BI TNG TRNH PHNG PHP CHUN OXY HA KH

H v tn: Nguyn Th Minh Phng M s nhm thc tp: 27A Ngy thc tp: 21/05/2011 M s dung dch kim tra: 22 I/ Xc nh nng chnh xc ca KMnO4 theo acid oxalic 1/ Mc ch th nghim Do KMnO4 l cht oxy ha mnh, d b thy phn to thnh MnO2 v cng chnh MnO2 li l cht xc tc tng cng cho s thy phn xy ra nhanh hn theo phng trnh phn ng sau: 4KMnO4 + 2H2O 4MnO2 + 3O2 + 4KOH V th, ta khng th dng KMnO4 lm cht gc c m phi chun li dung dch KMnO4 bng acid oxalic bit chnh xc nng v KMnO4 s c dng lm cht chun cho th nghim sau. 2/ Nguyn tc - Chun KMnO4 bng dd H2C2O4 0.050000 0.000010 N trong mi trng acid n khi xut hin mu hng nht bn vng - Phn ng chun : 2MnO4- + 5C2O42- +16H+ 2Mn2+ + 10CO2 + 8H2O 3/ Tin hnh - Trng buret bng dd KMnO4 - Rt 10.00ml dd acid oxalic 0.050000N cho vo erlen 250ml, thm vo 1ml dd H2SO4 (1:1). - un nng n khong 80 90C . - Chun bng cch cho tng git dd KMnO4, lc u cho ti khi mu hng bin mt ri mi cho tip. Chun cho ti khi xut hin mu hng nht bn vng th dng chun , ghi li th tch KMnO4 tiu tn. - Lp li th nghim trn 3 ln, thu c cc gi tr sau: V1 7.00ml 4/Biu din kt qu
C N KMnO4 = C N H 2C2O4 V H 2C2O4 V KMnO4

V2 7.00ml

V3 7.00ml

Vtb Vtb= 7.00ml

= 0.0714285714 3N

 0.95, N KMnO4 = C KMnO4

0.95, N H 2C2O4 CM H C O 2 2 4

0.95, N V pipet + V pipet

0.95, N Vburet + Vtb

0.95, N H 2C2O 4 = 0.000010

Vi

0.95, N Vpipet = 1.96 0.95, N Vburet = 1.96

4

pipet
3

= 1.96

0.0070 3 0.030 3

= 0.0079

buret = 1.96 3

= 0.034

0.95, N KMnO = 0.00035 Vy nng ca KMnO4

.95 , N MO 0 Kn
4

= .0 1 3 0 74

.0 0 5 0 03

5/ Nhn xt chnh xc ca qu trnh chun : 0.95, N KMnO 0.00035 1 = 1 = 99.51% 0.95, N KMnO 0.07143
4 4

Th nghim xc nh nng chnh xc ca dd KMnO4 theo acid oxalic khng cn dng cht ch th mu v bn thn dd KMnO4 dng oxi ha MnO4- c mu tm v dng kh Mn2+ khng mu, ta s chun cho ti khi nng MnO4- ln c th quan st c mu hng nht ca MnO4-. Do ion MnO4- v C2O42- cng du v s cho nhn in t gia ion MnO4-(MnO4- Mn2+: nhn 5e-), v ion C2O42- (C2O42-CO2: cho 2 e-) vi s electron khc nhau, ion MnO4- v ion C2O42- c cu trc khc nhau, ngoi ra cn do phn ng to thnh kh CO2 nn phn ng chun xy ra kh chm cn phi un nng 70-80 C cho phn ng xy ra nhanh hn. Tuy nhin khng nn un si v acid oxalic s b phn hy.ok Phn ng chun ban u to ra mt lng Mn2+, lng Mn2+ ny lm xc tc cho qu trnh to Mn3+(MnO4- + 4Mn2+ 8H+ 5Mn3+ + 4H2O), c Mn2+ v Mn3+ c tnh oxi ha c MnO4- v Mn3+ u c kh nng oxy ha C2O42-. iu ny c ngha l, khi mu hng nht xut hin bn vng c th vn cha ti im tng ng ca phn ng. Do Mangan c nhiu s oxy ha trung gian nn ra c ng s oxy ha ca phn ng chun ta cn phi thc hin ng h s t lng, thng thng ta thc hin phn ng trong mi trng acid, v thng l H2SO4(1:1) v dd H2SO4 c tnh oxi ha yu v tnh acid mnh thun li cho qu trnh phn ng . Ta khng th dng HCl v c tnh kh hoc HNO3 v c tnh oxi ha mnh.ok Do dd pemanganat khng bn, chun ca n thay i theo thi gian nn cn phi chun li trc khi s dng.
2

 Vic chun permanganat thng trnh s c mt ion Cl- v Fe2+ v cc ion ny s b oxy ha ln thnh Clo hoc Fe3+, cng l l do ngi ta khng dng acid Clohidric. Trn thc t ngi ta thng dng hn hp bo v Zymmerman, hn hp ny bao gm H2SO4 c tc dng ngn nga s thy phn ca mui st, v s oxi ha Fe2+ thnh Fe3+ bi oxy khng kh. Th 2 l H3PO4 c tc dng to phc vi Fe3+ to phc khng mu thun li cho qu trnh chun , v Fe3+ thng c mu vng s gy nh hng n vic quan st s thay i mu sc trong qu trnh chun . Th 3 l MnSO4 c tc dng hn ch phn ng cm ng. *C ch ca phn ng ph: MnO4- + Fe2+ Mn2+ + Fe5+ Fe5+ + Cl- Fe3+ + Cl2 (*) Khi c hn hp Zymmernan s xy ra phn ng: Mn2+ + Fe5+ Mn3+ + Fe3+ MnSO4 ngn nga phn ng (*) xy ra
E = E Mn3+ / Mn 2 + + 0.059 log [ Mn 3+ ] [ Mn 2+ ]

[Mn2+] ln s lm gim th ca cp Mn3+/Mn2+ok Trong qu trnh chun , nu KMnO4 b dnh vo thnh erlen, ta nn dng bnh tia y dd xung hn ch c sai s tha. II/ Xc nh nng H2O2 1/ Mc ch th nghim Do H2O2 rt d b phn hy thnh kh O2 v H2O nn b mt dn hot tnh v nng khng cn chinh xc na. Do ta cn xc nh li ng nng H2O2 vic s dng hiu qu hn. 2/ Nguyn tc - Xc nh hm lng H2O2 qua phn ng vi cht chun KMnO4 0.07143 0.00035 N trong mi trng acid sulfuric - Phn ng chun : Hai bn phn ng oxy ha kh Bn phn ng kh: MnO4- + 8H+ + 6e- Mn2+ + 4H2O Bn phn ng oxy ha: H2O2 - 2e- 2H+ + O2 Phn ng tng: 5H2O2 + 2MnO4- + 6H+ 2Mn2+ + 8H2O + 5O2 - im cui ca phn ng l khi cho lng d KMnO4, xut hin mu hng nht, bn. 3/ Tin hnh - Chun b buret vi dung dch KMnO4 - Rt 10.00 ml dung dch H2O2 vo erlen 250ml cha sn 20ml nc ct v 5ml H2SO4 1:1. - Chun vi KMnO4 va xc nh li nng lc ny cho ti khi dung dch chuyn sang mu hng nht bn trong 30s, ghi li th tch KMnO4 tiu tn. - Lp li th nghim trn 3 ln, ta thu c cc gi tr sau:
3

V1 3.60ml 4/ Biu din kt qu

C N H 2O2 =

V2 3.65ml

V3 3.60ml
Vtb =

Vtb
3.60 + 3.65 + 3.60 = 3.62ml 3

C N KMnO4 V KMnO4 V H 2O2

= 0.02585766 N 0.95, N V pipet + V pipet

2

0.95, N KMnO4 0.95, N H 2O2 = C H 2O2 C KMnO 4 Vi 0.95, N KMnO4 = 0.00035

0.95, N Vburet + Vtb

0.95, N Vpipet = 1.96

pipet
3

= 1.96

0.0070 = 0.0079 3 S n, x n = 0.0168

S n, x =

(x
i =1

xn ) 2

n 1

= 0.0292 S n , x =

0.95, N Vburet = t 0.95, f S n , x = 4.30 0.0168 = 0.072 0.95, N H 2O2 = 0.00053

Vy nng ca H2O2:
C N 2O2 =0.0 5 6 28 H .0 0 3 0 05 N

5/ Nhn xt: chnh xc ca qu trnh chun : 0.95, N H O 0.00053

1
2 2

C N H 2O2

=1

0.02586

= 97.95%

chnh xc khng cao, c th do thao tc chun cha c chun xc, do mt quan st vin khng tht nhy trc s thay i mu sc. Kh nng oxy ha ca KMnO4 mi trng acid mnh hn mi trng kim. Mt khc, sn phm oxy ha trong mi trng acid l Mn2+ khng mu nn d xc nh im tng ng, cn phn ng mi trng kim xy ra rt chm, sn phm to thnh sau phn ng l MnO2 c ta nu en nn kh xc nh im tng ng do ta thc hin phn ng trong mi trng acid, v chn acid H2SO4 v nhng u im trn <I>. Do H2O2 d b phn hy nn cn chun b sn erlen cha 20.0ml nc v 5.00ml H2SO4 (1: 1) trc ri sau mi rt 10.00ml H2O2 vo, pha long dd bng 20ml cng nhm hn ch iu ny.
4

 Chun b xong mt erlen ri chun lin, khng nn chun b cng lc nhiu mu v H2O2 rt d b phn hy to thnh O2 v H2O. Trong qu trnh chun khng nn lc erlen mnh v s lm cho H2O2 b phn hy. III/ Xc nh nng Fe2+ trong mui Mohr bng K2Cr2O7- ch th Diphenylamine(pp Bicromat) 1/ Mc ch th nghim: Do mui Mohr Fe(NH4)2(SO4)26H2O lu trong khng kh s b oxy ha lm cho lng Fe2+ b gim. Th nghim ny nhm mc ch xc nh li chnh xc nng Fe2+ c trong mui. 2/ Nguyn tc - Ha tan mui Mohr ri chun trc tip Fe2+ trong mi trng H2SO4 hoc HCl cho ti khi dd chuyn mu theo ch th th in cc (Ch th diphenylamine) - Chun trc tip bng dd K2Cr2O7 0.050000 0.000044 N - Phn ng chun : 6Fe2+ + Cr2O72- + 14H+ + 6e- 6Fe3+ + 2Cr3+ + 7H2O 2(Cr2O7 : vng cam ; Cr3+: xanh lc) 3/ Tin hnh - Chun b buret vi dd K2Cr2O7 0.050000N - Rt 10.00ml dd mui Morh cho vo erlen 250ml. - Thm 10ml H3PO4 c + 10ml HCl (1:2) + 3-4 git ch th DPh 0.1% - Pha long bng nc ct n khong 30ml - Chun bng dd chun K2Cr2O7 cho ti khi xut hin mu tm chm th dng, ghi li th tch K2Cr2O7 tiu tn. - Lp li th nghim trn 3 ln, ta thu c cc gi tr sau: V1 7.10ml 4/ Biu din kt qu
C N Fe 2 + =
2 7

V2 7.10ml

V3 7.05ml
Vtb =

Vtb
7.10 + 7.10 + 7.05 = 7.08ml 3

C N Cr O 2 Vtb V pipet

= 0.0354166666 7 N 0.95, N V pipet + V pipet

2

0.95, N Cr O 2 2 7 0.95, N Fe 2 + = C N Fe 2 + C N Cr2O7 2 Vi 0.95, N Cr 2O 72 = 0.000044

0.95, N Vburet + Vtb

 0.95, N Vpipet = 1.96

n i n

pipet
3
2

= 1.96

0.0070 = 0.0079 3 Sn, x

= 0.0168 n 1 n 0.95, N Vburet = t 0.95, f S n , x = 4.30 0.0168 = 0.072

i =1

Sn, x =

(x x )

= 0.0292 S n , x =

0.95, N Fe 2 + = 0.00036 Vy nng ca Fe2+:

CN e F
2+

=0.0 5 2 34

.0 0 6 0 03

5/ Nhn xt chnh xc ca qu trnh chun : 0.95, N Fe 0.00036

1
2+

C N Fe 2 +

= 1

0.03542

= 98.98%

Th nghim trn xc nh nng ca Fe2+ trong mui Morh s dng phng php Cromat da trn vic dng dung dch chun Kali bicromat. Do dd K2Cr2O7 rt bn tc chun ca n khng thay i trong thi gian di ngay c di nh hng ca cc yu t nh nhit , oxy hay kh cacbonic c trong khng kh nn ta c php dng K2Cr2O7 lm cht gc xc nh chun ca cc dd khc m khng cn phi chun li. Khc vi pp Permanganat, pp Cromat c th tin hnh trong mi trng acid Clohidric m khng cn dng hn hp bo v Zymmerman. Bn cnh , phn ng oxy ha kh ca bicromat thng xy ra kh chm, nhng tc phn ng tng r rt trong mi trng acid mnh v th oxi ha kh ca cp Cr6+/Cr3+ tng ln khi nng ion hidro tng v khi c mt mt s phi t. Phn ng chun s to ra ion Cr3+ c mu xanh lc. V vy, cn tin hnh pha long mu ring ca Cr3+ khng lm nh hng n mu ch th v s i mu ca dd ngay im cui chun (lu l khi xt khong bc nhy cn phi xt ti h s pha long) Ta thm acid Phosphoric vo to phc vi ion Fe3+ (Fe3+ c hnh thnh do Fe2+ b oxy ha bi oxy trong khng kh) lm cho vic chun Fe2+ d dng hn 6Fe3+ + 18HPO42- 6[Fe(HPO4)3]3-. Ngoi ra, vic cho thm H3PO4 cn gip cho s thay i th ca cc cp oxi ha kh c mt trong dung dch sao cho s i mu ca ch th nm trong khong bc nhy. K2Cr2O7 tuy l cht c mu nhng mu ca n rt nht rt kh quan st im tng ng. V vy, ta cn s dng cht ch th in cc DPh (cht ch th in cc c c im l mu sc ca n thay i t ngt khi th in cc ca dd i qua tng hoc gim ti mt gi tr xc nh c trng cho cht ch th ), chun cho n khi dd c mu tm chm. Mu tm chm ny xut hin l do DPh b oxy ha to thnh Diphenylbenzidin. Cht ny dng kh khng mu, dng oxy ha c mu tm. Tuy nhin dng oxy ha thng khng bn nn n thng kt hp vi phn cn li ca dng kh to nn dd c mu tm chm.
6

 Cn trng buret tht k trc khi cho K2Cr2O7 vo v trc buret cha KMnO4. IV/ Xc nh nng chnh xc ca Na2S2O3 theo K2Cr2O7 1/ Mc ch th nghim Do chun ca dd Na2S2O3 c th b thay i do nh hng ca: + Kh cacbonic (Na2S2O3 + CO2 + H2O NaHCO3 + NaHSO3 + S), nng ca dd thiosulfat tng ln do cc ion hidrosunfit hnh thnh phn ng vi iod theo phng trnh: HSO3- + I2 + H2O HSO4- + 2HI + Oxy khng kh ( 2Na2S2O3 + O2 2Na2SO4 + 2S) nng ca dd Na2S2O3 gim chun ca dd Na2S2O3 b thay i. Do ta cn chun li xc nh chnh xc nng ca dd Na2S2O3. 2/ Nguyn tc - Ly mt th tnh chnh xc dd chun K2Cr2O7 cho phn ng vi lng d dd KI trong mi trng acid to ra I3- Tin hnh chun trc tip lng I3- trn bng dd Na2S2O3 vi ch th h tinh bt. Thc cht y chnh l php chun thay th - Phn ng thay th tng ng: Cr2O72- + 6I- + 14H+ 2Cr3+ + 3I2 + 7H2O 3I2 + 3I- 3I3- Phn ng chun : I3- + 2S2O32- 3I- + S4O623/ Tin hnh - Chun b buret vi dd chun Na2S2O3. - Rt 10.00ml dd K2Cr2O7 0.020000 0.000018 N cho vo erlen 250ml. - Thm 15ml nc ct + 3ml H2SO4 c + 5ml KI 10%, lc nh. - y kn v yn 10 pht kh hon ton K2Cr2O7 - Chun t t tng git cho ti khi xut hin mu vng rm ri cho thm vi git dd h tinh bt cho ti khi dd c mu xanh chm r rt, va thm va lc u. - Tip tc chun bng dd Na2S2O3 cho ti khi mu xanh chm bin mt, ghi li th tch Na2S2O3 tiu tn. - Lp li th nghim trn 3 ln, ta thu c cc gi tr sau: V1 12.10ml 4/ Biu din kt qu
C N S O 2 =
2 3

V2 12.10ml

V3 12.10ml

Vtb Vtb= 12.10ml

V pipet C N Cr O 2
2 7

Vtb

= 0.0165289256 2 N 7

 0.95, N Cr O 2 2 7 0.95, N S O 2 = C N S O 2 2 3 2 3 C N Cr2O7 2 0.95, N Cr O 2 = 0.000018

2 7

0.95, N V pipet + V pipet 0.0070

0.95, N Vburet + Vtb

0.95, N Vpipet = 1.96

pipet
3

= 1.96

Vi
0.95, N S O 2
2 3

0.95, N Vburet = 1.96

buret = 1.96 3 = 0.000050

3 0.030 3

= 0.0079

= 0.034

Vy nng ca Na2S2O3:
C N S
2 O3 2

=0.0 6 2 159

0.0 0 5 000

5/ Nhn xt chnh xc ca qu trnh chun : 0.95, N S O 0.000050

1
2 3 2

CN S O 2
2 3

= 1

0.016529

= 99.70%

chnh xc cao hn so vi 2 phng php permanganat v phng php bicromat. Cht kh dng trong phng php Iode lun l thiosulfate phn ng mang tnh nh lng v lu l Na2S2O3 lun lun nm trn buret . V thiosulfate d b phn hy trong mi trng acid nn phn ng thng cthc hin trong mi trng hi acid hoc trung tnh, khng tin hnh chun trong mi trng kim mnh v to ra IO-, IO- c tnh oxy ha mnh hn I2, c th oxy ha S2O32- thnh SO42- lm sai kt qu nh lng I2 + 2OH- IO- + I- + H2O Na2S2O3 l mt cht kh tng i yu trong nguyn t c tnh kh l S c s oxy ha trung bnh l +2. trng thi oxy ha ny, S c th b kh v 0 hay -2, cng c th b oxy ha ln +2.5 (Na2S4O6) hay +4, +6. Cc qu trnh ny din ra ty thuc rt nhiu vo iu kin phn ng v thng khng t lng. Trong khi , K2Cr2O7 l cht oxy ha kh mnh, n s oxy ha Na2S2O3 v nhiu s oxy ha khc nhau nu ta chun trc tip K2Cr2O7 bng Na2S2O3 th phn ng chun s khng tha iu kin. V vy, ngi ta chuyn ha K2Cr2O7 thnh cht c tnh oxy ha l KI3( 3I2 + 3I- I3-) c th oxy ha t lng Na2S2O3 thnh Na2S4O6 Ta khng cho ch th h tinh bt vo lc bt u chun m ch cho khi dd chuyn sang mu vng rm (iod trong dd gn ht) v khi cho h tinh bt vo dd cha KI3 , ion I3- s chui vo cu trc xon ca phn t h tinh bt lm cho cu trc ny c mu. Mu ny ch mt i khi c mt lng d nht nh Na2S2O3 trong dd. S mt mu nhanh hay chm cn ty thuc vo lng d Na2S2O3 v mc thm nhp ca I3- vo cu trc ca h tinh bt, nu cho h tinh bt vo lc
8

u, khi lng I3- cn rt nhiu th n s xm nhp vo su cu trc h tinh bt cn dng mt lng d ln Na2S2O3 mi c th lm mt mu dd sai s tha kh ln V Iod l cht d bay hi v nhy sng nn trong qu trnh i cho K2Cr2O7 b kh hon ton ta nn y kn erlen li v trong ti I2 khng phn cc nn t tan trong nc nn vic cho KI vo to thnh phc I3- phn cc d tan hn gip cho qu trnh chun thun li hn.ok Cr3+ c mu xanh lc, d gy nhm ln vi mu ca ch th h tinh bt khi cho vo dd nn ta cho nc ct vo pha long dd nhm hn ch iu ny. Nn ch n thao tc chun , ta khng nn lc mnh erlen trnh cho I2 bay hi. Dd KI c mu vng nht do b oxy ha mt phn trong khng kh. Dd K2Cr2O7 c mu cam, khi thm lng d dd KI vo dd K2Cr2O7 trong mi trng H2SO4 th mu cam s chuyn sang mu vng nu do c iod sinh ra theo phn ng: K2Cr2O7 + 9KI + 3H2SO4 3KI3 + Cr2(SO4)3 + 3K2SO4 + 3H2O V/ Xc nh nng Cu2+ 1/ Mc ch th nghim Xc nh nng Cu2+ trong dung dch 2/ Nguyn tc - Trong mi trng acid Cu2+ oxi ha I- to thnh kt ta CuI v mt lng tng ng I3-. Chun lng I3- bng dung dch thiosulfat vi ch th h tinh bt - Phn ng thay th tng ng: 2Cu2+ + 5I- 2CuI + I3- (*) Phn ng trn xy ra l do vic to kt ta CuI lm th cp Cu2+/ CuI tng vt qua th ca cp I3-/I- Phn ng chun : I3- + 2S2O32- 3I- + S4O62Trn thc t ngi ta cn cho thm NH4SCN hoc KSCN phn ng xy ra hon ton hn do kt ta CuSCN t tan hn kt ta CuI nn th ca Cu2+/ CuSCN cao hn th ca cp Cu2+/ CuI (v
E = E Cu 2 + / Cu + 0.059 lg T , T ca CuSCN nh hn nn th ca n cao hn CuI) 2

2Cu2+ + 3I- + 2SCN- 2 CuSCN + I3Thm na, kt ta CuSCN khng hp ph mnh I3- nh kt ta CuI gip cho vic xc nh lng I3- chnh xc hn. 3/ Tin hnh - Rt 10.00mL dd Cu2+ cn nh phn cho vo erlen 250ml.
9

- Thm 3mL H2SO4 m c+ 5mL KI 10%,+ 5mL KSCN 10%, lc nh, y kn, trong ti trong 15 pht. - Sau pha long bng nc thnh 40ml - Chun dung dch bng Na2S2O3 n khi dd c mu vng rm cho vo tng git h tinh bt n khi dd c mu xanh chm r rt chun n khi dung dch mt mu xanh chm, ghi li th tch Na2S2O3 tiu tn. - Lp li th nghim trn 3 ln, ta thu c cc gi tr sau: V1 10.00ml 4/ Biu din kt qu
C N Cu 2 + =
2

V2 10.00ml

V3 10.00ml

Vtb Vtb = 10.00ml

Vtb C N S O 2
3

V pipet

= 0.016529 N 0.95, N V pipet + V pipet

2

0.95, N Cu 2 + = C N Cu 2 +

0.95, N S O 2 2 3 C N S 2O32

0.95, N Vburet + Vtb

0.95, N S O 2 = 0.000050
2 3

0.95, N Vpipet = 1.96

pipet
3

= 1.96

0.0070 3 0.030 3

= 0.0079

Vi
0.95, N Cu 2 +

0.95, N Vburet = 1.96

buret = 1.96 3 = 0.000076

= 0.034

Vy nng ca Cu2+
C N u C
2+

=0.0 6 2 159

.0 0 7 0 006

5/ Nhn xt chnh xc ca qu trnh chun : 0.95, N Cu 0.000076

1
2+

C N Cu 2 +

= 1

0.016529

= 99.54%

V I2 l cht d bay hi v t tan trong nc nn ta cn phi cho KI vo, th nht l v KI trong dung dch s phn ly hon ton thnh I-, I- ny s tc dng vi I2 to thnh I3-, c tc dng gi I2 li trong dung dch. Th hai, I3- l cht phn cc nn s tan tt trong dung mi phn cc l nc.ok Pha long dd nhm hn ch s bay hi ca iod

10

Trong qu trnh chun khng c lc mnh erlen v s lm bay hi iod nh hng n kt qu chun . Thm H2SO4 m c to mi trng acid c pH~ 2-3, mi trng ny th Cu2+ oxy ha I- to thnh kt ta CuI v mt ng lng I-, phn ng xy ra chm, cn nhiu thi gian phn ng xy ra hon ton. Nu phn ng thc hin trong mi trng acid mnh s xy ra phn ng ph oxy ha iodua oxi khng kh. V iod nhy sng nn cn phi y kn erlen v trong ti 15 pht phn ng xy ra. Do c xut hin kt ta CuSCN nn vic quan st mu xanh chm ca ch th h tinh bt s hi kh khn, cn ht sc tp trung. Thc cht ca phn ng (*) l: 2I- + 2Cu2+ + 2I- I2 + 2CuI (1) I2 + 4I- 2I3V [Cu2+] ln hn nhiu so vi [Cu+] nn th ca cp ECu 2+ / CuI s tng ng k (
E = E Cu 2 + / Cu + + 0.059 log [Cu 2+ ] ), vt qua th ca cp EI / I 2 . Do phn ng (1) thc cht xy [Cu + ]

ra hon ton t tri qua phi. V vy phn ng trn xy ra tt hn ta c th tng nng KI hoc ngn cn s to phc ca Cu2+ vi nhng ion l c trong dung dch. Cn lu l CuI hp th mt lng iod kt qu chun s b sai lch, cho nn ta thm KSCN vo hn ch iu ny. ((CuI)nI2 + nSCN- nCuSCN + I2 + nI-) VI/ Xc nh nng ClO- trong nc Javel 1/ Mc ch th nghim Trong dd, NaOCl b phn ly thnh Na+ v OCl-. Ion OCl- trong nc ty s tham gia phn ng oxy ha kh v b kh thnh ion Cl- vi tc nhn kh l cht mu hoc vt bn trn vi. Hot tnh ca nc Javel c th b gim dn theo thi gian nu iu kin bo qun khng c tt, vic nh gi hot tnh ca nc Javel da trn nng ca NaOCl c trong dung dch. Do , ta cn phi xc nh li nng ca OCl- trong dd, y cng l mc ch ca th nghim ny. 2/ Nguyn tc - Xc nh hm lng OCl- bng phn ng vi lng d tc nhn kh I- trong mi trng acid - Chun lng tng ng I2 sinh ra bng dd Na2S2O3 vi ch th h tinh bt - Phn ng chun : OCl- + 2I- + 2H3O+ I2 + Cl- + 3H2O I2 + S2O32- 2I- + S4O623/ Tin hnh
11

- Ly 10.00mL nc my cho vo erlen 250ml c sn 20ml nc ct v 5ml KI 10% - Thm 2mL HCl 1:1, lc u. - Chun vi S2O32- 0.016529 0.000050 N cho n khi dung dch chuyn sang mu vng nht, thm 10 git h tinh bt dung dch c mu tm en v chun tip cho n khi dd mt mu xanh lam, ghi li th tch Na2S2O3 tiu tn. - Lp li th nghim trn 3 ln, ta thu c cc gi tr sau: V1 15.50ml 4/ Biu din kt qu
C N OCl =
2

V2 15.50ml

V3 15.55ml
Vtb =

Vtb
15.50 + 15.50 + 15.55 = 15.52ml 3

Vtb C N S O 2
3

V pipet

= 0.0256474983 3N 0.95, N V pipet + V pipet 0.0070 3

2

0.95 , N S 2O32 0.95, N OCl = C N OCl C N S 2O32 0.95, N S O 2 = 0.000050

2 3

0.95, N Vburet + Vtb

Vi 0.95, N Vpipet = 1.96

pipet
3

= 1.96

= 0.0079

= 0.0168 n 1 n 0.95, N Vburet = t 0.95, f S n , x = 4.30 0.0168 = 0.072

i =1

S n, x =

(x

xn ) 2

= 0.0292 S n , x =

S n, x

0.95, N OCl = 0.00014

Vy nng ca OClCN C Ol

=0.0 5 5 26

.0 0 4 0 01

5/ Nhn xt chnh xc ca qu trnh chun : 0.95, N OCl 0.00014

1

C N OCl

= 1

0.02565

= 99.45%

Khng lc mnh erlen trong qu trnh chun nhm trnh s bay hi ca iod Khng nn cho ch th h tinh bt vo lc u v h tinh bt s hp th mt phn I2, nhng li gii hp ph chm(do cu trc c trng ca h tinh bt), dn n l khi ta cho d Na2S2O3 th mu xanh vn cha bin mt sai s tha ln. V vy, ta chun cho n khi dd chuyn sang mu vng rm (tc l trong dd lc ny cn t I2) th mi ch th h tinh bt vo nhm hn ch sai s
12

 Cho d KI I2 chuyn ha hon ton thnh I3-(c th ly KI bng ng ong v khng cn ly th tch chnh xc) Phn ng thay th xy ra nhanh nn khng c th chun lin m khng cn ch phn ng xy ra hon ton v cng nhm tranh I2 tht thot ra ngoi lm sai lch ti kt qu chun . VII/ Xc nh hm lng oxygen ha tan trong nc (DO) bng phng php Winkler 1/ Mc ch th nghim -Xc nh lng oxy ha tan trong nc 2/ Nguyn tc - Phng php da trn c s phn ng m Mn ho tr 2 trong mi trng kim (dung dch c cho vo trong mu nc trong cng hn hp vi dung dch KI) b O2 trong mu nc xy ho n hp cht Mn ho tr 4, s ng lng ca hp cht Mn ho tr 2 lc c kt hp vi tt c O2 ho tan. Mn2+ + 2OH- = Mn(OH)2 4Mn(OH)2 + O2 = 4MnO(OH) + 2H2O 4MnO(OH) + O2 + 2H2O = 4MnO(OH)2 - S ng lng ca Mn ho tr 4 c to thnh dng kt ta mu vng nu bng s ng lng xy ho tan trong nc. Khi thm axit H2SO4 vo trong mu, hp cht Mn ho tr 4 hay ni khc i l s ng lng ca O2 ho tan, chnh bng s ng lng I2 c trong mu nc. MnO(OH)2 + 4H+ + 3I- Mn2+ + 3H2O + I3I3- sinh ra d dng nh lng bng dung dch chun Na2S2O3. I3- + 2S2O32- 3I- + S4O62- Bit th tch v nng Na2S2O3 khi chun ta d dng tnh c hm lng xy ho tan trong mu nc. V th khi xc nh O2 ho tan trong nc c thc hin trong 3 giai on: Giai on I: C nh O2 ha tan trong mu (c nh mu) Giai on II: Tch I2 bng mi trng acia (acid ha, x l mu) Giai on III: Chun I2 bng Na2S2O3 (phn tch mu) 3/ Tin hnh a. C nh mu nc - Cho mu nc vo y erlen 250ml , cho vi cao su st y chai nc trn ra ht khong 1/3 th tch lc u. - Lp tc cho vo 1ml MnCl2 +1ml dd KI/ NaOH (lu l cm u pipet ht cc dung dch xung di mt thong ca cht lng), y nt chai li sao cho khng c bt kh, o u xut hin kt ta trng ri chuyn sang mu vng nu.
13

b. X l mu - yn bnh nh mc trong mt gi - Thm 1ml H2SO4 c, o u kt ta vng nu tan ht, dd lc ny c mu vng ca I2 c. Phn tch mu */Trc ht cn xc nh li chnh xc nng ca Na2S2O3 0.01N c trong phng th nghim. Tin hnh - Chun b buret vi dd chun Na2S2O3. - Rt 10.00ml dd K2Cr2O7 0.020000 0.000018 N cho vo erlen 250ml. - Thm 15ml nc ct + 3ml H2SO4 c + 5ml KI 10%, lc nh. - y kn v yn 10 pht kh hon ton K2Cr2O7 - Chun t t tng git cho ti khi xut hin mu vng rm ri cho thm vi git dd h tinh bt cho ti khi dd c mu xanh chm r rt, va thm va lc u. - Tip tc chun bng dd Na2S2O3 cho ti khi mu xanh chm bin mt, ghi li th tch Na2S2O3 tiu tn. - Lp li th nghim trn 3 ln, ta thu c cc gi tr sau: V1 23.30ml Tnh ton:
C N S O 2 =
2 3

V2 23.30ml

V3 23.30ml

Vtb Vtb = 23.30ml

V pipet C N Cr O 2
2 7

Vtb

= 0.0085836909 87 N 0.95, N V pipet + V pipet

2

0.95, N Cr O 2 2 7 0.95, N S O 2 = C N S O 2 2 3 2 3 C N Cr2 O7 2 0.95, N Cr O 2 = 0.000018

2 7

0.95, N Vburet + Vtb

0.95, N Vpipet = 1.96

Vi

0.95, N Vburet
0.95, N S
2

0.0070 = 0.0079 3 3 0.030 = 1.96 buret = 1.96 = 0.034 3 3 = 0.000016 O32 = 1.96

pipet

Vy nng ca Na2S2O3:
C N S
2 O3 2

=0.0 8 8 054

0.0 0 1 006

- Dng pipet rt 30ml mu cho vo erlen 250ml

14

- Chun bng Na2S2O3 0.008584 0.000016 N va xc nh nng li trn n khi dd chuyn sang mu vng nht th thm vo 3 git h tinh bt dd chuyn sang mu xanh tm. Tip tc chun cho n khi mu xanh ny bin mt, ghi li th tch Na2S2O3 tiu tn - Lp li cc bc trn 3 ln, ta thu c cc gi tr sau: V1 2.40ml V2 2.40ml V3 2.40ml Vtb Vtb = 2.40ml

Cc bc xc nh th tch gn ng ca bnh nh mc 250ml cha mu nc: - Np dd nc vo bnh ti y trn - y np li ui phn dd do np chim ch - B np ra, nh du mc dd trong bnh - Rt b phn dd trn vch nh mc - Np dd nc vo buret. Qua buret, cho nc vo bnh nh mc cho n vch mc nh du. Ghi li th tch V* tiu tn V*= 14.60ml V dd mu = V danh nh + V* 4/ Biu din kt qu Lng nc thc t c nh lng (tr 1ml MnCl2 v 1ml KI/ NaOH c thm vo) l:
VH 2 O = 30 250 + V * 2 = 29.77 ml 250 + V * VNa 2 S 2 O3 C N Na 2 S 2 O3 VH 2O
2

mgO2 / L =

8 1000 =

2.40 0.008584 8 1000 = 5.536204232 mg / L 29.77

Vi V1 = VMnCl 2 + VKI / NaOH = 2.00ml

V 1
pipet pipet + 1.96 = 0.019 = 1.96 VMnCl 2 1 VKI / NaOH 1
2 2 2

t A= Vb + V * V1 = 250.00 + 14.60 2.00 = 262.60ml

bm + 1.96 buret + V 1 = 0.010 A = 1.96 Vb 1 V * 1 V1
2

0.05, m gO2

0.95, N N a2 S 2 O 3 0.95, N V pipet 0.95, N Vburet A 2 + + + = m gO2 / L CN Na S O V pipet Vtb A 2 2 3

15

 0.95, N Na 2 S 2 O3 = 0.000016 bm = 0.027

0.0070 = 0.0046 3 9 0.030 0.95, N Vburet = 1.96 buret = 1.96 = 0.034 3 3 0.95, mgO 2 = 0.013

0.95, N Vpipet = 1.96

pipet

= 1.96

Vy: 5/Nhn xt chnh xc ca qu trnh chun : 0.95, mgO / L 0.013

1
2

mO g

/ L = .5 6 5 3

.0 3 m / l 0 1 g

mgO2 / L

= 1

5.536

= 99.76%

chnh xc khng cao, c l do qua nhiu bc trung gian, giai on pha ch, rt dd cha chun xc. Hn ch ca phng php ny l khng p dng trc tip vi nhng mu nc c cht oxy ha v n c kh nng oxy ha anion I- hoc cc cht kh (H2S). Mt s ci bin ca pp Winkler gip hn ch cc nhc im v phm vi p dng. V d : phng php ci bin azide c thm KF loi b nh hng ca ion nitite v Fe3+, phng php ci bin permanganat loi b nh hng ca ion Fe2+. Nhc im th hai ca phng php ny l chnh xc thng thay i, ph thuc nhiu vo kinh nghim v k thut thu muok Bn cnh , phng php ny c u im l c chnh xc rt cao nn thng c s dng trong phng th nghim. Dng c cn thit cho phng php ny cng kh n gin v r tin. V hm lng I3- trong mu thp nn mi ln chun ta ly khong 25-50ml Do phn ng gia Mn(OH)2 vi oxygen din ra kh chm nn ta cn mu nc c nh ch mt 1h lng oxygen c trong dd phn ng ht. Trong giai on c nh v x l mu nc phi ht sc cn thn, khng oxy khng kh ha tan vo dung dch (tt nhin khng th hon ton trnh c iu ny nhng cng hn ch c th kt qu cng chnh xc), c bit lu qu trnh thm MnCl2 v KI/NaOH vo mu, phi cm u ca pipet vo trong dd. Ta dng dd thiosulfat nng long ~0.01N v hm lng oxygen trong mu thp, nu dng nng c rt d mc sai s.
16

VIII/ Xc nh nng K2Cr2O7 bng Fe2+ - ch th Ferroin

1/ Mc ch th nghim: Xc nh chnh xc nng ca K2Cr2O7

2/ Nguyn tc - Chun trc tip K2Cr2O7 bng dd Fe2+ c nng chnh xc l ( 0.050000 0.000025 N ) c pha t cht gc l mui Morh vi s c mt ca ch th Ferroin. Qu trnh chun kt thc khi mu ca ch th th in cc chuyn t xanh chm sang . - Phn ng chun : Bn phn ng oxy ha: Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O E Cr 2O 72 , H + / Cr 3 + = 1.33V Bn phn ng kh: Fe2+ - e- Fe3+ E Fe 3+ / Fe 2 + = 0.77V Phn ng tng cng: 6Fe2+ + Cr2O72- + 14H+ 6Fe3+ + 2Cr3+ + 7H2O E = 0.56V 3/ Tin hnh - Rt 10.00ml dd K2Cr2O7 cn xc nh nng cho vo erlen 250ml. - Thm 5ml H2SO4 (1:1) + 3 git ch th ferroin. - Chun vi dung dch Fe2+ cho ti khi mu thay i t xanh chm sang nu bn trong 1 pht, ghi li th tch Fe2+ tiu tn. - Lp li th nghim trn 3 ln, ta thu c cc gi tr sau: V1 15.25ml V2 15.20ml V3 15.20ml
Vtb =

Vtb
15.25 + 15.20 + 15.20 = 15.22ml 3

4/ Biu din kt qu:

17

C N K 2Cr2O7 =

C N Fe 2 + Vtb V pipet

= 0.0760833333 3 N 0.95, N V pipet + V pipet

2

2+ 0.95, N K 2Cr2O7 = C N K 2Cr2O7 0.95, N Fe C N Fe 2 + 0.95, N Fe 2 + = 0.000025

0.95, N Vburet + Vtb

Vi 0.95, N Vpipet = 1.96

n

pipet
3

= 1.96

0.0070 = 0.0079 3

S n, x =

(x x )
i =1 i n

n 1

= 0.0292 S n , x =

Sn, x n

= 0.0168

0.95, N Vburet = t 0.95, f S n , x = 4.30 0.0168 = 0.072 0.95, N K 2Cr2O7 = 0.00037

Vy nng ca K2Cr2O7:
C N 2C 2O7 =0.0 6 8 70 K r .0 0 7 0 03 N

5/ Nhn xt chnh xc ca qu trnh chun : 0.95, N K Cr O 0.00037

1
2 2 7

C N K 2 Cr2 O7

= 1

0.07608

= 99.51%

Php chun mc sai s dng do bn thn ch th c cha St lm tng hm lng st trong dung dch. Trong qu trnh chun , cn ht sc cn thn, cho tng git Fe2+ vo dd d dng quan st s thay i mu sc. Ban u dd c mu vng lc lc vng xanh lcxanh dng nhtxanh ti, lc ny ngng nh Fe2+ xung, lc mnh erlen cho ti khi dd tr v xanh dng sng th mi chun tip, lc ny gn ti im cui, ta nn chun tht chm, na git mt, nu dd tip tc chuyn sang mu xanh ti th c tip tc lc mnh erlen dd chuyn sang mu cam th dng chun . -Khng nn un nng dd v cht ch th ferroin khng bn vi nhit, d b phn hy IX/ Kim tra: xc nh nng K2Cr2O7 bng Fe2+ ch th Ferroin MU S 22 1/ Tin hnh - Thm nc vo n vch mc ca bnh nh mc. - Rt 10.00ml dd K2Cr2O7 cn xc nh nng cho vo erlen 250ml.
18

- Thm 5ml H2SO4 (1:1) + 3 git ch th ferroin. - Chun vi dung dch Fe2+ ( 0.050000 0.000025 N ) cho ti khi mu thay i t xanh chm sang nu bn trong 1 pht, ghi li th tch Fe2+ tiu tn. - Lp li th nghim trn 3 ln, ta thu c cc gi tr sau: V1 8.90ml 2/ Biu din kt qu
C N K 2Cr2O7 = C N Fe 2 + Vtb V pipet = 0.0445833333 3N 0.95, N V pipet + V pipet 0.0070 3
2

V2 8.95ml

V3 8.90ml
Vtb =

8.90 + 8.95 + 8.90 = 8.92ml 3

Vtb

2+ 0.95, N K 2Cr2O7 = C N K 2Cr2O7 0.95, N Fe C N Fe 2 + 0.95, N Fe 2 + = 0.000025

0.95, N Vburet + Vtb

Vi 0.95, N Vpipet = 1.96

n

pipet
3

= 1.96

= 0.0079

S n, x =

(x x )
i =1 i n

n 1

= 0.0292 S n , x =

Sn, x n

= 0.0168

0.95, N Vburet = t 0.95, f S n , x = 4.30 0.0168 = 0.072 0.95, N K 2Cr2O7 = 0.00036

Vy nng ca K2Cr2O7:
CN 2C K r
2O7

= .0 4 8 0 45

.0 0 6 0 03

PTN: Cpotassium dichromate = 0.044625 N

X/ Kt lun chung Bi thc hnh tun ny ch yu kho st 3 phng php chun oxy ha kh in hnh Phng php permanganat - Chun bng pp permanganat l mt trong nhng pp phn tch ph bin v c s dng rng ri nht hin nay. Trong phng php ny, cht c bn c s dng iu ch dd oxy ha chun l KMnO4 thng c tin hnh trong mi trng acid sunfuric. u im ca phng php: + Khng cn s dng cht ch th do bn thn ca KMnO4 c mu tm, php chun kt thc khi xut hin mu hng nht bn vng d dng quan st im cui chun . + Permanganat c th oxi ha kh cao E MnO / Mn = 1.52V c th dng xc nh nhiu cht khc nhau.
4 2+

19

+ Permanganat l ha cht r tin v d kim Nhc im ca phng php : + dd permanganat khng bn, chun ca n thay i theo thi gian nn trc khi s dng n chun ta cn kim tra li nng ca n. + Khi chun bng permanganat, nn trnh s c mt ca ion Cl- v Fe2+ v s xy ra phn ng ph lm nh hng n kt qu chun . Nu c mt ng thi c hai ion trn ta phi dng hn hp bo v zymmerman. + Mt s phn ng xy ra rt chm nhit phng do cn un nng tng tc phn ng. Tuy nhin trong mt s trng hp c bit ta khng c un nng v s lm cho cc cht trong dd b phn hy hoc bay hi (in hnh trong bi ny l H2O2) Phng php bicromat - L pp phn tch chun da trn vic dng dd chun kali bicromat, pp ny thng c tin hnh trong mi trng acid sulfuric, clohidric hay phosphoric. u im ca phng php: + dd K2Cr2O7 rt bn, chun ca n t thay i trong thi gian di nn khng cn phi chun li khi s dng. + Khng cn dng hn hp bo v zymerman khi c Cl+ So vi permanganat, bicromat kh b kh bi cc cht hu c c trong nc + Khng cn un nng khi tin hnh chun Nhc im ca phng php : + K2Cr2O7 l cht oxi ha yu hn KMnO4 do n t c s dng hn l pp permanganat. + Phn ng xy ra tng i chm. Tc phn ng tng khi nng ion hidro tng, tc phn ng xy ra nhanh trong mi trng acid mnh. + Mc d l dd c mu nhng s thay i mu ca dd im cui chun rt kh quan st do cn phi dng cht ch th. Phng php Iode - Cht c bn c dng trong phng php ny l iode. Iod oxy ha tt c cc cht kh. Do iod rt t tan trong nc v d bay hi nn ngi ta thng dng iod trong dd KI lm dd chun. u im ca phng php: + C chnh xc cao. + Dd Iod c mu, v vy c th tin hnh m khng cn dng n cht ch th. Mu vng ca I3 c th quan st c ngay c khi nng rt nh . + Iod tan tt trong cc dung mi hu c c s dng rng ri. Nhc im ca phng php: + Iod rt d bay hi, cn tin hnh chun trong iu kin nhit thp, trong ti, v chun nhanh. + S oxy ha ca ion I- bng oxy khng kh 4I- + O2 + 4H+ 2I2 + 2H2O sai s thiu do tht thot Iod + Mt s cht nh Cu2+, NO2-, NO, c th lm tng s oxy ha I- bi oxy khng kh, do trong tin hnh chun cn trnh s c mt ca cc cht ny.
20

21