N TP PHN TCH NH TNH

Ni dung 1:

H THNG PHN TCH NH TNH

Cu hi
1. Trnh by h thng phn tch cc cation ?
2. Trnh by h thng phn tch cc anion ?
1. Cc h thng PTT
-

Phn ln cc cht v c tn ti trong dung dch di dng cc cht in ly. Cc cht

ny phn ly hon ton hay mt phn thnh cc ion, do phn ng gia cc cht vi
thuc th l phn ng ion

Trong PTT, cc ion c chia thnh nhm da trn c tnh ca chng i vi thuc
th: to ta, ging nhau v khc nhau v tan,

1.1. H thng phn tch cc cation

1.1.1. H thng H2S (h thng phn tch sulfur)
-

Cc cation c chia thnh 5 nhm da trn c s tan ca cc sulfur, clorid v

carbonat. Cho php thc hin phn tch theo mt trt t xc nh

t s dng v thi gian phn tch qu di 25 30 gi, vic tm cc ion ca nhm cui
khng chnh xc do dung dch b pha long, cn phng phn tch c thit b c bit

1.1.2. H thng acid - base

-

Cc cation c chia thnh 6 nhm ty theo phn ng ca chng i vi HCl, H2SO4,

kim, amoniac

u im: s dng c nhng tnh cht c bn ca cc nguyn t, quan h gia cc

nguyn t vi acid v kim, tnh lng tnh ca cc hydroxyd, kh nng to phc,
Ion

Thuc th nhm

c im

Ag+, Pb2+,
Hg22+

HCl 6M

Ta clorid trng, khng tan trong

HNO3

II

Ba2+, Sr2+, Ca2+

H2SO4 3M/cn 90o

Ta sulfat, khng tan trong acid v c,

acid acetic

III

Al3+, Cr3+, Zn2+

NaOH 3M d

Hydroxyd lng tnh, tan trong kim

d

IV

Fe3+, Mn2+,
Mg2+, Bi3+

NaOH v H2O2

Hydroxyd khng tan trong kim d

Nhm

Cu2+, Co2+,
Hg2+

NH4OH d

VI

Na+, K+, NH4+

Khng c thuc th
nhm

Hydroxyd, to phc tan trong NH4OH

d

1.1.3. H thng phosphat amoniac

-

Cc cation c phn thnh 5 nhm da trn thuc th nhm l phosphat v amoniac

Phng php tin hnh phc tp, t s dng thuc th ring bit

1.2. H thng phn tch cc anion

1.2.1. Cc phng php phn loi anion
-

Cha tm c cc thuc th nhm tht tt nh cation

Thuc th p dng cho anion thng ch dng th s b s hin din ca cc anion

hay khng

Cc thuc th nhm ca anion c phn loi nh sau:

-

Thuc th lm phn hy v gii phng cht kh: HCl v H2SO4 long

Thuc th to ta: BaCl2 trong mi trng trung tnh, AgNO3 trong HNO3

Thuc th l cht oxy ha: KMnO4, HNO3 c, H2SO4

Thuc th l cht kh: KI

1.2.2. Cc phng php phn tch anion

-

C 3 phng php: phn tch h thng, na h thng v ring bit

Tin hnh phn tch na h thng i vi cc anion trong mt s c th thng t

dung dch phn tch, mt s c chia thnh nhm
Ion

Thuc th

c im

Cl-, Br-, I-, SCN-, CN-,

S2-, S2O32-

AgNO3 trong HNO3 long

Ta

II

SO32-, SO42-, AsO33-,

PO43, BO2-, CO32-

BaCl2 trong mi trng

trung tnh hay kim nh

Ta trng tan trong

acid tr BaSO4

III

NO3-, NO2-, MnO4-,

ClO3-, CH3COO-, C2O42-

Khng c thuc th nhm

Nhm

Ni dung 2:

PHN TCH CATION NHM I (Ag+, Pb2+, Hg22+)

Cu hi
1. Trnh by c tnh chung v phn ng nh tnh chung ca cation nhm I ?
2. Vit cng thc ha hc, hin tng c trng ca cc phn ng nh tnh i vi cc
ion Ag+, Pb2+, Hg22+ v vit phng trnh ion minh ha ?
3. Da vo phn ng no phn bit Ag+ v Hg22+ ?
4. Lm th no tch Pb2+ ra khi hn hp cc cation nhm I ?
5. V s l thuyt phn tch cation nhm I ?
1. C TNH CHUNG CA NHM
-

Trong dung dch nc cc ion Ag+, Pb2+, Hg22+ khng mu

Mt s mui ca ion ny l nhng hp cht c mu.

Hp cht c mu ca bc (bromid, iodid: vng), (cromat, dicromat: )

Hp cht c mu ca thy ngn I l bromid c mu vng, iodid c mu xanh lc

Hp cht c mu ca ch nh iodid c mu vng ngh, sulfur c mu en, cromat c

mu vng ti

Trong cc phn ng oxy ha kh: ion bc v ion thy ngn I th hin tnh oxy ha.
Chng b kh n trng thi nguyn t

2. PHN NG CHUNG CA CATION NHM I

2.1. Vi HCl
Cc cation nhm I tc dng vi HCl long trong mi trng HNO3 m c to ta clorid trng
AgCl, PbCl2, Hg2Cl2 t tan trong nc
HCl l thuc th nhm ca cation nhm I
Dng thuc th ny tch cc cation nhm I ra khi cc nhm khc
-

AgCl tan trong dung dch NH4OH, (NH4)2CO3 to thnh phc [Ag(NH3)2]+

PbCl2 tan c trong nc nng. Dng phn ng ny tch Pb2+ ra khi hn hp c

cha Ag+ v Hg22+

Hg2Cl2 phn ng vi NH4OH cho ta en Hg v phc NH2HgCl (mercuri amido clorid)

2.2. Vi kim NaOH hay KOH

Cc cation nhm I tc dng vi NaOH hay KOH to ta hydroxyd v oxyd: Ag2O mu en,
Pb(OH)2 trng, Hg2O en
Hg22+ + 2OH- Hg2O + H2O

2.3. Vi kali hay natri carbonat

-

K2CO3 v Na2CO3 phn ng vi cation nhm I to ta Ag2CO3 v Hg2CO3 c mu trng,

Pb2(OH)2CO3 (ch carbonat kim) kt ta trng

Hg2CO3 b phn hy nhanh theo phng trnh

Hg22+ + CO32- Hg2CO3 vng
Hg2CO3 Hg en + CO2 + HgO

3. PHN NG NH TNH TNG ION

3.1. Ion Ag+
3.1.1. Vi HCl
Cho ta AgCl trng vn, khng tan trong acid, k c cc acid v c m c nh HNO3, H2SO4.
Vi HCl m c c th tan mt phn. Ngoi nh sng, ta b en mt phn do Ag+ b kh
thnh Ag.
Ag+ + HCl AgCl + H+
3.1.2. Vi kalicromat
Ag+ phn ng vi K2CrO4 to kt ta gch. Phn ng phi tin hnh trong mi trng trung
tnh, nu l mi trng kim s to ta Ag2O, mi trng acid mnh phn ng khng xy ra
2Ag+ + K2CrO4 Ag2CrO4 + 2K+
3.1.3. Vi KI
Ag+ + KI AgI (ng vng) + K+
3.2. Ion Pb2+
3.2.1. Vi HCl: to ta PbCl2 trng, hnh kim, tan trong nc nng, ngui, kt tinh tr li, tan
mt phn trong HCl m c
Pb2+ + 2HCl PbCl2 + 2H+
3.2.2. Vi kalicromat: to ta vng ti, tan trong NaOH. Phn ng ny dng phn bit vi
ta BaCrO4
Pb2+ + K2CrO4 PbCrO4 + 2K+
3.2.3. Vi KI: to ta PbI2 vng ngh, tan trong nc nng, ngui kt tinh thnh vy vng
ng nh
Pb2+ + 2KI PbI2 + 2K+
3.2.4. Vi H2SO4 long: to ta PbSO4 trng, tan trong NaOH m c do ch l kim loi lng
tnh
Pb2+ + H2SO4 PbSO4 + 2H+

3.3. Ion Hg22+

3.3.1. Vi HCl
To ta Hg2Cl2 trng vn nh bt. Vi NH4OH cho hn hp NH2HgCl v Hg c mu en xm
Hg22+ + 2HCl Hg2Cl2 + 2H+
3.3.2. Vi kalicromat
To ta gch
Hg22+ + K2CrO4 Hg2CrO4 + 2K+
3.2.3. Vi KI
To ta vng xanh, to ta en trong thuc th d
Hg22+ + 2KI Hg2I2 + 2K+
Hg2I2 + 2KI Hg + K2[HgI4]
Tm tt cc phn ng c trng ca cation nhm I
Thuc th

Ag+

Pb2+

Hg22+

HCl long

Ta trng
AgCl, tan trong
NH4OH d

Ta trng PbCl2, tan

trong nc nng

Ta trng Hg2Cl2, tc dng vi

NH4OH to hn hp NH2HgCl +
Hg0 en xm

Ta trng PbSO4

Ta trng Hg2SO4

H2SO4 long
NaOH/KOH

Ta en Ag2O

Ta trng Pb(OH)2, tan

trong kim d to PbO22-

Ta en Hg2O

NH4OH d

To phc
[Ag(NH3)2]+

Ta trng Pb(OH)2

Ta [Hg2ONH2]NO3 + Hg0

Ta trng
Ag2CO3

Ta trng Pb2(OH)2CO3

Hg2CO3 = HgO + Hg + CO2

Ta nu
Ag2CrO4

Ta vng PbCrO4, tan

trong kim d

Ta Hg2CrO4

Ta vng AgI

Ta vng PbI2, tan trong

nc nng

Ta vng xanh Hg2I2, nu d

thuc th to thnh Hg0 + HgI42-

K2CO3/
Na2CO3
K2CrO4

KI

Ni dung 3:

PHN TCH CATION NHM II (Ba2+, Sr2+, Ca2+)

Cu hi
1. Trnh by c tnh chung v phn ng nh tnh chung ca cation nhm II ?
2. Vit cng thc ha hc, hin tng c trng ca cc phn ng nh tnh i vi cc
ion Ba2+, Sr2+, Ca2+ v vit phng trnh ion minh ha ?
3. Lm th no tch Ba2+ ra khi hn hp cc cation nhm II ?
4. Mun tch Ca2+ ra khi Sr2+ th dng thuc th no ?
5. Gii thch ti sao Ca2+ ta c vi H2SO4 khi thm cn 96o vo ?
6. V s l thuyt phn tch cation nhm II ?
1. C TNH CA CATION NHM II
-

To ta trng sulfat vi H2SO4 long

Phn ln cc hp cht ca cation nhm II l khng mu v t tan, hp cht c mu l

cromat, dicromat

Bari l kim loi kim th mnh nht. Ba(OH)2 d tan trong nc. Mui kh tan thng
gp l sulfat, carbonat, phosphat, oxalat

Stronti cho cc mui tan nh halogenid, nitrat, acetat, v cc mui kh tan nh sulfat,
carbonat, oxalat, cromat

Calci cho mui d tan nh nitrat, acetat, v cc mui kh tan nh carbonat,

phosphat, oxalat. Ca(OH)2 c tan l 0,17 g/l

Tnh acid base: tng t Ca(OH)2 n Ba(OH)2. Ba(OH)2 d tan trong nc v tnh
kim kh mnh (so vi cc hydroxyd ca kim loi kim)

Tnh to phc: Ca2+ c th to vi (NH4)2SO4 bo ha mt phc d tan

(NH4)2[Ca(SO4)2]. Tnh cht ny c s dng tch Ca2+ ra khi Sr2+

tan ca mui: Ba2+, Ca2+, Sr2+ to nhiu mui ging nhau nn da vo s chnh
lch v tan cc mui phn tch
tan tnh mol/lt
Ion

Cromat

Sulfat

Oxalat

Carbonat

Hydroxyd

Ca2+

1,5.10-1

1,4.10-2

4,5.10-5

9,5.10-5

7,1.10-3

Sr2+

7,1.10-3

5,5.10-4

2,4.10-4

3,7.10-5

1,1.10-2

Ba2+

1,3.10-5

1,1.10-5

3,5.10-4

9,0.10-5

4,0.10-2

Nhn xt
-

tan ca mui oxalat gim t Ba2+ n Ca2+ ng dng xc nh Ca2+

tan ca mui sulfat gim t Ca2+ n Ba2+ dng phn ng ny xc nh Sr2+

sau khi loi Ba2+

tan ca hydroxyd gim t Ba2+ n Ca2+

2. PHN NG CHUNG CA CATION NHM II

2.1. Vi H2SO4
Cc cation nhm II phn ng vi H2SO4 to thnh ta sulfat tinh th trng
Ba2+ + H2SO4 BaSO4 + 2H+
Sr2+ + H2SO4 SrSO4 + 2H+
Ca2+ + H2SO4 CaSO4 + 2H+
Bari sulfat t tan nht, calci sulfat tan nhiu nht trong nc. Do khi thm H2SO4 vo hn hp
cation nhm II th BaSO4 s tch ra trc, tinh th rt nh, SrSO4 kt ta chm hn, CaSO4 ch
tch ra khi nng cao hoc thm ethanol lm gim tan ca CaSO4
2.2. Vi Na2CO3
Cc cation nhm II to ta carbonat tan trong acid v c nh HCl, HNO3; trong acid acetic v
gii phng CO2
Ba2+ + Na2CO3 BaCO3 + 2Na+
Sr2+ + Na2CO3 SrCO3 + 2Na+
Ca2+ + Na2CO3 CaCO3 + 2Na+
2.3. Vi amoni oxalat
-

Cho cc kt ta oxalat, trong calci oxalat t tan nht

Cc kt ta ny u tan trong acid v c tr H2SO4

Trong acid acetic: calci oxalat khng tan, stronti oxalat tan mt t, bari oxalat tan (trong
acid acetic nng)

2.4. Phn ng nhum mu ngn la

-

Ba2+ cho ngn la vng lc

Ca2+ cho ngn la gch

Sr2+ cho ngn la thm

Do cc mui kh bay hi nn cn lm khan, tm t bng HCl m c trc khi t

3. PHN NG NH TNH TNG ION

3.1. Ion Ba2+
3.1.1. Vi H2SO4
To ta trng BaSO4, khng tan trong acid v c v acid acetic
Ba2+ + H2SO4 BaSO4 + 2H+
3.1.2. Vi kalicromat
To ta vng ti, khng tan trong NaOH 3M v acid acetic
Ba2+ + K2CrO4 BaCrO4 + 2K+
3.1.3. Vi H2SO4/KMnO4 (phn ng Wohlers)
To ta BaSO4 vi H2SO4 khi c s hin din KMnO4. BaSO4 v KMnO4 kt ta ng hnh lm
cho ta BaSO4 c mu hng
3.1.4. Phn ng nhum mu ngn la
Cc mui bari d bay hi nhum ngn la khng mu thnh vng lc
3.2. Ion Sr2+
3.2.1. Vi H2SO4
To ta trng SrSO4. Ta kt tinh chm, sau 5 10 pht phn ng mi xy ra
Sr2+ + H2SO4 SrSO4 + 2H+
3.2.2. Vi amoni sulfat
To ta SrSO4. Phn ng ny dng tch Ca2+ ra khi hn hp Sr2+ sau khi tch Ba2+
Sr2+ + (NH4)2SO4 SrSO4 + 2NH4+
3.2.3. Phn ng nhum mu ngn la
Cc mui stronti nhum ngn la khng mu thnh thm
3.3. Ion Ca2+
3.3.1. Vi amoni oxalat
To ta trng, ta ny khng tan trong acid acetic, tan trong HNO3, HCl, H2SO4
Ca2+ + (NH4)2C2O4 CaC2O4 + 2NH4+
3.3.2. Phn ng nhum mu ngn la
Cc mui calci d bay hi nhum ngn la khng mu ca n kh thnh gch
3.3.3. Phn ng soi tinh th
Vi nng Ca2+ tng i cao, c th to thnh tinh th CaSO4.2H2O c hnh sao khi soi di
knh hin vi, phn bit vi ta BaSO4 v SrSO4

Tm tt cc phn ng c trng ca cation nhm II

Thuc th

Ba2+

Sr2+

Ca2+

H2SO4 long

Ta trng BaSO4

Ta trng SrSO4

Ta trng CaSO4 tan nhiu

trong nc

Na2CO3

Ta trng BaCO3

Ta trng SrCO3

Ta trng CaCO3

- Trung tnh

- Ta vng BaCrO4

- Acid

- Ta vng BaCrO4

(NH4)2C2O4

Ta trng BaC2O4

Ta trng SrC2O4

Ta trng CaC2O4

Th
mu
ngn la

Vng lc

thm

gch

K2CrO4
Ta vng SrCrO4

Ni dung 4:

PHN TCH CATION NHM III (Al3+, Cr3+, Zn2+)

Cu hi
1. Trnh by c tnh chung v phn ng nh tnh chung ca cation nhm III ?
2. Vit cng thc ha hc, hin tng c trng ca cc phn ng nh tnh i vi cc
ion Al3+, Cr3+, Zn2+ v vit phng trnh ion minh ha ?
3. So snh s ging nhau v khc nhau ca Al3+ v Zn2+ khi tc dng vi cc thuc th v
vit phng trnh ion minh ha ?
4. Lm th no tch Al3+ ra khi hn hp cation nhm III ?
5. V s l thuyt phn tch cation nhm III ?
1. C IM CHUNG CA CATION NHM III
-

Phn ng vi kim to ta trng hydroxyd Al(OH)3, Cr(OH)3 v Zn(OH)2. Ta tan trong

kim d to thnh aluminat AlO2-, cromit CrO2- v zincat ZnO22-

NaOH d l thuc th nhm

Trong dung dch: Zn2+ v Al3+ khng mu, Cr3+ mu xanh tm

Zn2+ tn ti di 2 dng Zn2+ v ZnO22-

Al3+ tn ti di dng Al3+ hay AlO2-

Cr3+ to ta xanh en Cr(OH)3 pH 5, tan trong kim d. pH 12,5 cho cromit mu

xanh nht

2. PHN NG CHUNG CA CATION NHM III

Vi NaOH hay KOH
To ta trng hydroxyd
Al3+ + 3NaOH Al(OH)3 + 3Na+
Cr3+ + 3NaOH Cr(OH)3 + 3Na+
Zn2+ + 2NaOH Zn(OH)2 + 2Na+
Cc hydroxyd c tnh lng tnh, tan trong kim th hin tnh acid
Al(OH)3 + OH- AlO2- + 2H2O
Cr(OH)3 + OH- CrO2- + 2H2O
Zn(OH)2 + 2OH- ZnO22- + 2H2O
V tan trong acid th hin tnh base
Al(OH)3 + 3H+ Al3+ + 3H2O
Cr(OH)3 + 3H+ Cr3+ + 3H2O
Zn(OH)2 + 2H+ Zn2+ + 2H2O
10

3. PHN NG NH TNH TNG ION

3.1. Ion Al3+
3.1.1. Vi NaOH
To ta keo Al(OH)3, tan trong NaOH d to thnh mui aluminat
Al3+ + 3NaOH Al(OH)3 + 3Na+
Al(OH)3 + NaOH NaAlO2 + 2H2O
Khi thm NH4Cl vo dung dch aluminat s xut hin ta tr li. y l phn ng thy phn
aluminat, c dng tch Al3+ ra khi hn hp cation nhm III
3.1.2. Vi thuc th Aluminon (amoni aurintricarboxylat)
To mui ni phc c mu . Ty nng ca Al3+ s c ta bng hay dung dch mu .
Phn ng thc hin trong mi trng acid yu pH 4 5 vi m acetat
Al3+ + aluminon ta bng
3.2. Ion Cr3+
3.2.1. Vi NaOH
To ta crom hydroxyd mu xanh en
Cr3+ + 3NaOH Cr(OH)3 + 3Na+
Crom hydroxyd tan trong NaOH d to thnh cromit mu xanh nht
Cr(OH)3 + NaOH NaCrO2 + 2H2O
Cromit khi un si s b thy phn cho li ta crom hydroxyd
3.2.2. Vi tc nhn oxy ha H2O2
Vi H2O2 trong mi trng kim to cromat c mu vng c trng
2Cr3+ + 3H2O2 + 10OH- 2CrO42- + 8H2O
3.2.3. Phn ng to ngc c mu
Cr3+ to ngc c mu khc nhau vi mt s mui nh natri borat hay natri hydrophosphat to
ngc c mu xanh l m hoc khi nung chy mu cha Cr3+ vi hn hp bt Na2CO3 v KNO3
to ngc c mu vng
3.3. Ion Zn2+
3.3.1. Vi NaOH
To ta hydroxyd km, tan trong kim d to mui zincat khng mu
Zn2+ + 2NaOH Zn(OH)2 + 2Na+
Zn(OH)2 + 2NaOH Na2ZnO2 + 2H2O

11

3.3.2. Vi NH4OH
To Zn(OH)2 tan trong NH4OH d to thnh phc [Zn(NH3)4]. Phn ng ny dng tch nhm
ra khi hn hp c km trong cation nhm III
3.3.3. Vi thuc th MTA (Mercuri Thiocyanat Amoni) (NH4)2[Hg(SCN)4]
Trong mi trng trung tnh hay acid nh, Zn2+ cho ta trng Zn[Hg(SCN)4]. Nu thm 1 git
Cu2+, khi cho MTA vo s to ta tm sim
Zn2+ + Cu2+ + 2[Hg(SCN)4]2- ZnCu[Hg(SCN)4]2
Mu ca ta ty thuc vo lng Cu2+ thm vo: t Cu2+ tm nht, hi tha Cu2+ tm en,
tha nhiu Cu2+ xanh vng ca Cu2+

Tm tt cc phn ng c trng ca Al3+ v Zn2+

Thuc th

Al3+

Zn2+

NaOH d

AlO2-

ZnO22-

Na2CO3

Ta keo trng Al(OH)3

Ta trng Zn2(OH)2CO3

NH4OH d

Ta keo trng Al(OH)3

Phc tan [Zn(NH3)4]2+

- C mt vt Cu2+: to ta tm

MTA

- C mt vt Co2+: to ta lc
Aluminon

Ta bng

12

Ni dung 5:

PHN TCH CATION NHM IV (Fe3+, Mn2+, Mg2+, Bi3+)

Cu hi
1. Trnh by tn, cng thc ha hc ca thuc th nhm IV, nu cc hin tng c trng
khi cation nhm IV tc dng vi thuc th nhm v vit phng trnh ion minh ha ?
2. Vit cng thc ha hc, phn ng c trng ca Fe3+, Mn2+, Mg2+, Bi3+ ?
3. Cho bit cation no trong nhm c tnh oxy ha, tnh kh. Vit phng trnh phn ng
minh ha ca Mn2+ v Bi3+ ?
4. p dng tnh cht no tch Mg2+ ra khi hn hp cation nhm IV ?
5. V s l thuyt phn tch cation nhm IV ?
1. C IM CHUNG CA CATION NHM IV
-

Tc dng vi kim cho ta hydroxyd khng tan trong kim d.

NaOH 3M v H2O2 l thuc th nhm

Trong dung dch cc ion khng mu tr Fe3+ c mu vng nu

Cc cation nhm IV tham gia phn ng oxy ha kh

Fe3+ l cht oxy ha, b kh thnh Fe2+
Mn2+ l cht kh b oxy ha thnh Mn7+ c mu tm
Mg2+ l cht oxy ha, b kh v Mg
Bi3+ l cht oxy ha, b kh thnh Bi c mu en

2. PHN NG CHUNG CA CATION NHM IV

Vi KOH, NaOH, NH4OH
Fe3+ + 3OH- Fe(OH)3
Mg2+ + 2OH- Mg(OH)2
Mn2+ + 2OH- Mn(OH)2
Bi3+

+ 3OH- Bi(OH)3

3. PHN NG NH TNH TNG ION

3.1. Ion Fe3+
3.1.1. Vi NaOH
To ta nu, khng tan trong NaOH d, tan trong acid v c
Fe3+ + 3NaOH Fe(OH)3 + 3Na+
3.1.2. Vi kali ferrocyanid K4[Fe(CN)6]
Trong mi trng acid, Fe3+ to ta keo xanh ph
Fe3+ + K4[Fe(CN)6] Fe4[Fe(CN)6]3
13

Phn ng ny rt nhy, lng ti thiu tm thy (1 2 git): 0,05 g, nng gii hn

1/(1x106), long gii hn 106
3.1.3. Vi kali sulfocyanid KSCN
To phc mu mu. Thnh phn phc thay i ty theo nng SCNFe3+ + 3KSCN Fe(SCN)3 + 3K+
3.2. Ion Mn2+
3.2.1. Vi NaOH, NH4OH
To ta trng Mn(OH)2, tan t trong kim d do to phc hydroxo Mn(OH)3-, tan trong acid v
c
Mn2+ + 2OH- Mn(OH)2
Mn(OH)2 d b oxy ha trong khng kh to thnh MnO(OH)2 (dihydroxido oxidomanganat (IV))
c mu nu
3.2.2. Phn ng oxy ha
Oxy ha Mn2+ bng PbO2 trong mi trng acid to thnh Mn7+ c mu tm
2Mn2+ + 5PbO2 + 4H+ 2MnO4- + 5Pb2+ + 2H2O
3.3. Ion Mg2+
3.3.1. Vi NaOH
To ta trng Mg(OH)2, khng tan trong kim d, tan trong NH4Cl
Mg2+ + 2OH- Mg(OH)2
3.3.2. Vi NH4OH
Cho ta trng Mg(OH)2, nu c s hin din ca NH4Cl th Mg(OH)2 khng kt ta c
3.3.3. Vi Na2HPO4
To ta v nh hnh, nu c s hin din ca NH4OH NH4Cl s cho ta trng tinh th hnh
sao MgNH4PO4.6H2O
Mg2+ + NH4+ + PO43- + 6H2O MgNH4PO4.6H2O
3.3.4. Vi vng thiazol
To ta nh tm trong mi trng kim
Mg2+ + vng thiazol + NaOH ta nh tm
3.4. Ion Bi3+
3.4.1. Vi NaOH
To ta keo trng Bi(OH)3, khng tan trong kim d, tan trong acid. un si ta s c mu vng
do b mt nc
Bi3+ + 3OH- Bi(OH)3

14

3.4.2. Phn ng thy phn

Pha long dung dch Bi3+ to thnh ta trng bismutyl, tan trong acid long
Bi3+ + Cl- + H2O BiOCl + 2H+
3.4.3. Vi kali iodid
To ta en BiI3, tan trong KI to thnh phc K[BiI4] mu cam
Bi3+ + 3KI BiI3 + 3K+

BiI3 + KI K[BiI4]

3.4.4. Vi thioure
To phc mu vng Bi3+ + 2SC(NH2)2 [Bi(NH2-CS-NH2)3]3+
3.4.5. Vi SnCl2/NaOH (phn ng stanit kim)
To Bi c mu en

2Bi3+ + 3SnO22- + 6OH- 2Bi + 3SnO32- + 3H2O

Tm tt cc phn ng c trng ca cation nhm IV

Thuc th

Fe3+

Mn2+

Mg2+

Bi3+

NaOH

Ta nu Fe(OH)3

Ta trng MN(OH)2,
ha nu trong khng
kh

Ta trng Mg(OH)2

Ta
Bi(OH)3

Na2CO3

Ta trng
Fe(OH)CO3

Ta trng MnCO3

Ta trng MgCO3

Ta
trng
Bi(OH)CO3

Na2HPO4

Ta vng
FePO4

Ta trng Mn3(PO4)2

Ta MgHPO4 hoc
trong mi trng
NH4OH - NH4Cl cho
ta MgNH4PO4

Ta
BiPO4

nht

trng

trng

Ta en BiI3,
nu d KI to
KBiI4 mu cam

KI

KSCN

Ta

mu
Fe(SCN)3
hoc
d
SCNto
phc tan mu
[Fe(SCN)6]3-

K4[Fe(CN)6]

Ta xanh ph
Fe4[Fe(CN)6]3

15

Ni dung 6:

PHN TCH CATION NHM V (Cu2+, Co2+, Hg2+)

Cu hi
1. Trnh by c im chung v phn ng chung ca cation nhm V ?
2. Vit cng thc ha hc, hin tng c trng ca cc phn ng nh tnh Cu2+, Co2+,
Hg2+ v vit phng trnh ion minh ha ?
3. Phn bit Cu2+ v Hg2+ bng thuc th no ? Vit phng trnh phn ng ?
4. V s l thuyt phn tch cation nhm V ?
1. C IM CHUNG CA CATION NHM V
-

Tc dng vi kim cho nhng hydroxyd khng tan trong kim d nhng tan trong
NH4OH hoc hn hp NH4OH NH4Cl thnh cc amonicat.

NH4OH 3M l thuc th nhm

KOH v NaOH cho ta hydroxyd lng tnh vi dung dch cha Cu2+ (v d tan trong
acid long v tan trong NH4OH to phc [Cu(NH3)4]2+), cho oxyd vi Hg2+, cho mui
c tnh kim vi Co2+

Cc cation nhm V c c trng bi kh nng to phc

Trong dung dch mui Hg2+ khng mu, mui Cu2+, Co2+ c mu

2. PHN NG CHUNG CA CATION NHM V

2.1. Vi KOH, NaOH
Cu2+ + 2KOH Cu(OH)2 xanh l + 2K+
Co2+ + KOH

CoOH+ xanh lam + K+

CoOH+ + KOH Co(OH)2 hng + K+

Hg2+ + KOH HgOH+ gch + K+
HgOH+ + KOH Hg(OH)2 + K+
Hg(OH)2 HgO vng + H2O
2.2. Vi NH4OH
Dung dch amoniac d phn ng vi cation nhm V to ra cc phc amonicat
Cu2+ + 4NH4OH [Cu(NH3)4]2+ + 4H2O
Co2+ + 6NH4OH [Co(NH3)4]2+ + 6H2O
Hg2+ + 4NH4OH [Hg(NH3)4]2+ + 4H2O
Cc amonicat bn tr amonicat cobalt, di tc dng ca oxy khng kh s chuyn thnh Co3+
c mu tm

16

3. PHN NG NH TNH TNG ION

3.1. Ion Cu2+
3.1.1. Vi NH4OH
To ta xanh l, ta tan khi cho NH4OH d, to phc xanh lam m
2Cu2+ + 2NH4OH Cu2(OH)22+ + 2NH4+
Cu2(OH)22+ + 8NH4OH 2[Cu(NH3)4](OH)2 + 6H2O

+ 2H+

3.1.2. Vi kali ferrocyanid K4[Fe(CN)6]

To ta ng ferrocyanid thm
2Cu2+ + K4[Fe(CN)6] Cu2[Fe(CN)6] + 4K+
3.1.3. Vi thuc th MTA
To ta xanh vng Cu[Hg(SCN)4]. Nu thm Zn2+ to ta tm sim
Zn2+ + Cu2+ + 2[Hg(SCN)4]2- ZnCu[Hg(SCN)4]2
3.1.4. Vi Na2S2O3
Trong dung dch mui Cu2+ c acid ha s lm mt mu dung dch do to thnh ta en
CuS khng tan trong HCl, H2SO4 c, tan trong HNO3
Cu2+ + 3S2O32- + 2H+ CuS + S4O62- + SO2 + H2O
3.2. Ion Co2+
3.2.1. Vi NH4OH
To mui kim CoOH+ mu xanh lam, khi un nng to thnh Co(OH)2 mu hng, tan trong
NH4OH d to thnh phc mu vng nu
Co2+ + NH4OH Co(OH)+ Co(OH)2
Co(OH)2 + 4NH4OH [Co(NH3)4](OH)2 + 4H2O
3.2.2. Vi NH4SCN
Cho mu xanh m do to thnh phc cht d phn hy trong nc v trong acid long. Tan
trong dung mi hu c nh aceton
Co2+ + 4NH4SCN [Co(SCN)4]2+
3.3. Ion Hg2+
3.3.1. Vi NH4OH
To ta trng HgNH2+, tan trong NH4OH d thnh phc
Hg2+ + NH4OH HgNH2+ (mercuri amido) + H+ + H2O
HgNH2+ + 3NH4OH + H+ [Hg(NH3)4]2+ + 3H2O

17

3.3.2. Vi kali iodid

To ta cam HgI2, tan khi cho KI d, to phc mu vng nht
Hg2+ + 2KI HgI2 + 2K+
HgI2 + 2KI K2[HgI4]
3.3.3. Vi dung dch SnCl2 mi pha
To ta trng thy ngn I sau chuyn thnh Hg mu xm en
2Hg2+ + Sn2+ Hg22+ + Sn4+ Hg
3.3.4. Vi Na2S2O3
Trong mi trng acid, khi un nng to ta en HgS khng tan trong HCl, H2SO4, HNO3
Hg2+ + 3S2O32- + 2H+ HgS + S4O62- + SO2 + H2O

Tm tt cc phn ng c trng ca cation Cu2+ v Hg2+

Thuc th

Cu2+

Hg2+

NaOH

Cu(OH)2 xanh ta en CuO

Ta vng HgO

NH4OH d

[Cu(NH3)4]2+ xanh lam m

[Hg(NH3)4]2+

Na2S2O3

Ta en CuS tan trong HNO3

Ta en HgS, khng tan trong HNO3

KI

Ta trng CuI + I2

Ta cam HgI2, nu d KI to phc tan

mu vng nht [HgI4]2Ta en Hg

SnCl2/NaOH
NH4SCN

Ta en Cu(SCN)2

Ta trng Hg(SCN)2, nu d NH4SCN th

to phc (NH4)2[Hg(SCN)4]

18

Ni dung 7:

PHN TCH CATION NHM VI (NH4+, K+, Na+)

Cu hi
1. Trnh by c im chung ca cation nhm VI ?
2. K tn, cng thc ha hc, hin tng c trng ca cc phn ng nh tnh NH4+, K+,
Na+ v vit phng trnh ion minh ha ?
3. Gii thch nguyn nhn phi xc nh NH4+ trc ?
4. Hy cho bit s khc nhau c bn gia cation nhm VI v cation 5 nhm u khi tc
dng vi thuc th natri carbonat ?
5. V s l thuyt phn tch cation nhm VI ?
1. C IM CHUNG CA CATION NHM VI
-

Cc Na+, K+ l cc ion kim loi kim, NH4+ do phn t NH3 v H+ to nn, khng bn
vng trong dung dch kim v nhit cao
NH3 + H+ NH4+
NH4+ + OH- NH3 + H2O

Cc hp cht hydroxyd (NaOH, KOH, NH4OH), cc mui (clorid, sulfat, carbonat) u d

tan trong nc. Do khi dng acid hoc kim lm thuc th nhm th cc cation ca 5
nhm u u kt ta, cn cation nhm VI khng cho ta

Cation nhm VI khng c thuc th nhm

xc nh cc cation nhm VI, tin hnh xc nh trc tip cation m khng phn tch
theo h thng

2. PHN NG NH TNH TNG ION

2.1. Ion NH4+
2.1.1. Vi NaOH
To thnh amoniac, kh bay ra c th nhn bit bng giy tm phenolphtalein (giy s c mu
hng) hoc dng giy qu tm s ha xanh
NH4+ + NaOH NH3 + Na+ + H2O
NH3 + giy tm phenolphtalein hng
NH3 + giy qu tm xanh
2.1.2. Vi thuc th Nessler
Trong mi trng kim, cho ta nu
NH4+ + 2K2[HgI4] + 3KOH 7KI + 2H2O +
Lu :

19

Hg
Hg

NH2 I

+ H+

Mt s cation kim loi chuyn tip (Cu2+, Zn2+, Ag+, Hg2+, Cr3+, Mn2+, Fe3+, Co2+) cn tr
phn ng do to hydroxyd c mu hoc lm h thuc th. Loi bng kim mnh v
carbonat hoc kha trong phc kali natri tartrat.
C hai phn ng u phi dng tnh khi nh tnh NH4+

2.2. Ion K+
2.2.1. Vi acid percloric
To ta trng kali perclorat:

K+ + HClO4 KClO4 + H+

2.2.2. Vi acid tartric

To ta trng trong mi trng trung tnh hay acid (pH 5 7)
K+ + H2C4H4O6 KHC4H4O6 + H+
2.2.3. Vi acid picric
To kt ta vng. NH4+ cng cho ta vng nn phi loi bng kim
K+ + C6H2(NO2)3OH C6H2(NO2)3OK + H+
2.2.4. Vi thuc th Garola Na3[Co(NO2)6]
To ta tinh th vng.
2K+ + Na+ + [Co(NO2)6]3- K2Na[Co(NO2)6]
Lu :
-

NH4+ cho phn ng tng t. Loi NH4+ bng kim v un nng, sau iu chnh pH
v trung tnh. I- gy cn tr. Loi I- bng HNO3 hoc H2O2. Ag+ lm tng nhy phn
ng

2.2.5. Phn ng nhum mu ngn la

t cc mui K+ trn ngn la khng mu th ngn la s c mu tm
2.3. Ion Na+
2.3.1. Vi thuc th Kontop (km uranyl acetat)
To ta tinh th vng (hnh mt nhn khi soi knh hin vi)
Na+ + Zn(UO2)3(CH3COO)8 + CH3COO- + 9H2O ZnNa(UO2)3(CH3COO)9.9H2O
iu kin:
-

Mi trng trung tnh hay hi acid (s dng acid acetic), mi trng acid mnh ta
tan. Cc NH4+, Ca2+, Sr2+, Ba2+, Al3+ gy tr ngi. Cc Ag+, Hg22+, Sb3+ cng to ta tinh
th hnh kim di vi thuc th

2.3.2. Phn ng nhum mu ngn la

t cc mui Na+ trn ngn la khng mu th ngn la s c mu vng. Phn ng rt nhy
nn phi ra dy bch kim tht sch trc khi tin hnh phn ng v ch kt lun c Na+ khi
ngn la vng tn ti vi giy tr ln.
20

Ni dung 8:

PHN TCH ANION NHM I (Cl-, Br-, I-, SCN-)

Cu hi
1. Trnh by c im chung v phn ng chung ca cc halogenid trong anion nhm I ?
2. K tn cng thc ha hc, hin tng c trng ca thuc th xc nh Cl-, Br-, I-, SCNv vit phng trnh ion minh ha ?
3. V s l thuyt phn tch anion nhm I ?
1. C IM CHUNG CA HALOGENID
-

Cc halogenid thng khng mu, c th to thnh cc acid mnh HCl, HBr, HI

Hu ht cc halogenid u d tan tr halogenid ch. tan ca mui halogenid gim t

clorid n iodid

Cc halogen l nhng cht oxy ha, tnh oxy ha tng t I2 n Cl2, cc halogenid l
nhng cht kh, tnh kh tng t Cl- n I-. V vy Cl- ch c th b oxy ha bng cc tc
nhn oxy ha mnh nh KMnO4, HNO3

Cc tc nhn oxy ha c Cl-, Br- v I- gm K2Cr2O7/H2SO4, HNO3 m c,

KMnO4/H2SO4

Cc tc nhn oxy ha c Br- v I- gm H2SO4 m c (vi Br- phi un nng),

PbO2/H2SO4

Cc tc nhn ch oxy ha c I- l nc clor, nc brom, NaNO2/CH3COOH

2. PHN NG CHUNG CA HALOGENID

2.1. Vi thuc th nhm AgNO3
To ta halogenid bc trong mi trng acid nitric m c. AgCl ta trng, AgBr ta trng ng,
AgI ta vng nht. tan ca cc mui gim t AgCl n AgI. Cc mui ny u khng tan
trong cc acid
2.2. Vi tc nhn oxy ha
-

Cl- l cht kh yu, ch phn ng vi cht oxy ha mnh nh KMnO4/H2SO4, khi un

nng to thnh Cl2

Br- b oxy ha trong mi trng acid bi MnO4-, Cr2O72-, H2SO4 c nng, Cl2 v HClO

I- c th b oxy ha bi Cl2, Br2, Fe3+, NO2- trong mi trng acid mnh

3. PHN NG NH TNH TNG ION

3.1. Ion Cl3.1.1. Vi AgNO3
To ta trng vn AgCl, en dn ngoi khng kh, khng tan trong HNO3, tan trong NH4OH to
thnh phc [Ag(NH3)2]Cl, tan trong (NH4)2CO3
Cl- + Ag+ AgCl trng
21

AgCl + 2NH4OH [Ag(NH3)2]+ + Cl- + 2H2O

Khi acid ha dung dch, AgCl ta tr li
[Ag(NH3)2]+ + Cl- + 2H+ AgCl + 2NH4+
3.1.2. Phn ng oxy ha
Cl- b oxy ha thnh Cl2, tc nhn oxy ha l KMnO4/H2SO4. Cl2 sinh ra c nhn bit bng
giy tm ortho toludin
Cl- + Mn7+ Mn2+ + Cl2
Cl2 + ortho toludin xanh en
3.2. Ion Br3.2.1. Vi AgNO3
To ta trng ng AgBr, khng tan trong HNO3, (NH4)2CO3 (khc vi AgCl) nhng tan trong
NH4OH to thnh phc [Ag(NH3)2]Br
Br- + Ag+ AgBr
3.2.2. Phn ng oxy ha
Vi cc tc nhn oxy ha nh K2Cr2O7, KMnO4, PbO2 v nc clor, Br- b oxy ha thnh Br2
mu nu. Kh Br2 sinh ra lm hng giy tm fluorescein hoc lm lp cloroform c mu nu
2Br- + Cl2 2Cl- + Br2
3.3. Ion I3.3.1. Vi AgNO3
To ta vng AgI, khng tan trong HNO3, NH4OH, (NH4)2CO3
I- + Ag+ AgI
3.3.2. Phn ng oxy ha
I- l cht kh mnh, d b oxy ha bi cc tc nhn nh Cl2, Br2, K2Cr2O7, KMnO4. Khc vi Clv Br-, I- cn b NO2-, Cu2+ v Fe3+ oxy ha
2I- + Cl2 2Cl- + I2
Kh I2 bay ra c mu nu hoc tan vo lp cloroform cho mu tm
3.4. Ion SCN3.4.1. Vi AgNO3
To ta trng, tan trong NH4OH:

SCN- + Ag+ AgSCN

3.4.2. Vi Fe3+
To phc mu mu
6SCN- + Fe3+ [Fe(SCN)6]322

Ni dung 9:

PHN TCH ANION NHM II (SO42-, BO2-, PO43-, CO32-)

Cu hi
1. Trnh by hin tng c trng ca anion nhm II khi tc dng vi mui bari, bc nitrat
v vit cc phng trnh ion minh ha ?
2. K tn cng thc ha hc, hin tng c trng ca thuc th xc nh SO42-, BO2-,
PO43-, CO32- v vit phng trnh ion minh ha ?
3. V s l thuyt phn tch anion nhm II ?
1. C IM CHUNG CA ANION NHM II
-

Kt ta c vi mui Ba2+

Tr BaSO4, cc mui khc u tan c trong HNO3, HCl v CH3COOH

2. PHN NG CHUNG CA ANION NHM II

2.1. Vi mui Ba2+
To ta trng. Ba(BO2)2 tan nhiu nht, ch tch ra t dung dch m c
2.2. Vi AgNO3
To ta bc tan trong acid v c (khc vi anion nhm I)
3. PHN NG NH TNH TNG ION
3.1. Ion SO423.1.1. Vi BaCl2
To ta trng BaSO4, khng tan trong HCl, HNO3
SO42- + Ba2+ BaSO4 trng
3.1.2. Vi AgNO3
Dung dch mui sulfat m c phn ng vi AgNO3 cho ta Ag2SO4, tan khi cho thm nc
SO42- + Ag+ Ag2SO4 trng
3.1.3. Vi BaCl2 v KMnO4
To ta BaSO4 mu hng do hp ph thuc tm
3.2. Ion BO23.2.1. Vi BaCl2
To ta Ba(BO2)2, tan trong acid v c
BO2- + Ba2+ Ba(BO2)2
3.1.2. Vi ru ethylic
BO2- trong H2SO4 tc dng vi ru ethylic cho ester borat ethyl. Cht ny chy cho ngn la
mu xanh lc
23

BO2- + 3C2H5OH (C2H5O)3B + OH- + H2O

phn ng xy ra theo chiu thun, cn thc hin trong mi trng khan bng cch lm bay
hi n kh dung dch v thm H2SO4 nc c to thnh trong qu trnh phn ng
3.3. Ion PO43Cc mui phosphat tn ti di dng PO43-, HPO42-, H2PO43.3.1. Vi BaCl2
To ta trng BaHPO4, tan trong HCl, HNO3 v CH3COOH. Khi un nng li cho Ba3(PO4)2
HPO42- + Ba2+ BaHPO4 Ba3(PO4)2
3.3.2. Vi hn hp mui Mg2+, NH4Cl v NH4OH
To ta trng tinh th hnh sao MgNH4PO4.6H2O
Mg2+ + NH4+ + PO43- + 6H2O MgNH4PO4.6H2O
3.3.3. Vi amoni molybdat
To ta vng, tan trong NH4OH. AsO43- cho phn ng tng t
PO43- + 12(NH4)2MoO4 + 12H2O (NH4)3PO4.12MoO3 + 21NH4OH + 3OH3.4. Ion CO32-

CO2 ha tan trong nc cho H2CO3 l mt acid yu

H2CO3 cho hai loi mui: carbonat v hydrocarbonat (bicarbonat)

Cc carbonat u tan trong acid, ch c carbonat kim, hydrocarbonat kim v kim th

l tan trong nc

3.4.1. Vi AgNO3
To ta trng Ag2CO3, tan trong HNO3 v NH4OH
CO32- + Ag+ Ag2CO3
3.4.2. Vi BaCl2
To ta BaCO3, tan trong acid v c v acid acetic
CO32- + Ba2+ BaCO3

24

Ni dung 10:

PHN TCH ANION NHM III (NO3-, C2O42-)

Cu hi
1. K tn cng thc ha hc, hin tng c trng ca thuc th xc nh NO3-, C2O42- v
vit phng trnh ion minh ha ?
2. V s l thuyt phn tch anion nhm III ?
1. PHN NG NH TNH ANION NITRAT
-

Mui nitrat th rn khi t nng l cht oxy ha rt mnh v d b phn hy

Dung dch nitrat trong nc khng c kh nng oxy ha

1.1. Vi FeSO4
Trong mi trng H2SO4, NO3- b kh thnh oxyd nit, cht ny to vi FeSO4 d thnh phc
sulfat nitrozil c mu nu xut hin mt tip xc gia H2SO4 m c v nc
6FeSO4 + 2NO3- + 3H2SO4 3Fe2(SO4)3 + 2NO + 2H2O + 2OHNO + FeSO4 d [Fe(NO)]SO4
Phc to thnh khng bn, b phn hy khi lc ng nghim hay un. Nn tin hnh phn ng
khi ngui
1.2. Vi Al nguyn t
Trong mi trng kim, nhm kh NO3- thnh NH3, lm xanh giy qu
3NO3- + 8Al + 5OH- + 2H2O 3NH3 + 8AlO21.3. Vi diphenylamin (C6H5)2NH
Trong mi trng acid sulfuric c, NO3- tc dng vi diphenylamin to hp cht xanh l
2. PHN NG NH TNH ANION OXALAT
Vi KMnO4/H2SO4
Trong mi trng H2SO4, C2O42- kh Mn7+ v Mn2+ lm mt mu thuc tm v phng thch CO2
5C2O42- + 2MnO4- + 16H+ 10CO2 + 2Mn2+ + 8H2O

25

Ni dung 11:

PHN TCH ANION V CATION

Cu hi
1. Trnh by trnh t xc nh cation v anion trong dung dch phn tch ?
2. Hy m t li qu trnh tin hnh v vit phng trnh ion minh ha khi xc nh c
dung dch u l BaCl2 ?
3. Yu cu th mt l ha cht (th rn) c dn nhn Magnesi clorid tinh khit th phi
lm th no ?
1. TH S B
1.1. Xc nh c tnh ca mu
-

Rn: p dng mt s c tnh ring xc nh. Phn ln mu rn c ha tan vi

dung mi thch hp ri mi phn tch

Lng: dung dch trong sut. Phn tch trc tip

1.2. Th pH ca dung dch

Dng giy qu hay giy th vn nng
-

pH trung tnh: khng c ion d b thy phn nh Bi3+, Hg2+,

pH < 7: nu dung dch c phn ng vi acid mnh th khng c CO32-, HCO3-. Khng th
c ng thi ion c tnh oxy ha v ion c tnh kh nh MnO4- vi I-, Fe3+ vi I-

pH > 7: c th c cc cation lng tnh nh Al3+, Zn2+, hu ht cc anion; khng c cc

ion d b ta mi trng kim nh Bi3+, Ca2+, Ba2+

1.3. Mu ca dung dch

-

Xanh lam: ty nng , c th c Cu2+

Hng: c Co2+

Vng: ty nng , c th c Fe3+, I- (chuyn thnh I2)

Xanh ru: c Cr3+

Mt s ion c mu nhng trng thi phc cht th khng mu hay c mu khc. V d:

Fe3+ c mu vng nhng khi to thnh phc Fe(SCN)3 c mu mu. Do nu dung
dch khng mu th loi cc ion c mu nhng phi kim tra s c mt ca cc phc
khng mu ca cc ion

Trong dung dch nu c nhiu ion c mu th dung dch s c mu phi hp gia cc

mu ring l. V d: nu trong dung dch c Cu2+ v Co2+ th dung dch c th c mu tm
hng, xanh tm

1.4. Mi ca dung dch

-

Mi gim: c acid acetic. Mi khai: c NH4OH

26

1.5. Cc phn ng nhn din s b

1.5.1. Cc ion to hydroxyd t tan
Dung dch phn tch + NaOH 3M tng git. Kt ta c mu:
-

R st: c Fe3+. Trng ha nu: c Mn2+. Xanh: c Cu2+

1.5.2. Cc ion c tnh oxy ha hay kh

-

1 git DDPT + 1 git HCl + 1 git KI dung dch nu c th c ion c tnh oxy ha

1 git DDPT + 1 git KMnO4 long + 1 git HNO3 mu tm mt c th c ion c

tnh kh

2. PHN TCH ANION V CATION

-

Vic xc nh cation v anion tin hnh c lp vi nhau. Tuy nhin c 1 s cation gy

tr ngi cho vic xc nh anion v ngc li. khc phc tr ngi trn v trnh nhm
ln cn tin hnh xc nh cation v anion theo mt trnh t sau:
Nu dung dch phn tch c mu th xc nh cation c mu tng ng trc,
xc nh anion sau
Nu dung dch phn tch khng c mu th tin hnh th anion trc,
cation sau

Bit c anion c th gip loi tr mt s cation

-

C nhm halogenid th khng c cation nhm I

C SO42- th khng c cation nhm II

Phn tch theo h thng da vo thuc th nhm

C mt vi ion c th tm trc tip t dung dch u. V d: Fe3+, Bi3+, Zn2+,

27

Cau hoi
1. Nguyen tac chung cua phng phap phan tch the tch (PTTT) ?
2. iem tng ng va iem ket thuc ?
3. Cac ky thuat chuan o ?
4. Nong o dung dch dung trong PTTT ?
5. Cach tnh ket qua trong PTTT ?
6. Pha dung dch chuan o ?
1.

Nguyen tac chung cua phng phap PTTT

Phng phap PTTT la phng phap nh lng hoa hoc da vao the tch thuoc th (a biet chnh xac
nong o) dung e phan ng va u vi mot the tch chnh xac dung dch chat can xac nh. T the tch,
nong o cua dung dch thuoc th va the tch cua dung dch chat can nh lng tnh c nong o cua
dung dch can nh lng.
Gia s e xac nh nong o cua dung dch X, thuoc th la dung dch R co nong o a biet c s
dung. Phan ng gia X va R phai xay ra hoan toan:
R+X=P+Q
Tien hanh bang cach nho t t tng giot dung dch R xuong mot the tch chnh xac dung dch X en khi
lng thuoc th R nho xuong tng ng hoa hoc vi lng X th dng lai, oc the tch dung dch R
a phan ng tren buret. Da vao the tch dung dch R, nong o cua R va the tch dung dch X a lay,
tnh c nong o cua X. Qua trnh tien hanh nh vay goi la s chuan o hay s nh phan bang
phng phap the tch. Dung dch thuoc th a biet nong o (dung dch R) goi la dung dch chuan o.
So vi phng phap PTKL th phng phap PTTT co o chnh xac khong cao, nhng van at c mc
yeu cau can thiet. Mat khac phng phap PTTT n gian va nhanh hn nen c s dung rong rai.
2.

iem tng ng va iem ket thuc

2.1. iem tng ng

iem tng ng la thi iem ma lng thuoc th a phan ng tng ng hoa hoc vi lng chat
can xac nh, noi cach khac iem tng ng la thi iem ma so ng lng gam thuoc th a phan
ng bang so ng lng gam cua chat can xac nh. iem tng ng con goi la iem ket thuc cua
s chuan o ly thuyet hay iem ket thuc cua s nh phan ly thuyet.
V du: khi chuan o dung dch acid hydrocloric bang dung dch chuan o natri hydroxyd
HCl + NaOH = NaCl + H2O
28

Khi so ng lng gam HCl bang so ng lng gam NaOH th trong dung dch ch co NaCl va H2O,
pH cua dung dch la 7, iem tng ng ng vi pH = 7.
2.2. Cach xac nh iem tng ng
Co nhieu cach xac nh iem tng ng, nhng n gian va thng dung nhat la dung chat ch th.
Chat ch th la nhng chat co kha nang bien oi mau hoac tao ket tua hoac phat huynh quang hoac gay
ra mot dau hieu nao o lan can iem tng ng, nh vay iem tng ng c xac nh.
V du: khi nh lng acid oxalic bang dung dch natri hydroxyd co the chon ch th phenolphtalein v
trc iem tng ng trong dung dch con acid, nen phenolphtalein khong mau. Sau iem tng
ng dung dch d kiem, phenolphtalein co mau hong. Do o thi iem tng ng dung dch t
khong mau chuyen sang mau hong (tai thi iem nay ta ket thuc s chuan o).
H2C2O4 + 2NaOH = Na2C2O4 + 2H2O
2.3. iem ket thuc
iem ket thuc la thi iem ma o chat ch th co nhng bien oi giup ta ket thuc s chuan o. Trong
trng hp ly tng iem ket thuc chuan o trung vi iem tng ng, trong thc te iem ket thuc
chuan o thng sai lech vi iem tng ng.
V du: khi nh lng acid hydrocloric bang dung dch chuan o natri hydroxyd dung ch th
phenolphtalein, iem tng ng ng vi pH = 7, nhng ch th phenolphtalein lai chuyen mau pH =
9, nen thng ket thuc chuan o sau iem tng ng.
S sai lech gia iem tng ng va iem ket thuc gay ra sai so cua phep nh lng, nen can chon
ch th sau cho sai so nho nhat (trong pham vi cho phep).
3.

Cac ky thuat chuan o

3.1. Chuan o trc tiep

Chuan o bang cach nho trc tiep dung dch chuan o vao mot the tch chnh xac dung dch can nh
lng.
3.2. Chuan o tha tr
Cho mot the tch chnh xac va qua d dung dch chuan o tac dung vi mot the tch chnh xac dung
dch can nh lng. Sau o chuan o thuoc th d bang mot dung dch chuan o khac. V du: nh
lng clorid, trc het cho AgNO3 d e ket tua hoan toan AgCl. Sau o chuan o AgNO3 tha bang
KSCN.
AgNO3 d + NaCl = AgCl + NaNO3
AgNO3 con lai + KSCN = AgSCN + KNO3
3.3. Chuan o the
Cho mot the tch chnh xac dung dch can nh lng tac dung vi mot lng d thuoc th nao o, phan

29

ng sinh ra mot lng chat mi tng ng hoa hoc vi lng chat can xac nh. Dung dung dch
chuan o e nh lng chat mi sinh ra. V du: nh lng K2Cr2O7 bang cach cho tac dung vi KI
trong moi trng acid. nh lng iod sinh ra bang Na2S2O3.
K2Cr2O7 + 6KI + 7H2SO4 = Cr2(SO4)3 + 3I2 + 4K2SO4 + 7H2O
I2 + Na2S2O3 = 2NaI + Na2S4O6
4. Nong o dung dch dung trong PTTT
Trong PTTT thng dung cac nong o sau:
4.1. Nong o phan tram (%)
Nong o phan tram la nong o bieu th bang so gam chat tan co trong 100 gam dung dch (ky hieu %).
V du: dung dch acid hydrocloric 10% co ngha la trong 100 gam dung dch nay co cha 10 gam HCl
nguyen chat.
Cong thc tnh

mct
100
mdd

(1)

C la nong o % cua dung dch.

mct la khoi lng chat tan (g).
mdd la khoi lng dung dch (g).
V mdd = dVdd
d la khoi lng rieng cua dung dch (g/ml).
Vdd la the tch dung dch (ml).
Cong thc (1) co dang:

mct
100
dVdd

(2)

Trong HHPTL va nganh Dc, lng chat tan cha trong cac dung dch qua nho so vi lng dung
moi, nen khi tnh toan thng coi khoi lng rieng cua dung dch bang khoi lng rieng cua nc
4oC.
ddd = dH2O = 1 (g/ml)
Cong thc (2) co dang:

mct
100
Vdd

(3)

Ap dung cong thc

30

V du 1: tnh the tch dung dch acid hydrocloric 37,23% (d = 1,19) can lay e pha 100 g dung dch acid
hydrocloric 10%?
Cach tnh nh sau:
+ Khoi lng HCl nguyen chat co trong 100 g dung dch acid hydrocloric 10%:

mct
Cm dd
100
100 mct
mct 10
10 gam
mdd
100
100

+ The tch dung dch acid hydrocloric 37,23% (d = 1,19%) can lay e pha:

mct
m
10
100 Vdd ct 100 Vdd
100 22 ,5ml
d Vdd
dC
1,19 x 37 ,23

V du 2: tnh lng natri clorid nguyen chat e pha c 3000 ml dung dch natri clorid 10%?
V dung moi la nc nen d = 1, cach tnh nh sau:

mct
CVdd
100 mct
Vdd
100

mct

10 3000
300gam
100

4.2. Nong o ng lng

4.2.1. ng lng gam
ng lng gam cua mot chat la khoi lng tnh ra gam cua chat o phan ng va u vi mot ng
lng gam hydro hay vi mot ng lng gam cua mot chat bat ky nao khac, ky hieu la E.
4.2.2. Cach tnh ng lng gam
Cong thc tnh

M
n

E la ng lng gam cua chat can xac nh (g).

M la khoi lng mol phan t cua chat can xac nh (g).
n la mot so, tuy theo loai hp chat ma co gia tr khac nhau:
-

oi vi base th n la so nhom OH- tham gia phan ng cua mot phan t base.

oi vi acid th n la so proton H+ tham gia phan ng cua mot phan t acid.

31

oi vi muoi th n la tong hoa tr cua cac nguyen t kim loai tham gia phan ng cua mot phan
t muoi.

oi vi chat oxy hoa va chat kh th n la so electron (e) thu hay mat cua mot phan t chat oxy
hoa hay mot phan t chat kh khi tham gia phan ng.

V du 1:
2NaOH + H2SO4 = Na2SO4 + 2H2O

E NaOH

M 40

40g
n
1

E H 2 SO 4
V du 2:

M 98

49g
n
2

Bi(OH)3 + 2HCl = Bi(OH)Cl2 + 2H2O

M 260
E Bi (OH ) 3

130g
M n36,5 2
E HCl

36,5g
n
1
V du 3:
Na2CO3 + HCl = NaHCO3 + NaCl

E Na 2 CO 3

M 106

106g
n
1

Na2CO3 + 2HCl = 2NaCl + CO2 +H2O

E Na2CO3
V du 4:

M 106

53g
n
2

2KMnO4 + 5H2O2 + 3H2SO4 = K2SO4 + 2MnSO4 + 5O2 + 8H2O

2

Mn7+ + 5e = Mn2+

O22- - 2e = O2

M 158

31,6g
n
5
M 34

17 g
n
2

E KMnO4
E H 2O 2
4.2.3. Dung dch ng lng

Dung dch ng lng la dung dch co nong o bieu th bang so ng lng gam chat tan co trong
1000 ml dung dch (ky hieu CN).
32

V du: dung dch natri hydroxyd 0,1 N co ngha la trong 1000 ml dung dch nay co cha 0,1 ng
lng gam NaOH hay cha 0,1 x 40 = 4 g NaOH (v ENaOH = 40 g).
Cong thc tnh:

CN

mct
1000
EV dd

CN la nong o ng lng cua dung dch (N).

mct la khoi lng chat tan cua dung dch (g).
E la ng lng gam chat tan (g).
Vdd la the tch dung dch (ml).
V du 1: tnh lng natri hydroxyd nguyen chat can lay e pha 100 ml dung dch NaOH 0,1 N ?

CN

mct
C EV
1000 mct N dd
EV dd
1000

m ct

0,1 x 40 x 100
0,4g
1000

V du 2: tnh nong o ng lng cua dung dch acid sulfuric 14,35% (d = 1,1; EH2SO4 = 98/2 = 49) ?
+ Khoi lng H2SO4 nguyen chat co trong V ml dung dch acid sulfuric 14,35% la:

(1)

mct
CdVdd
100 mct
dVdd
100

+ Nong o ng lng cua dung dch acid sulfuric 14,35% la:

CN

mct
1000
EVdd

(2)

+ Thay (1) vao (2) ta co:

CN

CdVdd
1000
100 EVdd

CN

14,35 x 1,1
x 1000 3,22N
100 x 49

CN

Cd
C
1000 d 10
100 E
E

Vay dung dch acid sulfuric 14,35% (d = 1,1) co nong o ng lng la 3,22 N.
4.2.4. Tac dung gia cac dung dch ng lng
Theo nh luat tac dung ng lng co the rut ra ket luan: trong cac phan ng hoa hoc c bao nhieu
ng lng gam cua chat nay th phan ng va u vi bay nhieu ng lng gam cua chat kia hay
hai chat co so ng lng gam bang nhau th tac dung va u vi nhau.
33

T ket luan tren suy ra:

-

Khi 2 dung dch co nong o ng lng bang nhau th chung tac dung vi nhau theo nhng
the tch bang nhau. V du: 10 ml dung dch bac nitrat 0,1 N tac dung u vi 10 ml dung dch
natri clorid 0,1 N.

Khi 2 dung dch co nong o ng lng khac nhau ma tac dung va u vi nhau th the tch
cua chung t le nghch vi nong o.

Gia s dung dch A co nong o la N1 va the tch la V1. Dung dch B co nong o la N2 va the tch la V2.
Neu dung dch A tac dung va u vi dung dch B th:

N1 V2

N 2 V1

N1V1 N 2 V2

V du: xac nh nong o ng lng cua dung dch acid acetic, biet rang 10 ml dung dch nay tac dung
va u vi 20 ml dung dch natri hydroxyd 0,1 N ?

N 1V1 N 2V2

N1

N1

N 2V2
V1

0,1 20
0,2N
10

4.3. o chuan
4.3.1. o chuan cua dung dch
o chuan cua dung dch c bieu th bang so gam chat tan co trong 1 ml dung dch (ky hieu la T)
V du: TH2SO4 = 0,0098 g/ml co ngha la trong 1 ml dung dch acid sulfuric nay co cha 0,0098 gam
H2SO4 nguyen chat.
Cong thc tnh T:

m ct
Vdd

T la o chuan cua dung dch (g/ml)

mct la khoi lng chat tan (g)
Vdd la the tch cua dung dch (ml)
4.3.2. o chuan theo chat can xac nh
o chuan cua dung dch A (dung dch chuan o) theo chat can xac nh B (chat can nh lng) la
so gam chat B tac dung va u vi 1 ml dung dch chat A (ky hieu la TA/B)
V du: THCl/Na2CO3 = 0,0053 g/ml co ngha la 1 ml dung dch acid hydrocloric tac dung va u vi 0,0053
g Na2CO3 nguyen chat (hay 1 ml HCl tng ng 0,0053 g Na2CO3).

34

Cong thc tnh:

TA B

N A EB
1000

TA/B la o chuan cua dung dch A oi vi chat can xac nh B

NA la nong o ng lng cua dung dch A
EB la ng lng gam cua chat can xac nh B
V du: tnh o chuan cua dung dch acid hydrocloric oi vi natri hydroxyd, biet rang khi nh lng
dung dch natri hydroxyd dung dung dch chuan o la acid hydroclorid 0,1 N ?

THCl

NaOH

0,1 40
0,004g / ml
1000

5. Cach tnh ket qua trong PTTT

5.1. Vi ky thuat chuan o trc tiep hoac chuan o the
V du: hut chnh xac V ml che pham A (hoac can chnh xac a gam che pham A) pha thanh Vdm ml trong
bnh nh mc. Lay V1 ml dung dch nay em chuan o bang dung dch chuan o B co nong o N2 het
V2 ml. Xac nh nong o % cua che pham (hoac ham lng % cua che pham)?
Cach 1: Tnh theo nong o ng lng
-

Tnh nong o cua dung dch A trong bnh nh mc:

N 1V1 N 2V2
-

N1

N 2V2
V1

Tnh khoi lng chat tan A co trong 1 lt dung dch (a pha trong bnh nh mc), ky hieu la P (g/l):
P(g/l) = N1EA

Tnh khoi lng chat tan A co trong V ml che pham (hoac trong Vdm dung dch )

mct
-

P
Vdm
1000

Tnh nong o % (hoac ham lng %) cua che pham

mct
100
V

hoac

mct
100
a

Cach 2: Tnh theo o chuan

-

Tnh o chuan

Tnh lng chat tan A co trong V1 ml dung dch:

TB A

N B EA
1000

35

( g / ml )

m1 = V2TB/A (g)
-

Tnh lng chat tan co trong Vdm ml dung dch (hay co trong V ml mau)

mct
-

m1
Vdm
V1

(g)

Tnh nong o % (hay ham lng) cua che pham:

hoac

m
C ct 100
V

mct
100
a

5.2. Vi ky thuat chuan o tha tr

V du: hut chnh xac V ml che pham A (hoac can chnh xac a gam che pham A) pha thanh Vdm ml trong
bnh nh mc. Lay V1 ml dung dch nay cho tac dung vi V2 ml dung dch B co nong o N2 (lng B
d so vi lng A). e chuan o lng B d phai dung het V3 ml dung dch C co nong o N3. Xac nh
nong o % che pham A?
N1V1 + N3V3 = N2V2

N1

N 2V2 N 3V3
V1

Sau o tnh ket qua nh trng hp chuan o trc tiep.

6. Pha dung dch chuan o
Dung dch chuan o la nhng dung dch a biet nong o chnh xac dung e xac nh nong o cac dung
dch khac.
Pha dung dch chuan o co 3 cach:
6.1. Dung ong chuan
Ong chuan la ong thuy tinh co cha mot lng chnh xac hoa chat tinh khiet c han kn. Tren ong co
nhan in ten, cong thc hoa chat va nong o dung dch chuan o pha c. Khi pha dung dung cu uc
ong, chuyen het lng hoa chat trong ong vao bnh nh mc co dung tch 1000 ml, them nc cat va
u, lac eu, c dung dch chuan o co nong o nh a ghi tren nhan.
6.2. Dung hoa chat tinh khiet
Dung nhng hoa chat tinh khiet a c qui nh phan Cac thuoc th trong DVN IV.
e pha dung dch chuan o t hoa chat tinh khiet phai tien hanh cac bc sau:
Tnh lng hoa chat can lay e pha
Ap dung cong thc:

CN

mct
C EV
1000 mct N dd
EV dd
1000
36

mct la khoi lng chat tan can lay

CN la nong o dung dch can pha (N)
Vdd la the tch dung dch can pha (ml)
E la ng lng gam chat tan
Pha dung dch
Can chnh xac hoa chat a tnh tren, chuyen het vao bnh nh mc, hoa tan bang nc cat roi them
nc cat va u the tch muon pha, lac eu se c dung dch chuan o co nong o can pha.
6.3. Pha gan ung roi ieu chnh nong o
e pha dung dch chuan o t hoa chat khong tinh khiet (hoac ieu chnh lai nong o dung dch co
thay oi trong qua trnh bao quan) can tien hanh cac bc:
6.3.1. Tnh lng hoa chat can lay e pha
Ap dung cong thc va cach tnh muc 6.2 nhng do hoa chat khong tinh khiet nen khi pha can phai
can lng hoa chat ln hn lng tnh toan.
6.3.2. Pha dung dch
Can chnh xac mot lng hoa chat ln hn lng hoa chat a tnh, hoa tan trong bnh nh mc co dung
tch bang the tch muon pha, them nc va u, lac eu se c dung dch co nong o xap x bang
nong o dung dch muon pha.
6.3.3. Xac nh he so hieu chnh cua dung dch
Muon ieu chnh nong o dung dch va pha (hoac ieu chnh lai nong o cua dung dch chuan o co
thay oi trong qua trnh bao quan) phai xac nh c he so hieu chnh K cua dung dch.
He so hieu chnh la t so gia nong o thc cua dung dch chuan o vi nong o ly thuyet cua no. He
so hieu chnh cho biet nong o thc ln hn hay nho hn nong o ly thuyet bao nhieu lan.
Neu goi nong o thc cua dung dch la NT va nong o ly thuyet cua dung dch la NLT ta co:

NT
N LT

Theo DVN IV nen s dung nhng dung dch chuan o co 0,970 K 1,030.
Xac nh K cua dung dch thng s dung mot trong hai cach sau:
Cach 1: Ap dung oi vi trng hp dung dung dch chuan o e xac nh o chuan cua dung dch
pha, K c tnh theo cong thc:

V0
K0
V

37

K la he so hieu chnh cua dung dch pha.

V0 la the tch cua dung dch chuan o (ml).
V la the tch cua dung dch pha (ml).
K0 la he so hieu chnh cua dung dch chuan o.
Cach 2: Ap dung vi trng hp dung hoa chat tinh khiet e xac nh o chuan dung dch pha, K c
tnh theo cong thc:

a
VT

K la he so hieu chnh cua dung dch pha.

a la khoi lng hoa chat tinh khiet (g).
V la the tch cua dung dch pha (ml).
T la o chuan ly thuyet cua dung dch hoa chat tinh khiet (g/ ml).
K c xac nh en ba ch so thap phan, ch so th t phai lam tron.
e xac nh K phai tien hanh t nhat 2 mau chuan, cac mau khac nhau khong qua 0,05 ml.
6.3.4. ieu chnh nong o dung dch
Can c vao tr so K tnh c e tien hanh ieu chnh nong o dung dch pha:
-

Neu K = 1,000; ngha la NT = NLT; dung dch chuan pha ung khong can phai hieu chnh.

Neu K > 1,000 ngha la NT > NLT; dung dch pha co nong o ln hn nong o can pha, trng hp
nay phai hieu chnh bang cach them nc.
The tch nc can them c tnh theo cong thc:
VH2O = (K - 1,000)Vdc
VH2O la the tch nc can them (ml).
K la he so hieu chnh cua dung dch pha.
Vdc la the tch dung dch pha can ieu chnh (ml).

Neu K < 1,000 ngha la NT < NLT; dung dch pha co nong o nho hn nong o can pha, trng hp
nay phai hieu chnh bang cach them hoa chat.
Lng hoa chat can pha c tnh theo cong thc:

(1,000 K )a
Vdc
1000

m la khoi lng hoa chat can them (g)

38

K la he so hieu chnh cua dung dch pha

a la khoi lng hoa chat co trong 1000 ml dung dch ly thuyet: a = NE (g)
Vdc la the tch dung dch pha can ieu chnh (ml)

39

N TP PHNG PHP ACID - BASE

Cu hi
1. Phng php nh lng acid base: nguyn tc, im tng ng, cch xc nh
im tng ng, la chn ch th ?
2. Php nh lng bng base: nguyn tc, cch xc nh im tng ng ?
3. Php nh lng bng acid: nguyn tc, cch xc nh im tng ng ?
4. Th no l ch th acid base ? Cho bit khong pH chuyn mu ca 3 ch th thng
dng phenolphtalein, methyl, methyl da cam ?
5. Hy chn ch th cho cc trng hp nh lng sau:
-

Acid mnh bng base mnh hoc ngc li

Acid yu bng base mnh
Base yu bng acid mnh
Na2CO3 bng HCl

1. Nguyn tc
Acid + Base = Mui + Nc
HA + MOH = MA + H2O
2. im tng ng
-

Qu trnh nh lng: qu trnh bin i [H+] v [OH-]

pH ca dung dch thay i lin tc

im tng ng ng vi 1 gi tr pH xc nh

pH T: ph thuc vo bn cht acid, base v nng

Thc hnh: gn im tng ng

pH dung dch thay i t ngt

Bc nhy pH ca php chun

im gia bc nhy = pH im tng ng

3. Cch xc nh im tng ng
-

Thng dng ch th mu pH (ch th acid base): methyl, methyl da cam,

phenolphtalein

Khong pH i mu ca ch th: nm trong bc nhy pH ca php chun

V d: nh lng HCl bng dung dch chun NaOH

Bc nhy pH: 4 10

Chn 1 trong 3 ch th methyl, methyl da cam, phenolphtalein

40

4. Ch th mu pH Yu cu chung
-

Tan c trong nc hoc trong cn

Bn trong iu kin thng: khng b oxy, kh carbonic, nhit , . ca mi trng lm

nh hng

Mu xut hin kh r nng thp (10-5 10-4 M)

Chuyn mu nhanh, r trong mt khong pH hp

Khong pH i mu ca ch th: nm trong bc nhy pH ca php chun

Mt s ch th mu pH v khong pH chuyn mu
Nng
(%)

Dung
mi

c
tnh ch
th

Dng acid

Dng base

Phenolphtalein

0,1 v 1

Cn 90%

Acid

Khng

Hng

8,0 - 10,0

Phenolphtalein

0,05

Cn 20%

Acid

Khng

Hng

7,4 - 9,0

0,1 v 0,2

Cn 60%

Base

Vng

4,2 - 6,2

Methyl da cam

0,1

Nc

Base

Hng

Vng

3,1 - 4,4

Lc bromocresol

0,02

Cn 20%

Acid

Vng

Xanh

4,0 - 5,4

0,1 v 0,01

Nc

Base

Vng

1,4 - 3,2

Ch th

methyl

Tropeolin 00

Mu

Khong pH
chuyn mu

5. nh lng acid bng base

5.1. Nguyn tc
-

Dung dch chun : base mnh

Thng s dng nh lng

Acid mnh: HCl, H2SO4,

Acid yu: CH3COOH,

Mui ca acid mnh v base yu: NH4Cl, novocain HCl,

5.2. Cch xc nh im tng ng

-

S dng ch th mu pH

nh lng acid mnh: phenolphtalein, methyl, methyl da cam

nh lng acid yu, mui c tnh acid: phenolphtalein (bc nhy pH ca php chun
nm trong vng c pH > 7)
41

6. nh lng base bng acid

6.1. Nguyn tc
-

Dung dch chun : acid mnh

Thng s dng nh lng

Base mnh: NaOH, KOH,

Base yu: NH4OH, CH3NH2,

Mui ca base mnh v acid yu: Na2CO3, Na2B4O7,

6.2. Cch xc nh im tng ng

-

S dng ch th mu pH

nh lng base mnh: phenolphtalein, methyl, methyl da cam

nh lng base yu, mui c tnh base: methyl, methyl da cam (bc nhy pH ca
php chun nm trong vng c pH < 7)

Lu
-

Trong thc t phn tch, khng p dng nh lng

Acid qu yu bng base mnh

Base qu yu bng acid mnh

Acid yu bng base yu hoc ngc li

Do ln cn T pH bin i qu nh (coi nh khng c bc nhy) nn khng chn

c ch th, sai s rt ln khi nh lng

Khc phc: nh lng trong mi trng khan

42

N TP PHNG PHP OXY HA KH

Cu hi
1. Trnh by nguyn tc chung ca phng php chun oxy ha kh ?
2. Nu cc iu kin ca phn ng oxy ha kh dng trong phn tch nh lng ?
3. Trnh by nguyn tc, iu kin, xc nh im tng ng v mt s ng dng ca
phng php nh lng bng kali permanganat ?
4. Thit lp cng thc nng theo th tch oxy ca dung dch H2O2 khi nh lng theo
phng php kali permanganat ?
5. Trnh by nguyn tc, cc k thut nh lng, xc nh im tng ng, iu kin
tin hnh v mt s ng dng ca phng php nh lng bng iod ?
6. Trnh by nguyn tc, iu kin, xc nh im tng ng v mt s ng dng ca
phng php nh lng bng nitrit ?
1. Nguyn tc
-

Phng php nh lng th tch da vo phn ng oxy ha kh

pOx1 + qKh2 =

pKh1 + qOx2

ng dng nh lng cc cht c tnh oxy ha hoc c tnh kh

C th p dng nh lng nhng hp cht khng c tnh oxy ha kh nhng

phn ng hon ton vi cht oxy ha hay cht kh (to ta hoc phc cht)

nh lng cht kh (Fe2+, Mn2+, I-, SO32-, H2O2, C2O42-, ): dung dch chun l cht
oxy ha

nh lng cht oxy ha (Fe3+, Cu2+, MnO4-, CrO42-, IO3-, H2O2, Cr2O72-, ClO3-, ): dung
dch chun l cht kh

2. iu kin phn ng
-

Phi xy ra hon ton

Phi xy ra tng i nhanh

D xc nh im tng ng

3. Phng php nh lng bng kali permanganat

3.1. Nguyn tc
-

Da vo kh nng oxy ha mnh ca kali permanganat

Dung dch chun KMnO4 0,1 N hay 0,05 N (DVN IV)

nh lng cht c tnh kh

3.2. iu kin tin hnh

-

Mi trng acid sulfuric

43

KMnO4 th hin tnh oxy ha cao nht

Phn ng xy ra nhanh

Sn phm phn ng khng mu

Ion sulfat khng cn tr

MnO4- + 5e + 8H+ = Mn2+ + 4H2O
(tm)

(khng mu)

Khng nh lng trong mi trng base, trung tnh hoc acid yu v

KMnO4 th hin tnh oxy ha yu hn

Phn ng xy ra chm hn

Sn phm c mu

Kh xc nh T

Kt qu nh lng km chnh xc
MnO4- + 3e + 2H2O = MnO2 + 4OH- (trung tnh)
(xm en)

(tm)
MnO4- + 1e =
(tm)
-

MnO42-

(kim)

(xanh lc)

Phi duy tr nng acid sulfuric cao trong khi nh lng trnh phn ng ph
2MnO4- + 3Mn2+ + 2H2O = 5MnO2 + 4H+

Khng tin hnh trong mi trng HCl v Cl- kh KMnO4

Khng tin hnh trong mi trng HNO3 v oxy ha cht cn nh lng gy sai s

3.3. Xc nh im tng ng
-

Ti im tng ng
NKMnO4VKMnO4 = NCPTVCPT

1 git KMnO4 d dung dch mu hng nht (Php nh lng t ch th)

3.4. Mt s ng dng
3.4.1. nh lng acid oxalic
5H2C2O4 + 2KMnO4 + 3H2SO4 = 2MnSO4 + 10CO2 + K2SO4 + 8H2O
Mn+7 + 5e = Mn+2
C2O42- - 2e = 2CO2

EH 2C2O4

M H 2C2O4
n

90
45 g
2

TKMnO4

H 2C2O4

N KMnO4 EH 2C2O4
1000

0,1 45
0,0045 g / ml
1000

(1 ml dung dch kali permanganat 0,1 N tng ng vi 0,0045 g H2C2O4)

44

3.4.2. nh lng nc oxy gi

-

H2O2 va c tnh oxy ha, va c tnh kh

2KMnO4 + 5H2O2 + 3H2SO4 = K2SO4 + 2MnSO4 + 5O2 + 8H2O
Mn+7 + 5e = Mn+2
O22- - 2e = O2

EH 2O2
-

M H 2O2
n

34
17 g
2

ng lng th tch ca H2O2 l s lt oxy gii phng ra do 1 ng lng gam H2O2

b phn hy hon ton
2H2O2 = O2 + 2H2O
34 g

11,2 lt

17 g x
-

17 11,2
5,6 lt
34

S lt oxy gii phng do 1 lt dung dch H2O2 c nng N:

VO2 = 5,6NH2O2 (lt oxy)

4. Phng php nh lng bng iod

4.1. Nguyn tc
-

Iod c tnh oxy ha mnh, nh lng cht kh

I2 + 2e = 2I-

Ion iodid (I-) c tnh kh, nh lng cht oxy ha

2I- - 2e = I2

Dc in Vit Nam IV qui nh ty i tng phn tch m s dng mt trong ba k thut nh

lng
4.2. nh lng trc tip
-

nh lng mt s cht kh: S2O32-, SO32-, CN-, AsO33-, vitamin C,

Khng nh lng cht oxy ha theo k thut trc tip v khng c ch th xc nh

im kt thc (gia iodid vi cht oxy ha)

Iod oxy ha trc tip cht cn chun : I2 + 2e 2I-

Mi trng: pH 5 8

Ch th: h tinh bt, dung dch khng mu xanh

Tnh nng dung dch cn nh lng

NxVx = NI2VI2
45

4.3. nh lng th (gin tip)

-

nh lng mt s cht oxy ha: halogen, hypohalogenic, iodat, ferricyanid, KMnO4,

K2Cr2O7, HNO2, H2O2, Fe3+, Cu2+,

Thm lng tha KI vo mu cha cht oxy ha cn nh lng, I- b oxy ha to lng

I2 tng ng vi cht cn nh lng v c chun bng natri thiosulfat
K2Cr2O7 + 6KI + 7H2SO4 = Cr2(SO4)3 + 3I2 + 4K2SO4 + 7H2O
2Na2S2O3 + I2 Na2S4O6 + 2NaI

Ch th: h tinh bt, dung dch xanh khng mu (hoc mu ca mui trong dung dch)

Tnh nng dung dch cn nh lng

NxVx = NI2VI2 = NNa2S2O3VNa2S2O3

4.4. nh lng tha tr

-

nh lng mt s cht kh: lu hunh hu c c nhm thiol, hydrazin, glucose,

aldehyd acetic, aldehyd formic, phenol, methyl hydroxybenzoat, propyl hydroxybenzoat,
phenidion, sn phm m vng lactam t penicillin,

Thm mt th tch chnh xc v qu d dung dch chun iod

nh lng iod d bng natri thiosulfat (cng nng dung dch iod)

T th tch dung dch natri thiosulfat dng suy ra th tch dung dch iod d, th tch
dung dch iod tc dng vi cht kh
I2 + 2e 2II2 (d) + 2S2O32- 2I- + S4O62-

Ch th: h tinh bt, dung dch xanh khng mu

Tnh nng dung dch cn nh lng

NxVx = NI2VI2 - NNa2S2O3VNa2S2O3

4.5. Cch xc nh im tng ng

-

Chn ch th h tinh bt

Tnh kh yu, tc dng vi cht oxy ha mnh

I2 + h tinh bt phc xanh dng (hp ph nhanh v gii phng Iod chm)

un nng mt xanh, ngui mu xanh ti hin

Khng cho mu vi iodid

T: lng tha iod dung dch mu vng khng cn ch th. Khi [I2] thp,
nn thm h tinh bt

nh lng trc tip: pH 5 -8. Nu pH > 9

I2 + 2OH- = IO- + I- + H2O
46

IO- (hypoiodid) c tnh oxy ha mnh hn iod, chuyn S2O32- thnh S4O62- dn n sai
s
-

Nhit phng. Nu nhit cao iod b thng hoa, nhy ch th gim

nh lng th v tha tr: cho h tinh bt vo thi im gn tng ng (dung

dch vng nht). Nu cho sm, tinh bt hp ph mt phn iod v gii phng iod chm

nh lng th:

Phn ng gia KI v vi cht oxy ha cn nh lng cn thi gian 10 15

xy ra hon ton

Trnh nh sng KI khng b phn hy thnh iod

-

4I + O + 4H 2I + 2H O
2
2
2
as
4.6. Mt s ng dng
4.6.1. nh lng natri thiosulfat
-

nh lng trc tip

Ch th h tinh bt: dung dch khng mu xanh

Mi trng trung tnh hay base yu

Khng tin hnh trong mi trng acid v

2H+ + S2O32- = S + SO2 + H2O
I2 + 2Na2S2O3 = 2NaI + Na2S4O6

EI 2

M I2
n

M Na 2 S 2O3 158
253
126 ,5 g ; E Na 2 S 2O3

158 g
2
n
1

4.6.2. nh lng glucose

-

Glucose c nhm aldehyd nn c tnh kh

nh lng tha tr

Ch th h tinh bt: dung dch xanh khng mu (cho ch th khi dung dch c mu vng
nht)
CH2OH-(CHOH)4-CHO + I2 + 3NaOH CH2OH-(CHOH)4-COONa + 2NaI + 2H2O
I2 (tha) + 2Na2S2O3 = 2NaI + Na2S4O6

Phn ng ph: 2NaOH + I2 = 2NaOI + NaI + H2O

Phi acid ha bng acid sulfuric trung ha kim v gii phng iod tha t IOH+ + OH- = H2O
NaOI + NaI + 2H+ = I2 + 2Na+ + H2O

EC6 H12O6

M 180

90 g
n
2

47

4.6.3. nh lng kali permanganat trong thuc tm dc dng

-

Kali permanganat c tnh oxy ha

nh lng th

Mi trng acid sulfuric

Ch th h tinh bt: dung dch xanh khng mu (cho ch th khi dung dch c mu vng
nht)
2KMnO4 +10KI + 8H2SO4 = 2MnSO4 + 6K2SO4 + 5I2 + 8H2O
I2 + 2Na2S2O3 = 2NaI + Na2S4O6

EKMnO4
-

M KMnO4
n

158 ,036
31,607 g
5

Lu

Phn ng gia thuc tm v KI thc hin t nht 10 pht v phi trnh nh sng

Lng acid sulfuric cho vo va nn khng cn trung ha bng kim hay

natri carbonat

5. Phng php nh lng bng nitrit

5.1. Nguyn tc
-

Phng php nh lng th tch, oxy ha kh

Xc nh nng hoc hm lng cc cht hu c c nhm amin thm bc 1

Dung dch chun : NaNO2 0,1 N

NaNO2 + HCl HNO2 + NaCl
Ar-NH2 + HNO2 + HCl [Ar-N+ N]Cl- + 2H2O

5.2. iu kin tin hnh

-

Mi trng acid hydrocloric v long

Nhit thp, khong 10oC (lm lnh trong nc )

Khuy u dung dch cn chun sao cho khng to ra dng xoy khng kh trong
dung dch (s dng my khuy t)

L c u nh dung dch chun khong 2 ml ph t, n trc im tng ng

khong 1 ml th nh tng 0,1 ml mt v yn t nht 1 sau m i ln thm dung dch

5.3. Cch xc nh im tng ng

Ch th ni
-

Tropeolin 00: 1 git tha dung dch natri nitrit s phn ng vi ch th to sn phm
nitroso c mu vng (dung dch vng nht)

H n hp tropeolin (4 git) v xanh methylen (2 git): dung dch tm xanh ngc

48

Ch th ngoi: giy tm h tinh bt v KI (t s dng)

5.4. Mt s ng dng
Amin thm bc nht (benzocain, dapson, primaquin, procainamid, procain, sulfacetamid,
sulfadoxin, sulfaguanidin, sulfamethoxazol, sulfaxylum, sulfathiazol, sulfapyridin, sulfamethizol)

49

Cau hoi
1. Nguyen tac chung cua phng phap ket tua ?
2. Phan loai phng phap ket tua va ai cng ve phep o bac ?
3. Phep o bac trong moi trng trung tnh - phng phap Mohr va phng phap Fajans ?
4. Phep o bac trong moi trng acid - phng phap Charpentier Volhard ?
5. Neu mot vai ng dung cua phng phap ket tua ?
1.

Nguyen tac chung cua phng phap ket tua

Phng phap ket tua da vao s tao thanh chat ket tua t tan trong cac phan ng trao oi. Nhng phan
ng tao thanh ket tua c dung trong phng phap ket tua phai thoa man cac ieu kien sau:
-

Ket tua phai rat t tan.

S ket tua phai xay ra nhanh.

Ket tua tao thanh trong qua trnh nh lng khong b phan huy vi mot mc o nhat nh ang ke.

Phai co kha nang xac nh c iem tng ng.

Phng phap ket tua thng c dung e xac nh nong o cac anion Cl -, Br-, I-, SCN-, CN- va cac
cation Ag+, Hg2+
2.

Phan loai phng phap ket tua va ai cng ve phep o bac

Phng phap ket tua c phan loai nh sau

-

Phep o bac: dung kha nang tao tua muoi cua ion bac vi nhng anion khac nhau (clorid, bromid,
iodid, cyanid, sulfocyanid).

Phep o thuy ngan: da vao phan ng hoa hoc tao muoi thuy ngan t tan (clorid, bromid, iodid).

Pho bien nhat la phep o bac.

Phep o bac
-

o trong moi trng acid:

Halogenid (tr F-) va thiocyanat tao tua khong tan vi Ag+ trong moi trng acid. Acid thng c
dung la HNO3 v:
o

HNO3 tao vi Ag+ mot muoi AgNO3 rat tan.

Lam ha pH cua moi trng.

50

o trong moi trng trung tnh:

Mot vai anion co the hoa tan t hoac nhieu trong moi trng acid do vay phai o bac trong moi trng
trung tnh
V du: CN- va S- hoa tan trong moi trng acid am ac
Oxalat va chromat hoa tan trong moi trng acid loang
Vai hp chat hu c (barbituric)
Chat goc (chat chuan hoa hoc, chemical standard)
-

Halogenid: nhieu muoi halogen c dung lam chat goc nh NaCl (M = 58,45), KCl (M = 74,55),
KBr (M = 119,01). Ngi ta hay dung cac chat goc nay e xac nh o chuan cua dung dch chuan
o bac nitrat .

Dung dch chuan o

-

Dung dch chuan o bac nitrat 0,1 N: cha 16,989 g bac nitrat /lt.

Dung dch thiocyanat (ammonium, Na hay K) 0,1 N: Muoi nay co o tinh khiet cao nhng lai hay
hut am. Do o, khi pha dung dch chuan phai pha cao hn o chuan mong muon va khi dung th
nh lng lai bang bac nitrat chuan.

3.

Phep o bac trong moi trng trung tnh

3.1. Phng phap Mohr

-

Nguyen tac: cho dung dch bac nitrat vao dung dch halogenid can nh lung, lac can than sau moi
lan them dung dch bac nitrat. Ket thuc nh lng khi them dung dch bac nitrat vao ma khong
xuat hien them tua.
Ag+ + X- = AgX

Ch th: dung dch kali cromat trung tnh. Kali cromat cho tua cromat bac o gach khi nong o bac
cao hn nong o clorid.
2Ag+ + CrO42- = Ag2CrO4 (o gach)

Tien hanh: phai them t t dung dch bac nitrat vao dung dch Cl - ban au a c them 1 t ch th
cromat.
o

o
-

Viec chon pH rat quan trong:

pH < 6: cromat muoi acid yeu se t hoa tan: 2H+ + CrO42- = H2CrO4

pH 10,5: bac nitrat se phan huy thanh bac oxyd ket tua en lam cho ket qua
nh lng thieu chnh xac.

Nong o ch th: thng la 0,003 M.

Pham vi s dung va gii han

51

Ap dung nh lung Cl- va Br -.

Khong ap dung e nh lng iodid va thiocyanat v kho nhan biet luc phan ng ket thuc
do hien tng hap phu va tao thanh he keo.

Khong the chuan o dung dch co mau v mau cua dung dch che mau cua Ag2CrO4 iem
tng ng.

Ap dung nh lng nhng ion tao muoi bac 1 chat kem tan trong moi trng trung tnh.

Cac cation tao tua vi ion cromat phai c kh trc khi nh lung. V du: Pb 2+ va Ba2+
phai kh thanh dang sulfat.

Dung dch acid phai c trung tnh hoa bi phan ng cua carbonat calci, loc lng tha va
kh anhydrid carbonic bang un soi.

3.2. Phng phap Fajans

-

Nguyen tac: tat ca halogenid bac eu co mot kha nang hap phu nao o, tang t Cl-, Br-, I-.

V du: nh lng halogenid bang AgNO3.

o

Khi cha en iem tng ng, tua tao thanh trong dung dch tha ion halogenid hap phu
nhng ien tch am cua halogenid. ien tch nay ay nhng ion khac va loi keo mot t
cation khac ma halogenid hoa tan (H+, Na+, K+, ).

Va khi vt qua iem tng ng, tua tiep xuc vi dung dch cha mot lng tha Ag+.
Chnh Ag+ hap phu vao tua gay tch ien dng keo nhng ion khac e tao thanh muoi
tng oi t tan (nh anion cua fluorescein hay dan chat cua brom (eosin)) hay clor
(dichlorofluorescein).
Eosin la Tetrabromofluorescein

C6H4COO
Br

Fluorescein

C6H4COO

Br

+
2Na

2Na

O
Br

Br

Eosin (muoi dinatri mau o)

-

Muoi dinatri mau o

C che chuyen mau cua ch th fluorescein

o

Trc iem tng ng, ch th mau co ien tch giong chat hap phu tren tua se b ay vao
dung dch nen dung dch co mau hong vang phat quang.

Va khi vt qua iem tng ng, Ag+ hap phu vao tua lam tua mang ien tch dng cua
52

Ag+. Fluoresceinat bac hoa tan yeu hn bac nitrat, s hap phu cua ch th anion mang mau tren
tua lam tua tr nen mau hong am.
o

Ch th mau cua phng phap:

Eosin: e nh lng I-, Br-, CN- (pH # 2) va khong nh lng Cl- v eosinat b tua AgCl
hap phu sm nen tua o trc iem tng ng.

Fluorescein va dichlorofluorescein: e nh lng Br-, I-, Cl-, SCN-.

Khi thay oi ch th th co the nh lng hon hp Cl- va 1 halogenid khac nh Br- hoac I-.

Chu y: thng dung moi trng acid yeu (them lng nho CH3COOH e s hap phu de dang) va e
tranh s ong von ket tua hoan toan thng them ho tinh bot, dextran e bao ve keo.
4.

Phep o bac trong moi trng acid Phng phap Charpentier Volhard

Trong moi trng acid manh (HNO3): ion Ag+ tao tua chuyen biet hn, do o dung nh lng Cl-, Br-,
I-, SCN-, va CN- ke ca khi co mat nhng ion gay can tr moi trng trung tnh.
Khi nh lng nhng halogenid trong moi trng acid khong co ch th chuyen biet nen phai thc hien
phng phap tha tr. Tien hanh qua 2 bc:
-

Cho lng tha AgNO3 vao dung dch halogenid can nh lng e tao dan chat tua bac khong tan.

nh lng Ag+ tha bang dung dch chuan o thiocyanat vi ch th phen sat ammoni, moi trng
acid nitric.

Trong dung dch, phen sat amoni phan ly nh sau:

Fe(NH4)(SO4)2.12H2O = Fe3+ + NH4+ + 2SO42- + 12H2O

Tai iem tng ng mot giot dung dch thiocyanat tha lam cho dung dch co mau hong nhat.
3SCN- + Fe3+ = Fe(SCN)3 (hong nhat)

Mau hong nhat cua dung dch se mat dan do phan ng:
3AgX + Fe(SCN)3 = 3AgSCN + FeX3

o chnh xac cua phng phap

-

S chuyen mau kho xac nh va thay oi theo muoi can nh lng.

o chnh xac tuy vao s hap phu Ag+ tren tua. Do o, khi thc hanh phai dung dung dch pha loang
va thao tac lac ky.

o chnh xac tuy vao s khac biet ve o tan gia halogenid bac va thiocyanat bac
o

SAgSCN > SAgX: khong sai so nhieu. Trng hp I- vaBr-

SAgSCN < SAgX: sai so nhieu. Trng hp Cl-

(do lng tha thiocyanat dch chuyen halogenid a tua nen san pham hoa tan thiocyanat 170 lan yeu
53

hn san pham cua Cl-).

Khac phuc bang 1 trong nhng cach sau
-

Loc loai tua AgCl.

Tch tu tua bang cach un soi.

Them dung moi hu c (ether, nitrobenzen) e tua AgCl ong von lai mat phan cach cua nc
va dung moi hu c va nh vay khong tac dung vi SCN-.

Thc hanh nhanh (vung chuyen sang hong ch keo dai phut va ke en la thiocyanat dch chuyen
Cl-).

ng dung
-

Phng phap nay thng nh lng Cl- va Br- khi tua trong moi trng acid nitric.

nh lng iodid co hai kho khan do iodid bac hap phu nhieu va acid nitric oxy hoa nhng iodid.
e khac phuc se tua trc trong moi trng trung tnh (e tranh oxy hoa), ke tiep them acid nitric.

Phng phap nay con dung nh lng nhng hp chat tao muoi bac khong tan trong moi trng
trung tnh hay amoniac nh methyl arsinat, barbituric, cafein. Chu y la sau khi tao tua, loc tua va
ch them acid nitric vao dung dch loc trc khi nh lng bang thiocyanat.

5.

Mot vai ng dung cua phng phap ket tua

5.1. Trong Dc ien Viet Nam IV

-

nh lng kali clorid: cho 10 ml dung dch vao bnh non + 50 ml nc + 5 ml HNO3 13% (TT) + 25
ml dung dch AgNO3 0,1 M + 2 ml dibutylphthalat (hoac 2 ml nitrobenzen) (TT). Chuan o bang
amoni thiocyanat 0,1 M. Mot ml dung dch amoni thiocyanat 0,1 M tng ng vi 0,007455 g
KCl.

nh lng natri bromid: ch th la dung dch sat (III) amonisulfat 10%.

nh lng natri clorid: ch th la dung dch sat (III) amonisulfat 10%.

5.2. Mot so ng dung khac cua phng phap ket tua

oi tng nh lng

Phng phap

Cl, Br

Pp Mohr (Ag2CrO4)

BH4

Pp Volhard
Chuan o tha tr Ag+ sau khi phan ng vi BH4
BH4 + 8Ag+ + 8OH 8Ag(s) + H2BO3 + 5H2O

K+

Pp Volhard: K+ au tien c tao tua vi 1 lng tha (C6H5)4Br;

(C6H5)4Br tha c tao tua vi 1 lng tha a biet Ag+. Ag+ khong

54

phan ng c chuan o bang SCN

Cl, Br, I,

Pp Fajans

SCN, Fe(CN)64

Chuan o vi Ag+. Ch th fluorescein, dichloro-fluorescein, eosin,

xanh bromophenol

Pp Fajans
Chuan o bang Th(NO3)4 e tao ThF4. Ch th o alizarin

Zn2+

Pp Fajans
Chuan o bang K4Fe(CN)6 e tao K2Zn3[Fe(CN)6]2.
Ch th diphenylamin.

SO42

Pp Fajans
Chuan o bang Ba(OH)2 trong nc methanol 50%.
Ch th o alizarin

Hg22+

Pp Fajans
Chuan o bang NaCl e tao Hg2Cl2.
Ch th xanh bromophenol

PO43,

Pp Fajans

C2O42

Chuan o bang Pb(CH3COO)2 e cho Pb3(PO4)2 hay PbC2O4.

Ch th: dibromofluorescein (PO43) hay fluorescein (C2O42)

55

Cau hoi
1. Phc chat: nh ngha, phan loai, phan biet phc chat vi muoi
2. Gii thieu ve complexon ?
3. Nguyen tac nh lng bang phng phap complexon ?
4. Dung dch chuan o va dung dch goc trong phng phap complexon ?
5. Ch th kim loai trong phng phap complexon ?
6. Cac ky thuat chuan o trong phng phap complexon ?
7. Neu mot so ng dung cua phng phap complexon ?
1.

Phc chat

1.1. nh ngha
Phc chat la nhng hp chat phan t xac nh, c tao thanh do mot kim loai (nguyen t trung tam)
nh Ag, Cu, Ni, Co, Fe, Hg noi vi cac phoi t co the la ion am hay phan t ( NH 3, H2O, Cl-, F-, CN,). Nguyen t trung tam va phoi t tao thanh cau noi phc va c viet trong dau [ ], cac ion trai dau
vi cau noi phc goi la cau ngoai phc viet ngoai dau [ ].
V du : [Ag(NH3)2]Cl
Cau noi phc / cau ngoai phc. Ch so phoi tr: 2
1.2. Phan loai
Phc chat thng chia lam 2 loai: phc chat cong va noi phc.
1.2.1. Phc chat cong (lien ket phoi tr)
Phc chat cong gom mot nguyen t trung tam lien ket phoi tr vi nhng tieu phan phan cc . V du :
Zn2+ co the phoi tr vi 4 phan t NH3 e tao thanh ion phc [Zn(NH3)4]2+ ma cong thc khai trien la

2+

NH3

..
N
H

NH3

Zn

NH3

Zn NH

2+

3 4

NH3
Phan t NH3 lng cc, cc am quay ve pha ion kim loai va tao thanh lien ket phoi tr bang 2 ien t
t do lp ngoai cung cua nit.

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Trong dung dch nc tat ca nhng ion eu hydrat hoa, chung tao thanh nhng phc chat vi nc
(phan t lng cc) theo c che giong nh oi vi NH3.

O
H

H
H

Zn

O
H

ZnH2O4 2

Nhng e n gian, nc hydrat hoa thng khong ghi vao trong cong thc cua cac ion.
So tieu phan toi a co the gan vi nguyen t trung tam goi la ch so phoi tr thng la 6, 4, 2 hoac 8.
1.2.2. Noi phc
Trong noi phc, kim loai tao thanh vi phoi t (thng la phan t hu c) va bang lien ket phoi tr
va bang lien ket chnh.
V du :

HO
N
2

CH3 C NOH
CH3 C NOH

+ Ni2+

CH 3

C
C

Dimethylglioxin

C
O

CH 3

OH

H3C

CH3
C

C CH2 C

CH3

+ Be 2+

HC
C

Acetylaceton

C
CH

Be
O

H3C

Niken dimethylglioximat

Acetylaxeton

N
Ni

H3 C

CH3

CH 3

C
CH3

Beri acetylacetonat

T cac cong thc cau tao tren cho thay cac hp chat noi phc c ac trng bang s ton tai cac
cum vong chu yeu la cac vong 5 hoac 6 canh. Nhng phc chat ma phoi t cha nhieu nguyen t
lien ket vi ion trung tam goi la phc a cang. Cac ion trung tam (ion kim loai) b kep chat trong

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cac vong bi cac phoi t nh trong gong km . Do o phoi t tao vi ion trung tam mot vong kn
goi la phc cang cua (phc chelat).
-

Cac hp chat noi phc co nhieu tnh chat ac trng, trong o cac tnh chat quan trong nhat la: o
ben cao, o tan nho trong nc, o ien ly yeu, o tan ln trong mot so dung moi hu c (thuoc th
Garola vi K+).

1.3.
-

Phan biet phc chat vi muoi

Trong dung dch nc, phan t phc chat hoac ion phc chat phan ly mot phan thanh cac cation,
anion hoac phan t.

V du:

[Ag(NH3)2]+ Ag+ + 2NH3

HgCl2 Hg2+ + 2Cl[Fe(CN)6]3- Fe3+ + 6CN-

Cac muoi thong thng va muoi kep trong dung dch nc phan ly hoan toan thanh cac ion n
gian.

V du:

NaNO3 Na+ + NO3KAl(SO4)2.12H2O K+ + Al3+ + 2SO42- + 12H2O

2.

Cac ion nh SO42-, NO3-, PO43-, tuy co cau tao giong ion phc nhng co o phan ly vo cung nho
(gan nh khong phan ly) nen coi chung la cac ion n.
Gii thieu ve complexon

Cac dan xuat cua acid amin polycarboxylic thng goi la cac complexon.

Complexon I ( chelation I, Trilon A), viet tat la H3Y

CH2COOH
N CH2COOH
CH2COOH
Acid nitril triacetic (NTA). Ky hieu H3X

Complexon II ( chelaton II, Trilon BS)

Acid etylen diamin tetra acetic (EDTA), viet tat la H4Y. ay la acid 4 nac. Trong dung dch cua
EDTA co the ton tai cac dang: H4Y, H3Y-, H2Y2-, HY3-, Y4- va tuy thuoc vao pH cua moi trng dang
nao se la chu yeu. pK1 = 2,0, pK2 = 2,73, pK3 = 6,24, pK4 = 10,34.

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HOOCH2C
HOOCH2C

CH2COOH
N CH2

CH2

N
CH2COOH

Complexonn III (Chelaton III, Trilon B)

HOOCH2C
NaOOCH2C

CH2COONa
N CH2

CH2

N
CH2COOH

Muoi dinatri cua EDTA. Viet tat la Na2H2Y.

Trong nc, Na2H2Y phan ly thanh Na+ va H2Y2-, thanh phan cua dung dch complexon III phu thuoc
vao pH cung giong nh thanh phan cua dung dch EDTA. V vay, ngoai phan t lng ra tat ca cac tnh
chat oi vi complexon II eu ung vi complexon III va ngc lai. Nhng v complexon III de ieu
che c di dang tinh khiet nen hay dung hn ca.
3. Nguyen tac nh lng bang phng phap complexon
-

Phng phap complexon la phng phap nh lng da vao phan ng tao phc cua cac
complexon vi ion kim loai tao thanh cac muoi noi phc vo cung ben t phan ly, tan trong nc.

Khi chuan o, cac ion kim loai tao phc vi EDTA xay ra cac phan ng sau trong giai oan ket
thuc s xac nh
Na2H2Y 2Na+ + H2Y2Me2+(Ca2+)+ H2Y2- MeY2- + 2H+
Me3+(Al3+) + H2Y2- MeY- + 2H+
Me4+(Th4+) + H2Y2- MeY+ 2H+

Theo cac phng trnh tren mot ion kim loai bat ky hoa tr eu phan ng vi mot phan t EDTA
nen trong phng phap complexon nong o ng lng hoac nong o mol eu co the s dung.

1 mol cation phan ng vi EDTA khong phu thuoc vao hoa tr cua no lien ket vi 1 mol Na-EDTA.

4.

Dung dch chuan o va dung dch goc trong phng phap complexon

4.1. Dung dch complexon III

-

Neu co Complexon III tinh khiet: ch can can chnh xac mot lng complexon em pha trong
nc thanh dung dch vi the tch xac nh. V du e pha mot lt dung dch complexon III 0,1 M,
can chnh xac 37,22 g complexon III hoa tan trong nc cho u 1 lt. Neu complexon III co b hut
am th em say kho 1500C trc khi can.

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Neu khong co complexon III tinh khiet th ta ch pha c dung dch co nong o xap x. Sau o
xac nh lai nong o (xem phan di).

Neu khong co complexon III ma ch co complexon II (EDTA ) th pha nh sau : can 29,21 g
complexon II va 8 g NaOH hoa tan trong mot t nc, sau o them nc va lac eu cho u 1 lt
nc, c dung dch complexon III 0,1 M.

4.2. Dung dch goc

-

Dung dch MgCl2 0,1 M : can 4,032 g MgO hoa tan trong 1 t HCl ac, them nc cho u 1 lt, lac
eu.

Dung dch ZnSO4 0,1 M : can 6,538 g Zn kim loai tinh khiet, hoa tan trong 1 t H2SO4 tinh khiet,
roi them nc cho u 1 lt, lac eu.

Chu y:
-

Nc cat phai tinh khiet v neu co nhng ion kim loai th co the tao nhng phc complexonat tan
trong nc.

Hoa chat phai cha trong nhng bao b bang thuy tinh tinh khiet hoac lo nha.

5.

Ch th kim loai trong phng phap complexon

La nhng chat thay oi mau tuy vao s co mat cua chung dang ion kim loai t do hay a tao
phc.

Thng thng, mau cua phc kim loai la mau cua anion t do va s oi mau do 1 hay nhieu
proton c thay the bang nhng ion kim loai.

Giong nh trng hp cua ch th pH, ngi ta sap xep theo nhom mang mau chu yeu:

Mau do anion la cac nhom mang mau gom cac azoic, phtalein, dan chat cua triphenyl-methan
hay cua anthraquinon hay dan chat cua phenol co nhng tnh chat gan giong nh nhng ch th
cua phng phap trung hoa.

Mau do cation la cac nhom mang mau nh cac ion thiocyanat, sulfosalicylat hay thioglycolat
trng hp nay can lng ch th cao.

Sau ay la cac ch th kim loai hay c s dung:

5.1. Ch th la dan chat azoic

Ch th en Eriocrom T (ch th NET)

La acid (hydroxy-1 naptylazo-2) -1 nitro 6 naphtol 2 sulfonic 4. (Ngoai ra, con co nhng ong
phan eriocrom A, B). pH nh lng, nhom acid sulfonic thng b ion hoa toan bo.

Trong moi trng kiem ch th nay co mau xanh, khi tac dung vi ion Ca++, Mg++ tao phc mau o.

60

en Eriocrom T c dung e nh lng ong thi Ca++ va Mg++ trong mot dung dch hoac dung
khi nh lng ion Mg++.

Khi pH = 7-10, mau ch th thay oi t xanh dng sang o di s hien dien cua nhieu cation kim
loai. V du nh khi nh lng Mg2+ mau ch th chuyen ro do tao thanh phc cang cua. ay la phc
c nhuom mau o va hang so phan ly cua no (10-7) ln hn hang so phan ly cua phc Mg-EDTA
(10-8). Khoang chenh lech hang so phan ly nay cho phep s dung ch th e phat hien Zn2+, Cd2+.
OH
OH
HO3S

N N

O2N

Ch th NET
5.2. Ch th khong azoic

Ch th murexid

La muoi amoni cua acid purpuric - mot hp chat giau nit va nhom carbonyl. Khoang oi mau t
xanh tm sang o khi co mat cua nhieu ion pH t 9 11.

Thuan li: ieu kien thc hanh rat ro, co the thay ro khoang oi mau chuyen biet cua Ca2+ ngay ca
khi dung dch co lan nhng ion Mg2+, Sr2+, Ba2+ vi lng tng ng.

H O
N

NH4+

O H

O C

C N
C N C

C O

C N

H O

O H

Ch th murexid
5.3. C che cua s oi mau
Cac ch th kim loai la cac chat hu c co kha nang tao phc mau vi ion kim loai. Cac phc nay kem
ben hn phc cua ion kim loai vi complexon. Mau cua ch th tao phc vi ion kim loai khac mau cua
ch th dang t do. Gan iem tng ng, complexon lay kim loai ch th ay ch th ra dang t
do nen dung dch thay oi mau va bao cho ta biet iem ket thuc nh lng.
V du: nh lng Ca2+ vi ch th murexid, pH = 9 - 11
Ca2+ + H4I-

CaH2I- + 2H+

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o tm

Khi nho complexon xuong:

Ca2+ + HY3- CaY2- + H+
Gan iem tng ng co s canh tranh tao phc
CaH2I- + HY3- CaY2- + H3I2o

Tm

5.4. Cac ieu kien oi vi ch th kim loai

-

Phan ng tao phc vi ion kim loai la phan ng thuan nghch va mau cua dang t do phai khac vi
mau cua dang phc
Mn+

+ Indm-

Khong mau

Mau 1

Ca2+ + H4IKhong mau

-

MInd(n-m)

Mau 2
CaH2I- + 2H+

o tm

Hong o

Phc cua ch th vi kim loai phai kem ben hn phc cua complexon vi kim loai.
MIn(n-m)+ + Y4- MY(n-4)+ +Indm2CaH2I- + 2H2Y2- 2CaY2- + 2H3I2- + 2H+
Hong o

Tm

Thng cac ch th kim loai ong thi cung la ch th acid base, nen khi s dung ta phai co nh pH cua
dung dch bang cac he em thch hp.
6.

Cac ky thuat chuan o trong phng phap complexon

6.1. Chuan o trc tiep

-

Ap dung: cac cation c nh lng pH bat buoc e thu c mot phc ben hoan toan (pH = 9 10 oi vi cation hoa tr 2). Rat nhieu ion kim loai co the nh lng trc tiep nh Mg2+, Zn2+, Ba2+,
Ca2+,

Tien hanh: cho dung dch trilon B va ch th mau thch hp tac dung trc tiep vi mot the tch chnh
xac dung dch muoi kim loai can nh lng.

Ham lng (hoac nong o) muoi kim loai c tnh theo cong thc:

Ttr / AV
100
a

P la nong o (hay ham lng) muoi kim loai (%).

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Ttr/A la o chuan cua dung dch trilon B theo muoi kim loai A.
V la the tch cua dung dch trilon B a phan ng.
a la khoi lng mau th.
V du: nh lng Mg2+ bang EDTA vi ch th en Eriocrom T, pH = 10. Luc au trong dung dch co
mau o vang do phan ng cua Mg2+ vi ch th
Mg2+ + HIn2- MgIn- + H+
o vang
Khi nho EDTA xuong, Mg2+ t do se phan ng trc
Mg2+ + HY3- MgY2- + H+
Luc ay mau cha bien oi, gan iem tng ng ta co s canh tranh tao phc
HY3- + MgIn- MgY2- + HIn2Xanh
Ket thuc nh lng khi mau chuyen t o vang sang xanh hoan toan.
6.2. Chuan o the
-

Ap dung: cac cation tao vi ch th mot phc qua kem ben dan en s oi mau khong ro.

Tien hanh: cho mot lng tha phc chat cua trilon B vi mot muoi kim loai M tac dung vi mot
the tch chnh xac dung dch muoi kim loai M can nh lng, khi o xay ra phan ng:
M + MZ = MZ + M
Sau o nh lng muoi kim loai M giai phong ra bang cac phng phap trc tiep hay tha tr, t
o tnh c ham lng (hoac nong o) muoi kim loai can nh lng.

V du: dung ch th NET khi nh lng Ca2+ rat kem chnh xac v phc Ca2+ + NET kem ben. Trong
trng hp nay them moi t complexonat Mg th s chuyen mau se ro. Xet pK lan lt cua cac phc
khac nhau, theo th t o ben:

Ca2+ + NET

(M+I) pK = 5

Mg2+ + NET

(M+I) pK = 7

Complexon + Mg2+

(Z+M) pK = 8

Complexon + Ca2+

(Z+M) pK = 10

Trong hon hp au, phc complexonat Mg b phan huy, phong thch Mg2+ cung luc tao nen phc
complexonat Ca. Moi Ca2+ c thay bang 1 Mg2+.

Mg2+ c phong thch se ay Ca2+ cua phc [Ca2+ + NET] cho mau ben vng hn cua phc [Mg2+
+ NET].

o ben tang dan

63

Tiep tuc nho EDTA xuong nh trong phng phap trc tiep.

Nh vay oi vi hai tac nhan tao phc Y1 va Y2, neu pKY2 > pKY1 th Y2 se ay Y1 khoi phc cua no.
6.3. Chuan o tha tr
-

Ap dung: dung cho nhng cation tao hydroxyd khong tan pH thc hien. o la trng hp cua
Pb2+, Hg2+, Mg2+ va tong quat la tat ca cac muoi khong tan trong moi trng kiem.

Phng phap nay thng dung trong cac trng hp:

Khong chon c ch th kim loai thch hp cho ion can xac nh, chang han khong the chuan
o trc tiep Co2+, Al3+ vi ch th NET c v ch th nay tao vi Co2+, Al3+ cac phc ben vng
en noi khong b EDTA pha v.

Ion can xac nh nam trong tua (BaSO4, PbSO4..) lam phan ng vi EDTA xay ra cham.

Tien hanh: cho mot the tch chnh xac va qua tha dung dch chuan o trilon B cung vi ch th
mau thch hp tac dung vi mot the tch chnh xac dung dch muoi kim loai can nh lng, xac
nh lng trilon B tha bang dung dch chuan o cua muoi kim loai khac. T o tnh c the tch
dung dch trilon B a phan ng ban au.

V du: nh lng bang cach cho EDTA d chnh xac vao dung dch cha ion can xac nh, khi o co
phan ng:
Mn+ + HY3-

MY(n-4) + H+

Sau khi phan ng xong, nh lng EDTA d bang dung dch Mg2+ hay Zn2+ a biet nong o. T o
tnh ra lng Mn+.
7.

Mot so ng dung cua phng phap complexon

7.1. Xac nh o cng cua nc

o cng toan phan cua nc la tong muoi Ca2+ va Mg2+ tan trong nc. Co the xac nh o cng toan
phan bang complexon III vi ch th en eriocrom T.
Lay mau nc can nh lng, cho them ch th en eriocrom T vao, ch th se tao phc mau o vang
vi mot phan Mg2+ trong mau. Khi nho EDTA vao, EDTA se phan ng vi Ca2+ t do, sau o vi Mg2+
t do (v phc CaY2- ben hn phc MgY2- ), en lan can iem tng ng EDTA se pha phc cua ch
th vi Mg2+, giai phong ra ch th t do co mau xanh.
7.2. nh lng Fe3+
Trong moi trng acid (pH 2 3), EDTA tac dung vi Fe3+ mot phc chat mau vang nhat FeY-. Neu
dung ch th la acid salicylic hay acid sulfosalicylic pH o no tac dung vi Fe 3+ tao thanh phc co
mau hong. Tai iem tng ng mau hong bien mat va dung dch co mau vang nhat.
7.3. nh lng Ba2+

64

Cho Ba2+ can nh lng tac dung vi mot lng d chnh xac EDTA. nh lng EDTA d bang dung
dch Mg2+.

65