sai s ngu nhin n kt qu phn tch ha hc. Nhng iu quan trng l: ch c th m t chnh xc bng cc phng php thng k c in khi s quan st i tng vi s lng ln v hn. Phng php thng k c in ly ng cong th Gause lm ng chun, gm:
( xi x ) 2

Phng trnh th l: y =

Z2 2

171

lch tiu chun

n

l hng s c trng cho

mt dy ca mt s ln php o.
( xi )2

i :1

, trong (xi - ) l lch trung bnh

l gi tr tht khng cha sai s h thng, l trung bnh s hc ca mt s v hn php o lp li. Chiu rng ca ng cong phn b chun sai s lin quan n phn tn ( 2): l mt c trng khc ca lp li thng c s dng rng ri trong thng k. Phn ln cc nh phn tch a thch dng i lng Ch : cc gi tr , hn, v
2

c din t bng

n v ca i lng c o. hoc x nn c tnh theo my tnh c nhn 5.3.3.2. Phng php thng k: Vic s dng phng php thng k c in vi s ln thc nghim t 2 n 20 thng cho kt qa sai, nn cn tin hnh thng k hin i vi s ln o t 3 n 5 nhng vn cho kt qu ng tin cy v sai s ngu nhin. i vi mt vi php o lp li khng th dng trc tip cc phng trnh trn v l s khng bit c, mt cht, hn thay th chng phi dng gi tr trung bnh ca s nh php o. Trong phn ln trng hp x nhin l do sai s ngu nhin gy nn. Cn ch bt k mt sai st ca xi u dn n s sai s trong i lng 172

. Do vi t ln o, th s nh gi lch tiu chun cng c th khng ng tin cy. Nh vy c n 2 sai s xut hin trong gi tr trung bnh v trong gi tr lch tiu chun. Khi c gi tr m ngha l do gi tr trung bnh v lch tiu chun nhn c t mt v ch mt dy nh d kin, nn tr lch chun (S): S= c thay bng gi
n

( xi
i :1

x) 2

n -1

V d: Tnh lch chun i vi 5 ln o sau: STN Ga tr o 1 9,99 2 9,986

6

3 9,973

4 9,983

5 9,98

Tnh c lch chun S l: S = 165,4.10 5 1

6,4.10- 3 =

0,006

Trung bnh tht

lun khng bit c, nhng

c th xc nh vng chung quanh gii hn ca gi tr trung bnh x bng thc nghim m trong vng hy vng vi mt xc sut cho tm c . Gii hn gi l gii hn tin cy v khang gii hn gi l khong tin cy. R rng l d an ng gi tr tuyt i cn phi chn mt khang ln v bao gm trong cc gi tr c th chp nhn l xi c th c c. Ngc li, xc sut ri vo vng l 99 kt qa ng so vi 100 kt qa th khong khng cn phi ln n nh th v c th lm 173

cho n cn c th nh hn nu chp nhn xc sut l 95%. Ni mt cch khc, nu xc sut d an ng cng nh th khong gii hn tin cy cng nh. Khong tin cy l i lng xut pht t lch chun S ca phng php o, ph thuc vo tin cy ca cc gi tr o c v t cc ga tr ny, S c xc nh. Thng thng cc mu o u chp nhn nhng nguyn nhn gy sai s ngu nhin l nh nhau. S tht trong thc t S v l ng nht nu s ln o 20 V d: Kho st hm lng Hg b nhim trong 7 mu c cu h ERI bng phng php hp th nguyn t th cho nhng kt qa hm lng Hg nh sau. Hy tnh lch chun S theo phng php thng k. Bng 5.2. s liu cho phng php hp th nguyn t
S php o song song 3 4 2 6 4 5 4 Kt qu (hm lng Hg) . 10 - 4 % 1,8 - 1,58 - 1,64 0,96 - 0,98 - 1,02 - 1,1 3,13 - 3,35 2,06 - 1,93 - 2,12 - 2,16 - 1,98 -1,95 0,57 - 0,58 - 0,64 - 0,49 2,35 - 2,44 - 2,7 - 2,48 2,44 1,11 - 1,15 - 1,22 - 1.04 Gi tr trung bnh N. 10 - 4 % 1,673 1,015 3,24 2,018 0,57 2,482 1,13 Tng s cc bnh phng lch khi gi tr trung bnh 0,0259 0,0115 0,0242 0,0611 0,0114 0,0685 0,017

Mu s

1. 2. 3. 4. 5. 6. 7.

174

S php o l 28 Tng bnh phng l 0,2196 c bng tnh: xi 1,8 1,58 1,64 3[5,02]
x = 1,673

| xi - x | 0,127 0,093 0,033 0,0161 0,0087

(xi - x )2

0,0011 Tng bnh phng = 0,0125

Nn: S =
0,0295 0,0115 0,0242 0,0611 28 1 0,0114 0,0685 0,0170

= 0,10.10- 4 % Hg Khang tin cy khi S rt gn vi , chiu rng ca ng cong phn b chun c xc nh bi i lng , v Z cng ng vai tr tng t trong cc phng trnh trn. T y c th tnh din tch di ng cong phn b chun sai s theo din tch chung i vi mi gi tr Z.

175

Bng 5.3. Bng xc sut tin cy i vi nhng gi tr Z khc nhau Xc sut tin cy % 50 68 80 90 95 0,67 1,00 1,29 1,64 1,96 Z Xc sut tin cy % 96 99 99,7 99,9 2,00 2,58 3,00 3,29 Z

T s (c biu din bng %) gi l xc sut tin cy v l s o xc sut ca Z, i ( xi - ). Chng hn din tch di ng cong Z = ) tnh ton s c bng hoc nh hn trng hp trong s 100. Do gii hn tin cy: =x Z . 1 l 95% din tch, nh th i vi s ln php o gi tr ( xi 1,96 trong 95 nh hn lch tuyt

V d: Hy tnh gii hn tin cy xc sut tin cy l 50% v 90% i vi kt qa do hm lng Hg trong h ERI: 1,80.10- 4 %Hg Gii: Ta c S = 0,10. 10- 4 % Hg ( v Nn: Gii hn xc sut tin cy 50%: =x 176 Z = 1,80. 10- 4 = (1,8 0,67. 0,10. 10- 4 0,067). 10- 4 % ) v Z = 0,67 1,96 tng ng vi 50% v 90% xc sut tin cy.

Gii hn xc sut tin cy 90%: =x Z = 1,80. 10- 4 1,96. 0,10. 10- 4 = (1,8 0,196). 10- 4 % C ngha l 50 trng hp s 100 trng hp, trung bnh tht (hoc gi tr tht khng c sai s h thng) nm trong khong (1,733 - 1,867). 10- 4 %Hg, v 95 trng hp trong 100 trng hp, gi tr tht ri vo khong (1,604 - 1,996). 10- 4 %Hg. Cng thc c ng dng nh gi kt qu mt php o duy nht. C th ni rng khong tin cy gim
n ln i vi gi tr trung bnh t n php o song song.

Vy gii hn xc sut tin cy l

= x

Z n

V d: Hy tnh gii hn tin cy gi tr trung bnh (1,673. 10- 4 %Hg ) ca mu s 1 trong d liu c trong h ERI, vi xc sut tin cy 50% v 95%. Gii: chp nhn php o mu 1 Gii hn tin cy 50%: = (1,673
0,67 .0,10 3

S = 0,10. 10-

%Hg trong c 3

). 10- 4 %Hg

= (1,673 0,04). 10- 4 %Hg Gii hn tin cy 95%: = (1,673 = (1,673

1,96 .0,10 3

). 10- 4 %Hg

0,11). 10- 4 %Hg

Nh vy: 50 trng hp trong s thc nghim 100 ln, gi tr trung bnh tht s nm trong khang (1,633 177

1,173) 10- 4 %Hg v 95 trng hp trong s 100, s nm trong khang (1,563 - 1,783) 10- 4 %Hg. V d: Hy tnh s php o song song cn thit lm gim khang tin cy vi xc sut tin cy 95% n 0,005 mL khi hiu chun pipet th tch 10mL. (xem cc s liu bng 1) Gii: lch chun ca php o bng 0,0065mL. V gi tr S thu c t 24 ln o nn c th gi s Khang tin cy: = 0,005 =
Z n

S = 0,0065.

1,96 .0,0065 n

n = 6,5

Nh vy s dng gi tr trung bnh th 7 ln o, thu c th tch trung bnh chy ra t pipet vi chnh xc n 0,0065mL, vi xc sut tin cy 95% Tiu chun (t): t =
x S

c dng tnh gii hn

tin cy trong trng hp cha bit , theo cng thc = x

t n

v t theo bng sau:

Bng 5.4. Gi tr t nhng xc sut tin cy khc nhau. S bc t do 1. 2. 3. 178 Xc sut tin cy (%) 80 3,08 1,89 1,64 90 6,31 2,92 2,35 95 12,7 4,3 3,18 99 63,7 9,92 5,84 99,9 6,37 31,6 12,9

4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.

1,53 1,48 1,44 1,42 1,40 1,38 1,37 1,36 1,36 1,35 1,34

2,13 2,02 1,94 1,90 1,86 1,83 1,81 1,80 1,78 1,77 1,64

2,78 2,57 2,45 2,36 2,31 2,26 2,23 2,20 2,18 2,16 1,96

4,60 4,03 3,71 3,50 3,36 3,25 3,17 3,11 3,06 3,01 2,58

8,6 6,86 5,94 5,4 5,04 4,78 4,59 4,44 4,32 4,22 3,29

V d: Trong mu ngi ung ru c hm lng etanol (tnh %) l 0,084 - 0,089 - 0,079. Hy tnh khang tin cy i vi gi tr trung bnh xc sut tin cy 95%. Gi s rng bit. S = 0,005% etanol, v lp li cha
0,084 0,089 0,079 = 0,0840 3

Gii: Ta c x = S=

0 0,0052 0,0052 = 0,005 3 1

Cch 1: Theo bng 3: vi bc t do l 2 th t = 4,30 vi xc sut 95% Nn khang tin cy l: = x

t n

= 0,084

4,3.0,0050 3

= 0,084

0,012

Cch 2: v c , nn dng bng 2 ;

179

= x

Z n

= 0,084

1,96 .0,0050 3

= 0,084

0,006 th

Vy nhn nh c: nu xc nh c gi tr thu hp khong tin cy mt na 5.3.3.3. Phng php thng k gi thit

hiu r bn cht nhng quan st m t m hnh l thuyt c hnh thnh cn thc hin nhng thc nghim kim tra ng n ca n. Nu kt qa ca nhng thc nghim khng khng nh m hnh th m hnh buc phi b i tm mt m hnh khc. Ngc li, nu quan st thy s ph hp gia thc nghim v nhng kt qa mong i th m hnh gi thit c th c dng lm c s cho nhng thc nghim tip theo. Nu ga thit c khng nh bng mt lng ln nhng d kin thc nghim th gi thit c chp nhn l l thuyt cho ti khi nhng d kin thc nghim khc khng bc b n. Khng th c nhng thc nghim ph hp chnh xc vi nhng m hnh l thuyt. Do nh phn tch thng xuyn phi dng phng php kim tra thng k bng phng php gi thuyt KHNG, da trn nhng gi tr bng s ca hai i lng thc t bng nhau (nh gia x1 v x2 ; gia S1 v S2 ;...) Gii thng k bi tan ny bao hm s so snh hm s (x - ) vi hiu s cn phi c trong nhng iu kin bnh thng c k ti sai s ngu nhin. Nu hiu s quan st nh hn hiu s tnh ton xc sut tin cy la chn th xem nh "Gi thit Khng" (x v khc nhau) c khng nh. V khi c th rt ra kt lun, khng c sai s trong h thng thc nghim. Ngc li, nu (x 180

) tng i ln hn so i gi tr mong i hay gi tr chun th c th cho rng: hiu s c ngha v sai s h thng c chp nhn. Gi tr chun ph nh gi thuyt KHNG c th vit li: x =
t.S n

. Nu nh gi c tin cy , th

thay th t v S bng Z v tng ng. V d: xc nh nhanh lng lu hunh c trong du ha, cn phn tch 4 mu du c hm lng S bit trc l 0.123%, th thu c t l lu hunh theo phn trm l 0,112 - 0,118 - 0,115 - 0,119. C phi nhng d kin ny ch ra sai s h thng m ca phng php ? Gii: Ta c gi tr tnh: x =
0,112 0,118 0119 0,115 = 0,116 4

( x - ) = 0,116 - 0,123 = - 0,007 S=

(0,00040) 2 (0,0020) 2 (0,0010) 2 4 1 (0,0030) 2

= 0,0032 Tra bng xc sut tin cy 95% v tra bc t do t l 3,18 th

t.S n

3,18 .0,0032 3

0,0059

M: x -

=- 0,007

C th hy vng rng nm ln trong s 100 ln thc nghim, trung bnh tm c bng thc nghim s sai lch l 0,0059 hoc ln hn. Nh vy nu chng ta kt 181 lun rng 0,007 l hiu s c ngha th trung bnh ng

trong 95 trng hp v sai trong 5 trng hp trong s 100 ln lm thc nghim. 5 4. nh lng mt s mu th 5.4.1. nh lng nhm trong qung Boxit 5.4.1.1. Nguyn tc Cn m(g) mu qung, ph mu thnh dung dch ri chuyn ton b Al3+ thnh Al(OH)3 bng dung dch (NH3 + NH4Cl) pH 6 8. Nung Al(OH)3 1200 0C c dng cn Al2O3 Cc phn ng: Al3+ + 3 NH3 + 3 H2O Al3+ + 3 OH Al(OH)3 Al(OH)3 + 3 NH4+

2 Al(OH)3 Al2O3 + 3 H2O Ion cn tr l cc cht oxy ho v cc ion c kh nng to kt ta hydroxyt. Kt ta Al(OH)3 l mt hydroxyt lng tnh, v nh hnh mu trng, nn ch kt ta trong mi trng c pH thch hp, tu thuc vo nng Al3+ ban u c trong dung dch 5.4.1.2. K thut phn tch Cn m(g) mu qung ri chuyn thnh dung dch V'(mL). Ht VmL dung dch mu un gn si, thm 2 git MR dung dch c mu hng, thm tng git NH3 m c n khi dung dch chuyn sang mu vng, c kt ta trng. Thm V" (mL) dung dch NH3 nng, lc kt ta. Nung kt ta trong chn snh nhit 800 0C trong thi gian t 20 n 30 pht. Cn chn tnh khi lng cht rn sau khi nung (m' ). Tnh kt qu. Cng thc: 182

% Al = m. K.

2.M Al 3 100 V ' . ; trong K = m V M Al2O3

5.4.2. nh lng Fe3+ trong dung dch Fe2(SO4 )3 5.4.2.1. Nguyn tc Cation Fe3+ trong mi trng axit pH ~ 4 s kt ta bi dung dch NH3 to kt ta Fe(OH)3 lc, sy, nung nhit 900oC, thu c dng cn Fe 2O3, t tnh c hm lng ca Fe 3+ c trong mu. Phn ng kt ta: 3+ 2Fe + 6NH3 + (x+6)H2O = 2Fe(OH)3.xH2O + 6NH4+ dng kt ta Phn ng chuyn dng ta sang dng cn:

2Fe(OH) 3 .xH 2 O dang ket tua

5.4.2.2. K thut -

to 900 o C

Fe 2 O 3 dang can

(x 3)H 2 O

Nung chn Ni 900 0C trong 30 pht. ngui trong bnh ht m, ri cn chn khng (m 0 ) Cn chnh xc khong 0.4 gam FeCl 3 mu, tm t mu bng 5mL HCl c, ha tan v nh mc n 250mL bng nc ct. Ly 25mL mu cho vo chn (lm thm mu i chng) +2mL HNO3 2N. un nng khong 75 - 80 0C (khng lm si dung dch ) + 30mL dung dch NH3 1N + 50mL H2O nng, yn trong 5 pht. 183

Th dung dch kt ta hon ton cha bng cch nh 5 git NH3 1N vo dung dch, nu dung dch cn ta th cho thm vo 10mL dung

dch NH3 1N Lc nhanh ngay tc khc bng giy lc bng vng khng tro. Ra ta bng NH 4NO3 0,5N c un nng. Tip tc ra ta bng nc nng loi tr Cl- (th li bng AgNO3 )

Cho ta vo chn nung v tro ho (lm giy ho en v khng cn khi). em nung 900 0C trong 30 pht (khng c nung qu lu). ngui trong bnh ht m n nhit phng, cn li (m1 ) Ap dng cng thc tnh khi lng xc nh

hm lng Fe3+. Gii thch Phng trnh phn ng: FeCl3 + 3NH3 + 3H2O Fe(OH)3 + 3NH4Cl 2Fe(OH)3 Fe2O3 + 3H2O Nu nung ta mnh v lu qu th: 3Fe2O3 Vai tr ho cht Cho HCl vo FeCl3 tm mu khi ho tan bng nc ct th khng lm thay i tnh cht ca mui HNO3 to mi trng axit v Fe3+ trong mi trng axit pH = 4 s b kt ta bi NH3 Cho vo NH3 to ta 2Fe3O4 + O2

184

Thm nc ct nng lm gim hp ph Ra bng NH4NO3 v: l mt cht in ly mnh s lm ng t ta Fe(OH) 3 l mt kt ta v nh hnh in hnh Cho HCl vo FeCl3 tm mu lm cho mu khng thay i tnh cht khi ho tan bng nc ct + HNO3 to mi trng axit mu d dng to ta v trng c hnh thnh ta c st, trnh dnh vo cc v trnh c thu phn. Sau un nh v: Fe(OH)3 l mt kt ta v nh hnh in hnh, d to thnh dung dch keo nn khi lm ta n cn phi un nng + NH 3 to ta + nc ct nng lm gim hp ph.Sau lc ngay v lu kim ho tan c thu tinh gy sai s.Lc bng giy lc bng vng v kt ta l v nh hnh nn d lm bt giy lc kh lc ta.Ra ta bng NH4NO3 l mt cht in ly mnh lm ng t ta, kh b thu phn.Ra ta cho ht Cl- v Cl- trong dung dch s kh ln n +7 v n s oxi ho Fe gy sai s cho mu

185

THC HNH PHN TCH KHI LNG

BI THC HNH BI 1: NH LNG KHI LNG - NH LNG ION Fe3+ I. CHUN B Ho cht: Dung dch AgNO 3 0.05N; NH4NO 3 0,5N; NH3 1N; NH3 6N; HNO3; FeCl3 II. NGUYN TC Cation Fe3+ trong mi trng axit pH ~ 4 s kt ta bi dung dch NH3 to kt ta Fe(OH)3 lc, sy, nung nhit 900oC, thu c dng cn Fe 2O3, t tnh c hm lng ca Fe 3+ c trong mu. Phn ng kt ta: 2Fe + 6NH3 + (x+6)H2O = 2Fe(OH)3.xH2O + 6NH4+ ( dng kt ta) Phn ng chuyn dng ta sang dng cn:
3+

2Fe(OH) 3 .xH 2 O dang ket tua

to 900 o C

Fe 2 O 3 dang can

(x 3)H 2 O

II. THC HIN Rn mu l tinh th FeCl3 c hm lng xc nh do gio vin giao, nhng sinh vin khng c bit trc hm lng ny. Nung chn Ni 900 0C trong 30 pht. ngui 186 trong bnh ht m, ri cn chn khng (m 0) Cn chnh xc khong 0.4 gam FeCl 3 mu bng

cn k thut, tm t mu bng 5mL HCl c, ha tan v nh mc n 250mL bng nc ct. Ly 25mL mu cho vo chn (lm thm mu i chng) + 2mL HNO3 2N. un nng khong 75 - 800C (khng lm si dung dch) + 30mL dung dch NH3 1N + 50mL H2O nng, yn trong 5 pht. Th dung dch kt ta hon ton cha bng cch nh 5 git NH3 1N vo dung dch, nu dung dch cn ta th cho thm vo 10mL dung dch NH3 1N Lc nhanh ngay tc khc bng giy lc bng vng khng tro. Ra ta bng NH 4NO3 0,5N c un nng. Tip tc ra ta bng nc nng loi tr Cl- (th li bng AgNO3) Cho ta vo chn nung v tro ho (lm giy ho en v khng cn khi). em nung 9000C trong 30 pht (khng c nung qu lu). ngui trong bnh ht m n nhit phng, cn li (m1)

Cu hi 1. 2. 3.

Ap dng cng thc tnh khi lng xc nh hm lng Fe3+.

Vit y cc phng trnh phn ng trong bi thc tp? Gii thch vai tr ca tng ha cht s dng trong bi thc tp? a ra v chng minh cc cng thc tnh? Gii thch 187

 ngha ca cc cng on trong qui trnh xc nh?

188

BI 2: NH LNG KHI LNG - NH LNG ION Mg2+ I. CHUN B Ho cht: Dung dch HCl 1:1; NH3 1:10; AgNO3 0.05N; NH3 1: 10; NH4NO3 0,05N; (NH4)2HPO 4 0,1N. Ch th: MR 0.1% pha trong cn; Giy lc bng xanh. II. NGUYN TC Cation Mg2+ trong mi trng kim nh amnic s kt ta bi dung dch (NH4)2HPO4 to kt ta MgNH4PO4.6H2O, lc, sy, nung nhit 850 oC, thu c dng cn Mg2P2O7, t tnh c hm lng ca Mg2+ c trong mu. III. THC HIN Rn mu l tinh th MgSO4.7 H2O c hm lng xc nh do gio vin giao, nhng sinh vin khng c bit trc hm lng ny. Nung chn Ni 8500C trong khong 40 pht. Sau ngui 5 pht th em cn (m 1) Cn khong 0.3 0.5 gam MgSO4.7H2O cha bit hm lng, cho vo chn nung (lm thm mt cc lm mu song song), thm 3mL HCl 1:1 + 40mL nc ct + 2 git MR 0.1% + 15mL (NH4)2HPO4 5% un nh dung dch 40 - 450C + thm tng git dung dch NH3 c, cho n khi dung dch 189

ho vng ngui hn thm tip 5mL NH3 c un cch thy 30 pht. Tin hnh lc nng qua giy lc bng xanh vi k thut lc gn (bng cch dng dung dch NH3 1:10 ra kt ta cho n ht ion Cl , th bng AgNO3). Tip tc ra kt ta 2 ln, mi ln 5mL NH4NO3 5%. Chuyn giy lc cha kt ta vo chn nung, tro ha chn mu trn bp in n khi giy lc chy en v ht khi, chuyn vo l nung chnh ti nhit 850oC, nung khong 40 pht (ti khi kt ta trng), ly ra bnh ht m 5 Cu hi 1. 2. 3. Vit y cc phng trnh phn ng trong bi thc tp? Gii thch vai tr ca tng ha cht s dng trong bi thc tp? a ra v chng minh cc cng thc tnh? Gii thch ngha ca cc cng on trong qui trnh xc nh? BI TP 1. Tnh hm lng % P v P2O5 trong mt 5(g) mu phn, khi em kt ta P di dng MgNH4PO4, ri nung nhit 650 0C, thu c 1,235(g) Mg2P2O7. 2. 190 Ho tan 1(g) mt loi qung thnh dung dch (A) cha Fe3+. Hi cn dng bao nhiu mL dung dch pht, cn m2 T tnh c hm lng ca Mg2+ c trong mu.

3.

NH3 1,19% (d = 0,99 g/mL) kt ta hon ton lng Fe3+. Bit trong qung c cha n 10% Fe Lng K trong mt loi phn c chuyn t dng K2O thnh KClO4. Hi khi lng phn l bao nhiu % K2O thu c gp 100 ln khi lng dng cn KClO4

191

BI 6. PHNG PHP CHUN TH TCH M bi: HPT 6

Gii thiu xc nh hm lng mt mu cht phn tch, ngoi kh nng dng khi lng ca mu ban u v khi lng dng rn thu c sau khi nung, c th dng th tch ca cc cht chun chun cc dung dch ca mu. T th tch tnh c nng cht trong dung dch suy ra hm lng cht trong mu ban u Mc tiu thc hin Hc xong bi ny hc vin s c kh nng: 1. M t c s ca phng php phn tch th tch. 2. Thc hin phn tch nng . 3. Chuyn i nng . 4. Pha ch cc dung dch vi nng khc nhau. Ni dung chnh 1. 2. 3. C s ca phng php phn tch th tch. Cch thc hin phn tch. Nng , cch biu din chuyn i.

4. Pha ch v thit lp nng . 6.1. C s v nguyn tc phng php phn tch th tch Trong nhiu trng hp gii quyt nhng nhim v phn tch, phng php phn tch khi lng l phng php tt nht. Tuy nhin, thi gian thc hin bng phng php ny thng qu di nn khng p ng nhu cu ca sn xut cng nghip. 192

Phng php phn tch nh lng da trn php o th tch l phng php phn tch th tch hay phng php chun . Phng php chun c s dng rng ri hn phng php khi lng v phng php ny nhanh hn, thun tin hn m nhy li khng thua km phng php khi lng 6.1.1. Khi nim c bn Chun l qu trnh nh lng cht phn tch da theo lng thuc th tiu chun tiu tn. Php chun c thc hin bng cch thm mt cch cn thn lng dung dch thuc th bit nng vo dung dch cht cn xc nh cho ti khi phn ng gia chng kt thc, sau , o th tch dung dch thuc th chun. i khi, nu iu khng thun tin hoc khng cn thit, th thm d thuc th v sau chun ngc bng mt thuc th khc bit nng xc nh lng d thuc th th nht khng tham gia phn ng. Dung dch thuc th c nng chnh xc bit dng chun c gi l dung dch chun. chnh xc ca nng dung dch chun gip nng cao tnh chnh xc ca phng php, do cn c bit ch vic iu ch cc dung dch chun t ban u l rt quan trng. Nng dung dch chun c xc nh hoc trc tip hoc gin tip.: 1. Bng cch ha tan han ton mt lng cn chnh xc thuc th chun gc v pha lang n th tch chnh xc bit Chun dung dch cha mt lng cn xc 193

2.

nh ca mt hp cht tinh khit bng dung dch thuc th. Hp cht ha hc c dng lm cht chun phi c tinh khit cao c gi l cht chun gc. Qu trnh xc nh nng dung dch chun theo cc chun bng dung dch cht chun gc c gi l php chun ha. Mc ch ca mt php chun bt k no cng l tm lng dung dch chun tng ng v mt ha hc vi lng cht phn ng vi n (cht cn xc nh). iu t c im tng ng. V d trong php chun dung dch NaCl bng dung dch AgNO3, im tng ng t c khi mt mol AgNO3 c thm vo mt mol NaCl trong mu hoc khi chun dung dch H 2SO4 bng NaOH, im tng ng l lc s ng lng ca chng bng nhau. im tng ng l mt khi nim l thuyt. xc nh v tr thc ca n, phi quan st s bin i tnh cht vt l lin quan ti im tng ng. Nhng bin i ch tr thnh r rng im cui ca php chun. Thng ngi ta cho rng hiu s th tch im tng ng v im cui nh nhng lun lun tn ti do s khng tng ng gia qu trnh bin i tnh cht vt l v phng php chng ta quan st chng V th thng xc nh im cui phi dng ho cht ph c kh nng bin i mu sc theo nng gn im tng ng. Nhng cht nh th c gi l nhng cht ch th. 194

6.1.2. Phn ng thuc th Ty thuc vo loi phn ng dng lm c s cho mi phng php m phng php th tch c t tn theo . Cc phng php th tch chia lm 4 lai da vo phn ng m chng dng xc nh im tng ng: Phng php kt ta: c phn ng to ta Phng php trung ha: c phn ng acid - baz Phng php oxy ha kh: c phn ng gia cc cht kh v cht oxy ho Phng php Complecxon: c phn ng to

phc gia ion kim loi vi Complecxon 6.1.2.1. Cht chun gc ng ca kt qu phn tch chun ph thuc rt nhiu vo cht chun gc c dng thit lp (trc tip hoc gin tip) nng dung dch chun. Cc cht c chp nhn l cht chun gc tt phi tha mn mt lat cc yu cu sau 1. Chng phi c tinh khit cao nht, hn na phi c nhng phng php n gin tin cy khng nh tinh khit ca chng Phi bn, ngha l khng tc dng vi cc cu t ca kh quyn. Khng cha nc hydrat. Khng phi l cht ht m hoc c xu hng phong ha v s kh lm kh v kh cn. Phi d kim trong th trngv c gi thnh va phi. Cht phi c khi lng mol phn t ln. 195

2. 3.

4. 5.

Dung dch c nng cho s cng ln nu khi lng mol phn t ca n cng ln. Khi khi lng tng, sai s ca php cn s gim, tc khi lng mol phn t ca cht cng cao th cht cng c kh nng lm gim sai s cng ln Ch c mt t cht c cc yu cu trn v do s cht quy cch dng lm cht chun gc b hn ch. Trong mt s trng hp, thay th cho cht chun th nht phi dng cht km tinh khit hn. tinh khit ca cht chun th hai, do cn phi c xc nh bng con ng phn tch cn thn. 6.1.2.2. Dung dch chun Dung dch chun l tng phn tch l dung dch c nhng tnh cht sau: 1. Sau khi iu ch nng ca n phi khng bin i, c bo qun lu (trong mt vi thng hoc hng nm) 2. Phn ng nhanh vi cht cn xc nh, tc thi gian ch i sau khi thm tng phn nh thuc th phi ngn Phn ng gia thuc th v cht cn xc nh cn phi xy ra han ton c th xc nh im cui tha mn. Phn ng gia thuc th v cht cn xc nh phi xy ra hp thc, nu khc i th khng th tnh c trc tip khi lng cht cn xc nh 5. 196 Cn phi c phng php xc nh im tng ng ca phn ng gia thuc th vi cht

3.

4.

cn xc nh, ngha l phi c phng php xc nh im cui tin cy. 6.2. Cch thc hin phn tch 6.2.1. Nguyn tc Xc nh im tng ng ca phng php phn tch chun th tch bng s i mu ca cht ch th. (y ch l im cui ca php chun , nn vic dng chun y rt d gy mt sai s h thng cho phng php ny) Da vo th tch trn Buret ca cht chun c

nng chnh xc tnh nng ca dung dch cn phn tch, t xc nh hm lng ca cht phn tch trong mu ban u 6.2.2. im cui trong php chun im cui trong php chun c xc nh bng phng php quan st bin i mt tnh cht vt l no im tng ng. C th xc nh im cui theo s bin i mu ca thuc th ca cht cn xc nh hoc ca cht ch th. xc nh im tng ng th s dng s bin i ca cc tnh cht v th in cc, dn, nhit , ch s khc x... Ti im cui ca php chun xy ra s bin i nng rt ln, t nht l ca mt trong nhng cht phn ng. Trong phn ln (nhng khng phi l tt c) trng hp xc nh im cui l xc nh nhng bin i xy ra vng ln cn im tng ng. Trong bng sau ch r s bin i nng ion [H +] v [OH-] khi chun 50mLdung dch HCl 0,1M bng dung dch NaOH 0,1M. 197

Bng 6.1. S bin i pH-pOH Th tch dung dch NaOH 0,1M 0,0 40,9 49,01 49,90 49,990 49,9990 50,0000 50,001 50,01 50,10 51,01 61,1 Nng H3O+ 10 -1 10 10 10 10 10 10 10 10 10 10 10
-2 -3 -4 -5 -6 -7 -8 -9

Nng OH 10 -13 10 10 10
-12 -11 -10 -9 -8 -7 -6 -5 -4 -3 -2

pH 1 2 3 4 5 6 7 8 9 10 11 12

pOH 13 12 11 10 9 8 7 6 5 4 3 2

10 10 10 10 10 10 10 10

-10 -11 -12

(Bng ny ch dng minh ha ch khng th thc hin trong phng th nghim c v cc th tch o vi chnh xc ln) lm gim nng [H +] t 0,1M n 0,01M cn phi thm vo 40,9mLkim. h thp nng n 0,001M i hi ph thm 8,1mL. giai an sau lm gim nng 10 ln ch cn phi thm 0,89mL... ng thi quan st thy s bin i tng t nng ion [OH -]. T cc d kin trong bng trn r rng l, gn im tng ng s bin i nng cc cht phn ng l cao nht. Trong nhiu trng hp, s xc nh thnh cng im cui c thc hin nh chnh gi tr ca s 198

bin i . Trn hnh sau dn ra th bin i ca bng trn:

Hnh 6.1. S bin i nng hnh dung d bin i trong vng tng ng, biu din nng khng dng tuyn tnh m dng logarit s thun li hn. V chng thng nh hn n v nn s dng m logarit l hp l v v vy hm s din t nng di dng hm s dng nh. m logarit (c s 10) ca nng phn t c bit di dng hm s p. Nhng gi tr pH v pOH c ghi r ct cui ca bng trn. V d: Hy tnh hm s p ca mi ion trong dung dch NaCl 0,02M v HCl 0,0054M Gii: Ta c [H3O+ ] = 0,0054 = 5,4. 10 -3 [Na + ] = 0,02 = 2. 10 -2 [ Cl- ] = 0,02 + 0,0054 = 0,0254 pH = 2,27 pCl = 1,6 199 p Na = 1,7

6.3. Nng - cc loi nng 1. Nng phn trm (C%): (t lng cht tan tnh theo khi lng) l khi lng (g) ca cht tan c trong 100g dung dch Cng thc: C%Dung dich A =
m A 100 mdungdchA

Ch rng nng phn trm cng c biu th theo lng o th tch, nh ru: C% =
V A 100 hay cng c biu th theo khi lng VdungdchA

(g) trong mt n v th tch Nng phn triu (Cppm): l khi lng (g) cht tan c trong 1 triu gam dung dch [hay khi lng gam cht tan trong 1 tn dung dch ] Cng thc: Cppm Dung dch A =
mA mdungdchA

. 10 6

Ch : + Trong trng hp dung dch c d = 1 g/mLth c th vit C(ppm) thnh dng C (mg/L): Cppm Dung dch A = Cmg/ L =
m A (mg ) V (lt) dungdichA

K hiu CM hay CM hay C(M) u c ngha hon ton tng ng nhau Nng phn t (Cppb): l khi lng (g) cht tan c trong 1 t gam dung dch [ hay l khi lng (mg) cht tan c trong 1 tn dung dch ] Cng thc: Cppb Dung dch A =
mA mdungdchA

. 10 9

200

2.

Nng mol/L (CM): (t lng cht tan tnh theo th tch ) L s mol cht tan c trong 1 L dung dch Cng thc: CM dung djch A =
nA (V: L) VddA .

3.

Nng ng lng gam (CN): l s ng lng gam c trong 1 L dung dch Cng thc: Trong : tan A v D = A = = CN =
A

VddA .

mA D.V ddA .

mA l s ng lng gam ca cht D

MA l ng lng cht Z

mA .Z MA

CN =

m A .Z M A .V

S Z c xc nh nh sau: Trong phn ng oxy ha kh: s Z l s electron trao i Trong phn ng trao i: s Z l s nguyn t H / OH trong phn t acid/baz tham gia phn ng. Hay l s tng n tch cation trong phn t mui. Trong cng thc trn: Nu m(g) vi V(L) th l s ng lng gam l s mili ng lng Nu m(mg) vi V(mL) th 4.

gam Nng molan (Cm): l s mol cht tan c trong 1000g dung mi

201

Cng thc: 5.

Cm =

nA n A1000 .1000 = m ddA n A .M A mdungmoi

Nng gam / L (Cp ): l khi lng (g) cht tan c trong 1 L dung dch Cng thc: Cp =
mA (g) V ddA .(l )

6.

chun (T): l khi lng (g) cht tan c trong 1 mLdung dch. TA =
mA (g) VddA .(ml)

7.

chun ca chun l khi lng (g) cht cn xc nh (A) tng ng vi lng cht thuc th (B) c trong 1 mLdung dch. TB/A =
mA ( g ) VddB .(ml)

Ch : Quy tc tnh theo chun: S D ca B = S D ca A hay TB= TB/A Ta c c t l (gi l h s phn tch) F=
B B

TB / A TB

V nng dung dch A, khi xt gia l thuyt tnh ton v thc t lun c mt gi tr sai bit nht nh, nn t l gia nng l thuyt v thc t (gi l h s t l) K =
N C A (tt ) T (tt ) mddA (tt ) = A = N C A ( Lt) T A ( Lt) mddA ( Lt)

Do : mA = VB.TB.F = VB.CB. 8. 202

MA ZA

Nng th tch: l t l th tch gia cht lng (A)

vi dung mi lng (B), c biu th dng: CV = V A (l ) : VdungmoiB (l ) 9. Hot Trong dung dch, cc ion c khuych tn vo trong dung mi to thnh mt h solvat. V th bn thn mi ion solvat u b nh hng tng tc ca lc tnh in ca chng. Tc dng cc lc ny lm thay i gi tr thc ca nng cc ion solvat, ngi ta gi gi tr thc ca cc ion solvat trong h dung dch l hot , k hiu l a :a = f. C Trong : C l nng ca ion solvat f l h s hot , c tnh theo Vi dung dch rt long: trong h ny, lc tng tc tnh in ca cc ion solvat c xem nh khng ng k, tc a=C = 0 hay f = 1. Khi :

Vi dung dch long : Gi Z1 , Z2 ... Zn ln lt l in tch ca cc ion solvat c nng tng ng C 1M , C2M.... CnM , th + + =
1 2
n

Z i2 C i
i 1

Khi gi tr

< 0,02: lg f = -

1 2 Z. 2

Khi gi tr 0,02 < f=1 2 Z. 2 1

< 0,2: lg

203

Khi gi tr 0,2 < lg f = 1 2 Z. 2 1

: + h.

V d: Cho 25g NaCl pha vi 100mLnc. Tnh cc loi nng trong dung dch. Ta c: 100g H2O tng ng vi 100mLH2O (do t khi H2O l 1) C% dung dch NaCl = CM dung dch NaCl = Cm dung dch NaCl = Cp dung dch NaCl = CN dung dch NaCl = T dung dch NaCl = V d: 25 = 0,2% 25 100
25 .1000 = 4,27 mol/L (23 35,5). 100 25 .1000 = 4,27 mol / g (23 35,5). 100

25.1000 = 2,5 g/ L 100

25 .1000 = 4,27 N /L (23 35,5). 100

25 = 0,25 g/ mL 100

Cho T(AgNO3 ) = 0,001699 g/mLc ngha l trong 1 mLdung dch AgNO3 c cha 0,001699 (g) AgNO3 Cho T (AgNO3 / HCl) = 0,0003646 g/mLc ngha l trong 1 mLdung dch AgNO3 em lm thuc th chun dung dch HCl c cha mt lng AgNO3 phn ng va vi

204

0,0003646 (g) HCl Tnh lng HCl c trong dung dch cn xc nh,

bit rng lng th tch dung dch AgNO 3 dng ht 29,45mLv T (AgNO3 / HCl) = 0,0003646 g/mL. Khi lng HCl phn ng l : 0,0003646. 20,45 = 0,007458g Khi chun 25mLdung dch HNO3 th ht

32mLdung dch NaOH c T(NaOH/HNO3) = 0,063 g/mL. Tnh hm lng HNO3 chun. Khi lng HNO3 chun l: 0,063. 32 = 2,016g V d: Tnh hm lng H2SO4 c trong 250mLdung dch H2SO4 0,1N. Bit K(NaOH) = 1,012 v khi ht 24,99mLdung dch ny em chun bng dung dch NaOH 0,1N th ht 21, 72mL. T tnh T(H2SO4 ), Gii: Ta c: K(NaOH) =
N C A (tt ) N C A ( Lt)

K(H2SO4 ), CN (H2SO4) CN (NaOH) tt = 1,012.

0,1 = 0,1012N M: C (H2SO4). V(H2SO4) = CN (NaOH). V(NaOH)

N

CN (H2SO4) = Nn:

21,72 .0,1012 = 0,08794N 24 ,99

T(H2SO4)tt = D. CN.10 - 3 = 0,004313 g/mL T(H2SO4)Lt = D. CN.10 - 3 =

98 . 0,08794. 10 - 3 = 2

98 . 0,1. 10 - 3 = 0,0049 g/mL 2

205

Do : K(H2SO4) =

0,004313 = 0,8794 0,0049

V khi lng ca H2SO4 (trong 24,99mL) =

98 21,72.0,1012 2 1000 98 21,72.0,1012 250 . = 1,078g 24 ,99 2 1000

Vy khi lng ca H2SO4 (trong 250mL) = V d: Tnh hot ca cc ion trong dung dch a) Dung dch KCl 0,1M b) Dung dch hn hp (KCl 0,001M + MgSO4 0,001M) Gii: a) Trong dung dch KCl 0,1M c = V lg f K = =
1 2
n

Z i2 C i
i 1

1 (12. 0,1 + 12. 0,1) = 0,1 2

< 0,2, nn
1 2 Z. 2 1

=-

1 . 2

12.
1

0,1 0,1

=- 0,121

M: lg f K = lg f Cl Nn: a K = a Cl = 10 - 0,121. 0,1 = 0,07568 M b) Trong dung dch hn hp (KCl 0,001M + MgSO 4 0,001M), c: = = 206
1 2
n

Z i2 C i
i 1

1 (12. 0,001 + 12. 0,001 + 22. 0,001 + 22. 0,001) 2

= 0,005 V < 0,02, nn

1 2 Z. 2 1 2 Z. 2 1 2 1. 2 1 2 2. 2

lg f K = lg f SO
2 4

==-

0,005 = - 0,035
0,005 = - 0,14

=-

Do : a K = a Cl = 10 - 0,035 . 0,001 = 0,00092 M

- 0,14 . 0,001 = 0,00072 M a Mg 2 = aSO2 = 10
4

Quan h gia cc nng : Chuyn i gia CM v C%: CM =

10. C%. D MA

Chuyn i gia CM v CN: CM =

CN

Chuyn i gia Cp v CN: Cp = D. CN 6.4. Pha ch dung dch 1. Pha V(mL) dung dch (A) CM t tinh th rn (A) c tinh khit (p%) theo thc t v theo l thuyt. a) Theo l thuyt S mol ca (A) trong dung dch v trong tinh th lun bng nhau, nn: V. CM. 10 - 3 =
m M

m=

V .C.M .10 3 .100 p

V .C.M . (g), ri p.10

Vy cn cn mt lng (A) l:

tin hnh nh mc nc ct V(mL) th thu 207

c V(mL) dung dch (A) CM b) Theo thc t V vic cn c mt lng cn ng theo gi tr (m g) cho mu (A) tnh l mt vic lm kh khn cho SV, nn c th thao tc tt, c th dng cch cn d mt lng (A) : m (g). V vy th tch c nh mc V(mL) th nng dung dch thu c sau khi ho tan s ln hn gi tr nng CM cn tnh. Khi cn phi pha long thm mt nc na thu c dung dch c nng cn thit ng bng CM. Sau ly li th tch V(mL) nu cn thit. Lng tinh th rn (A) c cn thc t l m' = m + (m (g) Dng bnh nh mc xc nh th tch nc ct pha vo V(mL) Sau dng pipet ht mt lng nc ct thm
m vo l: M .C .10.p (mL)

2.

Kt qu thu c V'(mL) dung dch (A) CM Tnh khi lng tinh th rn ( AaBb ) c tinh khit (p%) cn cn theo l thuyt pha c V(mL) dung dch (Ab+ ) Cppm (khi lng ring l d g/mL). Gi s trong dung dch in ly hon ton v khng c cc qu trnh khc Trong dung dch AaBb c s in ly: AaBb = a Ab+ + b Ba+ s mol AaBb: Ab+ = 1: a A
b+

s mol ca

= a. S mol AaBb

208

s mol ca Ab+ = a.

mA MA

Bb Bb

M S mol ca (Ab+ ) trong dung dch v trong tinh th lun bng nhau, nn:
V.C.d 106.M Ab
V.C.d.
mA MA

= a.

Bb Bb

mA

Bb

V.C.d M Aa Bb 100 = . . p 10 6 a.M Ab

M Aa Bb 10 -4 . a.M Ab p

M Aa Bb 10 -4 Vy cn cn mt lng (A) l: V.C.d. (g), . a.M Ab p

3.

ri tin hnh nh mc nc ct V(mL) th thu c V(mL) dung dch (Ab+) Cppm. Pha V(mL) dung dch (A) CM t dung dch (A) C% c d(g/mL) Dng pipet ht t dung dch (A) C% mt lng
C M .M A .V V0 = 10 .d .C %

4.

Cho vo bnh nh mc, pha nc ct n vch V(mL) th thu c V(mL) dung dch (A) CM Pha V(mL) dung dch (A) CN t dung dch (A) C% c d(g/mL) Dng pipet ht t dung dch (A) C% mt lng V0 =
C N .M A .V 10 .d .C % .z

Cho vo bnh nh mc, pha nc ct n vch 5. V(mL) th thu c V(mL) dung dch (A) CM . Pha V(mL) dung dch (A) CN t tinh th rn (A) c 209

tinh khit (p%) theo l thuyt. S ng lng ca (A) trong dung dch v trong tinh th lun bng nhau, nn V. CN. 10 - 3 =
m .z M

m=

V .C.M .10 3 .100 z. p

V .C.M . (g), ri tin z. p.10

Vy cn cn mt lng (A) l:

6.

hnh nh mc nc ct V(mL) th thu c V(mL) dung dch (A) CM Pha V(mL) dung dch (A) Cppm c khi lng ring d (g/mL) t tinh th rn (A) c tinh khit (p%) theo l thuyt. Khi lng ca (A) trong dung dch v trong tinh th lun bng nhau, nn: V. d. Cppm. 10 - 6 = m.
V .C.d .10 p
4

p 100

m=

V .C.d .10 6 .100 = p

Vy cn cn mt lng (A) l:

V .C.d .10 p

(g), ri tin

hnh nh mc nc ct V(mL) th thu c V(mL) 7. dung dch (A) Cppm . Pha V(mL) dung dch (A) Cppm c d g/L) t dung dch (A) C% c d0 (g/mL) Dng pipet ht t dung dch (A) C% mt lng V0 =
Cppm.V .d .10 - 4 % d 0 .C

210

Cho vo bnh nh mc, pha nc ct n vch V(mL) th thu c V(mL) dung dch (A) Cppm.

211

BI 7. PHNG PHP CHUN ACID BAZ M bi: HPT 7

Gii thiu xc nh hm lng mt mu dung dch phn tch, ngoi phng php khi lng, cn c cc phng php th tch nh lng chng. Tu vo vic p dng h cn bng no trong dung dch m c cc phng php chun tng ng. Nu xc nh hm lng cc cht acid hoc baz trong dung dch, tc kho st hm lng h acid baz th c php chun acid baz. Mc tiu thc hin Hc xong bi ny hc vin s c kh nng: 1. M t c s ca phng php chun acid baz. 2. 3. 4. M t ng cong chun Ph - V. Chun b dung dch m. Chun a acid.

5. Pha ch thit lp nng acid - baz. Ni dung chnh 1. C s ca phng php chun acid-baz. 2. ng cong chun pH - V. 3. Dung dch m. 4. ng cong chun a acid. 5. Pha ch thit lp nng acid - baz. 7. 1. C s v nguyn tc phng php chun acid-baz 7. 1. 1. C s ca phng php chun acid baz Phng php chun acid baz c xy dng 212

trn cc phn ng trung ho c trong h bng cch xc nh im tng ng v cc im cui. T vic nh lng v th tch cc dung dch acid v kim xy dng nn ng chun (VmL pH), l c s xc nh dung dch. Thuc th chun chun : trong phng php ny cc acid, baz mnh lun lun c dng lm thuc th chun bi v phn ng vi s tham gia ca chng phn ng xy ra hon ton hn so vi vic s dng cc acid hay baz yu Cht ch th chun acid baz: nhiu hp cht tng hp cng nh t nhin c mu khc nhau tu thuc vo pH ca dung dch. Mt trong s cc cht t lu c s dng lm r tnh cht kim hoc acid ca nc. Chng cng quan trng i vi vic xc nh pH ca cc dung dch v pht hin im cui trong phng php chun acid-baz Cht ch th acid-baz l nhng hp cht hu c biu l tnh acid yu hay baz yu. Phn ng phn ly hoc lin hp ca cht ch th km theo s chuyn v bn trong cu to dn ti s bin i mu. Chng hn: H2O + HIn (mu acid) hoc: In + H2O (mu kim) H3O+ + In (mu kim) HIn + OH (mu acid) 213

V th mu sc ca cc ch th ny ph thuc vo pH, ngha l s thay i pH ca dung dch s gip s chuyn mu trong dung dch nhanh hn hay chm i, cng chnh l kh nng gip xc nh im tng ng hay im cui. Bng 7.1. Mt s ch th acid-baz thng gp TN Khong pH 1,2 2,8 8,0 9,6 2,9 4,0 3,1 4,4 3,8 5,4 4,2 6,3 4,8 6,4 58 10 12 S bin i mu Dng acid Vng Vng Vng Vng Dng baz Vng Xanh bin Vng Vng Xanh bin Vng Vng Tm Loi ch th 1 2 2 1 2 1 1 2

Timol chm Metyl vng Metyl da cam BromCresol lc Metyl Clo phenol Qu Alizarin

im tng ng: Khi s ng lng gam thuc th cho vo bng s ng lng gam cht cn nh lng th h t ti im tng ng (v l thuyt im tng ng dung dch khng c s hin din ca cc cht ban u). Thc t cc phn ng dng trong phn tch chun l phn ng thun nghch nn im tng ng thc t vn cn cc lng cht ban u, tc l cc 214

phn ng khng i n cui cng c. V d: nh lng HCl bng NaOH Chun s dng phn ng: HCl + NaOH = NaCl + H2O Khi s ng lng gam ca NaOH cho vo bng s ng lng gam HCl th h ch c NaCl v H2O pH = 7. im tng ng l pH = 7 im kt thc: l thi im m cht ch th mu bin i mu ngng s nh lng V d nh lng HCl bng NaOH vi im tng ng l pH = 7 nhng ch th phenolphtalein chuyn mu pH = 8 - 10 (pT = 9) 7. 1. 2. Sai s trong phng php chun acid- baz Cn phn bit hai loi sai s chun : sai s h thng v sai s ngu nhin Sai s h thng do pH chuyn mu ca ch th khc vi pH im tng ng ca phn ng ho hc dng chun l sai s th nht. C th gim sai s n cc tiu bng cch la chn cn thn ch th. Th nghim trng s gip cho s chn la cht ch th tng ng. Sai s ngu nhin do kh nng ca ngi quan st phn bit mt cch lp li thi dim chuyn mu b hn ch l loi sai s th hai. Gi tr ca sai s ph thuc vo s bin i pH trn mt miliL thuc th im tng ng, nng ch th v phng php phn tch c dng phn bit hai mu ca ch th. Khi quan st bng mt vi ch th acid-baz sai s trung bnh khong 0,5 n v pH. So snh mu ca dung dch b chun cha 215

lng ch th i chng gi tr pH tng ng thng cho php h thp sai s n 0,1 n v pH hoc nh hn. R rng l nhng gi tr gn ng v chng mc ng k ph thuc vo bn cht ca cht ch th cng nh vo trnh nh phn tch 7. 2. ng cong chun pH V Trong qu trnh trung ho pH dung dch cn chun b thay i ph thuc vo th tch v chun ca dung dch thm vo. Da vo 2 yu t ny: gi tr pH thu c ti th tch (mL) dung dch chun cho vo xy dng ng chun. 7. 2. 1. ng cong chun acid mnh - baz mnh Phn ng chun l: H3O+ + OH- = 2 H2O Cc ion H+ trong dung dch l do s phn ly ca chnh nc v ca acid tan trong nc Trong cc dung dch khng qu long, phn ng gp ca phn ng gia cht tan vi dung mi vo acid tng cng ln hn nhiu phn ng gp do dung mi phn ly. Do vi dung dch HCl c nng ln hn 1.10-6 M th: [ H3O+ ] = CHCl [H3O+ ]= [Cl- ] + [OH ]= CHCl + (8.1)
W [ H 3O ]

Nu nng dung dch thp hn 1.10-6 M th:

Tng t trn cng ng trong dung dch baz mnh nh dung dch NaOH Xy dng phng trnh ng nh phn Acid mnh Baz mnh (n chc) 216

V d: Xy dng phng trnh ng nh phn khi chun Vb (mL) dung dch NaOH C b bng Va (mL) dung dch HCl Ca. Phn ng ti im tng ng: HCl + NaOH = NaCl + H2O Nn ti im tng ng c: Vtda Trong qu trnh chun : [H+] + [H+]p = [H+]pha trn =
Va .C a V a Vb

Vb .C b Ca

[OH-] + [OH-]p = [OH-]pha trn = [H+] [OH-] =

Va .C a Va Vb Vb .C b Vb

Vb .C b V a Vb

([H+]p = [OH-]p ) (1) ([H+] [OH-]).

Va Vb .C b

(1)
Va .C a Vb .C b F)

= F 1 (t

(2)

c gi l phng trnh nh phn Axit mnh baz mnh Khi Va = 0 ( cha chun ) (F = 0) pHdd = pH (NaOH) = 14 pOH = 14 + lg Cb Khi 0 < Va< V atng ng ( trc xa im tng ng ) (0< F < 1) Xem nh [OH-] >>> [H+] nn (2) vit li l: - [OH-].
V a Vb =F1 Vb .C b Vb .C b ) V a Vb

[OH-]= (F 1)(

pOH

pH 217

Khi Va ng:F (2)

Vtng
10
14

ng

(trc gn im tng
Va .C b ) V a Vb

1 hay F
[H ]

1)

[H+] -

=(F1)(

Gii phng trnh bc 2 theo [H+] -

pH

Khi Vt < Va (sau xa im tng ng ) ( F > 1) Xem nh [H+] >>> [OH- ], nn (2) vit li l: [H+].
V a Vb =F1 Vb .C b

[H+] = (F 1 ). -

Va Vb Vb .C b

pH

Ti im tng ng ( Va = Vtng ng ) ( F = 1) [H+] = [OH-] = 10-7 pH= 7

Sai s php chun Baz mnh bng Axit mnh (n chc) Khi gn st (trc hay sau ) im tng ng: Va Vt =
Vb .C b Ca C a Cb C a .C b

Vb .Cb Vb V .C Vb .C a Va Vb Ca = = b b Vb .C b Vb .C a .C b Vb .Cb

Nn (2) Do : -

([H+] [OH-]). S=

C a Cb =F1 C a .C b

C a Cb 10 14 ([H+] ) C a .C b [H ]

Nu S > 0 Cx)

c lng d khi chun ( tr

218

Nu S < 0 vo Cx)

c lng thiu khi chun (cng

Kt lun: C(X) = Cx + (Cx. S ) V d: tnh sai s php chun acid - baz gia dung dch NaOH 0,1M bng dung dch HCl 0,05M khi dung dch thu c c pH = 2,15 Gii : Theo pH dung dch thu c l 2,15 [H+] = 10 - 2,15 v [OH-]= 10 - 11,85. Nn
S=

C a Cb 0,1 0,05 10 14 ([H+] )= (10 - 2,15 - 10 - 11,85 ) = 0,2123 0,1.0,05 C a .C b [H ]

Hay sai s l S = 21,23%, mt sai s dng qu ln tc cho mt lng d acid HCl qu nhiu V d: em chun 50mL dung dch HCl 0,05M bng V(mL) dung dch NaOH 0,1M. a. Tnh gi tr pH ca dung dch chun c khi V(mL) ln lt l: 0 - 10 - 20 - 24,9 - 25 - 25,1 26 - 30 (mL) Xc nh bc nhy chun vi sai s 0,2%. Phng trnh phn ng: HCl + NaOH NaCl + H2O
50 .0,05 = 25 (mL) 0,1

b. Gii a)

Ti im tng ng: V =

Ti V = 0: dung dch ch c HCl phn ly mnh nn pH ca dung dch l pH ca acid ny: pH = - lg Cx = - lg 0,05 = 1,3 219

Ti V = 10: dung dch gm NaCl v HCl d [H+] dung dch = [H+]bd - [H+]phn ng [H+] =
50.0,05 10.0,1 = 0,025 50 10

pH dung dch = 1,6

Ti V = 20: [H+] =

50.0,05 20.0,1 = 7,14. 10 - 3 50 20

50 .0,05 24 ,9.0,1 = 1,34. 10 - 4 50 24 ,9

pH dung dch = 2,15 Ti V = 24,9: [H+] =

pH dung dch = 3,87 Ti V = 25: [H+] = [OH-] = 10 - 7 pH dung dch = 7 Ti V = 25,1: dung dch gm NaCl v NaOH d pH dung dch = pH (NaOH d). M: [OH-] = [OH-]bd - [OH-]phn ng = pOH = 3,88
25 .0,1 50 .0,05 = 1,33. 10 - 4 . 25,1 50

pH = 14 - pOH = 10,12

Ti V = 26: [OH-] = [OH-]bd - [OH-]phn ng =

26.0,1 50.0,05 = 1,315.10 - 3 26 50

pOH = 2,88 pH = 14 - pOH = 11,12 Ti V = 30: [OH-] = [OH-]bd - [OH-]phn =

30.0,1 50.0,05 = 6,25. 10 - 3 30 50

ng

pOH = 2,2 b)

pH = 14 - pOH = 11,79 0,2%, ngha l lng

Sai s chun l

NaOH cho vo dung dch s thiu ( - 0,2%) hoc tha (+ 0,2%) so vi lng acid HCl ti st im 220

tng ng, do : ([OH-] - [H+]). Hay:

(

C0 C = C .C 0

0,002

C C 10 14 - [H+]). 0 = 0,002 C .C 0 [H ]
[H+]2

0,05 0,1 10 14 - [H+]). = 0,002 0,05 .0,1 [H ]

pH = { 4,176 ; 9,824 }

6,67.10 - 5 [H+] - 10 - 14 = 0

Vy pH = 4,176 9,824 hay bc nhy chun khong 5,648 n v pH Bng sau th hin s bin i pH trong dung dch HCl khi chun bng dung dch NaOH vi cc nng ghi r Bng 7.2. Bin i pH khi chun HCl bng NaOH
pH V dung dch NaOH (mL) 0 10 20 24 24,9 25 25,1 26 30 Chun 50mL dung dch HCl 0,05M bng dung dch NaOH 0,1M 1,30 1,60 2,15 2,87 3,87 7,00 10,12 11,12 11,8 Chun 50mL dung dch HCl 0,0005M bng dung dch NaOH 0,001M 3,30 3,60 4,15 4,87 5,87 7,00 8,12 9,12 9,80

221

Hnh 7.1. ng cong chun HCl bng NaOH

(1) ng chun 50mL dung dch HCl 0,0005M bng dung dch NaOH 0,001M (ng nt chm) (2) ng chun 50mL dung dch HCl 0,05M bng dung dch NaOH 0,1M (ng nt lin) Nh vy khi chun dung dch NaOH 0,1M th bc nhy pH vng im tng ng ln, nhng dung dch NaOH 0,001M th bc nhy pH nh hn nhiu. V vic chn ch th cng gip cho vic xc nh im tng ng nhanh chng. R rng theo th th bromcrezol lc khng thch hp cho php chun bng dung dch chun 0,001M, khng ch v s chuyn mu ch th c quan st thy trong mt khong ln th tch cht chun, m cn v s chuyn mu ch th trong kim thc t xy ra 222

rt sm trc khi t ti im tng ng v do xut hin sai s xc nh ln, v ny sinh s bt ng v s s dng phenolphtalein. Trong s 3 ch th nu trn ch c Bromtimol xanh cho php xc nh im cui vi sai s b. Khong bc nhy pH t 4,3 n 9,7. V d: Tnh sai s ti im i mu ca ch th PP, MO, Bromcrezol lc v MR khi chun HCl 0,1M bng NaOH 0,2M. T kt qa c nhn xt g? Gii: (Hng dn SV t dng cng thc tnh sai s c bng sau) Ch th mu MO MR PP Bromcrezol lc pT 3,5 5,3 9,1 4,6 Kt qa sai s 10 - 2,32 10 - 4,02 10 - 3,72 10 - 3,42

Nh vy trong php chun trn, ch th c khuyn dng l PP v MR 7. 2. 2. ng cong chun acid yu baz mnh Trong dung dch CH3COOH c: HA = H+ + A- (Ka ) (1) Phng trnh chun : HA + NaOH = NaA + H2O (2) Ti im tng ng c: Vtd = Vb =
Va .C a Cb

Trong qu trnh chun lun c s to ra phn t NaA, nn lun c qu trnh: 223

A- + H2O = HA + OHV th:

( Kb =

10 14 ) Ka

(3)

CHApt = [H+] + [H+] p + [HA] CNaOHpt = [OH-] + [OH-]p Hay: [H+] + [H+] p + [HA] = [OH-] + [OH-]p = [H+] [OH-] + [HA] = ( [H+] [OH-] + [HA]). M: V: K= Ka =
[ H ].[ A ] [ HA ]

(4)

C a .Va V a Vb

C b .Vb V a Vb
C a .Va Va C b .Vb Vb

V a Vb =1-F C a .Va

(5)
Vb .C b ) C a .Va

( vi F =

[A-] = C0pt - [HA]

[ H ].( C 0 [ HA ]) [ HA ] [ H ].C 0 [ HA ] [ H ].C 0 [ HA ] [H ]

K + [H+] = (5)

[HA] =

C .V [H ] . a a K [ H ] Va Vb

([H+] [OH-] ).

V a Vb [H ] + =F1 C a .Va K a [H ]

(y l phng trnh ng nh phn) Khi Vb = 0 ( F = 0): cha chun nn pHdd = pHHA Ka =

[ H ]2 [ HA] [ H ]2 Ca [ H ]

[H+]2 + Ka. [H+] Ca.Ka = 0. Gii tm [H+] 224

pH

ca dung dch Khi 0 < Vb < 1 (0 < F < 1): trc xa im tng ng [OH-] b v [H+] << [A- ] nn xem ( [H+] [OH- ]. (5)
V a Vb ) C a .Va

0 [H+] =
1 F .K F

[H ] =1F K a [H ]

Khi Vb = Vt (F = 1): ti im tng ng dung dch ch c NaA, nn c phng trnh (3) m thi tc [H +] (5) - [OH- ].
V a Vb [H ] + =0 C a .Va K a [H ]

10 14 Va Vb [H ] = . [ H ] Ca .Va K a [H ]

Gii phng trnh ny tm [H +]. T tm pH ca dung dch Khi V nh [H+] 0 (5) - [OH- ].
V a Vb [H ] + =1F C a .Va K a [H ]

Vt ( F

1 ),st im tng ng cng xem

10 14 Va Vb [H ] . + = 1 F. [ H ] C a .Va K a [H ]

Gii phng trnh ny tm [H +]. T tm pH ca dung dch Khi Vb > Vt ( F > 1 ). Sau xa im tng ng c NaA v NaOH d, th xem nh phng trnh (3) khng c tc [HA] 0 225

pHdd = pH NaOH d. Hay theo (5) - [OH- ].

Va Vb = 1 F C a .Va

Gii phng trnh ny tm [OH-]. T tm pH ca dung dch Sai s trong php chun Axit yu Baz mnh S = ([H+]
C Cb 10 14 [H ] ). a + C a .C b K a [H ] [H ]

V d: Kho st chun 50mL dung dch CH3COOH 0,1M (K = 1,75.10-3) bng dung dch NaOH 0,1M. Phn tnh ton lm theo cng thc nu trn, kt qu c nu trong bng di y. Bng 7.3. Bin i pH khi chun CH3COOH bng NaOH V dung dch NaOH (mL) 0 10 25 40 49 49,9 50 226 pH Chun 50mL dung dch CH3COOH 0,1M bng dung dch NaOH 0,1M 2,88 4,16 4,76 5,36 6,45 7,46 8,73 Chun 50mL dung dch CH3COOH 0,001M bng dung dch NaOH 0,001M 3,91 4,30 4,80 5,38 6,45 7,46 7,73

50,1 60 75

10,00 11,96 12,30

8,00 9,96 10,30

Hnh 7.2. ng cong chun CH3COOH bng NaOH (1) ng chun 50mL dung dch CH3COOH 0,001M bng dung dch NaOH 0,001M (ng nt chm) (2) ng chun 50mL dung dch CH3COOH 0,1M bng dung dch NaOH 0,1M.(ng nt lin) Bc nhy pH ( pH) l 7,46 - 10,00 trong dung dch NaOH 0,1M nhng ch l 7,46 - 8,00 i vi dung dch NaOH 0,001M, c ngha l pH cng c s ph thuc vo nng dung dch chun. V d: Tm sai s trong php chun CH3COOH 227

0,1M bng dung dch NaOH 0,1M khi dng ch th l PP ti im i mu Gii PP i mu ti pH = 9 Do : S = ([H+] [H+] = 10 - 9 v [OH-] = 10 - 5.
C Cb 10 14 [H ] ). a + = C a .C b K a [H ] [H ]

= (10 - 9 - 10 - 5).

0,1 0,1 10 9 + 4, 75 0,1.0,1 10 10

= 5,62.10 - 5

Vy sai s khi dng ch th ny l 0,00562%, tc l dng ch th ny trong php chun CH3COOH bng NaOH cho kt qa t sai s. Tng t khi xem xt s chun dung dch baz mnh NaOH bng CH3COOH Nhn xt Vi cc dung dch long hn gi tr pH ban u ln hn, nhng khi v gn im cui th cc gi tr ny li b hn. cc im tng ng vi s thm vo mt th tch trung gian cht chun, pH bin i nhiu hn. Trong vng php chun, dung dch m cha CH3COOH v CH3COONa c to thnh. Trn th ny cho thy s pha lang khng nh hng n pH ca dung dch m. Khi lm gim cng acid, s bin i pH trong vng im tng ng tr nn t r rng hn bi v phn ng gia acid v baz xy ra km hon ton hn. nh hng ca nng thuc th n hon ton ca phn ng 228

tng t nh c m t trong chun kt ta S la chn cht cho php chun acid yu b hn ch hn so vi php chun acid mnh: Bromcerzol lc hon ton khng thch hp cho php chun CH3COOH 0,1M v s bin i mu ca n c quan st thy trong khong t 47 50mL NaOH 0,1M. Nhng c th dng Bromtimol chm nu chun n mu hon ton kim, bin php ny i hi phi dng dung dch kim chun cha cng mt lng ch th v dung dch i chng so snh. chun nhng ch th c s chuyn mu trong mi

trng kim nh phenolphtalein thch hp hn. (SV kim chng li bng vic tm S ca php chun ny) 7. 2. 3. ng cong chun acid mnh baz yu Cng tin hnh vic thit lp tng t nh trn cho vic kho st ng cong chun 100mL dung dch NH3 0,1M (K = 1,81.10-5) bng dung dch HCl 0,1M. p dng cc cng thc tnh ton nh nu: Phn ng xy ra ti im tng ng: HCl + NH3 = NH4Cl pOH =
pK B 2 lg C B

v [OH - ]= K(B)

CB CA

229

Hnh 7.3. ng cong chun NH3 bng HCl Tng t khi xem xt s chun dung dch acid mnh HCl bng NH3 Nhn xt: im trung ho ti im pH = 5,13 Bc nhy pH khong 4 - 6,26 i vi h chun baz yu Cht ch th nn chn l Metyl Bc nhy ph thuc vo phn ly ca baz

yu: baz cng yu th bc nhy cng ngn 7. 3. Dung dch m 7.3.1. Khi nim L dung dch c pH khng i trong sut qu trnh phn tch khi pha lang hay khi thm mt lng nh acid hoc baz vo dung dch Dung dch m c nng acid v baz lin hp vi n cao v xp x bng l tt nht. 7.3.2. nh hng ca s pha long Gi tr pH ca dung dch m thc t khng bin i khi pha lang cho ti khi nng ca n khng gim ti 230

mc l, s gn ng c s dng rt ra cc phng trnh [M] C(M) mt gi tr. V d: Tnh pH ca dung dch cha HCOOH 0,4M v HCOONa 1M. em pha lang dung dch ny 50 ln hay 10.000 ln th pH ca dung dch m mi ln lt l bao nhiu ? Bit Ka = 1,77. 10 -4 Gii Phng trnh phn ly: H2O + HCOOH Theo : [ HCOO - ] [HCOOH] Nn K=
[ H 3 O ].[ HCOO ] [ HCOOH ]

H3O+ + HCOO - . nng ca HCOONa = 1M nng ca HCOOH = 0,4M

[ H3O+ ] = 7,08. 10 -5 mol/L

pH = 4,15 Khi pha long 50 ln: [ HCOO - ] [HCOOH] Nn K= nng ca HCOONa = 1/50 = 0,02 M nng ca HCOOH = 0,4/50 = 0,008 M

[ H 3 O ].[ HCOO ] [ HCOOH ]

[ H3O+ ] = 7,08. 10 -5

pH = 4,15

Khi pha long 10.000 ln: Nng ca HCOONa = 1/10.000 = 10 -4 M Nng ca HCOOH = 0,4/10.000 = 4. 10 -5 M Nn K =
[ H 3 O ].[ HCOO ] [ HCOOH ]

[ H3O+ ] = 7,08. 10 -5

231

pH = 4,15 Mt khc, nu xt ring trong h pha lang 10.000 ln ny, th [ HCOO - ] = 10 -4 + [H3O+ ] - [OH - ] [HCOOH] = 4. 10 -5 - [H3O+ ] + [OH - ] V dung dch ny l dung dch acid nn chc chn [H3O+] >> [OH - ] [ HCOO - ] = 10 -4 + [H3O+ ] [HCOOH] = 4. 10 -5 - [H3O+ ] Khi K =
[ H 3 O ].[ HCOO ] [ HCOOH ]

1,77. 10 -4 =

[ H 3O ].(10 4 [ H 3O ]) 4.10 5 [ H 3O ]

[H3O+ ] 2 + 2,77. 10 -4 . [H3O+ ] - 7,08. 10 -9 = 0 [ H3O+ ] = 2,36. 10 -5 pH = 4,63. Vy khi pha lang dung dch m n 10.000 ln th pH dung dch bin i t 4,15 4,63. Cn khi pha lang dung dch m n 50 ln th thc t pH khng i. 7.3.3. nh hng khi thm acid - baz vo h m Kh nng ca dung dch m l gi gi tr pH khng b thay i khi thm mt lng nh acid hoc baz vo. V d: Hy tnh pH bin i nh th no khi thm vo 400mL dung dch m cha NH 3 0,2M + NH4Cl 0,3M, mt lng: a) 100mL dung dch NaOH 0,05M b) 100mL dung dch HCl 0,05M Gii Tnh gi tr pH ban u: 232

NH3 + H2O [NH3 ] [NH4+ ] Nn K=

[ NH 3 ]

NH4+ + OH-

nng ca dung dch NH 3 = 0,2M nng ca NH4Cl = 0,3M

[ NH 4 ].[OH ]

[OH - ] = 1,77. 10 -5

pH = 9,07

a)

Khi thm NaOH vo: c s chuyn i mt phn NH4+ thnh NH3 NH4 + + OH Khi : [NH3 ]= V [NH4Cl] = NH3 + H2O
400.0,2 100.0,05 = 0,17M 500

400.0,3 100.0,05 = 0,23M 500

Sau khi thay th nng tm c vo phng trnh hng s phn ly ca NH 3, ta thu c. [OH - ] =
1,76 .10 5.0,17 = 1,3. 10 -5 mol/L 0,23

pH = 9,11

Do : b)

pH = 9,11 - 9,07 = 0,04

Khi thm HCl vo: C s chuyn mt phn NH 3 thnh NH4+ NH3 + H2O Khi : [NH3 ] = V NH4Cl = NH4 + + OH - .
400.0,2 100.0,05 = 0,15M 500

400.0,3 100.0,05 = 0,25M 500

Sau khi thay th nng tm c vo phng trnh hng s phn ly ca NH 3, ta thu 233

c. [OH - ] =
1,76 .10 5.0,15 = 1,06. 10 -5 mol/L 0,25

pH = 9,02

Do : pH = 9,02 - 9,07 = - 0,05 7.3.4. Gii hn ng dng ca phng trnh Henderson - Schwazenbach Trong h m CH3COOH v CH3COONa c phng trnh Henderson - Schwazenbach l: pH = p Ka + lg
C CH 3COOONa C CH 3COOOH

Phng trnh ny c s dng rng ri tnh pH v iu ch dung dch m. Trong : pKa l hng s nn t s
C CH 3COOONa C CH 3COOOH

quyt nh gi tr pH ca dung dch, nhng

trong thc t, iu ch ng trong mt khong xc nh. Khi t s ny rt ln hoc rt nh, phng trnh trn tr thnh khng ng v khng th p dng c. V d khi
C CH 3COONa C CH 3COOH

1.10 1.10

1 7

= 1.106 th i vi h

(CH3COOH + CH3COONa), pH ca dung dch s l: pH = 4,76 + lg 10 6 = 10,76 Kt qu ny l khng th chp nhn c v n cho gi tr pH ln hn nhiu pH ca dung dch CH3COONa 0,1M, ng thi cng chnh l pH im rt gn vi im tng ng trong php chun dung dch CH3COOH 0,2M bng dung dch NaOH 0,2M (xem chun acid yu bng baz mnh). V lc ny [CH3COONa] >> [ CH3COOH], nn: 234

[OH - ] =

K b .Cb =

K H 2O Ka

.C CH 3COONa = 1. 10 - 5,12
1.10 = 1.10
7 1

pH = 8,88

Ngc li khi

C CH 3COOONa C CH 3COOOH

= 1. 10 -6 th i vi

h (CH3COOH + CH3COONa), pH ca dung dch s l: pH = 4,76 + lg 10 -6 = - 1,24 Kt qu ny cng khng th chp nhn c v dung dch ny thc t l dung dch CH 3COOH 0,1M, ng thi pH ca n cng chnh l pH im u, chnh xc hn l im cc k st vi im u ca ng chun dung dch CH3COOH 0,1M bng dung dch NaOH 0,1M (v [CH3COOH] >> [CH3COONa]) nn: [H3O+ ] =
- 2,88 K a .C a = 10

pH = 2,88

Khi sinh vin mun tnh pH im v cng st vi im u v im v cng st vi im tng ng ca php chun acid yu bng baz mnh nhng li bng phng trnh Henderson - Schwazenbach nn phm phi nhng sai lm nh trn. S tht l h m dung dch acid yu v baz lin hp vi n, c khi lng m cc i khi nng ca CH3COOH = nng ca CH3COONa, v khi lng m gim dn v c hai pha khi c hai nng ny gim dn. Khi nng ca CH 3COOH = 10-7 ngha l nng n ang tin v 0, v nng ca CH3COONa = 10 -7 ngha l cng tin v 0, l lc khi lng m ca h tin ti khng, nn h khng cn l h m na v do khng th dng cng thc ca Henderson 235

Schwazenbach tnh pH cho dung dch 7.3.5. iu ch dung dch m V nguyn tc c th iu ch dung dch m c pH cn thit bt k bng cch trn nhng lng c tnh ton trc ca nhng cp acid - baz lin hp thch hp V d: Hy trnh by cch iu ch dung dch m c pH = 5,00 t dung dch acid CH3COOH 0,5M (Ka = 1,75. 10 -5 ) v dung dch NaOH 0,426M Gii Ta tm c t s nng CH 3COOH v CH3COO pH = 5,00 t phng trnh hng s phn ly:
K [CH 3 COO ] 1,75 .10 = CH 3COOH = 1,00 .10 [CH 3 COOH ] [ H 3O ]
5 5

= 1,75

c c t s trn cn trn V(mL) ca CH3COOH vi V(mL) dung dch NaOH 0,426M, th sau khi trn ta c: Nng ca CH3COO - = Nng ca CH3COOH =
0,5.VCH 3COOH VOH 0,426.VOH VCH 3COOH

0,426.VOH VOH VCH 3COOH

= [ CH3COO - ]

= [ CH3COOH]

Nu thay [ CH3COOH] v [ CH3COO- ] bng nhng nng vo t s ban u th mu s c n gin ha:

0,426.VOH 0,5.VCH 3COOH 0,426.VOH

VOH VCH 3COOH

= 1,75 = 0,747

236

Nu cn thit iu ch 100mL dung dch m th: V(NaOH) + V(CH3COOH) = 100 mL

0,747. V (CH3COOH) + V ( CH3COOH) = 100 V ( CH3COOH) = 5,72mL v V(OH - ) = 100 - 57,2 = 42,8mL

Nh vy nu thm 57,2mL dung dch CH3COOH vo 42,8mL dung dch NaOH th v nguyn tc phi thu c dung dch c pH cn thit. Bng cc tnh tan tng t c th hng dn vic iu ch cc dung dch m c pH xp x pH tng ng cn thit. Thng khng nn mong i cc gi tr chnh xc bi v nhiu gi tr hng s phn ly thng c sai s. Cn mt iu quan trng na l lc ion ca cc dung dch m thng ln dn n mc l khng th thu c gi tr h s hat tin cy ca cc ion trong cc dung dch t phng trnh Debye Huckel. Nh trong v d va xt, lc ion khang 0,18 - v vy hng s phn ly Ka cn phi ln hn 1,75. 10 -5 mt cch ng k, nhng cha c xc nh chnh xc (khang 3. 10 -5 ) Nhng hng dn iu ch cc dung dch m c pH c vit y trong cc s tay tra cu Ha hc. Cc sinh vin hc vin cn nh hai h m quan trng hay s dng c l: H m Makilvein c pH = 2 8 c iu ch bng pha trn dung dch HNO3 v Na2HPO4 H m Klark - Labo c pH = 2 10, c iu ch bng pha trn acid phtalic + kaliphtalat +K2HPO4 + acid Boric + Natriborat 7.4. ng cong chun acid a chc baz a 237

chc 7. 4. 1. ng cong chun a acid Cc a acid trong dung dch s b phn ly theo cc nc, nn khi trung ho n bng phng php acid-baz th cc mui s c hnh thnh tng ng theo cc nc ny, v mi nc c mt im tng ng tng, tng ng vi gi tr hng s cn bng ca nc Kho st phng trnh ng nh phn khi chun Va (mL) dung dch acid H3PO4 Ca bng Vb (mL) dung dch NaOH Cb Trong dung dch H3PO4 (vit gn H3A) c s phn ly: H3A + OHH2O + H2A(K1) (1) 2H2A + OH H2O + HA (K2) (2) HA2- + OHH2O + A3(K3) (3) nc 1: H3A H++ H2A- (k1) Trong qu trnh chun c: [H+] + [H+]p = [H+]pt =
Va .C a V a Vb
Vb .C b V a Vb

[OH-] + [OH-]p = [OH-]pt = M: [H+]p = [H3A]

[OH-]p = [H2A- ] (v tuy ni nc i = 1, 2, 3, nhng c 3 nc u tn ti cc ion ny vi hm lng tnh theo K i tng ng) V: (2): [H2A-] = [HA2-] (3): 238 [H2A-] = 2[A3-] [H2A-] = [HA2-] + 2[A3-]

Do h (4) c vit li l: [H+]-[OH-]+[H3A]-([HA2-]+2[A3-])= ( [H+]-[OH-]+[H3A]-[HA2-]-2[A3-]).

Va .C a _ Vb .C b V a Vb

Va Vb Va .Ca

1 F (5)

y l phng trnh ng nh phn ca s chun acid H3PO4 bng baz NaOH. Mt khc:(1): K1 =
[ H ].[H 2 A ] [ H 3 A] [ H 3 A] [ H ].[H 2 A ] [ K1 ]

Tng t: (2): [H2A-] = (3): [A3-] =

K 1 .K 2 .[ H 3 A] [ H ]2

K 1 .K 2 . K 3 .[ H 3 A] [ H ]3

Nn: [H3A] [HA2-] 2[A3-] = [H3A] = = [H3A] . ( 1 gn ) = [H3A] .(

h3 K1 .K 2 .h 2 K1 .K 2 .K 3 ) h3
0 CX
n

K 1 .K 2 2 K 1 .K 2 .K 3 .[ H 3 A] .[ H 3 A] 2 [H ] [ H ]3

K 1 .K 2 2 K 1 . K 2 .K 3 ) 2 [H ] [ H ]3

(t h = [H +] vit

(6)

p dng cng thc tnh nng cn bng cu t X: [X] = th [H3A] = vi =1+

i 1

( K 1,i .[ p ] i )
3

C pt ( H 3 A)

vi

=1+
i 1

( K 1,i .[ H ]

239

Do [H3A] =

K1 1 h

Va .C a Va Vb K 1 .K 2 K 1 .K 2 .K 3 h2 h3

(7)

Thay (5, 6, 7 ) vo li (5):

V a Vb h.K1 .K 2 2K1 .K 2 .K 3 h 3 1 F = ( [ H ] [OH ] ). - 3 (8) Va .C a h K1 .h 2 K1 .K 2 .h K1 .K 2 .K 3
+ -

[Phng trnh (8) v (5) hon ton tng ng nhau, nhng tnh ton pH trong dung dch l tu vo thi im kho st no chn (5) hoc (8)] Khi Vb = 0 ( F = 0) tc lc cha chun (8) 1=
[H ] Ca h3 h3 (xem K2 = K3 = 0 ) K1 .h 2

h2 + K1.h Ca.K1 = 0 Khi 0 < Vb < Vt

Gii tm h = [H+] 0 v [OH-] 0

pH

( 0 < F < 1) xa trc im tng K3

V a Vb h3 + 3 Va .C a h K1 .h 2

ng vn xem K2 (8) 1 F = [H+]

t q = trnh:

Va Vb vit gn li, th (8) l phng Va .C a

q.h2 + ( q. K1 + F ) h + (F 1 ) K1 = 0 Gii tm h = [H+] pH (Kt qu thu c c th tnh gn ng vi: F1=

[H ] ) K1 [ H ]

Khi Vb = Vt (F = 1). Ti im tng ng lc ny trong dung dch vn cn axit (H2A2-), nn vn xem: [H+] = [OH-] = 0 240

(8)

1F=

h3

h.K1.K 2 h3 K1.h2 K1.K 2 .h

F. h2 ( K1 F.K1) h + (F 2).K1 K2 = 0 Gii tm h pH dung dch (Kt qu c th tnh gn ng: [H+] = Khi Vb Vt ( F
K1 .K 2 .C a .Cb ) K1 (C a Cb ) C a .Cb

1).Ti trc v sau st im tng 0 cc gi tr h3, K1K2K3,

ng nc 1 vn xem [OH-] hK1K2 qu b nn: (8) 1 F = [H+]

Va Vb h.K1 .K 2 h 3 + Va .C a K1 .h 2

( q K1 1 )h2 + (F 1 ) K1 h + K1.K2 = 0 Gii tm h pH dung dch nc 2: Xut pht t phng trnh (8) cho nc 1, c vit li l:
h.K1 .K 2 2K1 .K 2 .K 3 h 3 2 F = ( [H ] [OH ] ) q - 3 +1 h K1 .h 2 K1 .K 2 .h K1 .K 2 .K 3
+ -

2 F = ( [H ] [OH ] ) q hay l:
F 2 = ( [OH-] [H+] ) q +

h3

K1 .K 2 .K 3 K1 .h 2 2h 3 K1 .h 2 K1 .K 2 .h K1 .K 2 .K 3 K1 .K 2 .K 3 K1 .h 2 2h 3 K1 .h 2 K1 .K 2 .h K1 .K 2 .K 3

h3

(9)

Khi 1 < F < 2: xa trc im tng ng nc 2

241

(9)

F 2 = - [H+] q -

h3

K1 .h 2 2h 3 K1 .h 2 K1 .K 2 .h

Xem [OH-]
3

0 v K3 << K2 nn b qua pH dung dch

h K2 h

q.h + ( qK1 + F ) h2 + ( q K1K2 K1 + F.K1 ) h + (F 2) K1K2 = 0

Gii tm h F2= Khi F

(Kt qu c th tnh gn ng: )

2: ( ngay trc v sau st im tng ng 0

K1 .K 2 .K 3 K1 .h 2 K1 .K 2 .h K 2 .K 3 h 2 K 2 .h

nc 2 ).Xem K2 qu nh ( K2 = 10-7 ) nn [H+] (9) F 2 = [OH-].q + F2=

10 14 .q h

h2 + ( 2 - F ) K2. h ( K3 + q. 10-14) K2 = 0 . Gii tm h pH dung dch

K1 .K 2 .K 3 K1 .h 2 0 = [OH ] q + K1 .K 2 .h
-

Khi F = 2 ( ngay ti im tng ng nc 2 ) (9)

Gii tm h = [H+] = pH dung dch nc 3:

K 2 .K 3

K 2 .q.10

14

F 3 = ( [OH-] [H+] ) q +
F 3 = ( [OH-] [H+] ) q -

h3

K1.K2 .K3 K1.h2 2h3 -1 K1.h2 K1.K2 .h K1.K 2 .K3

(10)

h3

3h 3 2K1 .h 2 K1 .K 2 .h K1 .h 2 K1 .K 2 .h K1 .K 2 .K 3

Gii tm h = [H+] 242

pH dung dch

Khi 2 < F < 3: Xa trc im tng ng nc 3. B qua [H+] [H3A] pt (5) vit li l: F 3 = [OH-] q// h K3 h

( 2 F ) h2 +(q//.10-14 + 3K3 FK3 )h + K3.q//.10-14 = 0 Gii tm h = [H+] 0 = [OH-] q// pH dung dch
h K3 h

Khi F = 3: Ti im tng ng nc 3

h2 q//.10-14.h K3.q//.10-14 = 0. Gii tm h = [H+] Khi F nc 3 pH dung dch 3: St trc v sau im tng ng

V K3 qu b nn xa trc hoc st hoc sau im tng ng cc gi tr [H+] [H2A- ] [H3A]

h K3 h

0 .

F 3 = [OH-].q -

Gii tm h = [H+] pH dung dch Sai s ca php chun a acid yu bng baz mnh (nchc) Xt trong trng hp acid xt trn: Chun dung dch H3PO4 bng dung dch NaOH st nc 1: Ta c: Ca.Va
Ca Cb Cb Va Va Vb

Cb.Vb

Ca Cb

Vb Va V a Vb C a .Va q

C a Cb C a .C b

Nn sai s chun nc 1 c xc nh l: 243

S = ( F 1) =(
C Cb h.K1 .K 2 2K1 .K 2 .K 3 h 3 10 14 - h ). a + 3 C a .C b h h K1 .h 2 K1 .K 2 .h K1 .K 2 .K 3

st nc 2:
2C a C b Cb Va

2Ca.Va
Vb Va

Cb.Vb
2C a C b C a .C b

2C a Cb
Va Vb C a .Va

Vb Va
q //

Nn sai s chun nc 2 c xc nh l: S=
=(

1 ( F 2) 2

2C a C b K1 .K 2 .K 3 K1 .h 2 2h 3 10 14 - h ). + 2C a .C b h 2(h 3 K1 .h 2 K1 .K 2 .h K1 .K 2 .K 3 )

st nc 3:
3C a C b Cb Va

3Ca.Va
Vb Va

Cb.Vb
3C a C b C a .C b

3C a Cb Va Vb C a .Va

Vb Va q

Nn sai s chun nc 3 c xc nh l: S=
1 ( F 3) 3

3C a C b 10 14 3h 3 2K1 .h 2 K1 .K 2 .h =( - h ). + 3C a .C b h 3(h 3 K1 .h 2 K1 .K 2 .h K1 .K 2 .K 3 )

V d: Kho st ng chun acid a chc 100mL dung dch H3PO4 0,1M bng dung dch NaOH 0,1M. Phn ng phn ly ca dung dch acid: H3PO4 H+ + H2PO4(K1 = 1,1.10-2 ) H2PO4HPO42H+ + HPO42H+ + PO43(K2 = 2.10-7 ) (K3 = 3,6.10-13 )

Phn ng trung ho theo tng nc s cho cc mui l NaH2PO4 , Na2HPO4, Na3PO4 244

V K1 > K2 > K3 nn ch nhn ly gi tr K1 : p K1 = 1,96 pH =

1 (p K1 - lg [H+]) =1,48 2

Ti im tng ng th nht: pH =
1 (p K1 + p K2 )= 4,33 2 1 (p K3 + p K2 )= 9,57 2 1 (p K3 + lg [H+ ])= 12,22 2

Ti im tng ng th hai: pH =

Ti im tng ng th ba: pH = 7 + Nhn xt Chun acid a chc bng baz mnh, ng vi mi nc c mt im tng ng ca nc . S bc nhy trong ng chun khng c vt qua s mc phn ly

Cc im un ca ng cong khng r rng 7. 4. 2. ng cong chun a baz Kho st phng trnh ng nh phn khi chun Vb(mL) dung dch Na2CO3 Cb bng Va(mL) dung dch HCl Ca, bit hng s phn ly cc nc ca acid H 2CO3 l pK1 = 6,35 ; pK2 = 10,32. Trong dung dch Na2CO3 (Na2A) c s in ly: Na2A = 2 Na+ + A2A2- + H+ = HAHA- + H+ = H2A nc 1: 245
1 2

= K2-1 = K1-1

(1) (2)

[H+] +[H+]p = [H+]pt =

C a .Va V a Vb C a .Va V a Vb

[OH-] +[OH-]p = [OH-]pt = M [H+]p = [H2A] [OH-]p = [A2-] V (1): (2):

1

(3)

[ HA ] [ A 2 ].[H ]
[ H 2 A] [ HA ].[ H ]

[ HA ]
[ H 2 A]

[ H ][ A 2 ]
[ H ][ HA ]

[H2A] = 1. 2 [H+].[A2-] H (3) tr thnh: [H+] [OH-] + [H2A]- [A2-] =

([H+] [OH-] + [H2A]- [A2-]).
C a .Va Va C b .Vb Vb C a .Va ) C b .Vb

V a Vb C b .Vb

F 1 (F =

(4)

(phng trnh ny s dng cho c h c 2 nc) ([H+] [OH-] + [A2-]( 1. 2.h2 1).
V a Vb C b .Vb F 1

p dng cng thc tnh nng cn bng cho cu t X [X] =

0 CX

[ A2 ]

C b .Vb . V a Vb 1

1
1

.h

.h 2

Khi Va = O: [H+] = [H2A] = 0 th (4) ( ( [OH-] - [A2-]).

Cb
1

1 = -1 Cb
.h 2

10 14 + h 1

.h

) = Cb

Gii tm h = [H+] 246

pH dung dch

Khi 0< Va < Vtd (tc 0 < F < 1) khi trc xa im tng ng nc 1 xem [H+] = [H2A] = 0 v (4) ((- [OH-] - [A2-]).
C .V 10 14 - b b . V a Vb 1 h
V a Vb C b .Vb F 1
2

1
1

.h

.h

V a Vb C b .Vb

F 1

10 14 1 .q + . = 1 - F. Gii tm h = [H+] h 1 1 .h

pH dung dch Khi F = 1: ngay ti im tng ng nc 1 th xem [H ] = [OH-], nn

+

([H2A]- [A2-]).
1 2

Va Vb =0 Cb .Vb

[H2A] = [A2-]

h2 = 1
1 1.

[H+] = h = Khi F
(4)
+

pH = 8,35
2

1: ngay st im tng ng nc 1
-

C .V ([H ] [OH ] + b b . Va Vb 1 h 2 . 1. h.
2 1

V Vb . 2 .h 2 1 ). a 2 C b .Vb 1 .h 1 . 2 .h
1

F 1

= F - 1. Gii tm h = [H+]

pH dung dch

nc 2: Khi vt qua nc 1 (F > 1) th: (4) ([H+] [OH-] + [H2A]- [A2-]).

V a Vb C b .Vb
V a Vb -1 = F-2 C b .Vb

([H+] [OH-]).

-.

.h

.h

2 =F-2 2 1 . 2 .h

(5) 247

Khi 1 < F < 2; b qua [OH-] v [A2-], nn (5) l:

F - 2 = [H+]
V a Vb . C b .Vb 1 C 2C b 2 1 = [H+] a . . 2 C a .Vb 1 2 .h 1 . 2 .h

Gii tm h = [H+] [H+]

C a 2C b C b .Vb

pH dung dch
1 1
2

Khi F =2: ngay ti im tng ng nc 1 (4) =.

.h

Gii tm h = [H+] pH dung dch Sai s trong php chun a baz yu bng acid mnh Vi nc 1: Sai s c xc nh l S = ([H+] [OH-] - [A2-]). ( 1.
2.

h2 - 1)]

Ca Cb C a .C b 2 ] 2 1 . 2 .h

Vi nc 2: Sai s c xc nh l S =
C Cb 1 [ ([H+] - [OH-]) a -. C a .C b 2 1
1 1

.h

.h

7. 5. Pha ch thit lp nng acid baz 7. 5. 1. Pha dung dch chun Dung dch chun l dung dch c nng chnh xc c bit trc dng trong phn tch. Pha ch dung dch chun l tin hnh pha dung dch t cc cht chun gc hay t cc cht gc. (xem li phn 6.4) 1. Pha dung dch chun acid HCl 0,1M Dung dch HCl l dung dch ca kh HCl c ho tan trong nc (nn dung dch d bay hi), m c khong 36% (d = 1,18), nn c th pha dung dch HCl m c ri sau pha long c dung dch chun 248

cn thit: Dng cng thc: V =

C M .M .V pha 10 .C %.d

tnh th tch dung

dch HCl chun vi CM cn dng Trong : CM l nng chun cn pha; M l khi lng mol phn t, Vpha l th tch cn pha ; C% v d l nng % chun ban u ng vi d bit. V d: Tnh lng pha 1 L dung dch HCl 0,1M t dung dch HCl 36% c d = 1,18 g/mL: (Xem li cng thc thit lp chng 2) Dng cng thc hc, ta tnh c th tch ca dung dch HCl 36% cn ly l: V=
C M .M A .V 0,1.36 ,5.1000 = =8,59 mL % 10 .36 .1,18 10 .d .C

Cho khong 50mL H2O ct vo bnh nh mc 1 L, ri rt t t 8,59mL dung dch HCl 36% (m c) vo. Sau nh mc n vch 1 L. Trong thc hnh, cn tin hnh thm phn kim nh li dung dch ny ng vi nng 0,1M cha bng cch dng php chun bng dung dch NaOH 0,1M chun vi ch th PP 2. Pha dung dch chun acid NaOH 0,1M NaOH rn l cht rt d ht m khi trong khng kh, nn thng b bn nc v kh CO2 , do pha chun dung dch NaOH trc khi thc hnh phn tch l mt iu cn thit v bc buc cho cc th nghim tin hnh trnh i c nhiu sai s. c dung dch chun 249

NaOH th phi pha vi nng ng lng ln hn yu cu, sau iu chnh cho dung dch long v nng cn pha. Mun vy, trc tin ta phi tnh khi lng cht rn cn pha bng cch dng cng thc: m = tnh khi lng cn cn cht rn NaOH V d: Pha 1 L dung dch NaOH 0,1M: Khi lng cn cn lng NaOH l: m= K thut pha ch V NaOH l mt cht rt d ht m, hp th CO 2 mi trng v vy n d chy ra, v cho sn phm sai bit. Do , vic cn NaOH trong khng kh theo mt gi tr chnh xc cho trc l iu khng lm c trong iu kin bnh thng. Ni cch khc, khng th pha mt dung dch NaOH c nng chnh xc nh mong mun, m ch pha c dung dch NaOH c nng xp x gi tr nh trc. d dng trong vic hiu chnh bng cch pha long, cn phi cn mt lng ln hn lng cn tnh theo l thuyt (tuyt i khng nn cn d qu nhiu ri ly ngc ra tr li), khi cn phi cn tht nhanh. Chng hn pha ch 1L dung dch NaOH 0,1M ni trn th cn khong 4(g) NaOH rn trong cn k thut. Ri ha tan NaOH trong cc cn bng 50mL nc, dng a thy tinh khuy cho tan, ch ngui, sau cho vo bnh nh mc 1 L. Trng ra nhiu ln cc bng nc ct, lng nc ra cho ht vo bnh nh mc ny. Tin hnh nh mc n ngang vch 1 L 250
0,1.40.1000 = 4g 1000
C M .M .V pha 1000

Trong thc t, phi tin hnh kim nh li nng dung dch NaOH va pha bng dung dch H 2C2O4 chun. Hoc c th dng ng chun NaOH 0,1N pha thnh 1 L dung dch NaOH 0,1N. 7. 5. 2. nh lng mt s dung dch 1. nh lng dung dch CH3COOH Nguyn tc: dng dung dch chun kim mnh NaOH 0,1M nh lng Phn ng: CH3COOH + NaOH CH3COONa + H2O Cht ch th: phenolphtalein, chun t khng mu thnh mu hng K thut pha ch: nh lng 100mL dung dch CH3COOH CM Cn chnh xc m(g) rn CH 3COOH mu (khong 0,3 0,42g), ho tan thnh 100mL bng nc ct Ht chnh xc 10 mL dung dch mu CH3COOH cho vo erlen, lm 3 mu, Thm vo mi mu khong 20 mL nc ct + 3 git PP, lc nh. Np dung dch NaOH chun 0,1M ln buret 25 mL. T buret, nh tng git NaOH xung erlen cho n khi dung dch chuyn t khng mu sang hng nht (bn trong 10 giy). Ghi th tch NaOH tiu tn.Cng lm tng t vi 2 erlen cn li. T th tch o c 3 mu, tnh nng dung 251

dch CH3COOH Tnh ton: T 3 th tch V ca dung dch NaOH chun tm c Vtbnh = V1 Tnh CM CH3COOH = 2.
0,1.V1 10

nh lng dung dch NH3

Nguyn tc: dng dung dch chun HCl 0,1M nh lng. Phn ng: HCl + NH3 NH4Cl Cht ch th l MR (Metyl Red) chun t mu vng sang K thut pha ch: nh lng 100mL dung dch NH3 M C Cn chnh xc m(g) nc NH3 mu, ho tan vi nc ct thnh 100mL dung dch Ht 10mL dung dch mu cho vo bnh nn 250mL + 20mL nc ct, 3 git MR (0.1% trong cn), lm thnh 3 mu. Chun bng dung dch HCl n khi dung dch t mu vng chuyn sang mu cam, ghi th

tch HCl tiu tn T th tch o c 3 mu, tnh nng dung dch NH3. Tnh ton: T 3 th tch V ca dung dch HCl chun tm c Vtbnh = V1 CM dung dch NH3 = 252
0,1.V1 . 10

3.

nh lng dung dch H3PO4

Nguyn tc: acid H3PO4 l mt acid 3 chc nhng chc th 3 qu yu nn ch cn chun 2 nc u. Dng dung dch chun kim mnh NaOH 0,1M nh lng Phn ng: H3PO4 + NaOH NaH2PO4 + H2O K1 H3PO4 + 2 NaOH Na2HPO4 K2 Cht ch th MO (Metyl Orange), chun t mu sang mu cam vng-chun cho nc 1 Cht ch th PP (phenolphtalein), chun t mu cam vng sang mu - chun cho nc 2 K thut pha ch: Cn chnh xc a(g) H3PO4 mu Ho tan thnh 100mL bng nc ct Ht 10 mL dung dch H3PO4 CN bng pipet bu 5 mL cho vo erlen (lm 3 mu), thm vo mi mu khong 10 mL nc ct + thm 1 git MO 0,1%, lc nh. Np dung dch NaOH 0,1N ln buret 25 mL. T buret, nh tng git NaOH xung erlen cho n khi dung dch chuyn t mu sang vng cam. Ghi th tch NaOH tiu tn (VMO) Cho tip tc vo mu 3 git PP. Chun tip bng NaOH cho n khi dung dch chuyn t mu vng cam sang hng cam. Ghi th tch NaOH tiu tn (VPP). Lm tng t cho 3 mu cn li 253

T th tch o c 3 mu, tnh nng dung

dch H3PO4 CN Tnh ton: Tnh hm lng % H3PO4 c trong mu Nng dung dch H3PO4 c tnh theo: Chc 1: ( nc 1 xem H3PO4 l acid mnh n chc)
(V .C ) MO 0,1.V NaOH [H3PO4 ] = = = V(MO). 10 - 2. 10 VH 3PO4

C hai chc (b nc 3, xem H3PO4 l acid mnh 2 chc) [H3PO4 ] =

0,1.(VMO VPP ) (V .C ) NaOH = = V(Buret). 10 - 2. 10 VH 3 PO4

254

THC HNH PHN TCH TH TCH

BI THC HNH BI 1: CHUN ACID MNH BAZ MNH I. CHUN B Chun b cc dung dch sau: NaOH 0,1N - 2N 5N. Dung dch H2C2O4 0,1N. Dung dch HCl 0,1N. Dung dch Na2B4O7 0,1N 1. Cc ch th: phenolphtalein, MO, MR. Pha ch dung dch H2C2O4 0.1N

Sinh vin phi t tnh ton lng cn thc t ca H2C2O4.2H2O, c p% ( tinh khit) c ghi trn bao b ca ha cht tng ng ti phng th nghim, chng hn, pha c 100mL dung dch acid 0.1N, khi cn phi ly chnh xc n 0.0002g, cc cn loi 100mL, phi sch, kh v c nhit cn bng vi phng cn. Sau khi cn, thm nc ct loi CO2 (nc ct un si 10 pht, trong bnh kn v ngui n nhit phng) khong 30 40mL, dng a thy tinh khuy cho tan, chuyn vo bnh nh mc 100mL theo a thy tinh qua phu, dng nc ct trng cc 3 ln, mi ln 10mL, dng bnh tia ra a v nh mc ti vch, y np bnh nh mc, o ngc bnh 4 5 ln, ch o nh ch khng xc mnh bnh. Ch : Cc dung dch c s dng trong qu trnh phn tch nh lng ti Gio trnh ny u c tnh theo nng CN 0,05 - 0,1 N. y ch trnh by cch pha 255

chung i vi cc cht d ha tan trong nc v qu trnh ha tan ta hay thu nhit khng ng k. Cch pha vi cc cht khc cng vi k thut tng t, ch khc lng cn v th tch bnh nh mc, khng nn pha trc tip trn bnh nh mc. Cc dung dch gc phi c pha ht sc cn thn v chnh xc v n quyt nh n ng ca php nh lng. 2. Pha ch dung dch NaOH 0.1N

V NaOH l mt cht rt d ht m, hp th CO 2 mi trng v vy n d chy ra, v cho sn phm sai bit. Do , vic cn NaOH trong khng kh theo mt gi tr chnh xc cho trc l iu khng lm c trong iu kin bnh thng. Ni cch khc, khng th pha mt dung dch NaOH c nng chnh xc nh mong mun, m ch pha c dung dch NaOH c nng xp x gi tr nh trc. d dng trong vic hiu chnh bng cch pha long, cn phi cn ln hn lng cn tnh theo l thuyt mt lng nh (tuyt i khng nn cn d qu nhiu ri ly ngc ra tr li), khi cn phi cn tht nhanh. Chng hn pha ch 100mL dung dch NaOH 0,1N th cn chnh xc khong 0,4(g) NaOH rn bng cn k thut. Ri ha tan NaOH trong cc bng 50mL nc, dng a thy tinh khuy cho tan, ch ngui, sau lm tip nh phn pha dung dch axit trn. Hoc c th dng ng chun NaOH 0,1N pha thnh 1 L. 3. Pha dung dch HCl 0,1N Khc vi hai dung dch trn c pha t cc cht rn, dung dch HCl c pha t HCl , cn tnh th tch 256

HCl cn ly l bao nhiu pha c 100mL c nng 0.1N, sau chun b sn mt cc loi 100mL c cha sn 50mL nc ct. Ly pipt ht chnh xc th tch tnh, nhanh chng nhng ngp u pipet vo trong cc chun b, sau th t t, dng bnh tia ra sch pipet, nc ra cho lun vo cc pha, sau chuyn vo nh mc nh phn trn. Hoc nn pha t ng chun HCl 0,1N thnh 1 L dung dch.

I. NH LNG DUNG DCH NaOH

Th nghim 1 Ht chnh xc 5 mL dung dch H2C2O4 0,1N cho vo erlen, lm 3 mu. Thm vo mi mu khong 30 mL nc ct + 3 git phenolphtalein, lc nh. Np dung dch NaOH (l dung dch NaOH c pha t NaOH rn trn) ln buret 25 mL. T buret, nh tng git NaOH xung erlen cho n khi dung dch chuyn t khng mu sang hng. Ghi th tch NaOH tiu tn. Cng lm tng t vi 2 erlen cn li. Cu hi 1. Ti sao phi thm 30mL nc ct vo dung dch acid khi tin hnh chun H 2C2O4 0,1 N bng NaOH? Khi thm nc ct vo dung dch acid th nng 257 T th tch o c 3 mu, tnh nng dung dch NaOH

2.

 ca acid v th tch NaOH chun c thay 3. i g khng? Hy tnh khong nng dung dch NaOH

trong 3 th nghim trn vi tin cy 95%? Th nghim 2 Ht 10 mL dung dch mu NaOH + 30 mL nc ct +3 git pp cho vo erlen, lm 3 mu em chun bng dung dch HCl 0,1N cho n khi dung dch chuyn t mu hng tm sang khng mu. Ghi th tch axit HCl 0,1N tiu tn. Cu hi T th tch o c 3 mu, tnh nng dung dch NaOH. Gii thch s khc bit v gi tr ca nng dung dch NaOH trong 2 th nghim trn? Khi thm nc ct vo dung dch NaOH th kt qu chun c thay i g khng?

1. 2.

II. NH LNG DUNG DCH HCl

Th nghim 1 Ht 10 mL HCl va pha t dung dch HCl m c trn, vo erlen + 30 mL nc ct vi 3 git phenolphtalein, cng lm 3 mu. Cho dung dch NaOH C N va xc nh trn, vo buret: nh t t dung dch NaOH xung erlen c cha mu cho n khi dung dch chuyn t khng mu sang mu hng nht. Ghi th tch NaOH nh xung. 258 T th tch o c 3 mu, tnh nng dung dch HCl.

Th nghim 2 Lp li th nghim 1 vi ch th MR, so snh vi trng hp hiu chnh bng ch th phenolphtalein. Th nghim 3 Lp li th nghim 1 vi ch th MO, so snh vi trng hp hiu chnh bng phenolphtalein. Th nghim 4 Ht 10 mL Na2B4O7 0,1N vo erlen + 20 mL nc ct vi 3 git MR. Np dung dch HCl va xc nh C N trn, vo buret. T buret nh dung dch HCl xung erlen c cha mu cho n khi dung dch chuyn t mu vng chanh sang mu hng ta.Ghi th tch HCl tiu tn . T th tch HCl, tnh chnh xc li nng ca HCl v so snh vi trng hp hiu chnh bng dung dch NaOH. Hy tnh khong nng dung dch HCl trong 4 th nghim trn vi tin cy 95% V sao th nghim 4 khng th i v tr: trn

Cu hi 1. 2.

buret cha Na2B4O7 v erlen cha HCl ? Ch : bi ny ch gii thiu 3 cch pha ch dung dch v php hiu chnh chng. Cn nhng bi sau, phi t pha ch cc dung dch chun, cn dung dch mu l do gio vin pha t trc giao cho sinh vin. Qua bui thc hnh sinh vin xc nh nng ca dung dch mu v tr li cc cu hi vit bo co cho 259

gio vin. Gio vin nn thu bi bo co sau mi bui th nghim. Cc kt qa bo co nh lng, u c tnh cho tin cy = 95%. V th gio vin nn hng dn li cho sinh vin cc phn: Cch cn ho cht Cch hiu chnh cn khi lng v th tch o Tnh sai s thng k

Tnh sai s cho php chun th tch Cui mi bui Th nghim, cc sinh vin np cc l mu c ra sch, c dn nhn s t ca mnh gio vin chun b cc mu bui th nghim sau. Nng dung dch cn bo co ca sinh vin c th c gi l: Vi chun Acid - baz: CN hay CM Vi chun oxy ho kh: CN hay CM Vi chun to phc: CN hay CM Vi chun to ta v php khi lng: C% hay Cppm.

260

BI 2: CHUN ACID MNH BAZ YU V ACID YU - BAZ MNH I. 1. CHUN B Ho cht Dung dch chun HCl 0,1N. Ch th MR, nc ct. 2. Nguyn tc Da vo phn ng trung ha: H+ + OHH2O Dng dung dch acid mnh lm dung dch chun nh lng baz yu Dng dung dch baz mnh lm dung dch chun nh lng acid yu NH LNG BAZ YU BNG ACID MNH

II.

Da trn phn ng trung ha gia axit mnh bit trc nng vi baz yu NH 3 vi ch th metyl , im tng ng nhn c khi dung dch chuyn t mu vng sang mu cam. Phn ng chun : NH3 + HCl = NH4Cl Dung dch mu l dung dch NH3 CN (0,1N - 0,5N) c gio vin hng dn pha trc, sinh vin khng c bit trc. Th nghim 1 Dung dch mu l dung dch NH3 CN (0,1N - 0,5N) c gio vin pha trc, sinh vin khng c bit trc Ht 10mL dung dch mu cho vo bnh nn 261

250mL + 20mL nc ct, 3 git MR (0.1% trong cn) Np dung dch HCl 0,1N vo buret. Chun bng dung dch HCl n khi dung dch t mu vng chuyn sang mu cam, ghi th tch HCl tiu tn T th tch o c 3 mu, tnh nng dung dch NH3. Thay ch th Phenolphtalein bng MR v MO, nhn xt. Th nghim 2 Dung dch mu l dung dch NH3 CN (0,1N - 0,5N) c gio vin pha trc, sinh vin khng c bit trc Ht 10 mL HCl chun 0,1N vo erlen + 20 mL nc ct vi 3 git MR, lm 3 mu Np dung dch mu NH3 CN ln buret. T buret nh dung dch NH4OH 0,1 N xung erlen c cha HCl cho n khi dung dch chuyn t mu hng sang mu vng chanh. Ghi th tch NH4OH tiu tn (lm 3 mu). T th tch o c 3 mu, tnh nng dung dch NH3 Cu hi 1. Trong th nghim 1, khi thay Phenolphtalein bng MO v MR th cc gi tr V (NH3) thu c no c sai s b nht ? Gii thch? V sao trong 2 th nghim bi cng dung dch

2. 262

3.

HCl v NH3, cng ch th MR, nhng li c s chuyn mu ngc nhau? Vi 2 cch chun khc nhau 2 th nghim,

III.

cho bit th nghim no cho php xc nh nng NH3 chnh xc hn? Gii thch? NH LNG ACID YU BNG BAZ MNH

Da trn phn ng trung ha gia baz mnh NaOH bit trc nng vi axit CH3COOH vi ch th PP, im tng ng nhn c khi dung dch chuyn t khng mu sang mu hng nht bn trong 10 giy. Phn ng chun : CH3COOH + NaOH = CH3COONa + H2O Dung dch mu l dung dch CH 3COOH CN (0,1N 0,5N ) c gio vin hng dn pha trc, sinh vin khng c bit trc Th nghim 1 Dung dch mu l dung dch CH 3COOH CN (0,1N 0,5N) c gio vin pha trc, sinh vin khng c bit trc Ht chnh xc 10 mL dung dch mu CH3COOH bng pipet bu 5 mL cho vo erlen, lm 3 mu. Thm vo mi mu khong 20 mL nc ct + 3 git PP, lc nh. Np dung dch NaOH 0,1N ln buret 25 mL. T buret, nh tng git NaOH xung erlen cho n khi dung dch chuyn t khng mu sang hng nht (bn trong 10 giy). Ghi th tch NaOH tiu tn. Cng lm tng t vi 2 erlen cn li. 263

T th tch o c 3 mu, tnh nng dung dch CH3COOH Th nghim 2 Dung dch mu l dung dch NaOH CN (0,1N - 0,5N) c gio vin pha trc, sinh vin khng c bit trc Ht 10 mL dung dch NaOH CN + 20 mL nc ct +3 git pp cho vo erlen, lm 3 mu em chun bng CH3COOH 0,1N cho n khi dung dch chuyn t mu hng tm sang khng mu. Ghi th tch CH 3COOH 0,1N tiu tn. T th tch o c 3 mu, tnh nng dung dch NaOH Cu hi 1. Khi pha thm nc ct vo erlen trong bc 2 th nghim 1, c lm thay i s ng lng ca dung dch HCl khng? Cho bit cc tnh s ng lng th nghim ny? 2. Bc nhy chun ca vic chun dung dch CH3COOH bng dung dch NaOH c g khc vi bc nhy trong vic chun dung dch HCl bng dung dch NaOH? Gii thch? 3. Khi tin hnh chun axit yu bng baz mnh nu thay ch th pp bng MR hoc MO c c khng? Gia MR v MO c gy nh hng g khc nhau khng? ( chng minh, sinh vin cn thc nghim ngay bng cch thay Phenolphtalein bng MO v MR) 4. 264

IV. NH LNG ACID A CHC H 3PO4 Th nghim 1 Dung dch mu l dung dch H 3PO4 CN (0,1N - 0,5N ) c gio vin pha trc, sinh vin khng c bit trc Ht 20 mL mu + 10 mL H2O ct + 1 git MO 0,1 % vo erlen, lm 3 mu. Chun bng dung dch NaOH 0,1N cho n khi dung dch chuyn t mu sang cam. Ghi th tch NaOH tiu tn (t l VMO) Tip tc cho vo mu 3 git PP, ri chun tip bng dung dch NaOH, ghi th tch NaOH tiu tn ln sau (t l VPP). Lm tng t cho 2 mu cn li. T th tch o c 3 mu, tnh nng dung dch H3PO4 CN Th nghim 2 Dung dch mu l dung dch H 3PO4 CN (0,1N - 0,5N ) c gio vin pha trc, sinh vin khng c bit trc Ht 10 mL dung dch H3PO4 CN bng pipet bu 5 mL cho vo erlen (lm 3 mu), thm vo mi mu khong 10 mL nc ct + thm 1 git MO 0,1%, lc nh. Np dung dch NaOH 0,1N ln buret 25 mL. T buret, nh tng git NaOH xung erlen cho n khi dung dch chuyn t mu cam sang vng cam. Ghi th tch NaOH tiu tn (VMO) 265

Cho tip tc vo mu 3 git PP. Chun tip bng NaOH cho n khi dung dch chuyn t mu vng cam sang hng cam. Ghi th tch NaOH tiu tn (VPP). Lm tng t cho 3 mu cn li T th tch o c 3 mu, tnh nng dung dch H3PO4 CN Cu hi 1. 2. nh gi kt qa tm c 2 TN ny. Gii thch?

Nu thay MO bng Bromcrezol lc 0,1% / Etanol 20% (BCL) th kt qa c thay i khng? Gii thch? VI. NH LNG HN HP AXIT HCl + H3PO4 Ho cht: dung dch chun NaOH 2N Ch th MO, Phenolphtalein, nc ct Dung dch mu l dung dch hn hp [HCl + H3PO4 ] (0,1N - 0,5N) c gio vin pha trc, sinh vin khng c bit trc Ht 5 mL hn hp mu + 10 mL H2O ct + 1git MO 0,1 %. Chun bng dung dch NaOH 0.5N cho n khi dung dch chuyn t cam sang vng cam. Ghi th tch NaOH tiu tn (VMO). Sau cho thm 3 git Phenolphtalein vo erlen, tip tc chun bng dung dch NaOH cho n khi dung dch chuyn t vng cam sang hng cam. Ghi th tch NaOH tiu tn (Vpp). 266

Lm tng t vi 2 mu cn li. T th tch o c 3 mu, tnh nng tng dung dch acid trong hn hp Cu hi 1. Gii thch cc bc tin hnh trong k thut. T thit lp cng thc tnh nng tng acid 2. c trong hn hp? Tnh sai s chun nc I v nc II ca axit

Photphoric cho pK1=2.12, pK2=7.21, pK3=12.38? VII. NH LNG BAZ A CHC Na2CO3 Dung dch mu l dung dch Na 2CO3 CN (0,1N 0,5N) c gio vin pha trc, sinh vin khng c bit trc Ht 5 mL dung dch mu Na2CO3 CN + 10 mL nc ct + 3 git pp cho vo erlen, lm 3 mu, dung dch s c mu hng m. Ri ht 5 mL NaHCO3 0,1N + 10 mL nc ct + 3 git PP cho vo erlen th 4 lm bnh chng (c mu hng tm nht). Chun cc mu bng dung dch HCl 0,1N cho n khi dung dch chuyn t mu hng tm m sang mu ca bnh chng. Ghi th tch HCl tiu tn (Vpp). Thm tip tc 1 git MO vo mu, dung dch chuyn sang mu .em un si mu khong 2-3 pht, ngui ri cho tng git HCl t trn buret nh xung cho n khi dung dch chuyn sang vng cam.. Ri tip tc chun bng HCl 267

0,1N cho n khi dung dch chuyn t vng cam sang cam. Ghi th tch HCl tiu tn (VMO). (nn lm bnh chng xc nh mu cho d dng) T th tch o c 3 mu, tnh nng dung dch Na2CO3 Cu hi 1. V sao vic chun dung dch Na 2CO3 li dng dung dch NaHCO3 lm chng so snh mu ti im tng ng?

Thit lp cng thc tnh nng Na 2CO3. Gii thch v sao phi dng n hai ch th? VIII. NH LNG HN HP NaOH V Na2CO3 2. Ho cht: dung dch chun HCl 0,1N, dung dch NaHCO3 0,1N Ch th: Phenolphtalein, MO, nc ct Dung dch mu l hn hp dung dch (NaOH + Na2CO3) CN (0,1N - 0,5N) c gio vin pha trc, sinh vin khng c bit trc. Th nghim 1 Ht chnh xc 5 mL hn hp mu NaOH + Na2CO3 CN v 10 mL nc ct loi b CO 2 + 3 git PP cho vo erlen (lm 3 mu). Cn ht 5 mL NaHCO3 0,1 N+ 10 mL nc ct + 3 git PP cho vo erlen 4 lm bnh chng (c mu hng tm). Sau tin hnh chun cc mu bng dung dch HCl chun 0,1N cho n khi dung dch 268

chuyn sang mu ca bnh chng. Ghi th tch HCl tiu tn (Vpp ). Thm tip tc 3 git MO vo mu, em un si mu khong 2 - 3 pht, ngui ri cho tng git HCl t trn buret nh xung cho n khi dung dch chuyn t mu cam sang cam vng. Ri tip tc chun bng HCl chun 0,1N cho n khi dung dch chuyn t cam vng sang cam. Ghi th tch HCl tiu tn (V MO) T th tch o c 3 mu, tnh nng dung dch hn hp Th nghim 2 Cho 3 mu hn hp dung dch vo 3 bnh nn, mi bnh 10mL mu + khong 20mL nc loi ht CO2 + 3 git MO, chun bng dung dch HCl 0,1N cho n khi dung dch chuyn t mu vng sang mu da cam, ghi th tch HCl tiu tn tc l VMO. Li ly 3 mu cho vo 3 bnh nn, mi bnh 10mL mu + 20mL nc loi ht CO2 + 20mL dung dch BaCl2 0,1N, un nng khong 50oC, ngui + 3git Phenolphtalein. Chun bng dung dch HCl cho n khi dung dch chuyn t mu hng sang khng mu, ghi th tch HCl tiu tn tc l VPP. Cu hi 1. Trong hai th nghim trn, im khc bit quan trng ca chng l g? Vit phng trnh phn 269

ng minh ho. Tnh CN ca tng cht trong hn 2. hp 2 th nghim? So snh VPP v VMO trong chun nh lng Na2CO3 v hn hp NaOH + Na2CO3 th nghim 1? Nhn xt, t a ra cng thc tnh hm lng %? Tnh sai s ng vi hai ch th, b qua tan ca CO2? 3. V sao phi un si khi giai on chun vi ch th MO? IX. NH LNG HN HP NaHCO3 + Na2CO3 Th nghim 1 Dung dch mu l hn hp dung dch (NaHCO3 + Na2CO3) CN (0,1N - 0,5N) c gio vin pha trc, sinh vin khng c bit trc Ht 5 mL hn hp mu cho vo erlen + 10 mL nc ct + 2 git MO (lm 3 mu). Ri chun bng dung dch HCl chun 0,1 N cho n khi dung dch chuyn sang cam. Ghi th tch HCl tiu tn (VMO). Ht 5 mL hn hp mu cho vo erlen + 10 mL nc ct + 10 mL NaOH 0,1 N+ 10 mL BaCl2 0,1 N (lm 3 mu). em un nng khong 50 600C, ngui, khng cn lc kt ta ri cho 3 git PP. Sau em chun bng dung dch HCl chun 0,1 N cho n khi dung dch mt mu hng tm. Ghi th tch HCl tiu tn (Vpp ). T th tch o c 3 mu, tnh nng hn hp dung dch Th nghim 2 270

Dung dch mu l hn hp dung dch (NaHCO3 + Na2CO3) CN (0,1N - 0,5N) c gio vin pha trc, sinh vin khng c bit trc. Ht chnh xc 10 mL hn hp mu + 10 mL nc ct + 3 git Phenolphtalein cho vo erlen (lm 3 mu). Cn ht 10 mL NaHCO3 0,1 N + 10 mL nc ct +3git PP cho vo erlen 4 lm bnh chng (c mu hng tm nht). Sau tin hnh chun cc mu bng dung dch HCl chun 0,1N cho n khi dung dch chuyn t mu hng tm m sang mu ca bnh chng. Ghi th tch HCl tiu tn (Vpp). Thm tip tc 1 git MO vo mu ri cho tng git HCl t trn buret nh xung cho n khi dung dch chuyn t mu vng cam sang hng cam. em un si mu khong 2-3 pht, ngui. Ri tip tc chun bng HCl chun 0,1N cho n khi dung dch chuyn sang cam. Ghi th tch HCl tiu tn (VMO) T th tch o c 3 mu, tnh nng hn hp dung dch Cu hi: 1. 2. Nu s khc bit gia hai phng php c p dng trong 2 th nghim trn. Th nghim no cho kt qu c sai s b hn? Gii thch 271

BI 3: CHUN ACID BAZ NH LNG MUI I. CHUN B Cc dung dch: NaOH 0,1N; HCl 0,1N; HNO 3 1:1; KNO3 0,03N; NH4NO3 0,5N; (NH4)6Mo7O24 0,05N. II. Ch th: MR, phenolphtalein, giy pH, giy lc. NH LNG HM LNG MUI AMONI: Mui amoni s phn ng vi mt lng kim d chnh xc, lng kim d c xc nh bng cht chun HCl, ch th s dng l MR ng vi s chuyn mu ti im tng ng t vng qua hng da cam. Dung dch mu l dung dch NH 4Cl CN (0,1N - 0,5N) c gio vin hng dn pha trc, SINH VIN khng c bit trc Dng pipet bu ht 5 mL NH4Cl 0,1 N + 25mL NaOH chun 0,1 N cho vo erlen (lm 3 mu). un trn bp in khong 5 -10 pht i vi mi mu, cho n khi cn cn 1/ 3 th tch ban u, th xem bay ht hi NH3 cha (bng giy qu tm t), sau ngui Thm 2 git MR. em chun bng dung dch chun HCl 0,1N cho n khi dung dch chuyn t vng chanh sang hng tm. Ghi th tch HCl tiu tn. T th tch o c 3 mu, tnh nng dung dch NH4Cl. 272

Cu hi 1. Vit cc phn ng xy ra v cng thc tnh cho mi trng hp xc nh CH 3COOH, NH3, NH4Cl?

2. III.

Tnh sai s ng vi tng ch th s dng khi xc

nh CH3COOH v NH3? NH LNG HM LNG PHOTPHAT

Dung dch mu l dung dch H 3PO4 CN (0,1N - 0,5N) c gio vin pha trc, sinh vin khng c bit trc. Ly 5 bnh erlen, c ghi s nhn tin theo di Bnh 1 v 5: Dng pipet bu ht 10 mL mu H3PO4 + 5 mL HNO3 1:1 + 5 mL NH4NO3 3%, un nng khong 60 700C, thm t t 20 mL (NH4)6Mo7O24 10%, khuy nh, lng 2 gi. Bnh 3 v 4: Dng pipet bu ht 10 mL mu H3PO4 + 5 mL HNO3 1:1 + 5 mL NH4NO3 3% + 20 mL (NH4)6Mo7O24 10%, lc nh, un nng khong 60 700C, lng 2 gi. Bnh 2: Dng pipet bu ht 10 mL mu H3PO4 + 5 mL HNO3 1:1 + 5 mL NH4NO3 3% + 20 mL (NH4)6Mo7O24 10%, lc nh, un nng khong 60 700C, lng qua m ( bi 4 cc sinh vin chun b dung dch ny ri). Lc kt ta bng giy lc bng xanh, v ht kt ta rt mn v rt d tri theo nc trng nn khng c dch lc qu 1/3 phu. Sau khi chuyn ht kt ta ln phu, mt t kt ta vn cn bm trn thnh erlen, dng NH4NO3 3% 273

trng erlen 3 ln (mi ln l 5 mL), sau dng KNO3 3% trng v chuyn kt ta ln phu, ( ch thc hin i vi cc bnh 1, 3, 4 cn cc bnh 2, 5 th dng NH 4NO3 3% trng hon ton thay cho KNO3 3%). Thc hin trng cc bnh cho n khi nc trng trung tnh (th bng giy pH),v ra ta cho n khi ta ht axit (th bng giy pH). Chuyn kt ta cng giy lc vo ng cc erlen s dng trc , cho thm nc ct vo erlen v lc mnh ta khng cn bm trn giy lc. K tip cho vo mi erlen 3 git Phenolphtalein Chun bng dung dch NaOH 0,1N nh ha tan ta cho n khi dung dch chuyn t mu vng chanh sang mu hng nht (nu lng kt ta nhiu th c th dng NaOH c nng cao hn), sau cho d thm khong 2 mL NaOH na, ghi tng th tch NaOH s dng. Lc u, em chun lng NaOH d bng dung dch HCl 0,1 N cho n khi dung dch mt mu hng nht. Ghi th tch HCl tiu tn. T th tch o c 3 mu, tnh nng PO43-. Cu hi 1. 2. 274 Gii thch vai tr ca cc ha cht s dng trong bi thc tp? Hy thit lp cng thc tnh nng PO43 ?

3.

nh gi vic nh lng H 3PO4 bng dung dch NaOH (bi 3) v (bi 5). Rt ra nhn xt g v 2 cch nh lng thc hnh?

BI TP 1. em chun 100mL dung dch HCl 0,025M bng V(mL) dung dch NaOH 0,1M: a) Tnh gi tr pH ca dung dch chun c khi V(mL) ln lt l: 0 - 10 - 20 - 24,9 - 25 - 25,1 26 - 30 (mL) V ng chun (pH - VmL dung dch NaOH) ng vi cc gi tr pH va tm c cu a. Xc nh bc nhy chun vi sai s 0,2%.

b)

c) 2.

Ht 10 mL dung dch mu NaOH C x cho vo erlen 250mL cng vi 30 mL nc ct +3 git pp (lm 4 mu). em chun bng dung dch HCl 0,1N cho n khi dung dch chuyn t mu hng tm sang khng mu. Ghi th tch axit HCl 0,1N tiu tn V 0 (mL). Vi tin cy 95%. tnh nng dung dch NaOH Mu s 1 2 9,75 3 9,7 4 9,6 V0 (mL) 9,8 Bit rng: ST N

10

275

12,7

4, 3

3,18

2,78

2,57

2,45

2,37

2,31

2,23

1,22

0, 94

0,77

0,64

0,56

0,51

0,47

0,44

0,41

Gi s cc dung dch u c khi lng ring d = 1 g/mL

276

BI 8. PHNG PHP CHUN OXY HO KH M bi: HPT 8

Gii thiu xc nh hm lng mt mu dung dch phn tch trong h oxy ho kh, ngoi phng php khi lng, cn c phng php th tch l phng php chun oxy ho kh Mc tiu thc hin Hc xong bi ny hc vin s c kh nng: 1. 2. M t c s phng php oxy ha kh. M t cc phng php oxy ha kh c bn (KMnO4 C s ca phng php chun acid - baz.

3. Chun oxy ha kh. Ni dung chnh 1. 2. 3. 4. C s phng php oxy ha kh. Phng trnh ng nh phn Cc phng php oxy ha kh c bn Cch chun oxy ha kh.

8. 1. C s v nguyn tc ca phng php oxy ho kh 8.1.1. Khi nim v phn ng Oxy ho kh. Phng php cn bng
8.1.1.1. nh ngha Qu trnh Oxy ho kh l qu trnh xy ra s tng tc gia cc cht c kh nng cho v nhn electron 277

Cc cht c kh nng cho electron gi l cht kh Cc cht c kh nng nhn cc electron gi l cht oxy ho Qu trnh ca cht kh khi cho electron gi l qu trnh oxy ho Qu trnh ca cht oxy ho nhn electron gi l qu trnh kh. S cho v nhn cc electron ca cc cht hon ton ph thuc vo kh nng to th cc cho cc qu trnh . 8.1.1.2. Phn ng oxy ho kh Phn ng oxy ho kh l phn ng xy ra c km theo s trao i electron. Mt phn ng oxy ho kh bao gi cng gm hai qu trinh cho v nhn electron. Qu trnh oxy ho kh l qu trnh gm hai na phn ng l phn ng kh v phn ng oxy ho. Chng hn: Qu trnh kh: Ox1 + n. e Qu trnh oxy ho: Kh2 - n. e Kh1 Ox2

Qu trnh oxy ho - kh: Ox1 + Kh2 Ox2 + Kh1 Trong thc t phn tch thng s dng cc phn ng oxy ho kh tch v nhn ra cc ion. Vic tnh ton cn bng oxy ho kh s gip la chn d dng cc iu kin thc nghim. Tuy vy, cn ch khng phi tt c cc qu trnh oxy ho kh u l nhng qa trnh 278

thun nghch, trong cc phn ng thun v nghch xy ra v cng nhanh t ti trng thi cn bng, m trong thc t khng t cc trng hp cc phn ng oxy ho kh theo tnh ton cn bng th c kh nng xy ra, nhng li khng xy ra trong thc t. Trong nhng trng hp nh vy, cn s dng cc yu t lm tng tc phn ng nh tng nhit , dng cht xc tc... Cc phn ng oxy ho kh dng trong phn tch thng l nhng phn ng xy ra trong dung dch v do phn ng ga cc cht in ly oxy ho kh cng l cc phn ng ion 8.1.1.3. Phng php cn bng phn ng oxy ho kh (Phng php ion - electron) Phng php ny da trn s cn bng khi lng v cn bng in tch gia cc cu t tham gia phn ng trng thi tn ti thc t trong dung dch, m khng tnh theo s oxy ho. Thc hin cc bc sau cn bng: 1. Xc nh cht kh v cht oxy ho 2. Vit cc qa trnh oxy ho v qu trnh kh: Cc cht vit dng ion trong dung dch (cht khng tan - cht kh, cht rn, gi nguyn dng phn t) Cn bng nguyn t 2 v: thiu n. H+ v no th thm n. H+ vo v , cn thiu n. OH- v tri trong phn ng c mi trng acid, th thm n. H2O vo v phi, nhng c mi trng baz th thm n. OH- vo v phi. 279

Cn bng in tch 2 v: cn thm [n. ( -)] th thm [+ n. e], cn thm [n.( +)] th bt [- n.e] Cn bng h s cho v nhn electron Cng v theo v c qu trnh oxy ho kh. 3. 4. in cc h s va tm c trong qa trnh oxy ho kh trn vo phng trnh phn ng ban u. Kim tra li phng trnh phn ng cn bng, dng s lng nguyn t oxy 2 v kim tra li vic cn bng phn ng.

V d: Cn bng phng trnh phn ng sau:

K2Cr2O7 + FeSO4 + H2SO4 Fe2(SO4)3 + Cr2(SO4)3 + H2O

Gii: 1. 2. (Cc s u hng sau l cc s biu th cc bc) Cht kh l Fe2+ v cht oxy ho l Cr2O72Qu trnh oxy ho: 2 Fe2+ -2 e Qu trnh kh: Cr2O72- + 14 H+ +6 e Qa trnh oxy ho kh: 3Fe 3. 4.
2+

2 Fe3+

(x3)

2 Cr3+ + 7 H2O (x1) 3Fe3+ + 2 Cr3+ + 7 H2O

+ Cr2O72- + 14 H+

K2Cr2O7+ 6FeSO4 +7H2SO4 3Fe2(SO4)3 + Cr2(SO4)3 + K2SO4+7H2O Kim tra thy lng oxy 2 v bng nhau, chng t cn bng ng.

280

8.1.1.4. iu kin ca phn ng oxy ho kh 1. Vn tc ca phn ng oxy ho kh ph thuc vo cc yu t sau: Nhit : khi tng nhit ln th phn ng oxy ho kh tng theo Nng : C nhng trng hp khi tng nhit lm cc cht trong phn ng bay hi, lm gim nng , do phi tng nng cc cht phn ng tc tng theo. Cht xc tc: cht xc tc thng c dng l gim nng lng hot ho ca h, gip cho 2. phn ng xy ra nhanh hn Phn ng lin hp: l phn ng xy ra song song trong cng mt dung dch cng mt iu kin, lm cho phn ng xy ra nhanh hn C ch phn ng: c hai dng thng gp C ch ca phn ng xy ra c nh cu electron V d phn ng gia Fe3+ vi Sn2+ trong dung dch mui din ra theo 2 giai on: Fe3+ + Sn2+ = Sn3+ + Fe2+ Fe3+ + Sn3+ = Fe2+ + Sn4+ S vn chuyn electron t Sn2+ n Fe3+ c thc hin nh ion Cl - trong dung dch mui, ion ny ng vai tr l cu truyn electron C ch phn ng xy ra nh cht xc tc l chnh cc ion kim loi khc. Cc ion kim loi ny s tng tc vi cc ion oxy ho thnh mt 281

3.

dng oxy ho, sau dng oxy ho ca ion kim loi ny tc dng tip vi ion cht kh, v tr v li trng thi ion ban u. V d: Phn ng gia Cr3+ trng c ion Ag+ theo s Ag+ + S2O8 2vi K2S2O8 trong mi Ag+

Ag +, ri Ag+ + Cr3+

C ch phn ng gia cc ion phi kim V d: Phn ng gia I2 v S2O3 2- : I2 + S2O3 2I-S2O3 2- + IS2O3 2- + I- S2O3 22 S2O3 2- + I8.1.2. Th in cc Chiu phn ng 8.1.2.1. Th in cc Kh nng oxy ha kh ca cc cht phn nh qua kh nng nhn hoc cho electron ca chng, c nh gi bng i lng th in cc. Theo quy c c chp nhn ti hi ngh quc t ln th 17 ti StockHomn nm 1953 (IUPAC) v ho ng dng v ho thun tu th th in cc c o bi sc in ng ca pin to bi in cc hydro tiu chun t bn tri v in cc cn xc nh t bn phi. Khi gi tr sc in ng ca mt pin s bng hiu gia th in cc phi vi th in cc tri: E = Ep - Et. 8.1.2.2. Chiu phn ng Trong phn ng oxy ha kh lun c hai qu trnh oxy ha v qu trnh kh, th tng ng c 2 th in cc cho 2 cp ca 2 qu trnh ny Chng hn, trong phn ng gia Zn vo dung dch HCl c 2 qu trnh oxy ha kh ng vi 2 th in cc l H2 - 2e 282 2 H+ c th in cc c quy c l

0 E2 H

/ H2

= 0 (volt) Zn c th in cc c quy c l

Zn2+ + 2e
E
0 Zn 2 / Zn

= - 0,76v

Du ca th in cc cng chnh l du ca sc in ng ca pin. Nu in cc phi dng hn so vi in cc hydro th sc in ng ca pin c du dng, v ngc li. Mt cch tng qut th in cc cng dng th dng oxy ha ca h in cc lin quan s cng mnh hn nhiu so vi ion H+ v dng kh tng ng cng yu hn nhiu so vi hydro trn platin, ngc li th in cc cng m th dng kh ca h in cc tng ng cng mnh v dng oxy ha tng ng cng yu. phn ng s xyra d dng hn vi cc cp oxy ha kh u mnh, ngha l phn ng xyra thun li gia dng oxy ha ca cp c th in cc cng dng vi dng kh ca cp c th in cc cng m. Chng hn, phn ng gia Fe2+ vi Sn4+ l khng
0 th xy ra v EFe
3

/ Fe2

0 = 0,77v v ESn

/ Sn 2

=0,15 v, c ngha

l dng oxy ho ca Fe3+ mnh hn Sn4+ v dng kh ca Sn2+ li mnh hn Fe2+, nn ch c th xy ra phn ng gia Fe3+ vi Sn2+ m thi (ch khng c phn ng xy ra gia Fe2+ vi Sn4+ ) xc nh chiu phn ng v mt nh lng, cn phi tnh ton da vo nng lng GIBBS: G = - n. F. E Trong : n l s electron trao i trong phn ng oxy ho kh 283

F l hng s Faraday: F = 965000 Coulomb E l th in cc ca phn ng Nu E > 0 thun d dng Nu E = 0 bng ng Nu E < 0 G > 0: phn ng khng xy ra hay xy ra theo chiu nghch Nh vy phn ng oxy ho kh ch xy ra khi c E < 0 Phng trnh Nernst Trong trng hp tng qut: aOx + m H+ + n.e b Kh + p H2O ( 25 0C) Phng trnh Nerst c dng: E = E0 +
R.T (Ox) n ( H ) m . ln n.F ( Kh) b

G < 0: phn ng xy ra theo chiu G = 0: phn ng t trng thi cn

Nu (Ox1) = (Kh1) th E = E0 Thay cc gi tr ca R, T, F, th 25 0C: E = E0 +

0,059 (Ox) n ( H ) m . lg n ( Kh) b 0,059 [Ox]n [ H ]m . lg n [ Kh]b

Trong trng hp chp nhn f(Ox) / f(Kh) = 1, th: E = E0 +

(t y chp nhn vic xt cc h phn ng oxy ho kh u 250C) V d: Vit phng trnh Nerst cho h: ox1 + n.e Kh1 Phng trnh Nerst cho:

284

E = E0 +

(ox1) 0,059 . lg ( Kh1) n

(3.1)

Biu din qua nng : E = E0 +

[ox1] 0,059 f (ox1) 0,059 . lg + .lg [ Kh1] f ( Kh1) n n

(3.2)

Phng trnh (3.2) cho thy th in cc khng nhng ph thuc vo nng cc cht m cn ph thuc vo lc ion ca dung dch Trong trng hp chp nhn f(ox1) / f(Kh1) = 1, th: E = E0 +
[ox1] 0,059 . lg [ Kh1] n

V d: Vit phng trnh Nernst cho phn ng: PbO2+4H++2e Pb2++2H2O Ta c phng trnh Nernst l:
0 E = E PbO
2

/ Pb2

0,059 (H ) 4 . lg 2 ( Pb2 )

Trong trng hp chp nhn f(Ox) / f(Kh) = 1, th:

0 E = E PbO
2

/ Pb2

0,059 [ H ]4 . lg n [ Pb 2 ]

8.1.3. Cc yu t nh hng n chiu phn ng Phn ng oxy ho kh xy ra c s tc ng ca rt nhiu yu t. Mt s yu t quan trng c xem xt sau: 8.1.3.1. nh hng ca pH Cc phn ng oxy ho kh xy ra do s trao i cc electron gia cc cht, nn chng phi c di chuyn trong nhng khng gian nht nh, phi l dung mi hay ni rng hn l trong nhng mi trng thch hp. V 285

vy a s cc phn ng oxy ho kh u c tin hnh trong nhng mi trng hoc acid hoc baz hoc trung tnh. Do [H+] s nh hng rt ln n chiu ca phn ng. V d: Vit phng trnh Nernst cho Cr2O72-+14H+ + 6e
0 th E = ECr2O7 2 / Cr 3

2Cr3+ + 7H2O
2

(Cr2 O7 ) 0,059 0,059 + . lg + lg (H+ )14 3 2 6 6 (Cr )

8.1.3.2. nh hng ca cht t tan Trong mt s trng hp s to thnh cc hp cht t tan gia mt trong cc dng oxy ha - kh s lm gim nng ca n xung v do lm thay i th in cc ca h, dn n lm thay i chiu phn ng V d: Xt chiu phn ng gia Ag vi dung dch HNO3 Trng hp: trong dung dch khng c ion Cl - th kh nng phn ng oxy ho kh gia kim loi Ag vi HNO 3 l han ton c th thc hin c theo chiu: Ag + 2 HNO3 AgNO3 + NO2 + H2O Trng hp: Trong dung dch c ion Cl -, th s xut hin kt ta AgCl v tng ng trong h c na phn ng oxy ho kh mi: AgCl +e Ag+ + Cl0 E AgCl / Ag

0 E AgCl / Ag s c tnh theo t hp sau:

AgCl

Ag+ + Cl-

T(AgCl) = 1,78.10-10 K1 = 10 E
0 1

Ag+ + e = Ag Th na phn ng c: 286

/ 0 , 059

K2 = T. K1 = 10 E

0 2

/ 0 , 059

0 E 2 = E10 + 0,059 lgT

0 E AgCl / Ag = 0,799 + 0,05915.(-9,75) = 0,222v 0 0 Nh th: E AgCl / Ag =0,222 < E Ag

/ Ag

= 0,799v

Vy s to thnh kt ta AgCl lm gim hn tnh oxy ha ca ion Ag+, hay ni cch khc s c mt ion Cl to ra kt ta AgCl lm phn ng oxy ho kh gia Ag vi HNO3 b chm hn li. 8.1.3.3. nh hng ca cht to phc Trong nhiu trng hp phn ng oxy ho kh xy ra trong dung dch c cha cc cht to phc vi cc dng oxy ha v kh. S to phc l yu t quan trng lm thay i th in cc v do lm thay i chiu phn ng. Thng thng dng oxy ha c kh nng to phc mnh hn dng kh, do s to phc s lm gim nng ca dng oxy ha nhiu hn nng ca dng kh v th in cc khi c cht to phc thng gim xung. V d: Xt chiu phn ng gia Fe3+ vi Sn2+ trong mi trng c d EDTA Khi c d EDTA th Fe3+ v Fe2+ tn ti di dng phc bn FeY- (c hng s bn hng s bn FeYFe3+ + e Fe2+ + Y 42 1

= 10
-1 1

25,1

) v FeY 2- (c

= 10 14,3 ). Fe3+ + Y 4Fe2+ FeY 2K1 = 10 E

2
0 1

/ 0 , 059

Phng trnh na phn ng oxy ho kh (to phc) 287

FeY- + e

FeY 22 1

K2 =

K1
1

= 10 E

0 2

/ 0 , 059

Nn: E 20 = E10 + 0,059 lg

0 EFeY 0 = EFe

/ FeY 2

/ Fe2

+ 0,059 lg

2 1

= 0,133v

Phng trnh ny cho thy th in cc tng ng vi na phn ng khng ph thuc nng cc dng m ch ph thuc t s logarit hng s bn ca cc phc FeY v FeY 2-. Mt khc, gi tr E0 tnh c thp hn rt nhiu so vi gi tr th in cc tiu chun ca cp Fe3+ / Fe2+ . Nh vy s to phc vi EDTA lm tng tnh kh ca Fe2+ , v do lm gim kh nng phn ng ca Fe3+ xung rt nhiu, nn phn ng gia Fe3+ vi Sn2+ c th khng xy ra. 8.1.3.4. nh hng ca lc ion Khi lc ion thay i th h s hat ca cc dng oxy ha v kh cng thay i theo. Bi v in tch ca cc dng oxy ha - kh bao gi cng khc nhau nn s thay i h s hat ca chng theo lc ion cng khc nhau. i vi na phn ng: AZ+ + n e in cc c dng:
[ AZ ] R.T R.T f ( AZ ) E=E + . ln ( Z n ) + . ln [A ] n.F n.F f ( A( Z n ) )
0

A(Z-n)+, th th

(3.5)

Ngi ta chng minh c rng: lg

f ( AZ ) = f ( A( Z n ) ) 1

[n(n - 2Z)]

(3.6)

288

V n ch c th c gi tr ln nht l Z nn n < 2Z v s hng th 3 trong (3.5) phi m, ngha l th in cc khi k n lc ion th gim xung so vi khi b qua nh hng lc ion v lc ion cng gim. i vi na phn ng: AXZ- + n e AX(Z-n)(l trng hp dng oxy ha l anion, chng hn FeY-, [Fe(CN)6 ]3-... th in tch l z- v dng kh l (z + n)- ), th th in cc vit li l: E = E0 +
R.T R.T [ AX Z ] . ln + . ln ( Z n) n.F [ AX ] n.F

cng tng th th in cc

f ( AX Z ) f ( AX ( Z n) )

(3.5a)

V chng minh c rng: lg

f ( AX Z ) = f ( AX ( Z n) ) 1

[n(n + 2Z)]

(3.6a)

V d: Tnh th oxy ha kh ca cp Fe3+/ Fe2+ trong dung dch HCl 0,1N Phng trnh: Fe3+ + e Fe2+ Th th in cc l:
0 E = EFe3 / Fe2

E0 = 0,77v

[ Fe3 ] f ( Fe3 ) +0,059. lg +0,059. lg [ Fe 2 ] f ( Fe2 ) f ( Fe3 ) = 0,036 f ( Fe2 )

Vi z = 3; n = 1: lg

Vy E = 0,77 - 0,036 = 0,764v 8.1.4. Mi lin h gia hng s cn bng n th in cc Xut pht t biu thc bin thin nng lng t do 289

tiu chun i vi phn ng xyra trong pin thun nghch: G0 = - n. F. E0, v biu thc lin h gia bin thin G0 = - RT lnK Ta c: lg K = lg K =
1 nF 0 . E0 (vi E0 = E P - ET0 ) 2,3 RT

nng lng t do tiu chun v hng s cn bng:

0 0 n ( E P ET ) 0,059

K = 10 n ( E

0 P

0 ET ) / 0 , 059

Tng qut vi na phn ng: Ox1 + n e Kh1 c hng s cn bng l K1 = 10 nE

0 1

/ 0 , 059

Kh2 - n e
0 n. E2

Ox2 c hng s cn bng l

/ 0 , 059 K2 = 10 V d: Tnh hng s cn bng ca phn ng oxy ho

0 kh Fe2+ bng Cr2O72-, bit rng: ECr O

2

/ 2Cr 3

= E10 = 1,36v

0 v EFe

/ Fe2

= E 20 = 0,77v 2Cr3+ + 7H2O (K21-)6 = ( 10 K1 = 10 6 E

0 E2 / 0 , 059 0 1

Cc na phn ng: Cr2O72-+14H+ + 6e Fe3+ + e Fe2+

/ 0 , 059

)6

Cr2O72-+14H+ + 6Fe3+ K = K1. K2-6

2Cr3+ + 6 Fe3+ + 7H2O

Vy K = 106(1,36 0,77) / 0,059 = 10-10 . 8.2. Phng trnh ng nh phn 8.2.1. Thit lp phng trnh ng nh phn Cht ch th c dng trong phng php ny tu thuc vo cc phng php chun c bn m nh phn tch chn. Chng hn, 290

phng php pemanganat th dng cht ch th l lng d KMnO4, phng php Iod li dng ch th l h tinh bt. th biu din s thay i th oxy ho kh E ca dung dch da theo mc thm tng th tch dung dch chun. Thit lp phng trnh ng nh phn oxy ho kh: Gi s c qu trnh oxy ho kh xy ra khi chun cht kh (Kh1) bng cht oxy ho (Ox2) nh sau: Qu trnh oxy ha: Kh1 me Qu trnh kh
E2
0 E2

Ox1

E1

E10

Ox 1 0,059 lg m Kh1

(1)

: Ox2 + ne
Ox 2 0,059 lg (2) n Kh2

Kh2

Qu trnh oxy ha kh: n Kh1 + m Ox2 n Ox1 + m Kh2 Khi tin hnh chun :

Ti im tng ng: s ng lng ca cc cht trong phn ng l Ox2p = Kh1p. M:

291

Ox2 Kh1 n

Ox2 m Kh1

pu

1 VC m V V0 1 V0C0 n V V0

(3), (4)

pu

Do : (tr (3) vi (4) c )

Ta c phng trnh ng nh phn l:

n Ox 2 m Kh1 V V0 n C0V0 F 1

vi: (5) Trc xa im tng ng: [Ox2] qu b nn

M (1):

Thay vo (6):

292

Do :

Ti im tng ng:
Ox2 Kh1 = n m

v:

Ox1 Kh2 = m n

Nn:

Mt khc:

293

T suy ra: Et =
0 m.E10 n.E 2 m n

Sau xa im tng ng: [Kh1] qu b, nn: (5) tng ng: (7) M: [Kh1] + [Ox1] =
V0 C 0 (theo 1) V0 V

V lng cht sau phn ng th: Thay vo (7):

Ox1 Kh2 = m n

[Ox 2] =F-1; [ Kh 2]

ng vi tng gi tr th tch ca cht Oxy ho em chun vo dung dch Kh, suy ra gi tr F, tnh c th E tng ng. T v nn th ph thuc ca E - F 294

8.2.2. Sai s trong php chun Oxy ho kh tnh c sai s trong phng php chun oxy ho kh, phi tin hnh theo cc th t ca cc bc sau: Thay gi tr th in cc chun vo gi tr Etd ( th ti im tng ng) Tin hnh o th ti im kho st: Edo (th cc o c ti im xt) So snh hai gi tr ny xc nh thi im ang kho st l trc hay sau im tng ng. T mi chn c cng thc tnh E thch hp Tnh sai s: Ly cng thc c chn thay F -1 = S, chuyn ho v c S l sai s chun cn tm. V d: V ng chun hp cht Fe2+ bng dung dch amoni trisunfatoxerat IV ( NH4 )2 [Cr(SO4)3] Sau mi ln cho mt lng dung dch chun (NH4) 2 [Cr(SO4)3] vo dung dch Fe2+o, o E, v v c th:

295

Hnh 8.1. ng cong chun oxy ho kh Fe2+ im tng ng c E=

0 E Fe3 / Fe 2 0 ECr 6 / Cr 3

0,771 1,45 = 1,110V 2

Bc nhy nm trong khong pH = 9,8

12,2

Vng E ban u, dung dch c mu sm, khi qua vng tng ng v im cui dung dch chuyn sang mu xanh l, l do dng cht ch th pheroin V d: Tm sai s php chun oxy ho kh dung dch Ti2+ 0,1N bng dung dch Fe3+ 0,5N ti th o c l Edo = - 0,334V, bit E0 (Fe3+ /Fe2+ ) = 0,77V v E0 (Ti3+ /Ti2+ ) = - 0,37V Gii Ta c: Etd =
0,77 0,37 = 0,2 2

E o < Etd

im

tin hnh chun c o trc im tng ng, do sai s c tnh theo cng thc:

296

- 0,334 = - 0,37 + S = 0,325

0,0059 S 1 lg 1 S

Vy sai s ti thi im c xt l S =32,5% (Sai s ti im xt qu ln !) 8.2.3. Cc yu t cnh hng n ng cong chun Cng nh cc chng trc y, ng cong chun ph thuc nhiu vo mt s cc yu t nh, hiu ng nng cht phn ng v han tan ca phn ng v.v... Phn ny cp n mt s nh hng ca 3 yu t tc ng n ng chun oxy ha kh 8.2.3.1. Nng cht phn ng Trong phn c s l thuyt, xc nh E ca h chun oxy ha kh thng thng khng ph thuc vo s pha lang. V vy ng chun ca nhng phn ng oxy ha kh thng khng ph thuc vo nng cht cn phn tch v cht phn ng. iu ny hon ton tri ngc vi nhng iu xy ra vi cc ng chun 297

 khc 8.2.3.2. han ton ca phn ng Phn ng ca mt php chun oxy ha kh ch xy ra c han ton khi s bin i ca h vng im tng ng cng ln. Hiu ng v th in cc nh nu trong hnh sau, cho mt cht gi nh c th in cc chun l 0,2V bng mt s cht oxy ha gi nh c th in cc chun t 0,4 (1,2V v hng s cn bng tng ng nm trong khang 2.10 3 8. 1016 . R rng l s bin i th ln nht ca h gn lin vi phn ng xy ra han ton nht. V phng din , ng chun oxy ha kh tng t ng chun khc.

Hnh 8.2. Hiu ng th in cc ca cht chun nh hng ln han ton ca phn ng (1) Kcb = 8. 10 -16 (3) Kcb = 1. 10 -10 (5) Kcb = 2. 10 -3 (2) Kcb = 3. 10 -13 (4) Kcb = 6. 10 -6

8.2.3.3. Tc phn ng v th in cc Th in cc ca cc cp ng vai tr cht oxy ha 298

v cht kh s cho bit phn ng xy ra c han ton hay khng, c th s dng v c bit l cho mc ch phn tch, nhng th in cc khng cho mt thng tin no v tc t ti trng thi cn bng. Kt qa l, mt phn ng xt v mt in cc c th xy ra hon ton thun li nhng kt cuc li khng dc chp nhn theo quan im ng hc. Phn ng oxy ho kh Asen (III) bng Ce (IV) trong dung dch acid H2SO4 long l mt v d in hnh: H3AsO3 + 2 Ce 4+ + H2O H3AsO4 + 2 Ce3+ + 2 H+ Trong : Ce 4+ + e E0 = + 1,3V +2e
0

Ce3+ . H3AsO4 + H2O

H3AsO4 + H+

E = + 0,56V V c th suy ra hng s cn bng khang 10 28 . Nh vy theo quan im l thuyt th phn ng ny xy ra rt d dng nhng thc t khng th thc hin c, v khi chun As(III) bng Ce (IV), nu khng dng cht xc tc, th sau vi gi mi t ti cn bng 8.3. Cc phng php chun oxy ho kh c bn 8.3.1. Phng php pemangnat ( KMnO4) L phng php dng dung dch KMnO 4 d lm cht ch th nh git, lm dung dch chuyn t khng mu sang mu tm 1. Nguyn tc Tu vo mi trng m ion MnO 4- s chuyn ho thnh ion tng thch. Nhn chung trong dung dch nc, vi mi trng acid MnO 4- s thnh Mn2+ ; vi mi 299

trng trung tnh MnO4- s thnh MnO2 ; v vi mi trng baz MnO4- s thnh MnO42-. Chun trong mi trng acid MnO4- + 8 H+ + 5 e Mn2+ + 4 H2O Phn ng phi c tin hnh nhit v nng [H+] xc nh i vi cht oxy ha nhanh nh H 2C2O4 th c th dng phng php trc tip nhng vi cht oxy ha chm th dng phng php chun ngc dng bng lng d KMnO4, sau dng cht chun chun li lng KMnO4 d. Chun trong mi trng baz MnO4- + e Th: EMnO
/ MnO4 2 0 = EMnO

MnO4 2/ MnO4 2

0 EMnO

/ MnO4 2

+ 0,059. lg

[ MnO4 ] [ MnO4 ]
2

Khi thm Ba(NO3)2 s to c kt ta mu en xanh MnO4 2- + 2e + H2O Th: EMnO

2

MnO2
0 MnO4 2 / MnO2

+ 4 OH -

0 EMnO 2
4

/ MnO2

/ MnO2

= E

[ MnO4 ] 0,059 + . lg 2 [ MnO2 ].[OH ]4

2. K thut phn tch Pha ch dung dch chun KMnO4 Pha ch 1 L dung dch chun KMnO 4 0,05N trong mi trng acid Cn khang 1,6g KMnO 4, pha thnh 1 L vi nc ct trong bnh nu y kn, trong ch ti sau 24 h mang ra chun xc nh chnh xc nng 300

Ht 10mL H2C2O4 0,05N vo bnh nn + 5mL H2SO4 2N, un nng 80-90oC trong 3 pht, lc u. Lm 3 mu trong 3 bnh nn 250mL trong bnh nn 250mL. Chun bng dung dch KMnO 4 n khi dung dch c mu hng nht

T th tch o c 3 mu, tnh nng dung dch KMnO4 Tnh ton: T th tch o 3 ln ly gi tr trung bnh l V Nng dung dch KMnO4 l: CN =
10.0,05 V

Pha ch 1 L dung dch chun KMnO4 0,05M trong mi trng baz Ta dng cch tnh: ng lng KMnO4 trong acid l ng lng KMnO4 trong baz l Nn
DA M M 3 = : = = 0,6 5 3 5 DB
M 5

M 3

C ngha l 1 mL dung dch KMnO4 CM trong mi trng acid tng ng vi 0,6mL dung dch KMnO4 CM trong mi trng baz. 8.3.2. Phng php Iod (I2) 1. Nguyn tc Dng iod ha nhng cht kh nh S 2O32- , S2- , CN, SCN- ... v th oxy ha kh ca iod E I0
2

/ 2I

= + 0,5345V 301

ln hn th ca cc ion ny. Dung dch Iod trong KI c lm dung dch chun 2. Phn loi: c 4 phng php Phng php chun trc tip: dng chun cc cht d b oxy ha, tc nhng ion c th n cc nh hn th ca ion iod Phng php chun d: dng chun cc cht kh b oxy ha c th in cc gn vi th ca Iod, bng cch dng mt lng d dung dch chun Iod, sau nh lng li lng Iod cn tha bng dung dch chun Na 2S2O3 Phng php chun gin tip: dng chun cc cht c th in cc ln hn th ca Iod, E > 0,5345(V), tc kh b oxy ha, bng cch dng KI hoc NaI to phn ng, sau chun lng Iod sinh ra bng dung dch chun Na2S2O3 (lng KI hoc NaI dng phi tha nhng khng cn chnh xc) Phng php th: l phng php dng cht oxy ha thch hp oxy ha Iod n dng IO3-, sau ui ht cc cht oxy ha d v chun

li bng dung dch Na2S2O3 3. K thut phn tch Pha 250mL dung dch chun I2 0,1M Nguyn tc: Pha Iod c nng ln hn 0,1M trong dung dch KI, ri sau dng dung dch Na2S2O3 chun li. K thut pha: Cn 2.5 gam KI + 1.5 gam I2 + 10mL nc ct, 302

lc v trn u cho it tan, nu it cha tan ht th thm mt t KI, sau chuyn vo bnh nh mc 250mL, dng nc ct nh mc ti vch, chuyn vo bnh cha mu nu c nt nhm s dng. Dng pipet ly chnh xc 5mL Na2S2O3 0,05N + 5mL m actat + 5 git h tinh bt 1%, lc u, lm thnh 3 mu trong 3 bnh nn 250mL. Chun dung dch thu c bng dung dch I 2 mi pha n khi xut hin mu vng nu (c nh xanh bn) T th tch chun I 2 o c 3 mu, tnh nng dung dch I2 T th tch chun I 2 o cho 3 mu tnh ra lng V tb = V Nng dung dch I2 l:
5.0,05 (N) V

Tnh ton: -

Nng tnh c ln hn nng cn pha (

5.0,05 > 0,1), th lng nc cn thm vo V

250mL dung dch I2 bnh nh mc s l: 50(2V - 5) mL 8.3.3. Chun hn hp Vi hn hp c hai cht oxy ha hay hai cht kh, th dng cong chun s c hai im un, nu th chun ca hai cht cn phn tch khc nhau ln. Nu s khc bit ln hn 0,2V th hai im un thng 303

c phn bit r rng xc nh ring tng hp phn. Tnh hung han ton ging php chun hai acid c hng s phn ly khc nhau ln hoc php chun hai ion to kt ta c tan khc nhau ln Ngoi ra mt s t h oxy ha kh c tnh cht tng t nh h a acid, VO 2+ + 2 H+ + e V(OH)4+ + 2 H+ + e V 3+ + H2O VO 2+ + 3 H2O E0 = + 0,369V E0 = + 1,00V

ng chun V3+ bng cht oxy hamnh, nh KMnO4, c hai im un, im un tng ng vi s oxy ha V3+ n VO2+ v im un tng ng vi s oxy ha t VO2+ n V(OH)4+ Phn tch chi tit ngun gc ca ng chun cho tng cht ring bit trong hn hp ca nhng cht phn ng loi ny khng c g kh khn nu s khc bit v th chun ln. V d php chun dung dch cha ion Fe2+ v Ti3+ bng KMnO4: TiO
2+

+ 2 H+

+e

Ti 3+ + H2O

E0 = + 0,099V

Fe 3+ + e Fe 2+ E0 = + 0,77V Nhng phn ng thm KMnO4 u tin c dng cho ion Ti3+ v d dng b oxy ha hn. Cho n khi nng ca cht ny cn ln trong dung dch, th ca h khng th cao hn lm bin i nng ion Fe 2+. Nh vy l, c th thu c nhng im to nn phn th nht ca ng chun bng cch thay th nhng nng hp thc ca ion Ti 3+ v Ti4+ vo phng trnh:
[TiO 2 ].[H ] 2 E = + 0,099 + 0,059 lg [Ti 3 ]

on u ca ng chun Ti 3+ bng KMnO4 l 304

ng nht. Sau im tng ng th nht, nng c hai ion Fe2+ v Fe3+ u ln nn c th c cc im trn ng chun mt cch thun li nht theo h thc: E = E0 + 0,059 lg
[ Fe3 ] [ Fe 2 ]

Khp c vng ti im tng ng v c vng sau im tng ng th hai, ng chun thc cht l ng nht vi ng chun ion Fe 2+ ring bit. Nhng php tnh nh vy khng tnh c th im tng ng th nht. C mt cch thun tin tnh gi tr l cng cc phng trnh Nernst biu din th ca Fe 2+ v Ti3+. V th in cc ca hai h bng nhau im cn bng nn ta c th vit: E = + 0,099 + 0,77 + 0,059 lg
[TiO 2 ].[H ] 2 .[Fe3 ] [Ti 3 ].[Fe2 ]

Cc ion Fe3+ v Ti3+ tn ti lng nh v bng nhau do kt qu ca cn bng: 2H+ Nn + TiO4 2+ + Fe2+ Fe 3+ + Ti 3+ + H2O
0,87 0,059 [TiO 2 ].[H ] 2 + lg 2 2 [ Fe2 ]

[Fe 3+ ] = [Ti 3+ ]

E=

Cui cng nu TiO22+ v Fe2+ c gi s c nng ng nht th c th tnh c th tng ng.

305

Hnh 8.3. ng chun hn hp Fe 2+ v Ti3+ 8.3.4. Cht ch th oxy ha kh C hai loi cht ch th c dng pht hin im cui ca nhng php chun oxy ha kh: nhng cht ch th thng thng v nhng ch th oxy ha kh c bit 8.3.4.1. Nhng ch th thng thng y l nhng cht chuyn mu khi b oxy ha kh. Khc vi cc cht ch th c bit c mu bin i ph thuc nhiu vo bn cht ha hc ca cht phn tch v cht chun, s chuyn mu ca cc cht ch th tht s oxy ha kh ph thuc vo s bin i th in cc ca h xut hin do s tin trin ca php chun C th vit na phn ng tng ng vi s chuyn mu ca mt cht ch th oxy ha kh thng thng nh sau: In(ox) + n e In(Kh), th: E = E0 +
[ In Ox ] 0,059 lg [ In Kh ] 2

Mt ngi ch tht s quan st c s bin i mu khi

[ In Ox ] [ In Kh ]

10 chuyn thnh

[ In Ox ] [ In Kh ]

1 . 10

306

C th tm thy s bin i th cn thit to nn s chuyn mu han tan ca cht ch th thng thng in hnh bng cch thay th hai gi tr trn vo phng trnh: E = E0
0,059 n

Nh vy mt cht ch th thng thng ch c th biu l kh nng pht hin s chuyn th ca mnh khi cht chun gy nn s chuyn dch th ca h t E 0 +
0,059 n

n E0 -

0,059 hoc khong (0,118/n)V. Vi n

nhiu cht ch th n = 2 v s chuyn dch 0,059V l . Bng 8.1. Cc cht ch th oxy ha kh Mu Cht ch th Dng oxy ha
Xanh nht Xanh tm Xanh nht

Th Dng kh chuy n dch

+1,25

iu kin
H2SO4 1M H2SO4 7 - 10M H2SO4 1M

Fe(II)-5-nitro-1,10phenantrolin Acid diphenylamindicacb oxilic Fe(II)-1,10phenantrolin

tm Khng mu

+ 1,12

+ 1,11

Fe(III)-5metyl,1,10phenantrolin Eriglancin

Xanh nht Xanh

Vng lc

+ 1,02

H2SO4 1M H2SO4 0,5M 307

+ 0,98

Acid Diphenyl aminsunfonic Diphenylamin p-Etoxicrisidin Metyl xanh Indigo tetrasunfonat Phenosafranin

tm Tm vng Vng Xanh Xanh

Khng mu Khng mu Khng mu Khng mu Khng mu

+ 0,85 + 0,76 + 0,76 + 0,53 + 0,36 + 0,28

Acid lang Acid lang Acid lang Acid lang Acid lang Acid lang

8.3.4.2. Dung dch H tinh bt Mt ch th c bit c bit n nhiu nht l h tinh bt. Ch th ny to phc xanh thm vi Iodua. Phc ny cho tn hiu v im cui ca php chun nh phn ng lm xut hin hoc bin mt Iod. H tinh bt to thnh mt phc mu xanh da tri vi Iodua, nn c s dng rng ri lm cht ch th c bit trong cc phn ng oxy ha kh sinh ra Iod do mt cht oxy ha hoc sinh ra Iodua do mt cht kh. V vy, mt dung dch h tinh bt cha mt lng nh ion triIodua hoc Iodua cng c th lm chc nng ca mt cht ch th oxy ha kh thc s. Khi d cht oxy ha, t s nng Iod trn Iodua cao lm cho dung dch c mu xanh. Khi d cht kh, nng ion Iodua chim u th nn mu xanh bin mt. Nh vy, h ch th bin i t khng mu 308

n xanh trong php chun nhiu cht kh bng cc cht oxy ha. S chuyn mu ny han ton c lp vi thnh phn ha hc ca cc cht phn ng ch ph thuc vo th ca h ti im tng ng. Mt ch th c bit khc cng c dng l KSCN. C th s dng cht ch th ny chun Fe3+ bng Ti2(SO4)3 . im cui ca php chun c pht hin l s bin mt phc mu ca st(II) tioxianat do nng Fe3+ b gim ti im tng ng 8.4. Cch chun oxy ho kh 8.4.1. nh lng Fe3+ Nguyn tc: gm ba bc nh sau Bc 1: SnCl2
2FeCl 3 mau vang trong HCl do tao phc FeCl 4 SnCl 2 2FeCl 2 gan nh khong mau SnCl 4

Tin hnh kh trc Fe 3+

Fe2+ bng

iu kin: un nng ti 60o d rt t SnCl2:

70oC, ch c php

Bc 2: Loi b lng d SnCl2 bng dung dch HgCl2

SnCl 2

2HgCl 2

Hg 2 Cl 2 mau trang dai lua

SnCl 4

iu kin: Pha long dung dch ngui, cho ngay 309

ton b dung dch HgCl 2 lc mnh. Nh vy s trnh c phn ng to kt ta en.

SnCl 2 HgCl 2 Hg 0 SnCl 4

mu en xut hin khi cho SnCl2 qu d Bc 3: Chun bng dung dch KMnO4 n khi xut hin mu hng nht bn vng. Phn ng chun : 5Fe2+ + MnO4 + 8H = Mn2+ + 3Fe3+ + 4H2O iu kin: C mt hn hp bo v Zymmerman. K thut phn tch Ht 10mL mu + 5mL H2SO4 6N,lc u v un si dung dch 60-70oC Nh tng git SnCl2 10% cho n khi dung dch mt mu vng Khi dung dch chuyn mu th nh thm 2 git na v lm ngui dung dch bng cch pha long dung dch bng nc ct n tng th tch 100mL. Cho 5mL HgCl2 5% vo, dung dch c kt ta vn la trng (nu c kt ta trng bng,hoc xm en phi lm li t u). Thm 10mL hn hp Zymmerman. Chun bng dung dch KMnO4 0,05N ti dung dch c mu hng nht bn. Ghi th tch KMnO 4 chun, t tnh hm lng (mg/ L) Fe3+ c trong dung dch.
+

310

Gii thch Khi xc nh Fe3+, giai on cho SnCl2 vo, nu thy kt ta xm en th phi ht mu khc lm li t u v: SnCl2 + HgCl2 = Hgo Kt ta xm en l Hg
o en

+ SnCl4

do s kh tip Calomen

thnh thu ngn kim loi (mu en xut hin khi cho SnCl2 qu d ). Hg dng phn tn phn ng mnh vi KMnO 4 gy sai s, nh hng n th tch pemanganat chun . Cho d 2 git SnCl2 khi dung dch mt mu vng phn ng vi lng HgCl 2 cho vo to kt ta vn la trng
SnCl2 + 2HgCl2 = SnCl4 + Hg2Cl2
3+

(kt ta vn la trng)

Mu vng l mu ca Fe , dung dch mt mu vng chng t Fe3+ c kh hon ton thnh Fe 2+. Vai tr ca hn hp bo v Zymmerman: V ion clorua cn tr s xc nh Fe2+ do s oxi ho ca ion Cl bng pemanganat khi c mt ion Fe2+, khi mt th tch KMnO4 b tiu tn oxi ho ion Cl - to thnh Clo t do s lm sai lch kt qu chun . Do , khi trong dung dch nh phn c mt ion Cl - ngi ta thng thm vo hn hp thuc th bo v Zymmerman.Thnh phn thuc th bao gm c MnSO4, H2SO4 v H3PO4. ngha ca hn hp bo v: Khi c mt ion Mn2+ s oxi ho ph ca cc ion Cl - khng xy ra v ion Mn2+ b oxi ho nhanh hn ion Cl - to thnh ion Mn3+ l cht oxi ho mnh, cht ny c kh nng oxi ho nhanh ion Fe2+. 311

Tnh ton S ng lng ca Fe 3+ = S ng lng ca KMnO4 = (mL).0,05.10 - 3 khi lng Fe3+ = 0,05V 10 - 3.
M ( Fe 3 ) 2

= 1,4. 10 - 3 V (g) = 1,4V (mg) Nn Hm lng (mg/ L) Fe3+ = 1,4V.

1000 = 140.V (mg/ L) 10

8.4.2. nh lng Vitamin C theo phng php Iod Nguyn tc Vitamin C l mt cht kh, trong mi trng axit mnh phn ng vi it vi ch th h tinh bt, im tng ng nhn c khi dung dch va c mu xanh bn trong 30 giy. Vitamin c cng thc phn t l C6H8O6, trong phn ng trao i 2 in t. Phng trnh phn ng xy ra: C6H6O6 + 2H+ + 2IC6H8O6 + I2

Khi chun I2 vt qua im tng ng ca phn ng, th mt lng d rt nh ca I 2 s lm h tinh bt c trong dung dch s chuyn sang mu xanh, kt thc qu trnh chun K thut phn tch Ht 10mL mu + 10mL nc ct +5mL H2SO 4 6N + 5git h tinh bt 1%, lm thnh 3 mu th nghim Chun bng dung dch I2 0,05N n khi dung dch c mu xanh T th tch o c 3 mu, tnh hm lng

312

(g/ L) dung dch Vitamin C Tnh ton T th tch I2 o c khi chun 3 mu, tnh V tbnh l V(mL). S ng lng ca VitaminC = S ng lng ca I2 = 0,05. V. 10 - 3 Khi lng ca Vitamin C c trong 10 mL l: 0,05.V.10 - 3.
M (C 6 H 8 O6 ) =4,4. 10 - 3.V(g) 2

Nn hm lng Vitamin C: 4,4V.

1000 . 10 - 3 = 0,44. 10

V (mL) (g/L) 8.4.3. nh lng Pb2+ theo phng php Cromat Nguyn tc Mu mui ch c chuyn thnh dung dch, kt ta ch bng dung dch bicromat trong mi trng axit acetic c dung dch m acetat n nh pH = 5 6. Lc kt ta ch cromat, ra sch kt ta ht ion cromat, ha tan kt ta trn giy lc bng HCl nng sinh ra mt lng bicromat tng ng, c chun bng dung dch chun Fe2+ trong mi trng axit vi ch th feroin, im tng ng nhn c khi dung dch c mu nu. Cc phng trnh phn ng xy ra Pb2+ + Cr2O72- PbCr2O7
2+ vng

PbCr2O7 Pb + Cr2O72- (xt. HCl) Cr2O72- + 6Fe2+ + 14H+ = 2Cr3+ + 6Fe3+ + 7H2O Vai tr ho cht m acetat: n nh pH=5 6 313

AgNO3 0,05N: th xem ht ion cromat cha K2Cr2O7 1%: ra ta nhm to ion ng dng CH3COOH 0,1N: to mi trng axit

HCl 1:1 nng: ho tan kt ta Feroin: ch th nhn mu K thut phn tch Ht 10mL mu + 5mL dung dch m actat (th li bng giy pH v iu chnh v pH =5 6),thm 5mL K2Cr2O7 10% ( lng ta qua m), lm vi 3 mu trong 3 cc 250mL. Lc kt ta bng giy lc bng xanh vi k thut lc gn Dng dung dch K2Cr2O7 1% acid ha bng acid CH3COOH 0,1N ra ta, ra ht ta bng nc ct nng cho n ht ion cromat. Th bng dung dch AgNO3 0,05N ha tan kt ta trn giy lc bng HCl 1:1 nng khong 20mL ra sch ht acid trn giy lc th bng giy pH Thm 2mL HCl 1:1 +2mL H3PO4 +nc ct sao cho tng th tch khong 100mL + 3 git feroin Chun bng dung dch Fe2+ 0,1N cho n khi

dung dch c mu nu . T th tch o c 3 mu, tnh nng dung dch Pb2+. Tnh ton T 3 gi tr th tch chun c, tnh Vtbnh l V(mL). S ng lng ca Pb2+ = S ng lng ca Cr2O72- = S ng lng ca Fe2+ = V. 0,1. 10 - 3 314

Nn s mol ca Pb2+ = Do nng mol/L ca Pb2+ =

0,1.V . 10 - 3 = 0,05 V. 10 - 3 (mol) 2

0,05.V 10 - 3 = 5V. 10 - 3 = 0,005.V 3 10.10 THC HNH PHN TCH TH TCH

BI THC HNH BI 1: CHUN OXY HO KH NH LNG PERMANGANAT I. CHUN B Ho cht: H2SO4 2N, dung dch chun KMnO 4 0,05N; dung dch H 2C2O4 0,05N; dung dch H2SO4 2N, dung dch H3PO4. II. Hn hp bo v zymmerman NH LNG Fe2+

Ion st (II) s b pemanganat oxi ha ln st (III) trong mi trng axit, im tng ng nhn c khi dung dch c mu hng nht ng vi lc d mt git dung dch chun KMnO4. Khi dung dch c nhiu ion Cl , th phi dng hn hp bo v. Khi dung dch c nng cao, th phi dng axit H3PO4 6N trnh sai s nhn mu. Phn ng chun : MnO4 + 5Fe2+ + 8H+ = Mn2+ + 5Fe3+ + 4H2O E
o MnO4 /Mn2+ o Fe3+/Fe2+

= 1.51 V ; E

= 0.771 V 315

Th nghim 1 Xc nh chnh xc nng dung dch KMnO 4 Ht 10mL H2C2O4 0,05N vo bnh nn + 5mL H2SO4 2N, un nng 80-90oC trong 3 pht, lc u. Lm 3 mu trong 3 bnh nn 250mL trong bnh nn 250mL. Chun bng dung dch KMnO4 n khi dung dch c mu hng nht T th tch o c 3 mu, tnh nng dung dch KMnO4 Th nghim 2 Dung dch mu l dung dch Fe 2+ (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc nng . Ht 10 mL mu + 1mL H3PO4 m c + 5mL H2SO4 2N lc u, lm 3 mu trong 3 bnh nn 250mL trong bnh nn 250mL. Chun bng dung dch KMnO 4 0,05N n khi dung dch c mu hng nht. T th tch o c 3 mu, tnh nng dung dch Fe2+. Cu hi Ti sao khi chun Fe 2+ bng KMnO4 chun khng cn phi un nng? 2. Gii thch vai tr ca cc dung dch H 2SO4 v H3PO4 trong th nghim? NH LNG HM LNG CA NO 2 1. Dung dch mu l dung dch KNO 2 CN (0,01N 316

III.

0,05N) c gio vin pha trc, sinh vin khng c bit trc nng . Ht 5mL KMnO4 0,05N vo erlen + 5mL H2SO 4 2N (chnh v pH 5-6), lc u un si nh trn bp cch thy (40- 50oC) trong 3 pht, lm 3 mu trong 3 bnh nn 250mL. Chun bng dung dch mu n khi dung dch c mu hng nht (lc u cn chun nhanh cho ti khi c mu hng nht th chun chm cho n khi mt mu) T th tch o c 3 mu, tnh nng dung dch:NO2Ch nu dung dch khi un li xut hin vn c, th phi lm li th nghim ny (do c s to ta MnO 2 trong dung dch KMnO4) Cu hi 1. Ti sao khi bt u chun th ta phi chun nhanh v phi un nng dung dch trc khi chun ? C th chun nitrit bng KMnO 4 trong mi trng trung tnh hay kim hay khng? Khi chun thy xut hin kt ta nu th cn phi x l nh th no? IV. NH LNG HM LNG CA H2O2 3. Dung dch mu l dung dch H 2O2 (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc nng . Ht 5mL mu + 5mL H2SO4 2N, lc u, lm 3 317

2.

mu trong 3 bnh nn 250mL trong 3 bnh nn 250mL. Chun bng dung dch chun KMnO4 0.05N n khi dung dch c mu hng nht (bn trong 30 giy), ghi th tch KMnO4 0.05N tiu tn. T th tch o c 3 mu, tnh nng dung dch H2O2 c trong mu. Cu hi 1. Nu thay i v tr cc cht ngc li trong th nghim: cc ng KMnO4 v buret ng dung dch mu, th kt qu c thay i khng? Gii thch? Vi d liu thu c t th nghim, hy tnh sai s php chun ny? V sao khi chun axit Oxalic, Nitrit cn phi un nng, cn chun St II v Hydro peoxyt th khng cn un nng? V bi sau c dung dch c chun b trc t nht 1 ngy, nn cui bui thc hnh ny, sinh vin cn hi gio vin tp pha trc dung 2. dch K2Cr2O7 cho bi th nghim sau? Nu thm H2SO4 vo m dung dch b mt mu th phi chn li V dh H 2SO4 c dung dch phi cn mu vng ca ion Fe3+. 3. Khi dng dung dch H2SO4 2N cng c th un si nh, cn nu phi dng dung dch H2SO 4 0,01N th li cn un si mnh 318

2. 3.

Ch 1.

V. NH LNG ION Ca2+ Ion Ca2+ c chuyn thnh kt ta CaC2O4 bng dung dch (NH4)2C2O4 trong mi trng axit CH 3COOH 10% pH = 4 5. Ha tan kt ta trong mi trng axit H2SO4 10% v chun lng C2O42 tch ra tng ng bng dung dch chun KMnO 4 0.05N, im tng ng nhn c khi dung dch c mu hng nht. Dung dch mu l dung dch Ca 2+ (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc nng Ht 10mL dung dch mu + 20mL (NH4)2C2O4 0,05N + 5mL CH3COOH 10% + 1 git MO 0,1% + 50 git NH4OH 2N chnh dung dch v mu vng (ch th MO), lm 3 mu trong 3 bnh nn 250mL trong 3 bnh nn 250mL. un si 5 pht khuy u (lc) kt ta lng trn bp cch thy 45 pht Lc dung dch qua giy lc bng xanh bng k thut lc gn chuyn ht phn dung dch ln giy lc,gn kt ta bng dung dch Amonioxalat 1% (3 ln mi ln 10mL) Ra kt ta trn giy lc bng nc ct nng cho ht Ion C2O42- (kim tra ht C2O42- bng CaCl2) Ha tan kt ta ngay trn giy lc bng 30 mL H2SO4 10%. Thu dung dch qua lc v thm nc ct n th tch 50mL. un nng 80-90oC 319

Chun bng dung dch KMnO 4 0,05Ncho n khi c mu hng bn 1pht T th tch o c 3 mu, tnh nng dung dch Ca2+ Cu hi 1. Vit y cc phn ng xy ra trong qui trnh xc nh, vai tr ca tng ha cht s dng? 2. Thit lp cng thc tnh nng Ca 2+? VI. NH LNG Fe3+ Dung dch mu l dung dch Fe 3+ (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc nng . Ht 10mL mu + 2mL dung dch H2SO4 c, lc v un si dung dch 60-70oC (dung dch phi cn mu vng, nu khng phi lm li th nghim ny) Nh tng git SnCl2 10% cho n khi dung dch mt mu vng Khi dung dch chuyn mu th nh thm 2git na v lm ngui dung dch bng cch pha long dung dch bng nc ct n tng th tch 100mL. Cho 5mL HgCl2 5% vo,ri yn trong 10 pht dung dch c kt ta di la trng (nu c kt ta trng bng, hoc xm en phi lm li t u). Thm 10mL hn hp Zymmerman. Chun bng dung dch KMnO4 0,05N ti dung 320

dch c mu hng nht bn Ch Nu mu l qung st, mui c ln St II th hm lng l St tng ch khng phi l St III Cch pha hn hp Zymmerman, SV phi hi GVHD c ch cch pha hn hp ny. Cu hi 1. Khi xc nh Fe3+, giai on cho SnCl 2 vo, v sao nu thy kt ta xm en th phi ht mu khc lm li t u? Ti sao phi cho d 2 git

SnCl2 sau khi dung dch mt mu vng? Mu vng l g? 2. Vai tr ca hn hp Zymmerman? VII. NH LNG HM LNG CA Cr6+ Dung dch mu l dung dch Cr2O72- (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc nng nng . Ht 5mL mu vo erlen + 10 mL Fe2+ 0,05N + 5mL H2SO4 2N, lc u, un nng 70-80oC trong 3 pht, lm 3 mu trong 3 bnh nn 250mL trong 3 bnh nn 250mL. Chun bng dung dch KMnO 4 0,05N, im tng ng nhn c khi dung dch chuyn t mu xanh l cy sang mu hng nht. T th tch o c 3 mu, tnh nng dung dch Cr2O72-.

321

Cu hi 1. 2. a ra cc cng thc tnh v chng minh? Gii thch quy trnh k thut bng phng trnh phn ng?

322

BI 2: CHUN OXY HO KH - NH LNG IOD & CROMAT I. CHUN B Ho cht: dung dch K2Cr2O7 0,05N (Z = 6), H2SO4 , KI 5%, Na2S2O3 rn Dung dch Iot pha trong KI 0,05N; dung dch Iot 0,05N; dung dch m acetat; axit CH3COOH 2N, KI 5%, KSCN 10%, H 2SO4 4N, (NH4)2MoO 4 3%. II. Ch th h tinh bt1%. NH LNG DUNG DCH Na2S2O3 Xc nh chnh xc nng dung dch Na 2S2O3 Pha ch 250mL dung dch Na2S2O3 0,05N v cho thm 0.1g Na2CO3 Ht 5mL K2Cr2O7 0,05N + 40mL nc ct + 1mL H2SO4 m c + 5mL KI 5% lc nh y kn yn 10 pht trong ti, dung dch c mu nu , lm 3 mu trong 3 bnh nn 250mL trong 3 bnh nn 250mL kim tra. Chun bng dung dch Na2S2O3 cho ti khi dung dch c mu vng rm, sau thm 5 git h tinh bt, dung dch c mu xanh tm m ri chun tip bng Na2S2O3 cho ti khi dung dch mt mu xanh dng (VmL) T th tch o c 3 mu, tnh nng dung 323

Th nghim 1

dch Na2S2O3 Th nghim 2 Xc nh chnh xc nng I2 Cn 2.5 gam KI + 1.5 gam I2 + 10mL nc ct, lc v trn u cho It tan, nu It cha tan ht th thm mt t KI, sau chuyn vo bnh nh mc 250mL, dng nc ct nh mc ti vch, chuyn vo bnh cha mu nu c nt nhm s dng. Dng pipet ly chnh xc 5mL Na2S2O3 0,05N + 5mL m Actat + 5 git h tinh bt 1% lc, lm 3 mu trong 3 bnh nn 250mL trong 3 bnh nn 250mL kim tra. Chun dung dch thu c bng dung dch I 2 mi pha n khi xut hin mu xanh nht (hi tm) T th tch o c 3 mu, tnh nng dung dch I2. Cu hi 1. 2. III. V sao khi pha dung dch Na 2S2O3 phi cho thm lng 0,1g Na2CO3? V sao phi y kn v yn trong bng ti

trc khi hiu chnh nng Na 2S2O3? NH LNG VITAMIN C (AXIT ASCOBIC) Vitamin C l mt cht kh, trong mi trng axit

mnh phn ng ca It vi ch th h tinh bt, im tng ng nhn c khi dung dch va c mu xanh bn trong 30 giy (vitamin c cng thc phn t l C 6H8O6, 324

trong phn ng trao i 2 in t) Dung dch mu l dung dch acid Ascobic (0,01N 0,05N) c gio vin pha trc, sinh vin khng c bit trc nng nng Ht 10mL mu + 10mL nc ct + 5mL H2SO 4 6N + 5git h tinh bt 1% Chun bng dung dch I2 0,05N n khi dung dch c mu T th tch o c 3 mu, tnh nng dung dch Vitamin C Cu hi 1. 2. Vit phng trnh phn ng xy ra trong qu trnh th nghim?

im tng ng trong php chun I2 ny, c mu g? Gii thch? IV. NH LNG HM LNG SUNFIT Anion sunfit trong mi trng trung tnh phn ng vi mt lng d chnh xc dung dch chun It, lng It d c chun bng dung dch chun thiosunfat vi ch th h tinh bt, im tng ng nhn c khi dung dch mt mu xanh. Dung dch mu l mu SO 32- pha t Na2SO3 (97%) (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc. Ht 5mL mu vo erlen + 10mL I2 0,05N y kn lc yn trong ti 5 pht, lm 3 mu trong 3 bnh nn 250mL trong 3 bnh nn 250mL.( y dung dch thu c phi c mu tm) 325

Chun lng I2 d bng dung dch Na2S2O3 0,05N n khi dung dch mt mu nu c nh xanh T th tch o c 3 mu, tnh nng dung dch SO32Cu hi 1. 2. V sao phi y kn dung dch trong bng ti? Nu dng ngay c nh hng g khng? So snh hai cch nh lng bng Iod v Pemanganat? V. NH LNG HM LNG Cu2+ Dung dch mu l dung dch Cu(NO 3)2 (0,01N 0,05N) c GVHD pha trc, HS - SV khng c bit trc nng Ht 5mL mu +1mL CH3COOH (hay 5mL CH3COOH 2N) + 5mL KI 5% lc yn trong ti 10 pht, dung dch vn c mu trng. Lm 3 mu trong 3 bnh nn 250mL trong 3 bnh nn 250mL. Chun bng dung dch Na 2S2O3 0,05N n mu vng nht Thm 5 git h tinh bt 1% chun tip n gn mt mu xanh tm Thm 5nl KSCN lc k chun tip n khi mt mu xanh T th tch o c 3 mu, tnh nng dung dch Cu2+

326

Cu hi 1. 2. Gii thch quy trnh nh lng Cu2+ bng phn ng minh ho? V sao phi thm KSCN vo giai on cui ca qu trnh chun khi xc nh Cu2+, mL ca Cu2+ trong bi ny l bao nhiu? Gii thch v sao Cu2+ li phn ng vi I m khng xy ra theo chiu ngc li? KSCN d nhiu th c nh hng g? KI d nhiu th c phn ng no xy ra? VI. NH LNG HM LNG H 2O2 Dung dch mu l dung dch H2O2 (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc nng nng Ht 5mL mu H2O2 vo erlen + 5mL H2SO4 2N + 5mL KI 5% + 2git Amonimolypdat y bnh lc yn trong ti 10 pht, dung dch c mu vng rm, lm 3 mu trong 3 bnh nn 250mL. Thm 5 git h tinh bt 1% mi mu, th dung dch chuyn sang mu vng nu nh xanh. Ch rng nu y thu c dung dch ln cn en, th l do nng H2O2 c qu, cn phi lm long dung dch H2O2 ny Chun lng Iod sinh ra bng dung dch Thiosunfat n khi dung dch mt mu xanh. T th tch o c 3 mu, tnh nng dung dch H2O2. 327

Cu hi 1. 2. Vit y cc phng trnh phn ng thc hin trong bi thc tp?

Nu xc nh hydropeoxyt nng cao th c nh hng n kt qu khng, gii thch? VII. NH LNG CH Dung dch mu l dung dch Pb 2+ (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc nng Ht 10mL mu + 5mL dung dch m acetat (th li bng giy pH v iu chnh v pH =5 6), thm 5mL K2Cr2O7 10% lng ta qua m lm vi 3 mu trong 3 cc 250mL Lc kt ta bng giy lc bng xanh vi k thut lc gn, sau mi ln chuyn nc lc ln giy lc l mt ln nc ct xen k, kt ta trong cc c chuyn ln phu lc tng lng nh, mi ln km theo 5mL K2Cr2O7 1%. - Dng dung dch K2Cr2O7 1% acid ha bng acid CH3COOH 0,1N ra ta, ra ht ta bng nc ct nng cho n ht ion Cromat. Th bng dung dch AgNO3 0,05N, cho n khi nc ra khng xut hin mu ca Ag 2Cr2O7 th ta sch ion Cr 2O72-. Ha tan kt ta trn giy lc bng HCl 1:1 nng ( khong 20mL dung dch s ra sch ht acid trn giy lc. Th bng giy pH. 328 - Thm 2mL HCl 1:1 + 2mL H3PO4 m c +nc ct sao cho tng th tch khong 100mL

Cu hi 1. 2. BI TP 1.

+ 3git Feroin Chun bng dung dch Fe 2+ cho n khi dung dch c mu nu . T th tch o c 3 mu, tnh nng dung dch Ch. Vit y cc phng trnh phn ng trong bi tp? Gii thch y vai tr ca tng ha cht s dng trong bi thc tp?

Cho 2 cp oxy ho kh [MnO4- / Mn2+ ] v [ClO3- (H+)/ Cl- ] c E0 ln lt l 1,51(v) v 1,45(v). Xc nh chiu phn ng xy ra v hng s cn bng ca phn ng pH = 0. Cho ming ng kim loi vo dung dch AgNO 3 0,01M. Tnh KCB v nng cc ion kim loi trong dung dch to thnh.
0 Bit E Cu
2

2.

Cu

0 = 0,34(v) v E Ag Ag

=0,8(v)

3.

Vit cng thc tnh th in cc E (v) khi chun V0 (mL) dung dch Fe2+ C0N bng V (mL) dung dch Ce4+ CN trong cc trng hp sau: a) b) c) d) Tng qut khi chun Trc xa im tng ng Ti im tng ng Sau xa im tng ng
0 Bit E Fe
3

/ Fe2

0 = + 0,68 (v), ECe

/ Ce 3

= + 1,44(v) 329

4.

Tin hnh pha trn dung dch Cu+ 10 4 M vi dung dch Na2S 0,1M, ri o th in ca dung dch bng in cc ng-SCE th c gi tr - 0,906(volt). Gi s trong dung dch khng xy ra qu trnh to phc hydroxo ca ion Cu+, pH dung dch o c l 8, th
0 in cc chun ca ng l E Cu

= + 0,34 v H2S
Cu

c xem l mt dung dch acid yu hai chc c hng s phn ly acid 2 nc ln lt l: 107,10 12,89.Tnh nng [Cu+] ti thi im cn bng sau khi pha trn

330

BI 9. PHNG PHP CHUN TO PHC M bi: HPT 9

Gii thiu xc nh hm lng mt mu dung dch phn tch trong h phc cht, ngoi phng php khi lng, cn c phng php th tch l phng php chun phc cht Mc tiu thc hin Hc xong bi ny hc vin s c kh nng: 1. M t c s phng php phc cht. 2. Phn tch nh lng mt s mu th. 3. V ng cong chun . Ni dung chnh 1. C s phng php phn tch phc cht (Nguyn tc, khi nim v complexon, ng

cong chun ca phng php). 2. nh lng mt s mu th. 9.1. C s v nguyn tc ca phng php 9.1.1. Nguyn tc iu kin:iu kin xc nh ng cong chun ca phn ng to phc l phn ng phi xy ra nhanh. Phn loi: Gm cc phng php to phc sau: Chun halozen bng hp cht Hg2+: 2 Cl- + Hg2+ = HgCl2 Chun Xyanur (CN-) bng dung dch mui bc: 2 CN - + Ag+ = [Ag(CN)2 ] 331

Phng php Complecxon : dng EDTA xc

nh nhiu kim loi Cht ch th: 1) Eriocrom T en: vit tc l H3Ind

Mt s tnh cht ca Eriocrom T en: + + + + 2) Trong dung dch c dng phn ly: H+, H2Ind , HInd 2-, Ind 3-. Dung dch c mu xanh trong mi trng trung tnh Khi to phc vi cc ion Cu2+, Mg Al3+ c mu trng
2+

, Zn2+,

Thng cho hn hp m amoni lm mi trng duy tr pH Murexit

Mt s tnh cht ca Murexit: + 332 Dung dch c mu thay i theo pH:

pH < 9 : dung dch c mu tm pH = 9 + + 10 : dung dch c mu tm pH > 11: dung dch c mu tm xanh Dung dch c mu vng hoc trng khi to phc vi Ca2+, Ni2+, Co2+, Cu2+, Ag+.

Phn ng chun mui kim loi ti im tng ng s chuyn mu t sang tm xanh. im tng ng Cht ch th dng trong phng php Complecxon l cc cht gy mu hu c, to c phc vi cc cation thnh phc mu tan trong nc. Cc phc ny km bn hn mui to thnh t cation cn xc nh vi Complecxon ti im tng ng. S i mu ny l do phc cht vi cht ch th b phn hy, cht ch th b tch ra dng t do. Chng hn: kim loi Me2+ trong thuc ch th Eriocrom: Me 2+ + HInd 2Me Ind - + H+ (C mu ca cht ch th) Sau khi thm EDTA vo phc ny s c s phn hu phc ny Me Ind - + Na2H2Y + OH Na2MeY + HInd 2- + H2O (mu phc) (tr li mu ca cht ch th) K thut chun : 1) Phng php trc tip Cht ch th gy phn ng trn ion kim loi to phc trc tip. Phng php ny c p dng 333

khi c kim loi to mu phc tng i khng bn Chng hn: Zn2+ + H2Y 2ZnY 2- + 2 H+

Thc hin trong dung dch m (NH3 + NH4Cl) pH = 10 2) Phng php tha tr: Dng lng d Complecxon phn ng vi kim loi cn chun . Sau dng kim loi chun chun li EDTA d. V d: Xc nh nhm pH = 5, dung dch m acetat cho lng d EDTA, sau khi phn ng xong dng dung dch chun kim loi Zn chun EDTA d. Al3+ + n H2Y 2AlY - + 2 H+ + (n - 1) H2Y 2(pH = 5) Sau dng dung dch chun Zn2+ chun li EDTA d
(n - 1) H2Y 2- + (n - 1) Zn2+ (n - 1) ZnY 2- + 2 H+ (pH = 10)

3)

Phng php th: Ion Mg2+ phn ng vi Complecxon to phc kim loi km bn hn so vi cc cation khc. Vy nu trn cc cation ca kim loi phn tch vi Complecxon magi th s xy ra phn ng trao i.

Mg 2+

+ H2Y 2-

MgY 2- + 2 H+ ThY 2- + Mg 2+

(pH = 10) (pH = 2)

Th 4+ + MgY 2-

9.1.2. Khi nim v Complecxon Complecxon l cc hp cht hu c dng phc 334

c dng lm thuc th trong phn tch chun , thng dng cc dng sau: Complecxon I (Nitrilo Tri Acetic - NTA), vit tt l H3Y.

hay

Complecxon II (Etyl Diamin Tetra Acetic - EDTA), vit tt l H4Y

Hay:

Mui dinatri ca acid etylendiamintetra Acetic, Na2H2Y:

335

Trong phn ng vi kim loi lun lun theo t l 1:1 v s mol v vic gii phng [H +] khng ph thuc vo ha tr ca kim loi Chng hn: Mg 2+ + H2Y 2Al3+ + H2Y 2Th 4+ + H2Y 2MgY 2- + 2 H+ AlY - + 2 H+ ThY + 2 H+

Cc hp cht to thnh l Complecxonat, cc Complecxonat c hng s bn kh ln v rt khc nhau. iu ny cho php c th chun lin tip c mt s ion kim loi trong cng mt dung dch bng phng php Complecxon . Khi chun nhiu kim loi ngn qu trnh to phc hydroxo, cn phi to vi kim loi chun mt cht dng phc. Khi chun kim loi bng EDTA s xy ra cn bng gia cc phc , lm gim bn ca phc. Vy phng php Complecxon l phng php phn tch chun da trn vic dng phn ng ca ion kim loi to phc vi cc Complecxon, to thnh cc mui ni phc bn, t phn ly, tan trong nc. 9.1.3. Phng trnh ng cong chun to phc Trong qu trnh chun , nng ion kim loi [M] thay i, do c s bin i p[M] = - lg [M]. ng cong chun c thit lp da theo s bin i thm t t lng EDTA vo. 336 p[M] khi

Gi s chun V0 (L) dung dch kim loi M C0N bng V(L) dung dch chun EDTA C N. (trong cc phng trnh sau, khng ghi c th in tch. Gi s nh khng c cc qu trnh ph: qu trnh hydrua, hydroxo, qu trnh to ta ion kho st...) Phng trnh chun : M + Y (1) Khi tin hnh chun : [M] + [M]p = [M]b = [Y] + [Y]p = [Y]b = [M] - [Y] = M: T (1): Do
V0 .C 0 [M ] V V V C V .C V 0 V V0 V ( [M] ) 0 =( 0 0 ) V0 C 0 V0 V V0 C 0 .[M ]
V0 .C 0 [M ] V V V0 V ( [M] ) 0 = 1 - F (5) V0 C 0 .[M ]
V0 C 0 V .C V0 V V0 C 0 V0 V

MY

( )

(2) (3) (4)

VC V0 V

[M]p- = [Y]p- = [MY] [Y] =

[ MY ] .[ M ]

V0 .C 0 [M ] V0 V [Y] = .[M ]

(4)

rc xa im tng ng: gi s

rt ln, [Y] << [M]

V0 C 0 V0 V

Phng trnh (4) vit li: [M] = (1 - F)

337

Ti im tng ng : ( F = 1) Phng trnh (5) vit li: .[M]2 + [M] Ti st im tng ng : [M] [Y]
V0 C 0 =0 V0 V

Tin hnh gii phng trinh bc 2 theo [M] (5) tm c [M] Ti sau xa im tng ng: [M] << [Y] (5)
V0 .C 0 [M ] V0 V = (F - 1) .[M ]
V0 C 0 V0 V

9.1.4. Sai s trong php chun to phc Sai s c tnh theo cng thc:
C.C0 [M ] C C C C0 S = ( [M] ) 0 C .C 0 .[M ]

Ch ng cong chun hay sai s cn ph thuc vo hng s bn c iu kin ca phc, hng s bn ln th bc nhy ln theo. Bc nhy ln th s cho bit c s thay i mu r rt ca cht ch th, chun c chnh xc. Hng s bn ca phc ph thuc pH ca dung dch, mi ion kim loi phn ng pH thch hp. V th, trong thc t vic tnh ton phi tnh thm cc yu t nh hng ca cc qu trnh hydroxo, hydrua ho... tnh c '. Gi tr ' = ; trong = 107 th mi c gi tr nh lng: '.
M. Y.

T tnh c [M] =

[ M ]'
M

338

9.2. nh lng mt s mu th 9.2.1. Xc nh cng ca nc (phng php trc tip) Nguyn tc Nc cng c mui Ca2+ v Mg2+, Ion Ca2+ v Mg2+ trong mi trng pH = 8 10 s to phc vi ch th ETOO c mu nho. Cc phc ny km bn hn phc ca Ca2+ v Mg2+ vi EDTA. Khi chun dung dch cha phc ca Ca2+ v Mg2+ vi ch th bng dung dch chun EDTA th phc ca Ca2+ v Mg2+ vi ch th b ph hy bi EDTA, im tng ng nhn c ng vi thi im EDTA thay th ton b ch th trong phc Ca 2+ v Mg2+, dung dch chuyn t mu nho sang mu xanh lc (mu ca ch th t do). Trng hp mun xc nh ring tng ion trong cng hn hp, th nng pH ln khong 12 ton b ion Mg 2+ i vo kt ta hydroxyt, sau chun ring Ca 2+ bng dung dch chun EDTA vi ch th murexit nh trn. Nu gi th tch EDTA tiu tn khi chun dung dch hn hp vi ch th ETOO v vi ch th murexit ln lt l VETOO v Vmurexit th VETOO Vmurexit chnh l th tch EDTA tiu tn cho ring ion Mg 2+. T c th tnh c hm lng ca tng cht. Phn ng Ca2+ +H2Y2- + 2NH3 Mg2+ + H2Y2- + 2NH3 Mg2+ + HInd2- + NH3 CaY2- + 2NH4+ MgY2- + 2NH4+ MgInd- + NH4+ 339

MgInd- + H2Y2- + NH3 H2Y2- +Ca2+ + OHCa2+ + H2Ind3-

MgY2- + NH4+ + HInd2CaY2- + 2 H2O CaY2- + H2Ind3- + 2H2O

CaH2Ind-

CaH2Ind- + H2Y2- + OHK thut phn tch

Ln 1: (dng ch th ETOO) Ht 10mL hn hp dung dch mu + 5mL dung dch m + 0,01g ch th ETOO, lm 3 mu trong 3 bnh nn 250mL Chun b mt bnh lm mu trng vi th tch tng ng bnh mu v cc ha cht tng t, ch thay dung dch mu bng nc ct. Chun cc bnh bng dung dch EDTA 0,02N: dung dch va chuyn t mu nho sang mu xanh lc. T th tch o c 3 mu, tnh nng dung dch mu. Ht 10mL dung dch mu + 5mL dung dch NaOH 2N + 0,01g ch th murexit, lm 3 mu trong 3 bnh nn 250mL Chun b mt bnh lm mu trng vi th tch tng ng bnh mu v cc ha cht tng t, ch thay dung dch mu bng nc ct. Chun cc bnh bng dung dch EDTA 0,02N: dung dch va chuyn t mu nho sang mu tm hoa c. 340 T th tch o c 3 mu, tnh nng ca

Ln 2: (dng ch th Murexit) -

tng dung dch Ca2+ v Mg2+. Tnh tan T th tch o c 3 mu th nghim, tnh th tch trung bnh V Dng nh lut ng lng xc nh hm lng cc ion. S ng lng ca EDTA l V. 0,02.10- 3 = 2V.10- 5 ( ln 1 gi l V1 v ln 2 gi l V2 ) ln 1 l xc nh tng hm lng Ca 2+ v Mg2+ c trong nc cng: S ng lng (Ca2+ + Mg2+) = 2 V1.10- 5. ln 2 l xc nh hmLng ring phn Ca2+: S ng lng Ca2+ = 2 V2.10- 5 Hm lng Ca2+ S ng lng Mg2+ = 2( V1 - V2 ).10- 5 Hm lng Mg2+ 9.2.2. nh lng ion Ba2+ Nguyn tc pH = 9 10, Ba2+ l ion to phc vi EDTA bn hn Mg2+, nn khi cho ion Ba 2+ vo dung dch cha mt lng d MgY2 th c phn ng trao i v sinh ra mt lng ion Mg2+ tng ng vi lng ion Ba 2+ c trong mu, lng Mg2+ ny c chun bng dung dch chun EDTA vi ch th ETOO pH = 9 10, im tng ng nhn c khi dung dch t mu nho sang xanh lc. lg (BaY) = 7,78 lg (BaInd) = 3,0 lg (MgY) = 8,69 341 lg (MgInd) = 7,0

Phn ng chun : Mg2+ + HInd 2(mu xanh) MgInd- + H2Y 2( nho) Mg Ind - + H+ (mu ) MgY 2- + 2 H+ + Ind2- (1) (xanh)

Ba2+ + MgY 2BaY2- + Mg2+ (2) Khi chun bng EDTA s ch c Mg 2+ c to ra trong phn ng (2) mi tham gia phn ng chun ny Mg2+ ( 2) + HInd 2MgInd + H2Y2 K thut pha ch Ht 10 mL dung dch Mg2+ 0,02N (chnh mu v pH = 9-10 bng cch cho NH4OH vo )+ 10 mL m pH = 10 v t ch th ETOO ( lm 2 mu ). em chun bng dung dch EDTA 0,02N cho n khi dung dch chuyn t mu nho sang xanh chm.Ghi th tch EDTA tiu tn (V1). Ht 5 mL dung dch mu cha Ba2+ cho vo erlen trn, chun tip bng dung dch EDTA 0,02N cho n khi dung dch chuyn t mu nho sang xanh chm.Ghi th tch EDTA tiu tn (V2). T th tch o c 3 mu, tnh nng dung dch Ba2+ . Tnh ton V1 ca EDTA o (1) > V2 ca EDTA o (2) th php chun ng, nu ngc li: lng Mg2+ lng Ba2+ th phn ng (2) xy ra khng hon ton, s cn d 342 Mg Ind - + H+ MgY2 + 2 H+ + Ind2-.

Ba2+, nn khng tnh c hm lng Ba2+ c trong mu. S ng lng ca EDTA chun ( 2) = S ng lng ca MgInd ( 2) = S ng lng ca Mg 2+ ( 2) = S ng lng Ba2+. (C. V2 ) EDTA = (C.V) Ba2+ Vy: CN (Ba2+ ) =
C.V2 0,02 = V2 = 0,004. V2 5 V Ba

343

THC HNH PHN TCH TH TCH

BI THC HNH BI 1: CHUN TO PHC NH LNG Ca2+V Mg2+

I.

CHUN B Dung dch m pH =10 Dung dch chun Mg2+ 0,01M NaOH 2N Dung dch EDTA 0,01M. Ch th: ETOO Ht 10mL dung dch chun Mg2+ 0,01M + 5mL dung dch m pH = 10 + 0,01g ETOO (chun b mt bnh lm mu trng vi th tch tng ng bnh mu v cc ha cht tng t, ch thay dung dch Mg2+ bng nc ct), lm 3 mu trong 3 bnh nn 250mL. Dung dch chun s c mu nho Chun cc bnh bng dung dch EDTA mi pha cho n khi dung dch va chuyn mu t mu nho sang mu xanh chm. Ghi cc th tch EDTA ca mu tht v mu trng T th tch o c 3 mu, tnh nng dung dch EDTA. Vit cc phng trnh phn ng gii thch th nghim V sao li phi dng dung dch m pH = 10?

II.

XC NH NNG CA DUNG DCH EDTA -

Cu hi 1. 2. 344

III. NH LNG Ca2+

Dung dch mu l dung dch Ca(NO3)2 (0,01M 0,05M) c gio vin pha trc, sinh vin khng c bit trc Th nghim 1

Ht 10 mL dung dch mu (chnh mu v pH = 9 -10 bng cch cho NH4OH vo) + 5 mL m pH = 10 v t ch th ETOO + 10 mL nc ct cho

vo erlen (lm 3 mu). em chun bng dung dch EDTA 0,01M cho n khi dung dch chuyn t mu nho sang xanh chm. Ghi th tch EDTA tiu tn. T th tch o c 3 mu, tnh nng dung

dch Ca2+ Th nghim 2:

Ht 10 mL dung dch Ca2+ + 5 mL NaOH 2N v t ch th Murexit cho vo erlen (lm 3 mu). em chun bng dung dch EDTA 0,01M cho n khi dung dch chuyn t mu nho sang tm hoa c. Ghi th tch EDTA tiu tn. T th tch o c 3 mu, tnh nng dung dch.

Ch

Vi mt mu c mi trng axit hoc kim mnh, phi dng axit hoc baz iu chnh n gn gi tr pH qui nh ri mi cho m vo. Trng hp vi ch th murexit, th tch NaOH 2N phi tnh th tch ph hp sao cho a v c pH = 12, gn im tng ng cn 345

thm NaOH 2N. Cu hi 1. 2. Gii thch cc mu sc c trong thc nghim? Th nghim no cho kt qu gn ng hn, gii thch?

IV. NH LNG Mg2+

Dung dch mu l dung dch Mg(NO 3)2 (0,01M 0,05M) c gio vin pha trc, sinh vin khng c bit trc - Ht 10 mL dung dch mu (chnh v pH = 9 -10 bng cch cho NH 4OH vo) + 5 mL m pH = 10 v t ch th ETOO + 10 mL nc ct cho vo erlen (lm 4 mu, trong 1 mu chng).

em chun bng dung dch EDTA 0,01M cho n khi dung dch chuyn t mu nho sang xanh chm. Ghi th tch EDTA tiu tn. T th tch o c 3 mu, tnh nng dung dch Mg2+

V. NH LNG Ca2+ + Mg2+ TRONG HN HP

Th nghim 1 Dung dch mu l hn hp Ca 2+ v Mg2+ (0,01M 0,05M) c gio vin pha trc, sinh vin khng c bit trc nng .

Ht 10mL hn hp dung dch mu + 5mL dung dch m + 0,01g ch th ETOO, lm 3 mu trong 3 bnh nn 250mL. Chun b mt bnh lm mu trng vi th tch tng ng bnh mu v cc ha cht tng t, ch thay dung dch mu bng nc ct.

346

Chun cc bnh bng dung dch EDTA: dung dch va chuyn t mu nho sang mu xanh chm. T th tch o c 3 mu, tnh nng

dung dch mu. Th nghim 2 Dung dch mu l hn hp Ca 2+ v Mg2+ (0,01M 0,05M) c gio vin pha trc, sinh vin khng c bit trc nng - Ht 10mL dung dch mu + 5mL dung dch NaOH 2N + 0,01g ch th Murexit, lm 3 mu trong 3 bnh nn 250mL. Chun b mt bnh lm mu trng vi th tch tng ng bnh mu v cc ha cht tng t, ch thay dung dch mu bng nc ct.

Chun cc bnh bng dung dch EDTA: dung dch va chuyn t mu nho sang mu tm hoa c. T th tch o c 3 mu, tnh nng ca tng dung dch Ca2+ v Mg2+.

Cu hi 1. Vit y cc phn ng tin hnh trong bi thc tp? Cho bit ETOO pH trong qui trnh dng 2. H2Ind2 , EDTA l H2Y2 . Gi s th tch ca dung dch xc nh l 50mL c pH = 2, hy tnh cn thm bao nhiu mL NaOH 2N c pH = 12?

347

BI 2: CHUN TO PHC NH LNG Al3+ v Fe3+ I. CHUN B Ho cht: dung dch m acetat pH = 5,5; dung dch EDTA 0,02N; dung dch NH4OH 2 N. II. Ch th: Bromcresol lc; axit sunfosalicilic. NH LNG DUNG DCH Zn2+

Dung dch mu l dung dch Zn2+ (0,01M - 0,05M) c gio vin pha trc, sinh vin khng c bit trc nng Th nghim 1 Ht 10mL dung dch chun EDTA 0,01M + 5mL dung dch m acetat pH = 5,5 + 3 git ch th Xylenon da cam, lm 3 mu trong 3 bnh nn 250mL Chun b mt bnh lm mu trng vi th tch tng ng bnh mu v cc ha cht tng t, ch thay dung dch mu bng nc ct. Chun cc bnh bng dung dch mu cho n khi dung dch va chuyn mu t mu vng sang mu hng tm. T th tch o c 3 mu, tnh nng dung dch Zn2+. Th nghim 2 Ht 10 mL dung dch mu (chnh mu v pH = 5 - 6 bng cch cho NH4OH vo) + 5 mL m pH = 5,5 + 3 git Xylenol da cam + 10 mL nc ct 348

cho vo erlen, lm 3 mu v 1 mu trng Chun bng dung dch EDTA 0,01M: dung dch chuyn t mu cam sang vng cam. T th tch o c 3 mu, tnh nng dung dch Zn2+. Ch Cn bo ngay nng Zn2+ tm c cho gio vin c nh gi im v ng thi, gio vin s cho kt qa nng ny nhm thc hin tip cc th nghim sau. Cu hi 1. 2. III. Th nghim no c th cho kt qu t sai s hn. Gii thch? Gii thch s chuyn mu trong cc th nghim trn? NH LNG DUNG DCH Fe3+ Dung dch mu l dung dch Fe 3+ (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc nng Cho vo erlen 10mL dung dch mu, ri thm tng git dung dch NH 3 n khi dung dch c pH = 5 -6 (ly giy qu kim tra pH), thie thm 3 git ch th acid sulfoSalisilic. Lm 3 mu th nghim Tin hnh chun bng dung dch EDTA chun n khi dung dch chuyn t mu nu n khng mu. Ghi th tch dung dch EDTA tiu tn. 349

T th tch o c 3 mu, tnh nng dung dch Fe3+. IV. NH LNG Al3+ Ion Al3+ trong mi trng pH = 5 6, tc dng chm vi EDTA. V vy phi dng k thut chun ngc bng cch cho d chnh xc mt lng dung dch chun EDTA phn ng vi nhm. Chun lng EDTA d bng dung dch chun Zn2+ vi ch th Xylenon da cam, im tng ng nhn c ng vi thi im dung dch chuyn t mu vng chanh sang mu hng tm. Nu dng dung dch chun Fe3+ chun EDTA d vi ch th axit sunfosalicilic th im tng ng nhn c khi dung dch t khng mu sang mu nu. Phn ng chun : H2Y2 + Al3+ = AlY + 2H
+

AlY = 109.6
+

Chun lng EDTA tha bng dung dch chun M2+: M2+ + H2Y2 = MY2 + 2H M2+ c th l Zn2+, Pb2+, Cu2+, Fe3+. Phn ng to phc ZnY2 xy ra nhanh nhit cao, do chun khi dung dch nng khong 60 oC. Dung dch mu l dung dch Al3+ (0,01N - 0,05N ) c gio vin hng dn pha trc, sinh vin khng c bit trc nng Ht 5 mL dung dch mu (chnh mu v pH = 5 bng cch cho NH4OH vo) + 5mL m pH = 5,5 + 10 mL dung dch EDTA + 3 git ch th axit Sunfosalicilic, lm 3 mu trong 3 bnh nn 250mL 350

Chun bng dung dch Fe 3+

xc nh

c nng th nghim trn: dung dch chuyn t khng mu sang nu. T th tch o c 3 mu, tnh nng dung dch Al3+ Cu hi 1. Vit y cc phng trnh phn ng trong bi thc tp? 2. Gii thch vai tr ca tng ha cht s dng trong bi thc tp? NH LNG HN HP Al3+ + Fe3+ Dung dch mu l dung dch hn hp Fe3+ + Al3+ (0,01M - 0,05M) c gio vin pha trc, sinh vin khng c bit trc nng Ht 5mL dung dch mu + NH4OH 2N chnh n pH = 5,5 + 1 git axit Sunfosalicilic cho vo erlen, lm 3 mu trong 3 bnh nn 250mL Chun bng dung dch EDTA 0,01M cho n khi dung dch chuyn t nho sang mt mu. Ghi th tch EDTA tiu tn. Tip tc cho vo 1 git Bromcresol lc + NH4OH 2N chnh n pH = 5 + 2 mL m pH= 5,5 + un nh (800C). Lm ngui bng nc lnh v thm vi git Xylenon da cam vo erlen Chun bng dung dch Zn2+ xc nh nng trong th nghim trn: dung dch chuyn t xanh lc sang cam tm. Ghi th tch Zn2+ tiu tn. 351

V.

T th tch o c 3 mu, tnh nng ca tng dung dch Fe3+ v Al3+ Cu hi 1. 2. 3. Vit y cc phng trnh phn ng trong bi thc tp? Gii thch vai tr ca tng ha cht s dng trong bi thc tp? V sao phi un si dung dch phn tch trc khi cho ch th Xylenon da cam vo? 4. Thit lp cng thc tnh nng Al 3+ v Fe3+? VI. NH LNG HN HP Mg2+ + Zn2+ Dung dch mu l hn hp dung dch Zn2+ + Mg2+ (0,01M - 0,05M) c gio vin pha trc, sinh vin khng c bit trc nng Th nghim 1 Ht 10 mL dung dch mu + 10 mL m pH = 10 + 0,01g ETOO cho vo erlen, lm 3 mu trong 3 bnh nn 250mL Chun bng dung dch chun EDTA 0,01M: dung dch chuyn t mu nho sang xanh chm. Ghi th tch EDTA tiu tn. Cng tin hnh nh trn cho mu trng tng t, ghi th tch EDTA tiu tn. Th nghim 2 Ht 10 mL dung dch mu + 10 mL m pH = 10 v t ch th ETOO +5 mL KCN 20% cho vo erlen, lm 3 mu trong 3 bnh nn 250mL Chun bng dung dch chun EDTA 0,01M: 352

dung dch chuyn t mu nho sang xanh chm ca bnh chng. Ghi th tch EDTA tiu tn. Cng tin hnh nh trn cho mu trng tng t, ghi th tch EDTA tiu tn. T th tch o c 3 mu v 2 th nghim, tnh nng tng dung dch Zn2+ v Mg2+ Cu hi 1. 2. Vit y cc phng trnh phn ng trong bi thc tp? Gii thch vai tr ca tng ha cht s dng trong bi thc tp?

3. a ra v chng minh cc cng thc tnh? VII. NH LNG HN HP Ca2+, Mg2+, Al3+, Fe3+ Dung dch mu l dung dch hn hp Fe3+ + Al3+ + Ca2+ + Mg2+ (0,01M - 0,05M) c gio vin pha trc, sinh vin khng c bit trc nng Ht 20 mL dung dch mu + 5 git HNO3 m c, un nh trong khong 2 3 pht, ngui + 2 git MR 0,1% (dung dch c mu hng) + nh tng git NH4OH 2N cho n khi dung dch mu vng (c kt ta), c mi NH3 bay ra, un cho ht NH3 t do, lm 3 mu trong 3 bnh nn 250mL Lc kt ta bng giy lc bng vng, ra kt ta 5 ln bng NH4Cl 5% nng. Dch lc v nc ra c gp chung. Gi l dung dch 1, ri em nh mc thnh 100mL 353

Ho tan kt ta bng HCl 1: 4 nng, thu c dung dch mi, gi l dung dch 2. Vy (dung dch 1) em i xc nh Ca 2+ v Mg2+; (dung dch 2) em i xc nh Al3+ v Fe3+. 1. Dung dch 1: Xc nh Ca2+ v Mg2+ Th nghim 1 Ht 5 mL (dd 1) + 5 mL m pH = 10 + ETOO. Chun bng dung dch chun EDTA 0,01M: dung dch chuyn t mu nho sang xanh chm. Ghi th tch EDTA tiu tn. Lm mu trng tng t nhng thay mu bng nc ct. Ghi th tch EDTA tiu tn Th nghim 2 Ht 5 mL (dd1) + 2 mL NaOH 2N + 0,01g Murexit cho vo erlen Chun bng dung dch chun EDTA 0,01M: dung dch chuyn t mu hng c sang tm hoa c ca bnh chng. Ghi th tch EDTA tiu tn. Lm mu trng tng t nhng thay mu bng nc ct. Ghi th tch EDTA tiu tn T th tch o c 3 mu, tnh nng dung dch Mg2+ v Ca2+. Dung dch 2: Xc nh Al 3+ v Fe3+ Ht 5mL (dd2) + NH4OH 2N chnh n pH = 5,5 + 3 git axit Sunfosalicilic cho vo erlen Chun bng dung dch EDTA 0,01M: dung dch chuyn t tm nho sang mt mu. Ghi th 354

2.

tch EDTA tiu tn. Lm mu trng tng t nhng thay mu bng nc ct. Ghi th tch EDTA tiu tn Tip tc cho vo 1 git Bromcresol lc + NH4OH 2N chnh n pH = 5 + 2 mL m pH= 5,5 + un nh (800C). Lm ngui bng nc lnh +1 git Xylenon da cam vo erlen Chun bng dung dch Zn2+ xc nh nng trong th nghim trn: dung dch chuyn t xanh lc sang cam tm. Ghi th tch Zn2+ tiu tn (tin hnh chun nng). Lm mu trng tng t nhng thay mu bng nc ct. Ghi th tch Zn2+ tiu tn T th tch o c 3 mu, tnh nng dung dch Fe3+ v Al3+ Cu hi 1. 2. 3. Vit y cc phng trnh phn ng trong bi thc tp? Gii thch vai tr ca tng ha cht s dng trong bi thc tp? a ra v chng minh cc cng thc tnh?

355

BI 3: CHUN TO PHC NH LNG Ba2+ V SO42 I. CHUN B Ho cht: Dung dch m pH = 10; EDTA 0,02N; dung dch Mg2+ 0,02N; HCl 1:4; pha dung dch BaCl2 0,02N; NH4OH 2N; H2SO4 0,1N. II. Ch th: ETOO; MO 0,1 %. NH LNG BA2+ pH = 9 10, Ba2+ l ion to phc vi EDTA bn hn Mg2+, nn khi cho mt lng d MgY2 vo dung dch cha ion Ba2+ th c phn ng trao i v sinh ra mt lng ion Mg2+ tng ng vi lng ion Ba 2+ c trong mu, lng Mg2+ ny c chun bng dung dch chun EDTA vi ch th ETOO pH = 9 10, im tng ng nhn c khi dung dch t mu nho sang xanh lc. Phn ng chun : BaIn + MgY2 Phn ng ch th:
H2Y2 MgIn o nho MgY 2 In xanh cham 2H

MgIn + BaY2

Dung dch mu l dung dch BaCl 2 (0,01N - 0,05N) c gio vin hng dn pha trc, sinh vin khng c bit trc Th nghim 1 356

Ht 10 mL dung dch Mg2+ 0,01M (chnh mu v pH = 9 -10 bng cch cho NH 4OH vo) + 10 mL m pH = 10 v t ch th ETOO (lm 2 mu). em chun bng dung dch EDTA 0,01M cho n khi dung dch chuyn t mu nho sang xanh chm. Ghi th tch EDTA tiu tn (V 1). Ht 5 mL Ba2+ cho vo erlen trn, chun tip bng dung dch EDTA 0,01M cho n khi dung dch chuyn t mu nho sang xanh chm. Ghi th tch EDTA tiu tn (V2). T th tch o c 3 mu, tnh nng dung dch Ba2+ Th nghim 2 Ht 10 mL dung dch EDTA 0,01M (chnh mu v pH = 9 -10 bng cch cho NH 4OH vo) +10 mL m pH = 10 v t ch th ETOO (lm 3 mu). em chun bng dung dch Mg2+ 0,01M cho n khi dung dch chuyn t mu xanh chm sang nho. Ghi th tch Mg 2+ tiu tn (V1). Ht 5 mL Ba2+ cho vo erlen trn, lc ch 5 pht, chun tip bng dung dch EDTA 0,01M cho n khi dung dch chuyn t mu nho sang xanh chm. Ghi th tch EDTA tiu tn (V2). T th tch o c 3 mu, tnh nng dung dch Ba2+. Cu hi 357

1.

nh lng Ba2+ bng 2 th nghim trn c s khc bit g? Th nghim no c th cho kt qu gn ng hn? Gii thch?

2. 3. III.

Gii thch cc hin tng c trong 2 th nghim ny?

Vit cc phng trnh phn ng xy ra trong th nghim? NH LNG SUNFAT BNG PHNG PHP GIN TIP Anion sunfat trong mi trng pH = 4 5 c kt ta

bng mt lng d chnh xc dung dch BaCl 2 bit trc nng , sau khi lc kt ta, dch qua lc c em i xc nh lng BaCl 2 d bng chun th, da vo lng EDTA tiu tn v lng BaCl 2 ban u s tnh c lng BaCl2 phn ng vi sunfat, t tnh c nng sunfat c trong mu. Phn ng chun : Ba2+ + SO42 TBaSO4 = 10-9.97 BaY = 107.7 H2Y2 + Ba2+ = BaY2 + 2H Dung dch mu l dung dch Na 2SO4 (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc Ht 10 mL dung dch mu + 10 mL nc ct + 1 git MO 0,1% + 1 git HCl 1:4 (cho HCl 1:4 n khi dung dch c mu hng ), thm tip 2 git HCl 1:4 na. Lm tng t 3 mu trong 3 bnh nn 250mL. 358
+

BaSO4

un nng khong 800C, thm t t 30mL dung dch BaCl2 0,02N vo, khuy u, kt ta lng trn bp un cch thu 30 45 pht. Lc kt ta bng giy lc bng xanh, dch lc c hng vo bnh nn, ra kt ta bng nc ct cho n ht ion Ba 2+ (th bng H2SO 4 0.1N, khi dung dch c mu du). Ly dch lc chnh v pH = 9 - 10 bng cch cho tng git NH4OH 2N vo (th bng giy pH) lc dung dch c mu cam, gi l (dd 1). Ly 1 erlen khc ht 10 mL EDTA 0,01M + 10 mL m pH = 10 + 0,01g ch th ETOO, lc u. Chun bng Mg2+ 0,02 N cho n khi dung dch chuyn t xanh chm sang nho, gi l (dd 2) Ht 10mL (dd 1) cho vo erlen c cha (dd 2). em chun bng EDTA 0,01M cho n khi dung dch chuyn t nho sang xanh chm. Ghi th tch EDTA tiu tn. Lm tng t vi cc mu cn li. T th tch o c 3 mu, tnh nng dung dch SO42 Cu hi 1. 2. 3. Vit y cc phng trnh phn ng trong bi thc tp? Gii thch vai tr ca tng ha cht s dng trong bi thc tp? a ra v chng minh cc cng thc tnh? 359

BI TP 1. Vit cng thc tnh pMg khi chun V0 (mL) dung dch Mg2+ C0N bng V (mL) dung dch EDTA CN trong cc trng hp sau: a) Tng qut khi chun b) c) d) Trc xa im tng ng Ti im tng ng Sau xa im tng ng

Gi s rng Mg c kh nng to phc vi EDTA v hydroxyt, EDTA l acid a chc phn ly bn nc, hng s bn iu kin ca phc gia M v EDTA ln. 2. Ht 5mL dung dch mu (c cha ion Al 3+ ) cng vi 10 mL dung dch chun EDTA 0,1N thm 3 git ch th Bromcresol lc vo cng mt erlen, ri chnh dung dch pha trn v pH = 5-6 bng cch cho NH4OH vo n khi dung dch c mu xanh. Thm tip 2mL dung dch m pH = 5,5. un nh khong 60 - 800C, ri li thm 2 mL m pH = 5,5 + 1 git ch th Xylenon da cam (lm 4 mu trong cc bnh nn loi 250mL). Chun bng dung dch Zn2+ 0,1N (chun nng) cho n khi dung dch chuyn t xanh sang vng th o c th tch dung dch Zn2+ l V0(mL), theo kt qu: Mu s V0 (mL) Al
3+

1 9,8

2 9,7

3 9,7

4 9,6

Vi tin cy 95% hy tnh hm lng g / L ca ion c trong mu ban u.

2 3 4 5 6 7 8 9 10

STN

360

t Q

12,7 1,22

4,3 0,94

3,18 0,77

2,78 0,64

2,57 0,56

2,45 0,51

2,37 0,47

2,31 0,44

2,23 0,41

Gi s cc dung dch u c khi lng ring d = 1 g/mL

361

BI 10. PHNG PHP CHUN TO TA M bi: HPT 10

Gii thiu xc nh hm lng cht trong mu qung hay dung dch ban u, ngoi phng php khi lng, cn c th s dng phng php chun th tch, l phng php to ta Mc tiu thc hin Hc xong bi ny hc vin s c kh nng: 1. M t c s phng php kt ta. 2. M t phng php Mohr, Volhard. 3. Chun kt ta. 4. V ng cong chun Ni dung chnh 1. 2. C s phng php kt ta (nguyn tc chun , ng cong chun . Phng php Mohr, Volhard (phng php

Mohr). 3. nh lng mt s mu theo phng php to ta 10.1. C s v nguyn tc ca phng php to ta 10.1.1. Nguyn tc chun Phng php chun kt ta da trn phn ng to thnh cht kt ta trong qu trnh chun p dng phn ng to kt ta vo qu trnh chun th cc phn ng phi c tc phn ng nhanh, xy ra tc thi, cc kt ta phi c thnh phn xc nh tng ng vi cht ch th cho php 362

Chng hn chun Ag+ bng X- to kt ta AgX Ag+ + ClAgCl 10.1.2. Phng trnh ng cong chun to ta Xy dng phng trnh ng nh phn khi dng phng php ta bc. Gi s tin hnh chun V 0 (mL) dung dch Cl- C0N bng V (mL) dung dch Ag+ CN, th s bin thin nng ca Ag+ trong dung dch s lm thay i lng kt ta AgCl c to thnh. V th gi tr tch s tan ca AgCl s tham gia trong qu trnh chun ny. Da vo s thay i nng ion trong dung dch thc hin vic v ng cong chun . Phng trnh chun : Ag+ + Cl(Tt = 10 Khi chun : [Ag+ ] + [Ag+ ]pu = [Cl- ] + [Cl- ]pu = [Cl- ] - [Ag+ ] = ([Cl- ] - [Ag+ ])
V0 C 0 V .C V0 V
- 9,75

AgCl

)
VC V0 V

V0 C 0 V0 V

(t

V .C = F) V0 C 0

V0 V V0 C 0

= 1 - F (1)

Trc im tng ng: (0 < F <1) [Ag+ ] qu nh nn: (1): [Cl- ]

V0 V V0 C 0

= 1-F

363

V0 V Tt [ Ag ] V 0 C 0

= 1-F

[Ag+ ] =

V0 V Tt V 0 C 0 (1 F )

Tai im tng ng: (F = 1) lc ny [Ag+ ] = [Cl- ] [Cl- ] =

Tt = [ Ag ]

Tt

pAg = -

1 lg Tt 2

Trc st im tng ng: (F [Ag+ ] (1) [Cl- ] ( [Ag+ ] -

1) dung dch c

V V Tt ) 0 = F-1 V0 C 0 [ Ag ]

Gii Phng trnh bc 2 theo [Ag+ ] Sau xa im tng ng : (F > 1) dung dch c nng [Cl- ] qu b (1) [Ag+ ]
V0 V = F-1 V0 C 0

[Ag+ ] = (F-1)

V0 C 0 V0 V

Sau khi tnh c [Ag+ ] th chuyn logarit tnh c pAg. T gi tr pAg v V (Ag + ) xy dng c ng cong chun to ta theo phng php bc. 10.1.3. Sai s trong php chun to ta Da vo lng [Ag+] em chun s xc nh c sai s php chun to ta ti thi im kho st S = ( [Ag+ ] C C Tt ) 0 C .C 0 [ Ag ]

V d: Xc nh ng cong chun dung dch c Cl bng dung dch AgNO3, bit ga tr T(AgCl) v cc nng ion Ag+ v Cl- mi thi im xt.
-

364

Gii Da vo cc cng thc c tnh ton trn, ti mi im chun tm c [Ag+]: Vi dung dch NaCl 0,1M thi im ban u cha chun : [Cl- ]= CNaCl = 0,1 pCl = 1 Ti thi im tng ng: s mol ca NaCl v AgNO3 bng nhau [Ag+ ] = [Cl- ] =
T=

1,7.10

10

= 1,303. 10- 5 M

pAg = pCl = - lg [Ag+ ] = 4,885 ... (tip tc, sinh vin t thit lp c kt qa tip theo) Kt qu th c xy dng c dng nh sau:

Hnh 10.1 Kt qu th xy dng ng cong chun i xng qua im tng ng 365

Bc nhy ln nn kh nng chun chnh xc cao Nng dung dch cn chun v dung dch chun cng ln th bc nhy cng ln (khang nng 0,1M c nhy thch hp hn c) tan ca hp cht kt ta cng nh th bc nhy cng ln. V d: Xy dng ng cong chun dung dch Br bng phng php bc cc nng nu: a) Chun dung dch Br- 0,05M bng dung dch b) c) Ag+ 0,1M Chun dung dch Br- 0,005M bng dung dch Ag+ 0,01M Chun dung dch Br- 0,0005M bng dung dch Ag+ 0,001M Cho nhn xt v dng ng cong v c. Tng t cho php tm pM nh trn, ta c c kt qa sau: Bng 10.1. Bin i pAg v pBr trong qu trnh chun
Chun 50mL Br- 0,05M bng AgNO3 0,1M pAg 0 10 20 10,68 10,13 pBr 1,3 1,6 2,15 Chun 50mL Br- 0,005M bng AgNO3 0,01M pAg 9,68 9,13 pBr 2,30 2,60 3,15 Chun 50mL Br- 0,0005M bng AgNO3 0,001M pAg 8,68 8,13 pBr 3,30 3,60 4,15

Th tch AgNO3

366

23 24,9 24,95 25 25,05 25,10 27 30

9,72 8,41 8,10 6,14 4,18 3,88 2,58 2,20

2,56 3,87 4,18 6,14 8,10 8,40 9,70 10,08

8,72 7,41 7,10 6,14 5,18 4,88 3,58 3,20

3,56 4,87 5,18 6,14 7,10 7,40 8,70 9,08

7,72 6,50 6,33 6,14 5,95 5,78 4,58 4,20

4,56 5,78 5,95 6,14 6,33 6,50 7,70 8,08

Hnh 10.2. ng cong chun ca bng trn ( th c trc tung theo pAg) (1) Chun dung dch Br- 0,05M bng dung dch Ag+ 0,1M (2) Chun dung dch Br- 0,005M bng dung dch Ag+ 0,01M (3) Chun dung dch Br- 0,0005M bng dung dch Ag+ 0,001M

367

Hnh 10.3. ng cong chun ca bng trn ( th c trc tung theo pBr) R rng khi tng cht cn chun v cht chun, s bin i pAg vng gn im tng ng tr nn r hn Hin tng ny cng c quan st thy nu thay th pAg trn trc tung bng pBr. Nu chun nng Br- ln s dng nhng dung dch AgNO3 vi nng 0,1M hoc ln hn th im cui c xc nh d dng v sai s chun s l cc tiu. Ngc li, i vi cc dung dch c nng 0,001M hoc nh hn, s bin i pAg hoc pBr nh n mc l kh khn xc nh im cui. Trong trng hp sai s chun phi ln. Nng thuc th nh hng tng t n bc nhy ca php chun theo cc loi phn ng khc. V d: Chun cc dung dch Halozenua 0,1M bng AgNO3 bit pT ca ln lt AgCl; AgBr; AgI l 9,75 ; 12,28 ; 16,08 368

a) b) c)

Chun 50mL dung dch Cl- bng VmL dung dch AgNO3 0,1N Chun 50mL dung dch Br- bng VmL dung dch AgNO3 0,1N Chun 50mL dung dch I- bng VmL dung dch AgNO3 0,1N

T nhn xt v ng cong th chun ca chng V tan ca chng c sp xp l: SAgCl < SAgBr < SAgI . Nn ng cong chun c xc nh nh sau:

Hnh 10.4. ng cong chun (1) im tng ng ca NaCl (2) im tng ng ca NaBr 369

(3) im tng ng ca NaI 10.2. Cc phng php to ta c bn 10.2.1. Phng php Mohr 10.2.1.1. Nguyn tc C 2 phng php thng c p dng l phng php so snh c v phng php dng cht ch th Phng php ny c ng dng rng ri khi chun Clorua v Bromua bng dung dch AgNO3 chun. Ion cromat c dng lm cht ch th, im cui php chun xut hin kt ta Ag2CrO4 mu gch S to thnh kt ta th hai c mu khc vi mu ca hp cht kt ta l c s xc nh im cui theo phng php Mohr tan ca Ag2CrO4 cao hn hiu tan ca bc halozenua. Do , khi chun theo phng php Mohr, Ag2CrO4 cha to thnh khi thc t tt c halozenua cha kt ta ht. iu chnh nng cromat c th ngn nga s to thnh Ag2CrO4 cho ti khi nng ion Ag + cha t ti nng tnh tan l thuyt i vi vng im tng ng khi chun halozen. Tinh th AgNO3 c th c cha mt t tp cht do khi pha cn nh li nng chnh xc bng dung dch chun NaCl. Dung dch AgNO3 ngoi nh sng d b phn hy do cn cha trong chai thy tinh mu 10.2.1.2. K thut phn tch V d: Sai s 0,1% tng ng vi 0,025mL i vi th tch 25 mL cht chun. Nng ion Ag + c tnh l 4,78. 10
-6

mol/L nu thm 24,975mL dung dch Ag +

0,1M v sau khi thm 25,05mL cng dung dch vo 370

dung dch Cl- 0,05M th c 3,81. 10 -5 mol/L. C th thay i nng ion cromat cn thit to thnh Ag2CrO4 trong khong no chun qu hoc chun cha ti khng ln hn 0,025mL Khi thm 24,975mL cht chun, kt ta Ag2CrO4 c th xut hin nu: T(Ag2CrO4) < [CrO42- ]. [Ag+ ] Nu: [CrO4 2- ] = T / [Ag+ ]=
1,1.10 12 = 0,048 M (4,78.10 6 ) 2 1,1.10 12 = 0,048 M (3,81.10 6 ) 2

V khi thm 25,05mL cht chun, nu: [CrO4 2- ] = T / [Ag+ ]=

R rng p dng phng php Mohr mt cch chnh xc, th c th gi nng cht ch th trong mt khang kh rng, gia 0,0008 v 0,05M. Nhng thc t nng ln hn 0,05M mu vng m ca ion cromat s cn tr mu ca Ag 2CrO4. Nn phi dng nng cromat nh hn 0,05M. Khng nn tnh tan lng ti thiu cromat cn phi c to thnh m mt c th nhn bit ra n, m ch nn xc nh n bng thc nghim Cn ch n acid ca mi trng bi v khi tng nng ion [H+] cn bng xy ra: 2 CrO42- + 2 H+ Cr2O72- + H2O s chuyn dch v bn phi. tan ca dicromat bc cao hn kh nhiu so vi tan ca cromat bc, do i vi pH ch th trong mi trng acid i hi nng ion Ag+ ln ng k, nu phn ng c th xy ra. Trong 371

mi trng kim c th c oxyt bc lng xung: 2 Ag+ + 2 OH 2 AgOH Ag2O + H2O Nh vy phng php Mohr xc nh clorua bc cn phi c tin hnh trong mi trng trung tnh hoc gn trung tnh (pH = 7 10). C th gi nng ion [H+] trong khang mt cch thun tin bng cch thm vo NaHCO3 10.2.2. Phng php Volhard 10.2.2.1. Nguyn tc Phng php Volhard c dng nh lng clorua gin tip Thm vo mu clorua mt lng chnh xc d dung dch AgNO3 chun v lng d ion Ag + c xc nh bng php chun ngc bng dung dch Tioxyanat chun. u th c bit ca phng php ny l kh nng chun trong mi trng acid mnh bi v nhng ion nh CO32-, C2O42-, Asenat khng cn tr. Nhc im: Khc vi cc halozenua khc, AgCl tan nhiu hn AgSCN, nn c phn ng: AgCl + SCNAgSCN + ClS gy tr ngi nhiu cho s pht hin im cui php chun theo phng php Volhard. V vy quan st thy s tiu tn qu mc ion SCN- v xut hin sai s phn tch m. Gi tr sai s ph thuc vo nng cht ch th. trnh sai s lin quan vi phn ng gia SCN - v AgCl phi dng hai bin php sau: 372 To ra nng cht ch th cc i c php

(khang 0,2M Fe3+) Tch kt ta AgCl trc khi chun ngc bng dung dch SCN- Php chun mt phn nc lc sau khi lc AgCl cho kt qu tt nht trong iu kin kt ta ng t tt.

S tiu tn thi gian cho php lc chnh l nhc im ca phng php ny. Bng 10.2. Nhng phng php kt ta o Ag Cu t cn xc nh AsO42- ; Br- ; I SCN
-

Phng php xc nh im cui ; bc

Ghi ch

Khng cn tch mui Trc khi chun ngc lng Ag+ d, cn tch mui bc Chun tip theo lng Ag+ d trong phn ng: BH4- + 8 Ag+ + 8 OH 8 Ag + H2BO2 + 5 H2O

CO3- 2; CrO4 2- ; CN- ; Cl-; C2O42- ; PO43-

BH4Phng Php Volhard Epoxit

Chun lng Cl- d sau khi ch ha bng hydro clorua

373

Kt ta K+ bng lng K
+

d B(C6H5)4thm d Ag+

bit, to kt

ta AgB(C6H5)4v chun ngc Ag+ d Phng Br ; Cl

-

php Mohr

I - ; SeO32- ; Br- ; Ch th Clhp th V(OH)4+ ; acid bo, mecaptan Phng cc php Chun trc tip bng cc phn tch dung dch Ag+ in ha Kt ta di dng ZnHg(SCN)4. Lc v ha tan trong acid, thm d Ag+, chun ngc Ag+ d Kt ta di dng PbClF. Lc v ha tan trong acid thm d Ag+ ; chun ngc Ag+ d Trong phn ln cc trng hp, php chun kt ta da trn s dng dung dch AgNO3 chun, nn phng php ny cn gi l phng php o bc. Nhiu phng php xc nh nu trong bng trn, dng 374

Zn2+

Phng Php Volhard bin dng

F-

phng php kt ta cu t cn xc nh bng mt lng chnh xc dung dch AgNO 3 v chun tip theo bng dung dch KSCN chun theo phng php Volhard. C hai thuc th nu c th dng c di dng cht chun u nhng vi thuc th KSCN c kh nng ht m c, nn gy kh khn cho php cn n nhng iu kin th nghim c m cao. Nhng dung dch AgNO3 v KSCN bn trong thi gian lu khng gii hn. Bng 10.3. Cc phng php chun kt ta khc
Cht chun K4[Fe(CN)6] Pb(NO3)2 Pb(CH3COO)2 Th(NO3)2 Hg2(NO3)2 NaCl Ion cn xc nh Zn2+ SO42MoO42PO43C2O42F Cl-, BrHg2 2+ Sn phm phn ng Cht ch th

Zn3K2[Fe(CN)6]2 Diphenylamin PbSO4 PbMoO4 Pb3(PO4 )2 Pb C2O4 ThF4 Hg2X2 Hg2X2 Erotrozin B Eosin E Dibromfluoretxein Fluoretxein Alizarin Bromophenol chm Bromophenol chm

10. 3. nh lng mt s mu 10. 3. 1. nh lng Cl- theo phng php Mohr V d nh lng mui NaCl cng nghip Nguyn tc Da trn c s ca phng php chun kt ta 375

trc tip, dng dung dch AgNO3 tiu chun chun trc tip xung dung dch mu c cha thnh phn NaCl. Thc hin phn ng trong mi trng trung tnh hoc kim yu v nhn bit im tng ng bng ch th K2CrO4 khi kt ta xut hin kt ta mu gch. Phn ng chun :

Cl

Ag t AgNO 3

AgCl ket tua trang

+

pTAgCl = 9.75 Phn ng ch th: khi cho d mt git Ag

CrO 4 2 2Ag Ag 2 CrO 4 ket tua o gach

pTAg2CrO4 = 11.95 Mi trng cn c pH < 10 trnh cn bng ph: 2Ag + 2OH = 2AgOH = Ag2O + H2O pTAg(OH) = 7.8 V mi trng cng cn c pH > 6 trnh cn bng ph: Ag2CrO4 = 2Ag + CrO42
+ CrO42 + H = HCrO4 . K thut pha ch + +

Cn khong 0,2g mu mui, chuyn vo cc thy tinh loi 100mL, dng nc nng ha tan, sau lc cn qua giy lc bng xanh, dng nc ct nng ra cho n ht ion Cl (th

376

bng dung dch AgNO3) Dch qua lc v nc ra tp trung vo bnh nh mc 100mL, ngui v dng nc ct nh mc ti vch. Dng pipet ly 3 mu cho vo 3 bnh nn loi 250mL mi bnh 10mL mu + 5 git ch th K2CrO4, lc u

Chun bng dung dch AgNO 3 0.1N ti khi dung dch xut hin kt ta gch. Ghi th tch AgNO3 tiu tn. Tnh hm lng % NaCl trong mu ban u. Tnh ton T th tch chun c ca AgNO3 3 mu, tnh trung bnh c VmL(AgNO3). S ng lng ca AgNO 3 = S ng lng ca NaCl = (C.V) AgNO3 Nn: khi lng NaCl = (C.V) AgNO3. M (NaCl)= 0,1. V. 58,5 = 5,85VmL y l lng NaCl c trong 10mL dung dch c trch t bnh nh mc 100mL, do : khi lng NaCl trong mu ban u l 5,85V.
100 = 58,5V 10
100 = 2,925.10 3. VmL (%) 0, 2

Vy hm lng NaCl ban u l: 58,5 V.

10.3.2. nh lng Cl- theo phng php Volhard V d nh lng dung dch NaCl Da trn c s ca phng php chun kt ta 377

ca phn d, dng dung dch AgNO 3 tiu chun d chnh xc chun dung dch mu c cha thnh phn NaCl. Chun phn d ca dung dch AgNO 3 bng dung dch KSCN thc hin phn ng trong mi trng axit nhn bit im tng ng bng ch th Fe3+ khi kt ta xut hin mu hung . Phn ng chun : Cl + Ag Ag
+ +

= =

AgCl d

(pTAgCl = 9.75) kt ta trng

SCN t KSCN

AgSCN (pTAgSCN = 11.97) kt ta trng

cn li

Phn ng ch th: Fe3+ + SCN = FeSCN2+ Do TAgSCN < TAgCl nn gn im tng ng c th c cn bng ph: AgCl + SCN AgSCN + Cl loi tr cn bng ph ny bng cch loi hay c lp ta AgCl, c th dng bin php: Lc b ta AgCl khi dung dch trc khi chun . un si dung dch vi pht trc khi chun nhm to s ng t ta. Thm dung mi hu c khng trn ln vi nc nh nitro benzen bao ta li bng cch lc

tht mnh dung dch trc khi chun . K thut phn tch 378 Ht 5 mL mu + 3 git HNO3 + 10 mL AgNO3 0,1N + 3 git Fe3+, lc u, lm 3 mu

trong 3 bnh nn 250mL. Chun bng dung dch KSCN 0,1N cho n khi dung dch c mu hung.

T th tch o c 3 mu, tnh hm lng (mg/L) NaCl c trong dung dch mu ban u Tnh ton T kt qa chun 3 mu, tnh V tbnh ca dung dch KSCN l V S ng lng ca KSCN = S ng lng ca AgNO3 d = (C.V) KSCN S ng lng ca NaCl = S ng lng ca AgNO3 phn ng Nn s ng lng ca NaCl = S ng lng ca AgNO3 (ban u - d) khi lng ca NaCl c trong 5mL mu = (CV) AgNO3 b - (CV) KSCN chun = 10. 0,1. 10 - 3 - VmL0,1. 10 - 3 = 10 - 4 (10 - V) (g)= 0,1 (10 - V) (mg) Do , khi lng NaCl c trong 1 L dung dch NaCl l: 0,1 (10 - V).
5 = 5(10 - VmL) 10 - 4 (mg/L). 1000

379

THC HNH PHN TCH TH TCH

BI THC HNH NH LNG ION CLO I. CHUN B Ho cht: Nitro benzen ; NaCl 0,05 N ; HNO3 ; Fe2(SO4 )3 5% Ch th: H tinh bt 1 %; ch th Cromat: K2CrO 4 8% pha trong 100mL nc ct ; fluoressein

0.1% pha trong cn. II. XC NH NNG CC DUNG DCH CHUN Th nghim 1 Dung dch mu l dung dch AgNO3 (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc Ht 10 mL NaCl 0,05 N + 10 git ch th Cromat + khong 20mL nc ct. Lm 3 mu trong 3 bnh nn 250mL

Chun bng AgNO3 cho n khi ta c mu cam nht. T th tch o c 3 mu, tnh li chnh xc nng dung dch AgNO3 Th nghim 2 Dung dch mu l dung dch KSCN (0,01N - 0,05N) c gio vin pha trc, sinh vin khng c bit trc. Ht 10 mL AgNO3 (c nng va c hiu chnh trn) + 3git HNO3 m c + 5 git Fe3+, lm 3 mu trong 3 bnh nn 250mL (dung 380

III.

dch s c ln cn ta trng v vn c nh) Chun bng KSCN cho n khi dung dch c mu hung

T th tch o c 3 mu, tnh nng dung dch KSCN NH LNG HM LNG CA NaCl TRONG MUI N CNG NGHIP THEO PHNG PHP MOHR: Mu l mui NaCl cng nghip dng tinh th: Cn khong 0.2g mu mui, chuyn vo cc thy tinh loi 100mL, dng nc nng ha tan, sau lc cn qua giy lc bng xanh, dng nc ct nng ra cho n ht ion Cl (th bng dung dch AgNO3) Dch qua lc v nc ra tp trung vo bnh nh mc 100mL, ngui v dng nc ct nh mc ti vch. Dng pipet ly 3 mu cho vo 3 bnh nn loi 250mL mi bnh 5mL mu + 5 git ch th K2CrO4, lc u. Chun bng dung dch AgNO3 0.05N (c h s hiu chnh) ti khi dung dch xut hin kt ta

gch. Ghi th tch Nitrat bc tiu tn. Tnh hm lng % NaCl trong mu ban u. Dung dch NaCl cn gi li lm th nghim sau. IV. NH LNG HM LNG CA NACl TRONG MUI N CNG NGHIP THEO PHNG PHP VOLHARD Dung dch mu l dung dch NaCl (0,01N - 0,05N) 381

c HS - SV lm TN trn Th nghim 1 Ht 5 mL mu dung dch mui n pha trn + 3 git HNO3 m c + 10 mL AgNO3 ( c hiu chnh trn) + 3 git Fe3+, lc u, lm 3 mu trong 3 bnh nn 250mL. Chun bng KSCN ( c hiu chnh trn) cho n khi dung dch c mu hung T th tch o c 3 mu, tnh hm lng % NaCl c trong mu mui. Th nghim 2 Ht 5 mL mu + 1 git HNO3 m c + 10 mL AgNO3 ( c hiu chnh trn) + 3git Fe3+ + 2 git Nitro benzen, lc u, lm 3 mu trong 3 bnh nn 250mL. Chun bng KSCN ( c hiu chnh trn) cho n khi dung dch c mu hung T th tch o c 3 mu, tnh nng dung dch NaCl. Cu hi 1. So snh kt qu tnh tan nng ca NaCl trong 2 th nghim trn? 2. Gii thch vai tr NitroBenzen? VI. NH LNG HM LNG CA NACl THEO PHNG PHP FAJANS 382 Ht 25mL dung dch mu + 5mL Fluoressein, lm 3 mu trong 3 bnh nn 250mL. Chun bng dd AgNO 3 th dung dch c kt ta trng AgCl nhum mu (khi cho AgNO3

vo th dd b c, gn im tng ng AgCl kt ta dn dn ng t li lc ny ta phi lc mnh khi kt ta nhum th dng li). Cu hi 1. So snh kt qa 3 phng php Mohr, Volhard, Fajans. C nhn xt g v 3 phng php ny? Vit cc phng trnh phn ng xy ra trong th nghim, v gii thch chng? BI TP 1. Ho tan 1(g) mt loi qung thnh dung dch (A) cha Fe3+. Hi cn dng bao nhiu mL dung dch NH3 1,19% (d = 0,99 g/mL) kt ta hon ton lng Fe3+. Bit trong qung c cha n 10% Fe nh lng hm lng NaCl c trong mui n theo phng php Mohr: Cn 0,8849g mui n c tinh khit 99,5 %, em ho tan bng nc ct nng n khi thu c dung dch 100 mL. Ht 5 mL dung dch mu cho vo cc tam gic cng vi 5 git hn hp ch th (gm 4,2 g K2CrO4 + 0,7g K2Cr2O7 pha trong 100 mL nc ct) v thm 3 git h tinh bt, ri nh mc n 100mL. Tin hnh chun bng AgNO 3 0,1N cho n khi xut hin ta c mu cam nht th tn ht 5,76mL dung dch AgNO3. Tnh khi lng NaCl c trong mui n ban u. T th tch o c 3 mu, tnh nng dung dch NaCl.

2.

2.

383

CC BI TP M RNG, NNG CAO

Cu 1 Tnh pH ca cc dung dch sau: a) Metilamin 0.1M c pKb = 3.36 b) Cu 2 Tnh tan ca CaC2O4 trong dung dch (NH4)2C2O4 0.5M so snh vi tan ca n trong nc. Bit TCaC2O4 = 2,3.10-9 Cu 3 Ha tan 0.2486g K2Cr2O7 tinh khit thnh 500mL dung dch chun K2Cr2O7. Ht 20.00mL dung dch ny, thm mt lng nht nh HCl v KI thch hp ri chun bng 20.05mL Na2S2O3. Tnh nng ng lng ca dung dch Na2S2O3 v chun ca dung dch ? Cu 4 Mt mu Sud cn nng 0.9210g, c pha long thnh 250mL dung dch. Ht ra 50mL dung dch ny em chun bng dung dch HCl 0.1042N, th th tch HCl tiu tn l: a) Nu dng ch th PP VHCl = 20.50mL b) Nu dng ch th MO VHCl = 21.30mL Xc nh hm lng cc thnh phn trong mu ban u Cu 5 Nng cn bng ca NH3 trong 100mL dung dch cha 10-2 mol kt ta AgCl phi l bao nhiu ho tan 384 Acid Lactic C2H5OCOOH 0.2M v Kalilactat C2H5OCOOK 0.2M c pKa = 3.36.

lng kt ta. Tch s tan ca AgCl TAgCl = 10-9,75 v phc ca Ag+ v NH3 c logarit hng s bn tng cng ln lt 2 nc l 3,22 v 7,24. Cu 6 em chun 50mL dung dch HCl 0,05M bng V(mL) dung dch NaOH 0,1M: a) Tnh gi tr pH ca dung dch chun c khi V(mL) ln lt l: 0 - 10 - 20 - 24,9 - 25 - 25,1 26 - 30 (mL) V ng chun (pH - VmL dung dch NaOH) ng vi cc gi tr pH va tm c cu a. Xc nh bc nhy chun vi sai s 0,2%.
GII THIU MT S THI - KIM TRA

b)

c)

Thi gian lm bi: 90 pht S 01 Cu 1: 2 im Tnh pH ca dung dch sau khi trn nh sau: a. Trn 29.90mL dung dch axit pyridinecarboxylic c nng 0.020M vi 20.00mL dung dch KOH c nng 0.023M. Trn 29.90mL dung dch axit pyridinecarboxylic c nng 0.020M vi 26.00mL dung dch KOH c nng 0.023M. Bit axit pyridinecarboxylic (C5H4NCOOH) c hng s ion ha K=5.10-6. 385

b.

Cu 2: 1 im Anh (ch) hy tnh lng ha cht cn thit pha cc dung dch sau y a. b. 1L dung dch Fe2+ 50ppm 500mL dung dch Fe2+ 0.1N (dng lm cht chun cho phn ng oxy ha kh) Bit rng cc dung dch trn c pha t (NH4)2Fe(SO4)2.6H2O rn c tinh khit 99.8%. Cho bit N=14; H=1; Fe=56; S=32; O=16. Cu 3: 2 im xc nh hm lng ca CaCO3 trong mu vi ngi ta lm nh sau: Cn chn cn sy kh th c khi lng l: 23.1024g Cn c chn cn v mu th c: 23.4560g Ha tan thnh dung dch v kt ta ion Ca 2+ di dng CaC2O4 Lc, ra v nung 5000C n khi lng khng i Sau khi nung xong cn c chn v mu th c 23.2260g Hi trong mu vi c bao nhiu % l CaCO3? Cho Ca=40; C=12; O=16. Cu 4: 3 im Chun 10mL HCl 0.1M bng dung dch NaOH c cng nng a. 386 Tnh khong bc nhy pH ca php chun ng vi th tch ca cht chun l 9.99mL v

b.

10.01mL? Chn cht ch th no trong s cc ch th sau y vi sai s khng qu 0.1%: phenolphtalein (pT=9); metyl (pT=5); metyl cam (pT=4). Tnh sai s ch th khi s dng cht ch th chn?

c.

Nu tin trnh chun chun c 7mL HCl

th pH ca dung dch trong bnh chun lc ny l bao nhiu? Cu 5: 3 im nh phn Fe(III) v Al(III) trong cng mt hn hp, ngi ta lm nh sau: Ly 50.00mL hn hp mu m pH=2 ri chun bng dung dch EDTA 0.04016M vi ch th sunfosalixilic th ht 29.61mL. Tip theo, thm vo dung dch 50.00mL dung dch EDTA trn, un nng m pH=5 ri chun bng dung dch Zn2+ 0.03228M vi ch th xylenol da cam th ht 19.03mL. a. Gii thch v vit cc phn ng xy ra? b. Tnh nng mol/L ca mi ion c trong dung dch mu ban u?

S 02 Cu 1: 2 im Tnh th oxy ha kh tiu chun iu kin (E o) ca cp Cu2+/Cu+ khi cho lng KI d kt ta vi Cu+ to thnh CuI. Bit tch s tan ca CuI l 10-12, th oxy ha chun ca cp Cu2+/Cu+ l 0.170V. Cu 2: 1 im Anh (ch) hy tnh lng ha cht cn thit pha 387

cc dung dch sau y a. 1L dung dch K2Cr2O7 0.1N (pha xc nh cht kh trong mi trng axit)

b. 500mL dung dch K2Cr2O7 5% Bit rng cc dung dch trn c pha t K2Cr2O7 rn c tinh khit 99.8%. Cho bit O=16; K=39; Cr=52. Cu 3: 2 im xc nh hm lng MgO trong mu xi mng, ngi ta cn 2.0132g mu, em phn hy thnh dung dch ri nh mc thnh 250mL. Ly 25mL dung dch trn kt ta ion Mg2+ di dng MgNH4PO4. Sau khi lc, ra v nung nhit thch hp n khi lng khng i th cn c 0.1278g Mg2P2O7. Tnh hm lng % MgO c trong mu? Cho bit: Mg=27; P=31; O=16; N=14; H=1. Cu 4: 3 im Chun 10mL HCl 0.01M bng dung dch NaOH c cng nng a. Tnh pH v v ng nh phn ti cc im khi th tch cht chun HCl l: 0.00mL; 5.00mL; 9.00mL; 9.99mL; 10.00mL; 10.01mL; 12.00mL; 15.00mL. b. Chn cht ch th no trong s cc ch th sau y (pT=9; pT=6.5; pT=5; pT=4) vi sai s khng qu 0.1%. Nu tin trnh chun chun c 19.00mL

c.

HCl th pH ca dung dch trong bnh chun lc ny l bao nhiu? Cu 5: 2 im C 100mL dung dch hn hp Fe3+ v TiO2+, ngi ta 388

lm th nghim nh sau: Ly ra 25mL dung dch hn hp trn cho qua ct kh Ag kh Fe3+ xung Fe2+ ri chun lng Fe2+ sinh ra bng dung dch K 2Cr2O7 0.05N trong mi trng axit th ht 25.50mL Cng ly ra 25mL hn hp trn cho qua ct kh Zn kh Fe3+ xung Fe2+ v TiO2+ xung Ti3+, dung dch qua khi ct cng c chun nh trn v tn ht 40.25mL dung dch chun K2Cr2O7 0.05N. a. b. Vit cc phn ng xy ra trong qu trnh phn tch trn? Tnh s mg st v titan c trong dung dch ban u? S 03 Cu 1: 2 im Tnh tan ca BaSO4 v CaSO4 trong hai trng hp sau a. Trong nc nguyn cht b. Trong dung dch c cha 0.01M Na 2SO4 Bit tch s tan ca BaSO4 v CaSO4 ln lt l: 10-10 v 10-5. Cu 2: 1 im Anh (ch) hy tnh lng ha cht cn thit pha cc dung dch sau y a. b. 1L dung dch EDTA 0.1N 500mL dung dch EDTA 0.1M 389

Bit rng cc dung dch trn c pha t Na 2Y rn c tinh khit 99.8%. Cho bit khi lng phn t ca Na2Y l 372.24. Cu 3: 2 im xc nh hm lng lu hunh trong mu gang, ngi ta cn 1.0000g mu ha tan bng dung dch HCl dng kh H2S sinh ra c dn vo dung dch cha mui cadimi thu c kt ta di dng CdS, sau em ch ha kt ta CdS bng dung dch CuSO4 chuyn hon ton kt ta di dng CuS. Lc, ra v nung n khi lng khng i th thu c 0.0872g. Tnh % khi lng lu hunh c trong mu gang. Cu 4: 3 im Chun 10mL NaOH 0.1M bng dung dch HCl c cng nng a. Tnh khong bc nhy pH ca php chun ng vi th tch ca cht chun l 9.99mL v 10.01mL? b. Chn cht ch th no trong s cc ch th sau y vi sai s khng qu 0.1%: phenolphtalein (pT=9); metyl (pT=5); metyl cam (pT=4). Tnh sai s ch th khi s dng cht ch th chn? Nu tin trnh chun chun dng pH=12 th phi thm bao nhiu mL dung dch chun HCl na th t im tng ng? Cu 5: 2 im c. Cn 1.2500g mt axit yu HA, ha tan thnh 50.00mL dung dch. Dng dung dch chun NaOH 0.0900M chun dung dch axit HA . Bit rng khi 390

thm vo 8.24mL NaOH th pH=4.30 v khi thm 41.20mL th t im tng ng. a. Tnh khi lng phn t ca HA b. c. Tnh hng s phn ly ca axit HA Tnh pH im tng ng ca qu trnh chun S 04 Cu 1: 2 im Mt dung dch cha ng thi cc ion sau: Mn2+, Ag+, Zn 2+, Al3+, Fe3+, hy: a. V s dng nhnh cy phn tch h thng cc ion ny. b. Vit cc phng trnh phn ng minh ha cc hin tng d nu. CU 2: (2 im) 1. Tnh khi lng tinh th rn (NH4)2Fe(SO4)2.6H2O (M=392 vC) 98% cn cn theo l thuyt pha c 200(mL) dung dch (SO42 ) 10ppm (khi lng ring l d=1,02 g/mL). Gi s trong dung dch in ly hon ton 2. v khng c cc qu trnh khc Pha 200(mL) dung dch KMnO4 0,05N t tinh th rn KMnO4 (M=158vC) c tinh khit

(97%). CU 3: 2 im xc nh hm lng Al 3+ c trong mt mu qung Boxit, ngi ta tin hnh phng php phn tch 391

khi lng m0(g) mu , v chuyn v dng Al(OH)3, sau nung thnh Al2O3 nng m1(g), th qua 5 ln th nghim c cc gi tr cn nh sau: STN m0(g) m1(g) 1 0,5124 0,4981 2 0,5001 0,4882 3 0,5204 0,4996 4 0,5099 0,4788 5 0,5112 0,5019

Qua 5 ln th nghim trn, tm hm lng % ca Al 3+ c trong qung, bit vi xc xut tin cy 0,95 th: STN (n= ) t Q Cu 4: 2 im Thit lp cng thc tnh th in cc E (v) khi chun V0 (mL) dung dch Fe2+ C0N bng V (mL) dung dch Ce4+ CN trong cc trng hp sau: a) Tng qut khi chun b) Trc xa im tng ng c) Ti im tng ng d) Sau xa im tng ng
3

4 3,18 0,77

5 2,78 0,64

6 2,57 0,56

7 2,45 0,51

0 Bit E Fe

/ Fe2

0 = + 0,68 (v), ECe

/ Ce 3

= + 1,44(v)

Cu 5: 2 im Cho 50mL dung dch CH3COOH 0,1M c chun bi V (mL) dung dch NaOH 0,1M a) Hy xc nh pH ca dung dch thu c khi chun dung dch NaOH vi V = 0 25 49

392

b) c)

49,9 - 50 50,1 60 (mL), bit pka = 10-4,75 Khi chun vi V(NaOH) = 49,9 (mL) th sai s php chun l bao nhiu? Tnh sai s cho tng ch th sau, t nhn ra php chun c chnh xc, th trong cc ch th sau, ch th no nn c s dng ? Khong pH 2,9 4,0 3,8 5,4 4,8 6,4 10 12 S bin i mu Dng acid Vng Vng Vng Dng baz Vng Xanh bin Tm

Cht ch th Metyl vng BromCresol lc Clo phenol Alizarin S 05 Cu 1: 2 im

Mt dung dch cha ng thi cc ion sau: Mn2+, Ag+, Cu2+, Al3+, Fe3+, hy: a. V s dng nhnh cy phn tch h thng cc ion ny. Vit cc phng trnh phn ng minh ha cc hin tng d nu. Cu 2: 2 im b. 1. Pha 1(L) dung dch K4[Fe(CN)6] 200ppm (d= 1,12 g/mL) t dung dch K4[Fe(CN)6] 1% (d0 =1,24g/mL) Tnh khi lng tinh th rn 393

2.

(NH4)2Fe(SO4)2.16H2O (M=572 vC) 97% pha c 200(mL) dung dch (SO42 ) 10ppm (khi lng ring l d=1,02 g/mL). Gi s trong dung dch in ly hon ton v khng c cc qu trnh khc Cu 3: 2 im xc nh hm lng Fe3+ c trong mt mu qung Pyrit, ngi ta tin hnh phng php phn tch khi lng m0(g) mu , v chuyn v dng Fe(OH)3, sau nung thnh Fe2O3 nng m1(g), th qua 5 ln th nghim c cc gi tr cn nh sau: STN m0(g) m1(g) 1 0,5124 0,4981 2 0,5001 0,4882 3 0,5204 0,4996 4 0,5099 0,4788 5 0,5112 0,5019

Qua 5 ln th nghim trn, tm hm lng % ca Al3+ c trong qung, bit vi xc xut tin cy 0,95 th: STN (n= ) t Q Cu 4: 2 im Thit lp cng thc tnh pMg khi chun V0 (mL) dung dch Mg2+ C0N bng V (mL) dung dch EDTA CN trong cc trng hp sau: a) b) c) Tng qut khi chun Trc xa im tng ng Ti im tng ng 4 3,18 0,77 5 2,78 0,64 6 2,57 0,56 7 2,45 0,51

d) Sau xa im tng ng Gi s rng Mg c kh nng to phc vi EDTA v 394

hydroxyt, EDTA l acid a chc phn ly bn nc, hng s bn iu kin ca phc gia M v EDTA ln. Cu 5: 2 im Cho 50mL dung dch CH3COOH 0,001M c chun bi V (mL) dung dch NaOH 0,001M a) Hy xc nh pH ca dung dch thu c khi chun dung dch NaOH vi V = 0 25 49 49,9 - 50 50,1 60 (mL), bit pka = 10-4,75 Khi chun vi V(NaOH) = 49,9 (mL) th sai s php chun l bao nhiu? Tnh sai s cho tng ch th sau, t nhn ra php chun c chnh xc, th trong cc ch th sau, ch th no nn c s dng? Khong pH 2,9 4,0 3,8 5,4 4,8 6,4 10 12 S bin i mu Dng acid Vng Vng Vng Dng baz Vng Xanh bin Tm

b) c)

Cht ch th Metyl vng BromCresol lc Clo phenol Alizarin S 06 CU 1: 2 im

Mt dung dch cha ng thi cc ion sau: Fe3+, Ca2+, Ag+, Zn2+, Al3+, hy: a. b. V s dng nhnh cy phn tch h thng cc ion ny. Vit cc phng trnh phn ng minh ha cc hin tng nu. 395

CU 2: 2 im 1. Pha 500(mL) dung dch K3[Fe(CN)6] 20ppm (d= 1,12 g/mL) t dung dch K3[Fe(CN)6] 5% (d=1,24g/mL) Tnh khi lng tinh th rn

2.

(NH4)2Fe(SO4)2.16H2O (M=572 vC) 97% pha c 200(mL) dung dch (NH4+) 10ppm (khi lng ring l d=1,02 g/mL). Gi s trong dung dch in ly hon ton v khng c cc qu trnh khc Cu 3: 2 im Ht 5 mL dung dch mu Al3+ Cx (chnh mu v pH = 5 bng cch cho NH 4OH vo) + 5mL m pH = 5,5 + 10 mL dung dch EDTA 0,1N+ 3 git ch th axit Sunfosalicilic, lm 5 mu trong 5 bnh nn 250mL Chun bng dung dch Fe3+ 0,1N cho n khi dung dch chuyn t khng mu sang nu th o c th tch dung dch Fe3+ l V0(mL), theo kt qu: Mu s V0 (mL) 1 9,8 2 9,7 3 9,7 4 9,6 5 9,8

396

Vi tin cy 95% hy tnh nng C x ca ion Al3+ c trong mu ban u.

S th nghim T

2 12,7

5 2,78

6 2,57

10

4,3 3,18

2,45 2,37 2,31 2,23

1,22

0,94

0,77 0,64

0,56

0,51 0,47 0,44 0,41

Gi s cc dung dch u c khi lng ring d = 1 g/mL Cu 4: 2 im Thit lp cng thc tnh pAg khi chun V0 (mL) dung dch Cl- C0N bng V(mL) dung dch Ag+ CN trong cc trng hp sau: a) Tng qut khi chun b) Trc xa im tng ng c) Ti im tng ng d) Sau xa im tng ng Cu 5: 2 im Cn 0,1982 (g) MgSO4.7H2O (p = 98%), cho vo chn nung, thm 3mL HCl 1:1 + 40mL nc ct + 2 git MR 0,1% + 15mL (NH4)2HPO4 0,1N. un nh dung dch 40-45 0C. Thm 2mL NH3 c cho n khi dung dch ha vng. ngui hn thm tip 5mL NH3 c. un cch thy 30 pht. Tin hnh lc nng qua giy lc bng xanh vi k thut lc gn (bng cch dng dung dch NH 3 1:10 397

ra kt ta cho n ht ion Cl , th bng AgNO3). Tip tc ra kt ta 2 ln, mi ln 5mL NH4NO3 0,05N. Chuyn giy lc cha kt ta vo chn nung, tro ha chn mu trn bp in n khi giy lc ha en, chuyn vo l nung chnh ti nhit 850 oC, nung khong 40 pht (ti khi kt ta trng), ly ra bnh ht m 5 pht, cn c phn rn l 0,0725(g). a) b) b) Vit cc phng trnh phn ng xy ra. Cho bit vai tr ca HCl 1:1, MR, (NH4)2HPO4, NH3 Tnh hm lng ca MgSO4 c trong mu.

398

 TRC NGHIM

MN: HO HC PHN TCH Sinh vin c k ni dung cu hi trong ct (2) ri chn cc cu trong ct (3) ghi vo ct (4) ngay dng u tin ca ct ny (ch khng nh cho hay t m s la chn ct 3) STT (1) 1 NI DUNG (2) pha ch 100mL dung dch C2H2O4 0,1M, th + Cn bao nhiu gam lng tinh th C2H2O4. 7 H2O. Cn bao nhiu gam lng dung dch C2H2O4 20%( d= 1,24g/mL) 2 Cn bao nhiu (g) mui (NH4)2Fe(SO4)2.6H2O (M=392,14) 98% theo l thuyt pha thnh 80(g) dung dch mui (NH4)2Fe(SO4)2 5%. Tnh khi lng tinh th KMnO4 98% theo l thuyt pha 500mL dung dch KMnO4 0,05N. 399 LA CHN (3) a) 2,16 (g) v 4,5(g) b) 2,16 (g) v 5,5(g) c) 3,16 (g) v 4,5(g) d) 3,16 (g) v 5,5(g) a) 83,370(g) v 0,1344(g) b) 83,363(g) v 0,1344(g) c) 83,363(g) v 0,1340(g) d) 83,360(g) v 0,1344(g) S (4)

Tnh th tch nc ct cn pha vo: a. 100mL dung dch

a) 300(mL) 300(mL) 29,24(mL)

HCl 20% (d= b) 300(mL) 1,1g/mL) thu 330(mL) c dung dch c 29,24(mL) nng 5% b. 100g dung dch H2SO4 20% (d= 1,12g/mL) thu c) 330(mL) 300(mL) 29,20(mL) d) 330(mL)

c dung dch c 300(mL) nng 5% 29,24(mL) c. 100g dung dch NH3 2M (c d = 1,14g/mL) thu c dung dch c nng 1,5M 4 Ho tan 0,2g qung thnh dung dch (A) cha Fe3+. Hi cn phi dng bao nhiu mL dung dch NH3 1,89% (d = 0,99g/mL) kt ta hon ton Fe3+. Bit trong qung c cha n 30% Fe a) 2,90 (mL) b) 3,00 (mL) c) 2,82 (mL) d) 2,92 (mL)

400

T 0,4154g vi c ham lng CaO l 43%, c chuyn ho thnh 250mL, ri lm kt ta hon ton lng Ca2+ bng m(g) dung dch (NH4)2C2O4 4%. Bit tch s tan ca CaC2O4 l 1,78.10 -9. Tm m, nu lng Ca2+ coi nh kt ta hon ton nu trong dung dch hm lng [ CaC2O4 ] 10 - 4 g/L

a) 11,635 (g) b) 11,640 (g) c) 11,645 (g) d) 11,655 (g)

Tnh pH dung dch thu c khi pha trn 100 mL NaOH 0,1 N v 50 mL NH4OH 0,1 N (Kb =1,78.10 -5) Tnh pH dung dch thu c khi pha trn 100 mL HCl 0,1 N v 100 mL NaOH 0,1 N v 100mL Na2SO4 0, 2M

a) 12,63 - 5 b) 12,73 - 6 c) 12,83 - 7 d) 12,93 - 8

Tnh pH dung dch thu c khi pha trn 100 mL HCl 0,1 N v 100 mL NaOH 0,1 N v 50mL Na2SO4

a) 7 - 9,70 b) 7 - 9,72 c) 7 - 9,74 d) 8 - 9,72

401

Tnh pH hn hp 50 mL NaOH 0,1 N v 150 mL NH4OH 0,1 N 8 Tnh hng s cn bng ca dung dch sau: Dung dch NH3 0,1M c = 1,35% Dung dch CCl3COOH 10 3 M c = 54% a) 1,35. 10 5 54. 10 6 b) 1,35. 10 6 54. 10 7 c) 1,35. 10 5 54. 10 7 d) 1,35. 10 4 54. 10 7 9 Tnh nng [H+] ca cc a) 3,4 - 8,40 dung dch sau: b) 3,3 - 8,38 4 Dung dch HCl 5.10 M c) 3,2 - 8,40 Dung dch CH3COONa 10 d) 3,1 - 8,38 2 M (c pKa= 4,75) 10 Tnh nng [H+] khi pha trn cc dung dch sau: Dung dch CH3COOH 0,1M v dung dch CH3COONa 0,2M 100mL dung dch CH3COOH 0,1M v 50mL dung dch CH3COONa 0,2M Dung dch NH3 0,1M + dung dch NH4Cl 0,2M 50mL dung dch NH3 402 a) 5,04 - 4,70 - 8,90 - 8,60 b) 5,05 - 4,75 - 8,95 - 8,65 c) 5,06 - 4,80 - 8,96 - 8,70 d) 5,07 - 4,75 - 8,90 - 8,75

0,1M + 100mLdung dch NH4Cl 0,2M 11 Dung dch A l dung dch a) 2,02 - 2,48 HIO3 0,01N (pKa = 0,79) - 12,8 - 2,60 Tnh pH ca dung dch A. b) 2,04 - 2,47 Ht chnh xc 10 mL dung dch A cho vo 20 - 12,8 - 2,58 c) 2,03 - 2,47 -

mL dung dch HCl 10- 4 N. 12,7 - 2,58 Tnh pH ca dung dch d) 2,02 - 2,47 to thnh Ht chnh xc 10 mL dung dch A cho vo 20 mL dung dch NaOH 10- 1 N. Tnh pH ca dung dch to thnh: Ht chnh xc 10 mL dung dch A cho vo 20 mL dung dch NaOH 10-3 N. Tnh pH ca dung dch to thnh. 12 Dung dch A l dung dch HClO2 0,01N (pKa = 1,97) Tnh in ly dung dch A. Ht chnh xc 10 mL dung dch A cho vo 20 mL dung dch HCl 10- 4 N. a) 62,9% - 2,56 - 12,5 - 2,67 b) 63,0% - 2,50 - 12,8 - 2,67 c) 62,0% - 2,50 - 12,5 - 2,67 d) 62,9% 403 - 12,8 - 2,58

Tnh pH ca dung dch to thnh Ht chnh xc 10 mL dung dch A cho vo 20 mL dung dch NaOH 10- 1 N. Tnh pH ca dung dch to thnh Ht chnh xc 10 mL dung dch A cho vo 20 mL dung dch NaOH 10- 3 N. Tnh pH ca dung dch to thnh. 13 Dung dch A l dung dch HSCN 0,01N (pKa = 0,6) Tnh in ly v pH ca dung dch A. Ht chnh xc 10 mL dung dch A cho vo 20 mL dung dch HCl 10- 4 N. Tnh pH ca dung dch to thnh Ht chnh xc 10 mL dung dch A cho vo 20 mL dung dch NaOH 10- 1 N. Tnh pH ca dung dch to thnh 14 Trong bnh nh mc 100mL dung dch CH3 404

2,56 - 12,8 2,67

a) 96,3% 2,016 - 2,47 12,8 b) 96,3% 2,010 - 2,40 12,7 c) 96,0% 2,016 - 2,40 12,6 d) 96,0% 2,010 - 2,47 12,5

a) 126,67mL 2,49 - 3,61

COOH 20% ( d = 1,1g/mL), pKa = 4,75 Ht chnh xc 20 mL dung dch CH3 COOH trn, ri pha vi V mL H2O th thu c dung dch mi c nng 0,5M. Tnh V. Ht chnh xc 20 mL dung dch CH3 COOH trn ri pha vi 80 mL dung dch CH3COONa 10- 3 M th dung dch mi c pH l bao nhiu ? Ht chnh xc 20 mL dung dch CH3 COOH trn ri pha vi 80 mL H2O vo trong cng mt bnh erlen khc, sau em chun vi 10 mL dung dch NaOH 0,5N th ti im cn bng dung dch c chun c pH l bao nhiu? 15 Trong bnh nh mc 100mL dung dch CH3 COOH 20% ( d = 1,1g/mL), pKa = 4,75

b) 126,67mL 2,49 - 3,60 c) 126,60mL 2,50 - 3,60 d) 126,60mL 2,50 - 3,61

a) 20mL - 2,63 - 3,90 b) 20mL - 2,64 - 3,89 405

a)

Ht chnh xc 20 mL

c) 200mL -

dung dch CH3 COOH 2,65 - 3,89 trn, ri pha vi V mL d) 200mL H2O th thu c dung dch mi c nng 0,5M. Tnh V. b) Ht chnh xc 20 mL dung dch CH3 COOH trn ri pha vi 80 mL dung dch CH3COONa 10- 3 M th dung dch mi c pH l bao nhiu ? c) Ht chnh xc 20 mL dung dch CH3 COOH trn ri pha vi 80 mL H2O vo trong cng mt bnh erlen khc, sau em chun vi 10 mL dung dch NaOH 0,5N th ti im cn bng dung dch c chun c pH l bao nhiu? 16 Bng phng php gii chnh xc, hy xc nh 406 a) 11,12 10,62 - 2,87 2,66 - 3,89

pH ca cc dung dch sau 3,38 - 5,12 (tnh n 2 gi tr sau du p hy): 100mL dung dch NH4OH 0,1N (pKb = 4,75) 100mL dung dch NH4OH 0,01N (pKb = 4,75) 100mL dung dch CH3COOH 0,1N (pKa = 4,75) 100mL dung dch CH3COOH 0,01N (pKa = 4,75) 100mL dung dch H3BO3 0,1N pKa = 9,24) 17 Bng phng php gii chnh xc, hy xc nh pH ca cc dung dch thu c sau khi pha trn (tnh n 2 gi tr sau du p hy): Trn 100 mL NaOH 0,1 N v 50 mL NH4OH 0,1 N (pKb =4,75) Trn 100 mL NaOH 0,01 N v 50 mL NH4OH 0,01 N (pKb =4,75) Trn 100 mL NaOH 0,01 a) 9,00 - 8,95 9,95 - 9,72 10,65 b) 9,00 9,00 9,95 - 9,72 10,95 c) 8,95 9,00 9,95 - 9,72 10,95 d) 8,95 - 8,95 9,95 - 9,72 10,65 b) 11,12 10,72 - 2,90 3,38 - 5,10 c) 11,10 10,72 - 2,87 3,40 - 5,10 d) 11,10 10,62 - 2,90 3,40 - 5,12

407

N v 50 mL NH4OH 0,1 N (pKb =4,75) Trn 50 mL NaOH 0,1 N v 150 mL NH4OH 0,1 N (pKb =4,75) Trn 50 mL NaOH 0,01 N v 150 mL NH4OH 0,1 N (pKb =4,75) 18 Trong dung dch cha cc Th t xut anion: CO3-2, C2O4 2 -, hin ta s l: SO42-. Khi cho ion Ca 2+ vo th kt ta no to trc? bit tch s tan ca cc ta: T CaC2O4 = 3,8 .10 T CaCO3 = 1,7 .10-8 T CaSO4 = 6,26 .10-5
-9

a) CaC2O4 CaCO3 CaSO4 b) CaCO3 CaSO4 CaC2O4 c) CaC2O4 CaSO4CaCO3 d) CaCO3 CaC2O4 CaSO4.

19

Cho 2 cp oxy ho kh [MnO4- / Mn2 ] v [ClO3(H+)/ Cl- ] c E0 ln lt l 1,51(v) v 1,45(v). Xc nh hng s cn bng ca phn ng ny pH =

a) 10 -30,5 b) 10 -10,5 c) 10 20,5 d) 10 30,5

408

0. Cho ming ng kim loi 20 vo dung dch AgNO3 0,01M. Tnh nng ion Cu2+ trong dung dch to
0 thnh. Bit E Cu
2

a) 2,071. 10 3 M b) 2,0. 10 3 M c) 2,01. 10 3 M d) 2,071. 10 2 M a) 6,8987(g)15,7981(g) b) 6,8990(g)15,7981(g) c) 6,8990(g)15,7980(g) d) 6,8987(g)15,7980(g) a) 7,73(mL) b) 7,83(mL) c) 7,93(mL) d) 7,70(mL)

=
Cu

0,34(v) v E

0 Ag Ag

=0,8(v)

Tnh hm lng % P v 21 P2O5 trong mt 5(g) mu phn, khi em kt ta P di dng MgNH4PO4, ri nung nhit 650 0C, thu c 1,235(g) Mg2P2O7. Ho tan 1(g) mt loi 22 qung thnh dung dch (A) cha Fe3+. Hi cn dng bao nhiu mL dung dch NH3 1,19% (d = 0,99 g/mL) kt ta hon ton lng Fe3+. Bit trong qung c cha n 10% Fe Lng K trong mt loi 23 phn c chuyn t

a) 1,000(g) b) 0,007(g) 409

dng K2O thnh KClO4. Hi khi lng phn l bao nhiu % K2O thu c gp 100 ln khi lng dng cn KClO4 em chun 50mL dung 24 dch HCl 0,05M bng V(mL) dung dch NaOH 0,1M: Tnh gi tr pH ca dung dch chun c khi V(mL) ln lt l: 0 - 20 - 24,9 - 25,1 (mL) em chun 50mL dung 25 dch HCl 0,05M bng V(mL) dung dch NaOH 0,1M: Xc nh bc nhy

c) 0,008(g) d) 0,009(g)

a) 1,3 - 2,15 3,90 - 10,12 b) 1,3 - 2,2 3,90 - 10,12 c) 1,3 - 2,2 3,87 - 10,12 d) 1,3 - 2,15 3,87 - 10,12 a) 3,176 10,824 b) 4,176 10,824

c) 3,176 chun vi sai s 0,2%. 9,824 d) 4,176 9,824 26 Tnh th oxy ha kh ca phn ng khi cho 10 mL Fe2+ 0,1N pha trn vi 10 mL dung dch KMnO4 0,1N trong mi trng a) 1,38 (v) 0,70 (v) b) 1,38 (v) 0,68 (v) c) 1,40 (v) -

acid. Nu ch thm 5 mL 0,70 (v) dung dch KMnO4 0,1N th d) 1,40 (v) 410

th oxy ha kh ca phn ng l bao nhiu.

0 Bit: E Fe
3

0,68 (v)

/ Fe2

= + 0,68 (v) ;

0 E MnO

/ Mn2

= + 1,52(V)

411

P N CC CU HI V BI KIM TRA

HNG DN GII CC BI TP BI 1 1. Tnh hng s cn bng ca dung dch sau: 1.1. Dung dch NH3 0,1M c = 1,35% 1.2. Dung dch CCl3COOH 10 3 M c = 54% 2. Tnh nng [H+] ca cc dung dch sau: 2.1. Dung dch HCl 5.10 4 M 2.2. Dung dch CH3COONa 10 2 M (c pKa= 4,75) 3. Tnh nng [H+] khi pha trn cc dung dch sau: 3.1. Dung dch CH3COOH 0,1M v dung dch CH3COONa 0,2M 3.2. 100mL dung dch CH3COOH 0,1M v 50mL dung dch CH3COONa 0,2M 3.3. Dung dch NH3 0,1M + dung dch NH4Cl 0,2M 3.4. 50mL dung dch NH3 0,1M + 100mLdung dch NH4Cl 0,2M Gii 1.1. Trong dung dch c s in ly: NH3 + H2O NH4+ + OHNng ban u: 0,1 0 0 Nng phn ly: x x x Nng cn bng: 0,1 x x x M: =
x 0,1

x = 0,1. 1,35% = 1,35. 10 3.

x2 (1,35. 10 -3 ) 2 = 1,35. 10 5 0,1 x 0,1 1,35. 10 -3

Nn: KCB =

1.2. Tng t nh cu 1.1, th: CCl3COOH CCl3COO- + 412

H+

Nng ban u: Nng phn ly: Nng cn bng: =

x 0,001

0,01 x 0,001 x

0 x x

0 x x

x = 0,001. 54 % = 54. 10 5.

Nn: KCB =

x2 (54. 10 -5 ) 2 = 54. 10 7 -5 0,001 x 0,001 54. 10

2.1. Xt cn bng trong dung dch: HCl H+ + ClNn : [H+] = [HCl] = 5.10 4 M 2.2. Xt cn bng trong dung dch: NaCH3COO CH3COO- + Na+ CH3COO- + H2O CH3COOH + OHNng ban u: 0,01 0 0 Nng phn ly: x Nng cn bng: 0,01 x pKa = 4,75 ka = 10 4,75 Kb =
x2 0,01 x

pH = 3,3

x x Kb =

x x

10 14 = 10 9,25 4,75 10

x2 + 10 9,25 x - 10 11,25 = 0 Gii phng trnh ny c: x = 2,371.10 6 [OH-] = 2,371.10 6 Vy: pOH = 5,62 pH = 14 - 5,62 = 8,38. 3.1. Xt cn bng trong dung dch: CH3COOH Nng ban u: 0,1 Nng phn ly: x CH3COO0,2 x + H+ 0 x 413

Nng cn bng: 0,1 x pKa = 4,75

0,2 + x
x(0,2 x ) 0,1 x

ka = 10 4,75 =

x2 + (0,2 + 10 4,75) x - 10 5,75 = 0 Gii phng trnh ny c: x = 8,89.10 6 Vy: pH = 5,05. [H+] = 8,89.10 6

3.2. Nng khi pha trn cc cht l: [CH3COOH]=

100.0,1 =6,67.102M 100 50

[CH3COONa] =

50.0,2 = 6,67. 10 2 M 100 50

Xt cn bng trong dung dch: CH3COOH CH3COONng ban u: 6,67.10 2 Nng phn ly: x Nng cn bng:6,67.102x pKa = 4,75 ka = 10 6,67.10 2 x 6,67. 10 2 + x
4,75

H+ 0 x x

x(6,67 .10 2 x ) = 6,67 .10 2 x

x2 + (6,67. 10 2 + 10 4,75) x - 6,67. 10 6,75 =0 Gii phng trnh ny c: x = 1,77.10 5 [H+] = 1,77.10 5 Vy: pH = 4,75. 3.3. Trong dung dch c s in ly: NH3 + H2O Nng ban u: 0,1 Nng phn ly: x Nng cn bng: 0,1 x 414 NH4+ + OH0,2 0 x 0,2 + x x x

Nn:
Kb = 10 4,75 =
x(0,2 x ) 0,1 x

x2 + (0,2 + 10 4,75) x - 10 5,75 = 0

Gii phng trnh ny c: x = 8,89.10 6 [OH-] = 8,89.10 6 pH = 14 - 5,05 = 8,95 Vy pOH = 5,05

3.4. Nng khi pha trn cc cht l: [NH3] =

50.0,1 = 3,33. 10 2 M 100 50 100.0,2 = 13,3. 10 2 M 100 50

[NH4Cl ] =

Trong dung dch c s in ly:

NH3 + H2O Nng ban u: 3,33.10 2 Nng phn ly: Nng cn bng: NH4+ + 2 13,3. 10 OH0 x x

x x 2 3,33.10 x 13,3. 10 2 + x x(0,133 x ) Nn Kb = 10 4,75 = 0,033 x

x2 + (0,133 + 10 4,75) x 0,033.10 4,75 = 0 Gii phng trnh ny c: x = 4,41.10 6 [OH-] = 4,41.10 6 Vy: pOH = 5,35 pH = 14 - 5,05 = 8,65 HNG DN GII CC BI TP BI 2 1. Tnh th tch nc ct cn pha vo: 1.1. 100mL dung dch HCl 20% (d= 1,1g/mL) thu c dung dch c nng 5% 1.2. 100g dung dch H2SO4 20% (d= 1,12g/mL) thu c dung dch c nng 5% 1.3. 100g dung dch NH3 2M (c d = 1,14g/mL) 415

thu c dung dch c nng 1,5M 2. pha c dung dch m loi: 2.1. Dung dch m acid th phi pha theo t l nh th no v th tch gia V1(mL) dung dch CH3COOH C1M vi V2 (mL) dung dch CH3COONa C2M ? 2.2. Dung dch m baz th phi pha theo t l nh th no v th tch gia V 1(mL) dung dch NH 3 C1M vi V2 (mL) dung dch NH4Cl C2M ? Gii 1.1. Khi lng dung dch HCl 20% l V. d = 100. 1,1 = 110(g) p dng quy tc cho ta c c t l:
5 110 = 20 5 m

m = 330(g) hay th tch H2O

cn thm l 330(mL) 1.2. p dng quy tc cho ta c c t l:

5 100 = 20 5 m

m = 300(g) hay th tch H2O

cn thm l 300(mL) 1.3. Th tch dung dch NH3 2M l

100 = 87,72 (mL) 1,14

p dng quy tc cho ta c c t l:

1,5 87,72 = 2 1,5 V

V = 29,24 hay th tch H2O

cn thm l 29,24(mL) 2.1. Nng khi pha trn cc cht l:

416

CH3COOH] = =

V1.C 1 M v [CH3COONa] V1 V2 V2 .C 2 M V1 V2

Xt cn bng trong dung dch: CH3COOH Nng ban u: Nng phn ly: Nng cn bng:
V1.C 1 V1 V2

CH3COO- +
V2 .C 2 V1 V2

H+ 0 x x

x
V1.C 1 x V1 V2

x
V2 .C 2 +x V1 V2

x(

Lp biu thc: ka = 10 4,75 = Thay x = [H+] = 10

pH

V2 .C 2 x) V1 V2 V1.C1 x V1 V2

v cc ga tr C1M, C2M

vo biu thc lp t l V1 / V2. 2.2. Nng khi pha trn cc cht l: [NH3] =
V .C V1.C 1 M v [NH4Cl ] = 2 2 M V1 V2 V1 V2

Trong dung dch c s in ly: NH3 + H2O Nng ban u: Nng phn ly: Nng cn bng:
V1.C 1 V1 V2

NH4+ +
V2 .C 2 V1 V2

OH0 x x

x
V1.C 1 x V1 V2

x
V2 .C 2 +x V1 V2

417

x(

Lp biu thc: Kb = 10 4,75 =

V2 .C 2 x) V1 V2 V1.C1 x V1 V2

Thay x = [OH-] = 10 (14 pH) v cc ga tr C1M, C2M vo biu thc trn lp t l V1 / V2 HNG DN GII CC BI TP BI 3: 1. Khi trn 100mL dung dch Pb(NO3)2 104M vi 400mL dung dch Na2SO4104M th c kt ta to thnh khng ? Bit tch s tan (T) ca PbSO4=10 7,8. Bin lun cc gi tr a v b khi pha V1mL dung dch BaCl2 nng 2a(M) vi V2 mL dung dch H2SO4 nng 2b(M) th: 2.1. Dung dch thu c khng c ta BaSO 4 hnh thnh 2.2. Dung dch thu c c ta BaSO4 to ra Gii 1. Phn ng pha trn l: Pb(NO3)2 + Na2SO4 Theo khi pha trn: nng ca Pb(NO3)2 = PbSO4 + 2 NaNO3
100 .10 4 = 0,2. 10 - 4. 100 400

2.

400 .10 4 Nng ca Na2SO4 = = 0,8. 10 - 4. 100 400

Nn: [ Pb2+ ] = 0,2. 10 - 4, v [ SO42 ] = 0,8. 10 - 4. Do : [ Pb2+ ]. [ SO42 ] = 0,2. 10 - 4. 0,8. 10 - 4 = 0,16. 10 - 8. M: T (PbSO4 ) = 10 - 7,78 = 1,5. 10 - 8. Vy 418

T (PbSO4 ) > [ Pb2+ ]. [ SO42 ] dung dch khng thu c kt ta PbSO4 2. Phn ng khi pha trn dung dch: BaCl2 + H2SO4 BaSO4 + 2 HCl Khi nng mi cht khi pha trn s l: [Ba2+] = Do : [ Ba2+ ]. [ SO42 ] =
V1.2b V . 2a 4.V1.V2 .a.b . 1 = V1 V2 V1 V2 V1 V2

V1.2a V .2b v [SO42 ] = 1 V1 V2 V1 V2

M T (PbSO4 ) = 10 - 7,78 = 1,5. 10 - 8. 2.1. dung dch thu c khng c BaSO4 to ra th:
4.V1.V2 .a.b < 1,5. 10 - 8. V1 V2

2.2. dung dch thu c c BaSO4 to ra th:

4.V1.V2 .a.b > 1,5. 10 - 8. V1 V2

HNG DN GII CC BI TP BI 4 1. Khi cho dung dch Cu2+ 10 -2 M vo dung dch EDTA 10 -2 M, th nng Cu2+ ti cn bng l bao nhiu ? Bit rng ion Cu2+ c kh nng kt hp vi EDTA to phc bn (hng s bn = 10 18,8 ), v phc ny khng b nh hng bi cc ion H + hoc OH-. Ngoi ra Cu2+ cn c kh nng to phc vi OH- theo 4 phng trnh kt hp, cn EDTA l mt dung dch acid a chc phn ly 4 nc. Dung dch to thnh sau khi pha trn c pH = 6, v cc gi tr hng s cho 419

trc l: 2. Hng s bn 4 nc to phc Cu2+ vi OH- ln lt l 10 7 ; 10 6,68 ; 10 3,32 ; 10 1,5 Hng s bn 4 nc to EDTA t Y4- ln lt l 9,1.10 10 ; 1,85.10 6; 4,76.10 2 ; 103

Pha trn cng mt th tch dung dch Hg2+ 10 4 M vi dung dch EDTA 10 4M, th c th to c phc Hg-EDTA khng ? Tnh nng Hg 2+ ti thi im cn bng sau pha trn. Bit rng dung dch to thnh sau khi pha trn c pH

= 10, v ion Hg2+ c kh nng kt hp vi EDTA to phc bn (hng s bn = 1021,8), v phc ny khng b nh hng bi cc ion H+ hoc OH-. Ngoi ra Hg2+ cn c kh nng to phc vi OH- theo 3 phng trnh kt hp, cn EDTA l mt dung dch acid a chc phn ly 4 nc. Cc gi tr hng s cho trc l: Hng s bn tng cng 6 nc to phc Hg2+ vi OH- ln lt l: 1010,3 ; 1021,7 ; 0; 0; 0; 10 21,2. Hng s bn 4 nc to EDTA t Y4- ln lt l 9,1.10 10 ; 1,85.10 6; 4,76.102 ; 103 Gii 1. Phn ng pha trn: Cu2+ + Y4 CuY 2 Do c cc qu trnh: Cu2+ + OHY
4-

( = 10 18,8 ) (i = 1 (j = 1
-6

Cu(OH)i Hj Y [H ] = 10
+

4) 4) [OH-] = 10 - 8

+ H

Dung dch c pH = 4 420

Nn:
(Cu2+ / OH- ) = 1 + (Y4 -/H+) = 1 + [OH-]i = 1 + 10710 -8 + 10 710 6,68 10 -16 +

+10 7.106,68 10 3,32 10 -24 +10 7 10 6,68 10 3,32 10 1,5 + 9,1.10 10 1,85.10 6 4,76.10 2 10-18

[H+] j =1 +9,1.1010.10-6 + 9,1.1010.1,85.106.10-12

+ 9,1.10 10 1,85.10 6 4,76.10 2 103 10 -24 = 10 5,414 (CuY) = Do gi tr Ta c:

[CuY ] '= [Cu ][Y ]

(Cu2+ / OH- ). biu kin l ' =

(Y4 - / H+ ) = 10 5,414 = 10 13,386

10

13,386

10

(Vi x = [Cu2+ ])

10 13,386 x2 + x - 0,01 = 0 x = 2,02768. 10 - 8. Vy: [Cu2+ ] = 2,02768. 10 - 8 = 10 - 7,69 M 2. Phn ng pha trn: Hg2+ + Y4 CuY 2 Do c cc qu trnh: Hg2+ + OHY
4-

( = 10 18,8 ) 6) 4)

Cu(OH)i (i = 1 Hj Y [H+] = 10 - 10 (j = 1

+ H

Dung dch c pH = 10 Nn:

(Hg2+ / OH- ) = 1+ [OH-]i = 1 + 10 20,3 10 -4 + 10 21,7.10 -8 +

[OH-] = 10 - 4

+ 10 21,7 10 -24 (Y4 - / H+ )= 1 +

5,012. 10 13 10 13,7 [H+] j

= 1 + 9,1.10 10.10 -10 + 9,1.10 10.1,85.10 6.10 -20 + 421

+ 9,1.10 10 1,85.10 6 4,76.10 2 10-30 + + 9,1.10 10 1,85.10 6 4,76.10 2 103 10 -40 = 9,9 (CuY) = (Cu2+ / OH- ). (Y4 - / H+ ) = 10 13,7. 9,9 = 10 7,1

Do gi tr

biu kin l ' =

Nh vy ga tr = 10 7 < = 10 7,1, nn phn ng tp phc ny xy ra Khi ta c:[Hg2+ ] =

C

10 4 = 10 17,7 M. 13, 7 10

HNG DN GII CC BI TP BI 5 1. Tnh hm lng % P v P2O5 trong mt 5(g) mu phn, khi em kt ta P di dng MgNH4PO4, ri nung nhit 650 0C, thu c 1,235(g) Mg2P2O7. Ho tan 1(g) mt loi qung thnh dung dch (A) cha Fe3+. Hi cn dng bao nhiu mL dung dch NH3 1,19% (d = 0,99 g/mL) kt ta hon ton lng Fe3+. Bit trong qung c cha n 10% Fe Lng K trong mt loi phn c chuyn t dng K2O thnh KClO4. Hi khi lng phn l bao nhiu % K2O thu c gp 100 ln khi lng dng cn KClO4 Gii 1. H s chuyn K (P H s chuyn K (P2O5 Nn (%) P = K. 422
m2 1,235 . 100 = 0,2793. .100 = 6,8987(g) 5 m1
2.31 = 0,2793 222 142 = 0,6396 222

2.

3.

Mg2P2O7 ) =

Mg2P2O7 ) =

(%) P2O5 = K. 2. Ta c:

m2 1,235 . 100 = 0,6396. .100 = 15,7981(g) 5 m1

khi lng Fe c trong qung = khi lng Fe3+ = 1. 10% = 0,1(g) s mol ca Fe3+ =
0,1 56

Phn ng to ta: Fe3+ + 3 NH3 + 3 H2O

Fe(OH)3 + 3 NH4+ 3.
0,1 56

Nn: 3. s mol ca Fe3+ = s mol ca NH3 =

V .0,99.1,19 100.17

V = 7,73(mL) 3. Cng thc tnh % khi lng dng cn l:

m 2 V1 K. m1 . V 2 . 100

Theo : % K2O gp 100 ln lng cn KClO4 % K2O = 100. mKClO4 K.

mKClO4 . 100 = 100. mKClO4 mphan
94 = 0,009(g) 2.138 ,5

mphan =

HNG DN GII CC BI TP BI 7 1. em chun 100mL dung dch HCl 0,025M bng V(mL) dung dch NaOH 0,1M a) Tnh gi tr pH ca dung dch chun c khi V(mL) ln lt l: 0 - 10 - 20 - 24,9 - 25 - 25,1 423

26 - 30 (mL) b) V ng chun (pH - VmL dung dch NaOH) ng vi cc gi tr pH va tm c cu a. Xc nh bc nhy chun vi sai s 0,2%.

c) 2.

Ht 10 mL dung dch mu NaOH C x cho vo erlen 250mL cng vi 30 mL nc ct +3 git pp (lm 4 mu). em chun bng dung dch HCl 0,1N cho n khi dung dch chuyn t mu hng tm sang khng mu.Ghi th tch axit HCl 0,1N tiu tn V0 (mL). Vi tin cy 95%. tnh nng dung dch NaOH Mu s V0 (mL) Bit rng: 1 9,8 2 9,75 3 9,7 4 9,6

S th nghim t Q

2 12,7 1,22

3 4,3

4 3,18

5 2,78 0,64

10 2,23 0,41

2,57 2,45 2,37 2,31 0,56 0,51 0,47 0,44

0,94 0,77

Gi s cc dung dch u c khi lng ring d = 1 g/mL Gii 1. a) Phng trnh phn ng: HCl + NaOH NaCl + H2O
100 .0,025 = 25 (mL) 0,1

Ti im tng ng: V =

Ti V = 0: dung dch ch c HCl phn ly mnh nn pH ca dung dch l pH ca acid ny 424

pH = - lg Cx = - lg 0,025 = 1,60 Ti V = 10: dung dch gm NaCl v HCl d [H+] dung dch = [H+]bd - [H+]phn ng [H+] =
100.0,025 10.0,1 = 0,0136 100 10

pH dung dch

= 1,86 Ti V = 20: [H+] =

100.0,025 20.0,1 = 4,167. 10 - 3 100 20
100 .0,025 24 ,9.0,1 = 8. 10 - 5 100 24 ,9

pH dung dch = 2,38 Ti V = 24,9: [H+] =

pH dung dch = 4,09 Ti V = 25: [H+] = [OH-] = 10 - 7 pH dung dch = 7 Ti V = 25,1: dung dch gm NaCl v NaOH d pH dung dch = pH (NaOH d) M:
[OH-] = [OH-]bd - [OH-]phn ng =

25,1.0,1 100 .0,025 = 7,9. 10 - 5 25,1 100

pOH = 4,09 Ti

pH = 14 - pOH = 9,90 [OH-]phn ng

V = 26: [OH-] = [OH-]bd =

26.0,1 100.0,025 = 7,9310 - 4 26 100

pOH = 3,10 pH = 14 - pOH = 10,90 Ti V = 30: [OH-]= [OH-]bd [OH-]phn ng

425

30.0,1 100.0,025 = 3,85.10- 3 30 100

pOH = 2,41 b)

pH = 14 - pOH = 11,59 0,2%, ngha l lng

Sai s chun l

NaOH cho vo dung dch s thiu ( - 0,2%) hoc tha (+ 0,2%) so vi lng acid HCl ti st im tng ng, do : ([OH-] - [H+]). Hay:( (
(
C0 C = C .C 0

0,002

C C 10 14 - [H+]). 0 = 0,002 C .C 0 [H ]

0,025 0,1 10 14 - [H+]). = 0,025 .0,1 [H ]

0,002

10 14 - [H+]) = [H ]

4. 10 5

[H+]2

4.10 - 5 [H+] - 10 - 14 = 0 pH = { 4,39 ; 9,60 }

[H+] = 2,5.10 - 10 v [H+] = 4.10 - 5

Vy 2.

pH = 4,39

9,60 hay bc nhy chun

khong 5,21 n v pH Ta c s ng lng ca NaOH = s ng lng ca HCl Cx = Nn: Mu s Cx. 10

2

10. Cx = V0.0,1
0,1 . V0 = 0,01.V0. 10

1 9,8

2 9,75

3 9,7

4 9,6

Vi = 95%, n = 4 th: QLth = 0,77 v t= 3,18 Kim tra sai s th bo: 426

Cx (1) = Cx (2) = Cx (3) =

0,098 0,0975 = 0,25 < QLth. 0,098 0,096

0,0975 0,097 = 0,25 < QLth. 0,098 0,096 0,097 0,098 0,096 = 0,5 < QLth. 0,096

Vy dy s ny khng c sai s th bo, hay dy s thc nghim c tnh S liu thu c: Nng ca NaOH TBnh = 0,097125 (N) Phng sai mu = 0,000853912 =
t.S n
3,18 .0,000835912 4

= 0,00135772

Vy nng ca NaOH = 0,097125 0,00135772 0,097 0,001 Hay: 0,096(N) nng NaOH 0,098 (N) HNG DN GII CC BI TP BI 8 1. Cho 2 cp oxy ho kh [MnO4- / Mn2+ ] v [ClO3- (H+)/ Cl- ] c E0 ln lt l 1,51(v) v 1,45(v). Xc nh chiu phn ng xy ra v hng s cn bng ca phn ng pH = 0. Cho ming ng kim loi vo dung dch AgNO 3 0,01M. Tnh KCB v nng cc ion kim loi trong
0 dung dch to thnh. Bit E Cu
2

2.

= 0,34(v) v
Cu

0 E Ag Ag

=0,8(v).

3.

Vit cng thc tnh th in cc E (v) khi chun V0 (mL) dung dch Fe2+ C0N bng V (mL) dung dch 427

Ce4+ CN trong cc trng hp sau: a) b) c) d) Tng qut khi chun Trc xa im tng ng Ti im tng ng Sau xa im tng ng
3

0 Bit E Fe

/ Fe2

0 = + 0,68 (v), ECe

/ Ce 3

= + 1,44(v)

4.

Tin hnh pha trn dung dch Cu+ 10 4 M vi dung dch Na2S 0,1M, ri o th in ca dung dch bng in cc ng-SCE th c gi tr - 0,906(volt). Gi s trong dung dch khng xy ra qu trnh to phc hydroxo ca ion Cu+, pH dung dch o c l 8, th
0 in cc chun ca ng l E Cu

= + 0,34 v H2S
Cu

c xem l mt dung dch acid yu hai chc c hng s phn ly acid 2 nc ln lt l: 107,10 12,89 .Tnh nng [Cu+] ti thi im cn bng sau khi pha trn Gii 1. Cc bn phn ng Oxy ho kh: Mn2+ + 4 H2O Cl- + 3 H2O
E10 = 1,51(v)
0 E 2 = 1,45(v)

MnO-4 + 8 H+ + 5. e ClO3- + 6 H+ + 6 e

phn ng xy ra th E > 0 m vi pH = 0 th [H+] = 1N Nn E10 - E 20 = 1,51 - 1,45 = + 0,06 tng ng vi chiu ca phn ng: 6 MnO-4 + 5 Cl- + 18 H+ 6 Mn2+ + 5 ClO3- + 9 H2O
6.5.( E E ') 0 , 059

p dng tnh hng s cn bng: KCB = 10 2. 428

= 10 30,5

Xt qu trnh in ly: AgNO3 Ag+ + NO3Nn phn ng in ho xy ra gia Ag+ v Cu l:

2 Ag+ + Cu Nng ban u: 0,01 Nng cn bng: 0,01 x Ta c: KCB =

x 0,01 x
m.n. E 0,059

2 Ag + Cu2+ 0 x

Mt khc theo h qu t phng trnh Nernst: KCB = 10 Do : = 10

2.1.( 0,8 0,34 ) 0,059

=10 15,6

x = 10 15,6 0,01 x

x = 2,071. 10 3

Vy: [Cu2+ ] = 2,071. 10 3 M v [Ag+] = 5,858. 10 3M 3. Phn ng chun : Ce4+ + 1 e Fe3+ + 1 e Fe2+ + Ce4+ Khi chun : Ce3+ Fe2+
E10 = 1,44 (v)
0 E 2 = 0,68 (v)

(1) (2)

Fe3+ + Ce3+
V0 C 0 V0 V

[Fe2+ ] + [Fe2+ ]phn ng = [ Fe2+ ]pt = [Ce4+ ] + [Ce4+ ]phn ng = [ Fe2+ ]pt = t
V .C = F V0 C 0
V0 V = F-1 V0 C 0

VC V0 V

Cng thc tng qut s l: ([Ce4+ ] - [Fe2+ ]) (3) 0

Trc xa im tng ng: [Ce4+ ] (3) E= E + 0,059 lg

F [ Fe3 ] = 0,68 + 0,059 lg 2 1 F [ Fe ]

429

Ti im tng ng: F = 1v [Fe2+ ] = [Ce4+ ] Etd =

1,44 0,68 = 1,06 2

Sau xa im tng ng: [Fe2+ ]

0:

(3) E = 1,44 + 0,059 lg (F - 1) 4. Phn ng phng in ca cc ion: Cu+ + e Cu2+ Nn theo phng trnh Nernst:
0 ECB = E Cu

+
Cu

0,059 lg [Cu+] n

= 0,34 + 0,059 lg [Cu+]

Th o c trong dung dch l: ECB = Edo + Echuan= - 0,906 + 0,247 = - 0,659(v) Do : [Cu+] = 10 19,48. HNG DN GII CC BI TP BI 9 1. Vit cng thc tnh pMg khi chun V0 (mL) dung dch Mg2+ C0N bng V (mL) dung dch EDTA CN trong cc trng hp sau: a) b) c) d) Tng qut khi chun Trc xa im tng ng Ti im tng ng Sau xa im tng ng

Gi s rng Mg c kh nng to phc vi EDTA v hydroxyt, EDTA l acid a chc phn ly bn nc, hng s bn iu kin ca phc gia M v EDTA ln. 2. Ht 5mL dung dch mu (c cha ion Al 3+ ) cng vi 10 mL dung dch chun EDTA 0,1N thm 3 git ch th Bromcresol lc vo cng mt erlen, ri chnh dung dch pha trn v pH = 5-6 bng cch cho NH4OH vo 430

n khi dung dch c mu xanh. Thm tip 2mL dung dch m pH = 5,5. un nh khong 60 - 800C, ri li thm 2 mL m pH = 5,5 + 1 git ch th Xylenon da cam (lm 4 mu trong cc bnh nn loi 250mL). Chun bng dung dch Zn2+ 0,1N (chun nng) cho n khi dung dch chuyn t xanh sang vng th o c th tch dung dch Zn2+ l V0(mL), theo kt qu: Mu s V0 (mL) 1 9,8 2 9,7 3 9,7 4 9,6

Al

3+

Vi tin cy 95% hy tnh hm lng g / L ca ion c trong mu ban u.

2 3 4 5 6 7 8 9 10

S th nghim t Q

12,7 1,22

4,3 0,94

3,18 0,77

2,78 0,64

2,57 2,45 2,37 0,56 0,51 0,47

2,31 0,44

2,23 0,41

Gi s cc dung dch u c khi lng ring d = 1 g/mL Gii 1. Theo cho: Mg2+ (k hiu M) ch c kh nng to phc vi EDTA (k hiu Y) m khng c cc qu trnh ph nh hydroxo, hydrua... do hng s bn iu kin ca phc ny kh ln, nn cch gii b qua cc qu trnh ph ny. Phng trnh chun : M + Y MY ( ) Khi tin hnh chun : (1) 431

[M] + [M]pu = [M]bd = [Y] + [Y]pu = [Y]bd = t

V .C = V0 C 0

V0 C 0 V0 V

(2) (3)

VC V0 V

F: Phng trnh tng qut nh phn

chun l:
V0 .C 0 [M ] V V V0 V ( [M] ) 0 =1-F V0 C 0 .[M ]

(5) [Y] << [M]

Trc xa im tng ng: Gi s [M] = (1 - F)

V0 C 0 V0 V

Ti im tng ng: ( F = 1) .[M]2 + [M] V0 C 0 =0 V0 V

Ti sau xa im tng ng : [M] << [Y] (5)

V0 .C 0 [M ] V0 V = (F - 1) .[M ]
V0 C 0 . V0 V

2.

Ta c s ng lng ca Al 3+ = s ng lng ca EDTA phn ng = s ng lng ca EDTA ban u s ng lng ca EDTA d = s ng lng ca EDTA ba u - s ng lng ca Zn2+
5. C x = (10 - V0). 0,1 Cx = (10 - V0).

0,1 . V0 = 0,02. (10 - V0). 5

V khi lng ca Al3+ trong mu l 432

CN.V(L). D = CN.V(L).

M Z C.V.M C X .5.27 = = 9. Cx. 3.5 Z.V '

Hm lng g/L ca Al3+ =

(trong V v V ln lt l th tch c chun v mu ban u tnh theo L) Nn:

Mu s Cx. 10 3 Hm lng g/L ca Al3+ 1 4 36. 10 3
3

2 6 54. 10 3

3 6 54. 10 3

4 8 72.10

Vi = 95%, n = 4 th: QLth = 0,77 v t= 3,18 Kim tra sai s th bo: Cx (1) = Cx (2) =
0,072 0,072 0,054 = 0,5 < QLth. 0,036

0,054 0,036 = 0,5 < QLth. 0,072 0,036

Vy dy s ny khng c sai s th bo, hay dy s thc nghim c tnh S liu thu c: Hm lng Al3+ TBnh = 0,054 (g/L) Phng sai mu = 0,014687 =
t.S n

3,18 .0,014687 4

= 0,02337

Vyhm lng (g/L) ca Al3+ = 0,054 0,023 Hay: 0,031 (g/L) Hm lng Al3+ 0,077 (g/L) 433

HNG DN GII CC BI TP BI 10 1. Ho tan 1(g) mt loi qung thnh dung dch (A) cha Fe3+. Hi cn dng bao nhiu mL dung dch NH3 1,19% (d = 0,99 g/mL) kt ta hon ton lng Fe3+. Bit trong qung c cha n 10% Fe 2. nh lng hm lng NaCl c trong mui n theo phng php Mohr: Cn 0,8849g mui n c tinh khit 99,5 %, em ho tan bng nc ct nng n khi thu c dung dch 100 mL. Ht 5 mL dung dch mu cho vo cc tam gic cng vi 5 git hn hp ch th (gm 4,2 g K2CrO4 + 0,7g K2Cr2O7 pha trong 100 mL nc ct) v thm 3 git h tinh bt, ri nh mc n 100mL. Tin hnh chun bng AgNO 3 0,1N cho n khi xut hin ta c mu cam nht th tn ht 5,76mL dung dch AgNO3. Tnh khi lng NaCl c trong mui n ban u. Gii 1. Ta c khi lng Fe c trong qung = khi lng Fe3+ = 1. 10% = 0,1(g) s mol ca Fe3+ =
0,1 56

Phn ng to ta: Fe3+ + 3 NH3 + 3 H2O Fe(OH)3 + 3 NH4+ Nn s mol ca Fe3+ = s mol ca NH3 3. 2.
0,1 V .0,99.1,19 = 56 100.17

V = 7,73(mL)

S phn tch:
dung dch (1) 5mL dung dch (2) 100mL dung dch (3) AgCl

Mui n

0,8849(g) 100mL

434

(99,5%)

Ti dung dch (3) c: s ng lng gam Cl - = s ng lng gam Ag+ = 5,67.0,1. 10 - 3 Nn khi lng NaCl trong dung dch (1) l = 5,76. 10 - 4.
58,5.100 100.100 . = 76,54% 0,8849 .99 ,5 5

435

CC THUT NG CHUYN MN

1.

im tng ng: l khi nim m t thi im m ti s ng lng ca cc cht em chun bng nhau Cht ch th l mt cht hay hn hp cc cht c kh nng bin i mu khi dung dch cha n t n mt gi tr, i lng phn tch nht nh V d: phenolphtalein trong dung dch acid s khng c mu, nhng khi pH dung dch tng dn n pH = 8,2 th phenolphtalein s chuyn sang mu hng H tinh bt c mu xanh tm trong dung dch c I 2 nhng khi dung dch b oxy ho kh chuyn I 2 thnh I- th h tinh bt s mt mu xanh c trng ny.

2.

3.

Sai s chun l loi sai s ca phng php chun , khi dng ch th thch hp cho php chun Chun l qu trnh nh lng cht phn tch da theo lng thuc th tiu chun tiu tn. Php chun c thc hin bng cch thm mt cch cn thn lng dung dch thuc th bit nng vo dung dch cht cn xc nh cho ti khi phn ng gia chng kt thc, sau , o th tch dung dch thuc th chun. i khi, nu iu khng thun tin hoc khng cn thit, th thm d thuc th v sau chun ngc bng mt thuc th khc bit nng xc nh lng d thuc th th

4.

5. 436

nht khng tham gia phn ng. Cht chun gc: l cht phi tha mn mt lat cc

yu cu sau Chng phi c tinh khit cao nht, hn na phi c nhng phng php n gin tin cy khng nh tinh khit ca chng Phi bn, ngha l khng tc dng vi cc cu t ca kh quyn. Khng cha nc hydrat. Khng phi l cht ht m hoc c xu hng phong ha v s kh lm kh v kh cn. Phi d kim trong th trngv c gi thnh va phi. Cht phi c khi lng mol phn t ln. Dung dch c nng cho s cng ln nu khi lng mol phn t ca n cng ln. Khi khi lng tng, sai s ca php cn s gim, tc khi lng mol phn t ca cht cng cao th cht cng c kh nng lm gim sai s cng ln Ch c mt t cht c cc yu cu trn v do s cht quy cch dng lm cht chun gc b hn ch. 6. Dung dch chun l tng phn tch l dung dch c nhng tnh cht sau Sau khi iu ch nng ca n phi khng bin i, c bo qun lu (trong mt vi thng hoc hng nm) Phn ng nhanh vi cht cn xc nh, tc thi gian ch i sau khi thm tng phn nh thuc 437

th phi ngn Phn ng gia thuc th v cht cn xc nh cn phi xy ra han ton c th xc nh im cui tha mn. Phn ng gia thuc th v cht cn xc nh phi xy ra hp thc, nu khc i th khng th tnh c trc tip khi lng cht cn xc nh Cn phi c phng php xc nh im tng ng ca phn ng gia thuc th vi cht cn xc nh, ngha l phi c phng php xc 7. nh im cui tin cy. im cui trong php chun c xc nh bng phng php quan st bin i mt tnh cht vt l no im tng ng. C th xc nh im cui theo s bin i mu ca thuc th ca cht cn xc nh hoc ca cht ch th. xc nh im tng ng th s dng s bin i ca cc tnh cht v th in cc, dn, nhit , ch s khc x... Ti im cui ca php chun xy ra s bin i nng rt ln, t nht l ca mt trong nhng cht phn ng. Trong phn ln (nhng khng phi l tt c) trng hp xc nh im cui l xc nh nhng bin i xy ra vng ln cn im tng ng.

438

Bng tch s tan ca mt s hp cht 25 0C

Cht tan Al(OH)3 BaSO4 CdS Ca(OH)2 CuCl FeCO3 Fe(OH)3 PbO Mn(OH)2 Hg2Br2 HgO Ni(OH)2 Ag2CrO4 ZnCO3 T 3.10-34 1,1.10-10 1.10
-27 -6

Cht tan BaCO3 CdCO3 CaCO3 CaSO4 CuI Fe(OH)2 PbCO3 PbSO4 MnS Hg2CO3 HgS AgBr AgI Zn(OH)2

T 5.10-9 1,8.10-14 4,5.10 2,4.10

-9 -5

Cht tan BaCrO4 Cd(OH)2 CaF2 CuBr CuS FeS PbCl2 PbS Mg(OH)2 Hg2Cl2 NiCO3 AgCl Ag2S ZnS

T 2,1.10-9 4,5.10-15 3,9.10 1.10

-11

6,5.10

-10

1,9.10-7 2,1.10
-11

1.10-12 4,1.10
-15

8.10-37 8.10
-19

1.10-11 7,4.10-14 7,1.10-12 5,6.10

-20

7,4.10-14 1,6.10-8 3.10-11 8,9.10

-17

1,7.10-5 3.10-28 7,1.10-12 1,2.10

-18

3,6.10-26 6.10-16 1,2.10-12 1.10-10

2.10-53 5.10-13 8,3.10-17 3.10-16

1,3.10-7 1,82.10-10 8.10-51 2.10-25

439

TI LIU THAM KHO

1.

Nguyn Thc Ct, T Vng Nghi, o Hu Vinh, C s l thuyt ha hc phn tch - Xut bn ln 2, H Ni 1985 Lm Ngc Th, C s l thuyt ha hc Phn tch, Hu 3/ 2002 Nguyn Tinh Dung, Ha hc phn tch, phn I. L thuyt c s, NXB Gio dc - 1991 L Xun Mai, Nguyn Th Bch Tuyt, Gio trnh phn tch nh lng, NXB i hc quc gia Tp. HCM, 2000 Hong Minh Chu, C s ha hc phn tch, NXB Khoa hc k thut, H Ni, 2002 T Vng Nghi, Ha hc phn tch, NXB i hc quc gia H ni, 2000 Trng Bch Chin, Gio trnh C s l thuyt ho phn tch Lu hnh ni b, Trng Cao ng Cng nghip 4 Tp.HCM Trng Bch Chin, Gio trnh Phn tch nh Lng Lu hnh ni b, Trng i hc Cng nghip Tp.HCM

2. 3. 4.

5. 6. 7.

8.

440

MC LC
mc Trang GII THIU MN HC .............................................. 1 CC HNH THC HOT NG HC TP CHNH TRONG MN HC ........................................ 3 YU CU V NH GI HON THNH MN HC ................................................................... 4 BI 1: CC KHI NIM C BN ............................... 6 BI 2: PHN TCH NH TNH CATION NHM 1 ............................................ 75 BI 3: PHN TCH NH TNH CATION NHM 2 .......................................... 120 BI 4: PHN TCH NH TNH CATION NHM 3 .......................................... 135 BI 5: PHN TCH KHI LNG .......................... 154 BI 6: PHNG PHP CHUN TH TCH .... 192 BI 7: PHNG PHP CHUN ACID- BAZ ... 212 BI 8: PHNG PHP CHUN OXY HA KH ............................................. 277 BI 9: PHNG PHP CHUN TO PHC .. 331 BI 10: PHNG PHP CHUN TO TA ... 362 CC BI TP M RNG NNG CAO ................... 384 GII THIU MT S THI KIM TRA ..... 385 TRC NGHIM ................................................. 399 P N CC CU HI V KIM TRA .................. 412 CC THUT NG CHUYN MN ........................ 436 TI LIU THAM KHO ........................................... 440

441