H v tn: Phm Minh Tin Nguyn Th Th

1014220 1014212

MSSV:
MSTT:

T3 17

Th ba, ngy 27 thng 3 nm 2012

BI TNG TRNH PHN TCH NH LNG

PHNG PHP CHUN KT TA

I.

Xc nh Cl- theo phng php Mohr

1. Mc ch
Xc nh nng Cl- c trong mu bng phng php Mohr t so snh vi
nhng phng php khc.
2.

Nguyn tc

Chun Cl- bng dung dch AgNO3 : 0,010000 0,000056 (N) trong mi trng m
NaHCO3 khi c mt K2CrO4.
Phn ng chun :

(trng)

Phn ng ch th khi cho d 1 git Ag+:

CrO4

+ 2 Ag + Ag 2 CrO4 ( gch)

3. Tin hnh
- Rt 10,00 mL dung dch cha ion Cl- cho vo erlen 250mL.
- Thm 2,00 mL dung dch NaHCO3 5% + 10 git K2Cr2O4 6%.
- Nh t t dung dch AgNO3 vo erlen. Trong qu trnh chun lin tc lc mnh
erlen. Khi dung dch trong ra, kt ta trng vn cc li l du hiu gn n im tng
ng. Nh tht chm tng git lc mnh n khi xut hin kt ta mu gch. Ghi
li th tch.
- Lp li th nghim trn ba ln, ta thu c cc gi tr sau:

V1

V2

V3

Vtb

9,85 mL

9,80 mL

9,80 mL

9,82 mL

Vpipet = (10,00 0,02) mL

VKMnO4 = 9,82 + 0,02 = 9,84 mL
4. Biu din kt qu
C N Cl =

0,95; N Cl

CN AgNO3 *VAgNO3
VCl

0, 010000*9,84
= 0, 009840 N
10, 00

0,95; N AgNO3
= CN Cl *
C N AgNO
3

1,96* pipet
+
V * n
pipet

t0,95;n 1 * S n ,V
buret
+

Vtb * n

0, 000056 1,96*0, 020 4,30*0, 02887

= 0, 009840*
+

+
0, 010000 10, 00* 3 9,84* 3
= 0, 000093N

Vy nng ca Cl- : CN-Cl- = 0,009840 0,000093 N

Sai s ch th:
Gi s mi git K2CrO4 c th tch 0,05mL , ta c th tch K2CrO4 0,50 mL. Khi
:
mK2CrO4 = VK2CrO4 d K2CrO4 = 0.5 1 = 0,50 g
mK2CrO4 = 0,50*6% = 0, 03 g
Vdd = VCl + VNaHCO3 + VK2CrO4 + Vtb = 10, 00 + 2, 00 + 0,50 + 9,84 = 22,34mL
[CrO4 2 ]cuoi =

nK2CrO4
Vdd

0, 03
194
=
= 0, 0069 M
22,34*103

Tnh [Ag]cui, [Cl]cui:

+

[ Ag ]cuoi =

TAg 2CrO4
CM CrO 2
4

[Cl ]cuoi =

TAgCl
[ Ag + ]cuoi

10 11,95
= 1, 27*10 5M
0, 0069

10 9,75
= 1,39*10 5M
1,304 10 5

%
CrO
=
42 , Ag +

[ Ag + ]cuoi [Cl ]cuoi

1, 27 *105 1,39*105
100 =
100
C AgNO3
0, 010000
0, 00984
CCl
0, 00984 + 0, 010000
CCl + C AgNO3

%
CrO
= 0, 015%
42 , Ag +

5. Nhn xt
chnh xc ca qu trnh chun :
1

0,95; N Cl
C N Cl

= 1

0, 000093
= 99, 05%
0, 009840

Sai s m l do nng CrO42- 6% , nn khi n gn im tng ng lng

Cl- vn cn m khi TAgCr2O4 < [Ag+]2 * [Cr2O42-] lm xut hin kt ta, dng
chun trc im tng ng.
Khng s dng mi trng kim v Ag+ s phn ng ph vi OH- to kt ta

en, kh quan st mu sc ca kt ta. Khng s dng c mi trng acid v CrO42s tn ti di dng HCrO4- hoc H2CrO4 , khng ch th c.
Cht ch th dng trong phng php kt ta khng c i mu cho ti khi

lng ion cn xc nh chuyn ht v dng kt ta v cht ch th cn phi tht

nhy vi lng d nh ca AgNO3 hn ch gy ra sai s tha ln. Mt iu cn
lu na l ta quan st s thay i mu sc ca kt ta ch khng phi mu ca
dung dch. Trn thc t, ch cn kt ta chuyn mu, mu hng nht l ta c th
ngng chun , khng i n khi chuyn sang mu gch v s dn n sai s
tha ln.
Trong qu trnh chun cn lc mnh erlen kt ta vn cc li d quan st
mu sc ca kt ta .
Nhc im ca phng php Mohr l khng dng chun cc dung dch

c mu v mu ca dung dch s che i mu ca kt ta kh quan st. Ngoi ra,

phng php ny ch dng xc nh Cl- v Br-, khng dng xc nh I- , SCN-,
F- v AgF khng kt ta, cn AgI v AgSCN kt ta s hp th mnh CrO42- gy
sai s ln.

II. Xc nh Cl- theo phng php Fajans

1.

Nguyn tc:

Chun Cl- bng dung dch AgNO3 0,010000 0,000056N trong mi trng m
NaHCO3 khi c mt Fluorescein (HFl) lm ch th.
Phn ng chun :

(trng)

Phn ng ch th: khi cho d mt git Ag+, ht keo (AgCl)m tch in dng s hp
ph anion Fl- v tr thnh mu hng.

{ ( AgCl ) } xNO
+x

+ xFl

{ ( AgCl )

Ag x+ x xFl (mu hng) + xNO3

2. Tin hnh

- Rt 10,00mL dung dch Cl- cn nh phn vo erlen 250mL.

- Thm 2mL NaHCO3 5% + 3 git ch th Fluorescein (HFI) 0,5%.
- Chun bng dung dch AgNO3 0,0100000,000056N, lc mnh trong qu trnh tin
hnh chun . Cng gn im tng ng, kt ta dng ht keo cng tr nn trung
ho in tch nn vn li, dung dch trong ra.Quan st mu kt ta, kt thc qu trnh
khi mu kt ta thay i, chuyn sang mu hng nht.
- Lp li th nghim trn 3 ln, ta thu c cc gi tr sau
V1

V2

V3

Vtb

9,65 mL

9,65 mL

9,60 mL

9,63 mL

Vpipet = (10,00 0,02)mL

VAg+ = 9,63 + 0,02 = 9,65 mL
3. Biu din kt qu:

C N Cl =

0,95; N Cl

CN AgNO3 *VAgNO3
VCl

0, 010000*9, 65
= 0, 009650 N
10, 00

0,95; N AgNO3
= CN Cl *
C N AgNO
3

1,96* pipet
+
V * n
pipet

t0,95;n 1 * S n ,V
buret
+

Vtb * n

0, 000056 1,96*0, 020 4,30*0, 02887

= 0, 009650*
+
= 0, 000087N
+
0, 010000 10, 00* 3 9, 65* 3

Vy nng ca Cl- : CN-Cl- = 0,009650 0,000087 N

4. Nhn xt:

chnh xc ca qu trnh chun :

0,95; N Cl
C N Cl

= 1

0, 000087
= 99,10%
0, 009650

Phng php ny da trn s hp ph ca ch th ln kt ta to mu c trng

khi cho d Ag+. Sau khi va qua im tng ng cc ht keo AgCl tch in
dng (v cho d Ag+) nn ht keo s hp ph ion m Fl-. V vy trn b mt kt
ta s xut hin mu hng c trng ca Fluoresceinat bc. Phn ng ch th ch
din ra khi cho d Ag+ .
B mt kt ta cng ln th cng d hp ph, do ta cn lc erlen mnh h

keo AgCl phn tn trong ton b dung dch, dn n din tch b mt hp ph tng
ln, tuy nhin iu ny li dn n kh khn cho vic quan st mu sc ca kt ta.
V Fluoresceinat ch bn trong mi trng c pH > 8, m mi trng kim mnh

s lm kt ta hydroxide bc xut hin( hydroxide bc khng bn phn hy to oxid

bc mu en), v vy ta dng h m mui natri bicarbonate pH 8,3 , khng dng
h m amoni v ion bc s to phc bn vi NH3.

III. Xc nh Cl- theo phng php Volhard

1.

Nguyn tc, mc ch

Xc nh Cl- bng phng php Volhard da trn nguyn tc chun ngc. u tin
ta cho cc ion Cl- kt ta vi mt lng d chnh xc dung dch AgNO3, sau ta
chun li lng d AgNO3 bng SCN- vi cht ch th l phn st amoni. T ta xc
nh lng th tch dung dch AgNO3 tiu tn to kt ta vi Cl- bng cch ly
hiu s gia hai ln chun va thc hin.
- Phn ng chun khi cho lng d AgNO3
Cl- + Ag+ AgCl (trng)
- Phn ng chun lng d Ag+
Ag+ + SCN- AgSCN (trng)
Khi cho d 1 git KSCN s xy ra phn ng vi ch th:
Fe3+ + SCN- FeSCN2+ (mu hng)
Do pT AgSCN =12,0 > pT AgCl = 9,75 nn c th s xy ra phn ng:

AgCl + SCN- AgSCN + ClV th ta cho vo dung dch cn chun mt lng dung dch nitrobenzen trc khi
tin hnh chun lng Ag+ d. nitrobenzen bao bc kt ta AgCl li, khng cho
SCN- ph hy AgCl.
2. Tin hnh
a. Chun Cl- bng lng d AgNO3

- Rt 10,00mL dung dch Cl- cn nh phn cho vo erlen 250mL.

- Thm 2 git HNO3 m c.
- Chun bng dung dch AgNO3 0,010000 0,000056M n khi ht ion Cl-, thm
mt lng d chnh xc AgNO3 l 5,00mL, ghi li th tch VI ca AgNO3
- Lp li th nghim trn 3 ln, ta thu c cc gi tr sau:
V1

V2

V3

Vtb

15,00 mL

15,00 mL

15,00 mL

15,00 mL

Vtb1 = 15,00 + 0,02 = 15,02 mL

b. Chun lng d AgNO3
- Chun b ct buret cha dung dch KSCN 0,0174000 0,0000016 N
- Cho vo 3 erlen trn 15 git nitrobenzen, lc mnh nitrobenzen bao bc kt ta li
bng mt lp mng, tch bit vi dung dch.
- Thm vo 1,00mL dung dch phn st amoni (thm Fe3+).
- Chun bng KSCN 0,0174000 0,0000016 N, lc mnh n khi dung dch xut hin
mu cam, ghi li th tch VII ca KSCN
- Lp li th nghim trn 3 ln, ta thu c cc gi tr sau:
V1

V2

V3

Vtb

3,30 mL

3,35 mL

3,35 mL

3,33 mL

3. Biu din kt qu:

C N Cl =

CN AgNO3 *Vtb1 C N KSCN *Vtb 2

VCl

0, 010000*15, 02 0, 0174000*3,33
= 0, 009191N
10, 00

t A = CN-AgNO3 * Vtb1 = 0,010000*15,02 =0,1502

2

1,96 * buret
+
V
AgNO3 * n

0,95; A

0,95; N AgNO3
=A
C N AgNO
3

0,95; A

0, 000056 1,96*0, 05
= 0,1502*
= 0, 0010
+
0, 010000 15, 02* 3

t B = CN-KSCN *Vtb2 = 0,0174000*3,33 =0,057942

2

0,95 B

4,30* buret
= B * 0,95 N KSCN +

C N KSCN VKSCN * n

0,95 B

0, 0000016 4,30*0, 02887

= 0, 057942*
= 0, 0012
+
0, 0174000 3,33* 3

t W = CN-AgNO3 * Vtb1 CN-KSCN *Vtb2 = 0,1502 0,057942 = 0,092258

2

0,95;W

0, 0010 0, 0012
= W * 0,95; A + 0,95;B = 0, 092258*
+
= 0, 0020
0,1502 0, 0579
A B

0,95;Cl

2
0,95;W 1,96* pipet
= CCl *
+
W VCl * n

0,95;Cl

0, 0020 1,96*0, 020

= 0, 009191*
= 0, 00020 N
+
0, 0923 10, 00* 3

Vy nng ca Cl- : CCl- = 0,00919 0,00020 N

Sai s ch th:
pTAgSCN = 11,96
[ FeSCN 2 + cui ] = 6, 4*106 mol / L l nng nh nht m mt ta c th nhn thy mu

hng ca phc ny. Do :

[ SCN cu i ] = K FeSCN 2+ *

6
[ FeSCN 2+ ]
2,14 6, 4*10
=
10
= 3, 09*106 M
3+
[ Fe ]
0, 015

pAgcui = pTAgSCN pSCNcui => [Ag cui ] = 3,55*10-7 M

%
VInSCN
=+

[ SCN cui ] [ Ag cui ]

3, 09*106 3,55*107
*100 =
*100
C
0, 010000
C0
0, 0174000
C0 + C
0, 0174000 + 0, 010000

%
VInSCN
= +0, 04%

4.

Nhn xt:

Khi cho nitrobenzen vo cn lc tht mnh s bao bc xy ra tt.

Cho HNO3 vo nhm to mi trng acid ngn nga Fe3+(di dng phn
FeNH4(SO4)2.12H2O b thy phn to hydroxide st.
Phn ng ny lm kh nhn ra im cui chun v mu ca phc to ra s
nhanh chng phn ng v mt i, nn trnh phn ng trn xy ra cn lc tch kt
ta sau khi cho d AgNO3. Tuy nhin, ta AgCl l kt ta v nh hnh, phn tn
trong dung dch, kh lc nn th nghim ny khng tin hnh lc li ta, m tin
hnh bc cc kt ta li bng nitrobenzen; cht ny s bao bc ta AgCl v ngn
nga phn ng gia SCN- v AgCl.
phn ng chun ny sai s ch yu nm ch nitrobenzen cha bc k kt
ta AgCl, v lc khng k, cho t hoc v cn bng nn vn cn kt ta bc clorur
trong dung dch nh hng ti vic chun bc d bng KSCN. Do tch s tan ca
AgSCN thp hn AgCl do gin tip lm cho s liu o bng phng php
Volhard s thp hn cc phng php trn.

Kt lun chung v ba phng php xc nh Cl- trong dung dch:

Phng php Mohr
u im: Dng chun Cl- v Br- vi nguyn tc chun kh n gin, iu
kin chun bng AgNO3 vi s hin din ca K2CrO4 trong mi trng m pH thch
hp trnh s kt ta ca AgOH (nhanh chng chuyn thnh dng Ag2O).
Nhc im:
o

Ch c tin hnh trong mi trng 7,5 < pH < 11,06

Khng p dng chun I- hay SCN- v kt ta AgI v AgSCN hp

ph mnh ion CrO42- nn kt qu chun khng c chnh xc.
o

Lu l quan st s thay i mu ca kt ta ch khng phi mu ca

dung dch, s thay i mu ca kt ta kh kh quan st, khi kt ta chuyn mu
l ta c th ngng chun .
o

Kt qu chun cn ph thuc kh nhiu vo nng cht ch th do

cn tnh ton k trc khi chn nng cht ch th cho vo nhm hn ch sai s.
o

Phng php Fajans

u im: C th p dng xc nh ion Cl-, Br- v c I- v SCN- trn nguyn

tc chun trc tip bng AgNO3 vi cht ch th hp ph. Nguyn tc tin

hnh kh n gin, khi cho d mt git Ag+ th cc ht keo tch in dng lp
tc hp ph anion Fl- ca cht ch th v chuyn sang mu c trng ca keo
hp th ch th.

Nhc im:
Lun cho sai s dng (v phn ng ch th ch xy ra khi cho d Ag+)

Vic chun phi c tin hnh trong mi trng pH thch hp, tt

nht l tin hnh trong mi trng m pH trung ha. Nu tin hnh trong mi
trng acid th fluorssein s phn li yu nng ca Fl- s rt nh. Nu trong
mi trng kim th s xy ra phn ng ph gia Ag+ vi OH- to kt ta AgOH
nhanh chng chuyn thnh Ag2O c mu en gy sai s tha ln.

Phng php Volhard

u im:

C th p dng xc nh cc ion Cl-, Br-, I- bng phng php chun

ngc: cc ion X- c kt ta bng mt lng d chnh xc ca dung

dch chun AgNO3, sau chun li lng Ag+ d bng dung dch chun
SCN-.
Quan st s thay i mu ca dung dch ch khng phi ca kt ta, y
cng l mt thun li v mu dung dch d quan st hn.
Nhc im:
o Kt ta AgCl c th b ph hy bi SCN- nn trc khi chun lng

d bng dung dch KSCN ta nn dng cht bo v ht keo nitrobenzen d,

m bo ton b kt ta AgCl c bao bc bi nitrobenzen, lu cn
phi lc mnh vic bao bc kt ta xy ra tt nht, tuy nhin nitrobenzen
khng hon ton che ht AgCl nn mt phn AgCl s phn ng vi SCN-

dn n lng SCN- tiu tn ln. Sai s dng. Gy sai s dng, v phn

ng kt thc khi cho d lng SCN- , to phc vi st (III) c mu hng.
o Cn tin hnh trong mi trng acid v nu mi trng hi c tnh kim

th Fe3+ d kt ta hidroxide, khng dng lm ch th c.

IV. Xc nh ion Ca2+ bng phng php khi lng

1. Xc nh li chnh xc nng KMnO4 theo cht chun gc acid oxalic

a. Mc ch:
-

Xc nh li chnh xc nng dung dch KMnO4 c trong phng thc tp

tin hnh th nghim xc nh ion Ca2+ bng phng php khi lng.

Phn ng chun :
5C2O42- + 2MnO4- +

16H+ 2Mn2+ +

10 CO2 + 8H2O

b. Tin hnh:
+

10,00 mL acid oxalic 0,050000 0,000025 N

1 mL H2SO4 (1 : 1)

un nng n 80oC

Chun bng dung dch KMnO4 n khi dung dch chuyn sang mu

90oC

hng nht.
c. Kt qu:
V1

V2

V3

Vtb

5,80 mL

5,75 mL

5,75 mL

5,77 mL

Vpipet = (10,00 0,02)mL

VKMnO4 = 5,77 + 0,01= 5,78mL
d. Biu din kt qu.

C N KMnO4 =

0,95; N KMnO4

C N H 2C2O4 VH 2C2O4
VKMnO4

0, 050000*10, 00
= 0, 0865051N
5, 78

0,95; N H 2C2O4
= CKMnO4
CM H C O
2 2 4

2
1, 96* pipet 4, 30* buret
+

V buret * n
*
n
V pipet

0, 000025 1, 96* 0, 020 4,30*0, 02887

= 0, 086505
+
= = 0,0011N
+
0, 050000 10, 00 * 3 5, 78* 3

C N KMnO = 0,0865 0,0011 N

Vy nng ca KMnO4 :

2. Xc nh ion Ca2+ bng phng php khi lng

a. Nguyn tc:
-

Kt ta Ca2+ bng C2O4- sau ha tan kt ta trong dung dch H2SO4 ri

chun H2C2O4 sinh ra bng KMnO4.

Quy trnh gm 3 giai on sau:

1. Kt ta ng th ion Ca2+ di dng CaC2O4 bng dung dch (NH4)2C2O4

ly d:

Ca2+

C2O42-

CaC2O4

2. Ha tan kt ta CaC2O4 bng H2SO4

CaC2O4

2H+

H2C2O4

Ca2+

3. Chun lng H2C2O4 sinh ra bng KMnO4 (phn ng ch th)

5C2O4- + 2MnO4- + 16H+

10CO2 + 2Mn2+ + 8H2O

b. Tin hnh:
-

Rt 10,00 mL dung dch Ca2+ cho vo Becher 100 mL

Thm vo khong 40 mL nc ct

2 git ch th methyl cam.

Cho HCl vo dung dch n khi mu dung dch trong erlen chuyn sang
hng

5 mL dung dch (NH4)2C2O4 10%

5g urea

un si nh n khi dung dch chuyn sang mu vng.

Lc gn kt ta

Gn phn dung dch c trong becher, cho dung dch NH3 1% vo v ra vi

ln ra ht ion oxalate nm trn kt ta.

Chuyn phu lc sang erlen, ha tan kt ta bng H2SO4

un nng dung dch khong 80 90C.

Chun dung dch thu c bng dung dch KMnO4

c. Kt qu:
V1

V2

V3

Vtb

6,95 mL

6,95 mL

7,00 mL

6,97 mL

Vpipet = (10,00 0,02)mL

VKMnO4 = 6,97 + 0,02= 6,99 mL
d. Biu din kt qu
C N Ca 2+ =

0,95; M Ca 2+

C N KMnO4 VKMnO4

2*Vmu

0, 0865*10, 00
= 0, 061874 N
2*6,99

0,95; N KMnO4
= CM Ca 2+
CN KMnO
4

2
1,96* pipet 4,30 * s n;V
+

V pipet * n V buret * n
2

0, 0011 1, 96 *0, 020 4,30 * 0, 02887

= 0, 061874
+
= 0, 0011M
+
0, 0865 10, 00* 3 6, 99* 3

Vy nng ca KMnO4 :

2+

C M Ca = 0,0619 0,0011 M

e. Nhn xt:

Qu trnh ra v acid ha kt ta l qu trnh nh hng n ng v

lp li ca php phn tch nhiu nht. Ion C2O42- c xu hng bm ln b mt

tinh th v vy nu ra ta khng k, mt lng ln C2O42- cn li s lm cho
lng KMnO4 s dng ln hn lng thc t cn. Trong khi acid ha kt ta nu
ha tan khng ht s st li kt ta trn giy lc cng khin php chun b
sai lch.

Trnh cho qu nhiu ure, v mi trng ta cn l mi trng acid, nu cho

qu nhiu urea s lm cho pH ca mi trng tng ln v lm nh hng n kt

qu chun :
(NH2)2CO + 3H2O CO2 + 2NH4+ +2OH
Trong th nghim ny ta dng phng php kt ta ng th, phng
php ny khc so vi cc phng php kt ta trn ch l kt ta c tch
ring tin hnh chun . phng php ny, ta thu c tinh th c kch
thc ln hn, kh nng hp ph tp cht km, tinh khit cao hn v kt ta
hnh thnh ti cng mt thi im.

Ta dng phng php lc gn (tc l cho dung dch lng vo trc sau
mi n kt ta) nhm tit kim c thi gian v nu cho kt ta vo trc th
kt ta s lm bt giy lc, thi gian lc ko di.
Khng cho giy lc vo erlen lc chun v xenlulozo trong giy lc c
th b oxy ha bi KMnO4 dn n kt qu chun khng chnh xc, sai s tha
ln.

Cn ra ta tht k v nhiu ln bng NH3 cho n khi khng cn C2O42-,

th xem cn C2O42- khng bng dung dch KMnO4(cn thm acid H2SO4 phn
ng oxy ha xy ra), nu nc ra lm mt mu KMnO4 th vn cn C2O42-, cn
phi tht kin nhn trong giai on ny v phn ng gia KMnO4 vi C2O42- din
ra kh chm, mu tm ca KMnO4 cha mt thc cht l do phn ng cha xy ra
ch khng phi ht C2O42-.

Hn ch ca phng php khi lng l thi gian ko di, lu nn phi

tin hnh khu to ta ca th nghim ny ngay u bui thc tp.