thi mn Phn Tch nh Lng

Lp Ha 2006A, 15/06/2008, 12:45

Thi gian: 120 pht (khng tnh 5 pht c )
1. Hy xy dng quy trnh phn tch cho hn hp H2SO4 (20%) v H3PO4 (25%). Bit
rng t trng ca dung dch mu l 1.4 g/mL. H2SO4 c pKa2 = 2.0, H3PO4 c pKa1 = 2.12;
pKa2 = 7.21; pKa3 = 12.36. Cc ha cht v dng c c theo yu cu. (3 im)
Nng M ca mi acid trong mu: 0.25
CM

C %.d .1000 20 * 1.4 * 1000 280

2.857 M H 2 SO4
M H 2 SO 4
100 * 98
98

CM

C %.d .1000 25 * 1.4 * 1000 280

3.57 M H 3 PO4
M H 3 PO 4
100 * 98
98

Phn ng chun : 0.25; 0.25

H2SO4l acid mnh nn khi chun trong mi trng nc, s chun lun c hai nc theo
phng trnh phn ng H2SO4 + 2OH- SO42- + 2H2O
H3PO4 l acid 3 chc tng i yu nn mnh nn khi chun trong mi trng nc,
cc nc s ln lt chun nh sau
Nc 1: H3PO4 + OH- H2PO4- + H2O
Nc 2: H2PO4- + OH- HPO42- + H2O
Nu gi s nng u ca H3PO4 l 0.1M chun vi NaOH 0.1M th
iu kin chun nc 1: 0.25
pKa1 + pCo + pD = 2.12 + 1 + 0.6 = 3.72 < 8 < 10
6> pKa2 - pKa1 = 7.21 -2.12= 5.09 > 4
Nh vy khng th chun ring nc 1 ca H3PO4 vi chnh xc >99.9% m chp nhn
chnh xc mm hn l 99%
Tng t iu kin chun nc 2: 0.25
8< pKa2 + pCo + pD = 7.21 + 1 + 0.7 = 8.91 < 10
6> pKa3 - pKa2 = 12.36 - 7.21= 5.15 > 4
Nh vy khng th chun ring nc 2 ca H3PO4 vi chnh xc >99.9% m chp nhn
chnh xc mm hn l 99%.
Nc 3 c pKa3 + pCo + pD = 12.36 + 1 + 0.78 > 10 khng th chun chnh xc. 0.25
Do H2SO4 c nc 1 rt mnh v nc 2 c pKa2 =2 tng i yu nn khi chun hn hp
H2SO4v H3PO4, c hai nc H2SO4 v nc 1 ca H3PO4 c chun ng thi. Nc 2 ca H3PO4
c chun ring r tip theo. chnh xc ca php chun mi nc b l thuc vo H3PO4 v
chp nhn l 99%. Xy dng quy trnh phn tch v tm iu kin chun hn hp H2SO4 v

H3PO4 tng t nh chun ring H3PO4. Do nc 2 ca H2SO4 c mnh tng ung vi

nc 1 ca H3PO4 nn khi xt iu kin chun gn im tng ung c th xem 2 acid l
nh nhau v ly theo H3PO4 nhng c nng Co bng tng nng mol ca hai acid. Trong
mu, t l nng mol ca hai acid l 2.857M/3.57M; nu pha long sao cho nng H3PO4
0.1M th nng H2SO4 s l 0.08 M.
Cc thi im quan trng ca chun : 0.25; 0.25
F = 0.99; chun ht 99% H3PO4 v 99.5% H2SO4 (tc 100% nc 1 v 99% nc 2) dung
dch cha 1% H3PO4 v 1% NaHSO4, pH = pKa + 2 = 4.21.
F = 1.00; dung dch cha mui Na2SO4 v mui NaH2PO4 v pH tnh gn ng theo mui
lng tnh NaH2PO4: pH = (pKa1 + pKa2) = 4.665
F = 1.01; dung dch cha mui Na2SO4, 99% NaH2PO4 v 1% Na2HPO4 dung dch m
pH = pKa2 -2 = 5.21.
F = 1.99; dung dch cha mui Na2SO4 1% NaH2PO4 v 99% Na2HPO4 dung dch m
pH = pKa2 +2 = 9.21.
F = 2.00; dung dch cha mui Na2SO4 v mui Na2HPO4 v pH tnh gn ng theo mui
lng tnh Na2HPO4: pH = (pKa2 + pKa3) = 9.785
F = 2.01; dung dch cha mui Na2SO4, 1% Na2HPO4 v 99% Na3PO4 dung dch m
pH = pKa3 -2 = 10.36.
Chn ch th: 0.25
Khong bc nhy 1: 4.125.21 kh hp chn ch th hn hp pT 5.1 sai s tha
Khong bc nhy 2: 9.2110.36 kh hp chn ch th hn hp pT 10.2 sai s tha.
Thc nghim: 0.25; 0.25
Pha long dung dch mu n nng H3PO4 khong 0.1M, nng H2SO4 khong
0.08M. H s pha long: 3.57/0.1 = 35.7 ln. Th tch mu cn dng khong 100 mL
ht Vmu = 3 mL mu pha long thnh 100 mL (c th cn 4.2 g mu vo bnh nh mc
100 mL chnh xc hn), nh mc n vch bng nc ct.
Dung dch NaOH 0.15 M, pha t NaOH rn, nh phn li bng dung dch cht gc acid
oxalic 0.1000N ch th phenolphthalein.
Buret np NaOH: cn buret 25 mL
Dng pipet bu 10 mL
ht 10.00 mL mu vo erlen 250 mL,
o thm ch th pT 5.1, chun n mu trung gian th ngng s tn khong VI =1718 mL NaOH 0.15 M.

o Thm ch th pT 10.2, chun n mu trung gian th ngng, s tn khong VII =

24-25 mL NaOH 0.15 M.
Mi ch th nn chun lp ti thiu 3 ln tng chnh xc php chun .
Tnh tan: 0.25
C MH 3 PO4
C MH 2 SO4

VII VI * C NaOH
10

2VI VII * C NaOH

10

100
Vmau

100
Vmau

2. (3 im) Na2S2O3 c s dng rng ri nh l mt cht kh trong phng php iod.

Tuy nhin do Na2S2O3 khng phi l cht gc nn phi xc nh chnh xc nng ca
dung dch Na2S2O3 qua dung dch K2Cr2O7 c nng chnh xc (pha t cht gc). Cch
thc hin nh sau: ly 10 mL dung dch K2Cr2O7 0.1000N v erlen v thm 2 mL H2SO4
m c, thm 10 mL KI 10%. yn trong 10 pht ri chun I2 sinh ra bng dung dch
Na2S2O3 vi ch th h tinh bt.
Hy vit tt c phng trnh phn ng din ra trong quy trnh chun ny km theo cc
hin tng quan st thy.
- Cho bit: ECro O
2

7 ,H

/ 2Cr 3

1.33V ; E So O 2 / 2 S O 2 0.09V ; E Io / 3 I 0.545V

4

2 3

Dung dch KI khng mu hoc c mu vng rt nht do KI b oxy ha mt phn trong

khng kh 0.25. Dung dch K2Cr2O7 c mu cam. 0.25 Khi thm lng d dung dch KI
vo dung dch K2Cr2O7 trong mi trng H2SO4 mu cam chun sang mu vng nu
0.25 (dung dch A) do c Iod sinh ra theo phn ng:
o K2Cr2O7 + 9KId + 3H2SO4 3KI3 + Cr2(SO4)3 + 3K2SO4 + 3H2O. 0.25

Khi chun dung dch A vi Na2S2O3, mu vng nu nht dn cho ti mu vng rm do

Iod mt dn theo phung trnh phn ng: 0.25
o KI3- + 2Na2S2O3 KI + 2NaI + Na2S4O6. 0.25

Thm ch th h tinh bt, dung dch c mu xanh en do ion I3- b hp ph vo cu trc

xon ca phn t h tinh bt, t hp ny c mu xanh en. 0.25

Chun n ht mu xanh en, dung dch chuyn sang mu xanh lam ca ion Cr3+.0.25

Hy gii thch ti sao:

- Khng chun trc tip K2Cr2O7 bng Na2S2O3. 0.25; 0.25
Na2S2O3 l mt cht kh tng i yu trong nguyn t c tnh kh l S c s oxyha trung
bnh l +2. trng thi oxyha ny, S c th b kh v 0 hay -2 v cng c th b oxyha ln

+2.5 (Na2S4O6) hay +4 hay +6. Cc qu trnh ny din ra ty thuc rt nhiu vo iu kin phn
ng v thng khng t lng. K2Cr2O7 l cht oxyha tng i mnh v s oxyha Na2S2O3 v
nhiu s oxyha khc nhau. Nh vy phn ng ny khng tha cho iu kin ca mt phn ng
chun . V vy ngi ta phi gim cp K2Cr2O7 bng cch bin n thnh mt cht c tnh
oxyha yu hn l KI3 ch c th oxyha t lng Na2S2O3 thnh Na2S4O6.
- Khng cho ch th h tinh bt lc bt u chun m cho ch th khi gn ht iod trong
dung dch (mu vng rm). 0.25; 0.25
Khi cho ch th h tinh bt vo dung dch c cha KI3, ion I3- s chui vo cu trc xon ca phn
t h tinh bt v lm cho cu trc ny c mu. Mu ca t hp ny mt i ch khi c mt lng
d nht nh Na2S2O3 trong dung dch. S mt mu nhanh hay chm ty thuc v lung d
Na2S2O3 v mc thm nhp ca I3- nng hay su trong cu trc xon ca phn t h tinh bt.
Nu I3- qu nhiu, n s xm nhp qu su vo h tinh b v cn phi dng mt lung kh d
Na2S2O3 lm mt mu h phn ng t n im cui sai s tha kh ln.
3. Chun Ca2+ bng ETDA, dng ch th NET (4 im)
- Hy xc nh khong pH v khong nng Ca2+ phn ng chun trn c chnh
xc > 99.9%. 1.0
Phn ng chun : Ca2+ + Y4- CaY2Ca2+ + iOH- Ca(OH)i phn ng ny khng ng k trong khong pH

Phn ng ph:

<12 nn c th b qua.
nH+ + Y4- HnY
1

Y (H )

H H

K4

K4 K3

K4 K3K2

K 4 K 3 K 2 K1

iu kin chun chnh xc n 99.9%: pKCaY - pCo - pDF=1 pY(H) - pCa(OH)> 6; nu nh

hng ca OH- l khng ng k, [Ca] = [Y] pDF=1 = 0.3 pKCaY - pCo - pDF=1 pY(H) pCa(OH) = 10.7 pCo 0.3 - pY(H) > 6 pCo + pY(H) < 4.4.
S ph thuc ca gi tr pY(H) vo pH ghi trong bng sau:
pH

10

11

12

pY(H) 4.7 3.3 2.3 1.3 0.46 0.07 0.01

D dng nhn thykhi nng Ca2+ 0.1M th c th chun nh lng trong khang pH t 712. Nng ion Ca2+ gim i 10 ln th bin tri khong pH hu hiu tng ln 1 n v.
- Hy v ng cong chun dung dch Ca2+ 0.05M bng EDTA 0.05M. 1.0
Trong trng hp ny, pCo = 1.3 chun nh lng trong khong pH tng ng vi pY(H)
< 3.1 tc l pH tnh gn ng t 7-12.

 F = 0.99: pCa = pCo + pD + 2 = 1.3 + 0.3 + 2 = 3.6 (gi tr ny khng thay i theo pH
mi trng).
F = 1.00: pCa = (pKCaY + pCo + pD - pY(H) + pCa(OH)) = (10.7 + 1.3 + 0.3 - pY(H)) =
6.15 * pY(H). Gi tr ny ty thuc vo pH mi trng, trong khong pH gii hn
tnh t 7-12 th pCa dao ng trong khong 4.5- 6.15.
F = 1.01: pCa = pKCa - pY(H) 2 = 8.7 - pY(H). Trong khong pH tnh t 7-12 th pCa
dao ng trong khong 5.4- 8.7
pH
pY(H)

10

11

12

3.3

2.3

1.3

0.46

0.07

0.01

Bcnhy 3.6-5.4 3.6-6.4 3.6-7.4 3.6-8.24 3.6-8.63 3.6-8.69

- Hy cho bit kh nng ng dng ca ch th NET trong phn ng chun ny, c chng
minh bng tnh ton. 1.0
Khong pH s dng tt nht ca ch th NET l 7-11 do dng t do ca ch th NET c mu
chm tng phn vi mu nho ca phc CaNET. Tuy nhin cn phi xt xem im cui ca
php chun c nm trong khong bc nhy ca ung cong chun hay khng.
S ph thuc ca pH vo phn ng ph gia ch th NET v H+ nh sau:
pH

10

11

pNET(H)

4.6 3.6 2.6 1.6 0.6

pKCa(NET) 0.8 1.8 2.8 3.8 4.8

i chiu vi khong bc nhy ca ung cong chun CaY trong khong pH 7-11, khi im
cui mu trung gian th ch c cc gi tr pH mi trng 10-11 th im i mu ca ch th mi
nm trong khong bc nhy. Vy trong iu kin phn ng chun nh trn, ch dng uc
ch th NET trong khong pH t 10-11 m thi.
- Hy chng minh ti sao kh chun Ca2+ nng thp? Gii php ra l thm
MgY2-. Hy nu c s l thuyt chng minh tinh hp l ca gii php ny. 1.0
Nhn thy nng Ca2+ thp: pCa ti F = 0.99 s tng ln lm thu hp khong bc nhy ca
phn ng chun im cui nm ngoi bc nhy v mc phi sai s thiu. V d nh khi Co
= 0.001M th pCaF=0.99 = 3 + 0.3 + 2 = 5.3, pCaF=1.01 = pKCa - pY(H) 2 = 8.7 - pY(H) (=8.24 pH
10 v 8.63 pH11). Nh vy ch th NET s i mu trc im tng ung do pCacui = 4.8.
Ngoi ra ch th mu s kh nhn thy do phc CaNET c mu nho yu.
Gii php cn thit l dng MgY thm vo dung dch Ca2+ c thm ch th NET, lc xy ra
phn ng sau

CaNET ( nho nht) + MgY CaY + MgNET ( nho mnh); ti pH = 10, phn ng ny
c pK = 10.24 + 5.4 8.24 3.8 = 3.6.
Nh vy mu ch th trong dung dch l MgNET.
Khi chun vi EDTA, s c nhng phn ng sau y: Ca2+ + Y CaY,
Khi ht Ca2+ th MgNET ( nho mnh) + Y MgY + NET (xanh chm).
Nh vy im cui ca chun l s chuyn mu ca phc MgNET thay v CaNET,
Tuy nhin khi thm MgY vo dung dch Ca2+ th phi xt im cui c nm trong khong bc
nhy ca chun CaY hay khng, tc l phi xt pCa.
Trng hp chun ti pH 10
Mu trung gian: pMg = pKMgNET = 7.0 1.6 = 5.4 pCa cuoi 7.4 p
Mu r rt: pMg = pKNET + 1 = 6.4. pCa cuoi 8.4 p

C CaY
C MgY

C CaY
C MgY

Nhn thy pCacui ty thuc vo t l nng CaY/MgY nu CaY/MgY = 10/1

pCa cuoi 7.4 p

C CaY
6.4
C MgY

pCa cuoi 7.4 p

C CaY
7.4 i vi im cui mu r rt. C hai trng hp ny u
C MgY

vi

im

cui

mu

trung

gian

c pCacui nm trong khang bc nhy 5.38.24 pH 10

Trng hp chun ti pH 11
Mu trung gian: pMg = pKMgNET = 7.0 0.6 = 6.4 pCa cuoi 8.4 p
Mu r rt: pMg = pKNET + 1 = 6.4. pCa cuoi 9.4 p

C CaY
C MgY

C CaY
C MgY

Nhn thy pCacui ty thuc vo t l nng CaY/MgY nu CaY/MgY = 10/1

pCa cuoi 7.4 p

C CaY
7.4
C MgY

pCa cuoi 7.4 p

C CaY
8.4 i vi im cui mu r rt. C hai trng hp ny u
C MgY

vi

im

cui

mu

trung

gian

c pCacui nm trong khang bc nhy 5.38.63 pH 11

Cho bit: EDTA c pKa1 = 2.0; pKa2 = 2.67; pKa3 = 6.7 v pK4 = 10.33; pKCaY = 10.7; pKMgY =
8.7; pKCaNET = 5.4; pKMgNET = 7.0; NET c pKa2 = 6.3; pKa3 = 11.6.