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GTHoa Phan Tich
GTHoa Phan Tich
Gio trnh
HO PHN TCH
Nm 2007
http://hoahocsp.tk
Li ni u
Gio trnh Ho phn tch ny c bin son trn c s cng mn hc chnh
thc dng cho khi ngnh Nng- Lm- Ng nghip c Trng i hc Nng
nghip I duyt (Quyt nh Q 25/2004/Q-H1 ngy 14. 1. 2004).
Gio trnh nhm cung cp cho sinh vin nhng kin thc c bn v Ho phn tch
v dnh cho sinh vin khi Nng Lm Ng nghip.
tip thu c nhng ni dung trnh by trong gio trnh, yu cu sinh vin phi
c kin thc v ton hc cao cp, ton xc sut thng k, vt l hc, ho hc i cng,
ho hc v c v ho hc hu c.
D rt c gng cho gio trnh c nhiu thng tin, d c v d tip thu, song,
khng th trnh khi nhng khim khuyt, chng ti rt mong nhn c nhng kin
ng gp ca bn c v ng nghip khi ti bn gio trnh c hon thin hn.
H Ni, 2006
Cc tc gi
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Bng k hiu
K hiu
A
C
D
E
E%
e
e%
I
Ind
K
K
L
l
l
M
M
M
N
p
ppb
ppm
Q
q
T
T%
TKHH
TKPT
TK
w
Ting Vit
hp th quang
nng
mt quang
ng lng gam
th in cc, hiu in th
phn trm chit
electron
sai s phn trm
cng nh sng
ch th
hng s cn bng
hng s cn bng biu kin, hng s cn bng
thc nghim
phi t, ligand
chiu di
lt
bc sng nh sng
nng mol/lt (nng phn t gam)
kim loi M
khi lng mol phn t (phn t gam), khi
lng mol ion (iongam),
nng ng lng gam
-lg
mt phn t
mt phn triu
h s phn b
t s phn b
tch s tan
truyn quang
tinh khit ho hc
tinh khit phn tch
tinh khit
khi lng
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Mc lc
Trang
Li ni u
Bng k hiu
Chng I: Cc khi nim c bn ca Ho phn tch
1. Ho phn tch v vai tr ca n
2. Phn loi phng php phn tch
2.1. Phn loi theo bn cht ca phng php phn tch
2.2. Phn loi theo khi lng v lng cha ca cht phn tch trong mu
2.3. Chn la phng php phn tch
3. Cc bc c bn trong Ho phn tch
4. Ly mu v x l mu phn tch
4.1. Ly mu
4.2. Lp h s mu
4.3. Khong ho mu
5. Ho phn tch nh tnh
5.1. Phn tch nh tnh cc hp cht v c bng phng php ho hc
5.2. Phn tch nh tnh cc hp cht hu c bng phng php ho hc
5.3. Phn tch nh tnh cc hp cht bng phng php cng c
6. Ho phn tch nh lng
7. Dng c, thit b o v ho cht
7.1. Dng c thu tinh
7.2. Thit b o
7.3. Ho cht sch, nc ct
8. Mt s loi nng dung dch thng dng trong Ho phn tch
Cu hi n tp, bi tp
Chng II: Phn tch khi lng
1. Cc khi nim c bn trong phn tch khi lng
1.1. Phng php tch
1.2. Phng php chng ct hoc t chy
1.3. Phng php nhit phn
1.4. Phng php kt ta (Phng php phn tch khi lng kt ta)
2. Phng php phn tch khi lng kt ta
2.1. Yu cu ca dng kt ta
2.2. Yu cu ca dng cn
2.3. S gy bn kt ta
2.3. Mt s k thut trong phng php phn tch khi lng kt ta
2.4. Mt s ng dng c th
2.5. u nhc im ca phng php phn tch khi lng kt ta
Cu hi n tp, bi tp
Chng III: Phn tch th tch
1. Nhng khi nim c bn v phn tch th tch
2. Yu cu ca phn ng chun
3. Phn loi phng php chun
3.1. Phn loi phng php chun theo loi phn ng
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Trang
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3.2. Phn loi phng php theo cch tin hnh chun
4. Cch pha dung dch tiu chun
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5. Cch tnh kt qu phn tch
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6. ng chun
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6.1. nh ngha
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6.2. ng chun trung ho
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6.3. ng chun oxi ho kh
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6.4. ng chun kt ta
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6.5. ng chun to phc
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6.6. Nhn xt chung v ng chun . ng dng ca ng chun
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7. Ch th
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7.1. Phn loi ch th
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7.2. Khong i mu ca ch th
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7.3. Nguyn tc chn ch th
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8. Cc php chun thng dng
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8.1. Chun trung ho
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8.2. Chun oxi ho kh
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8.3. Chun kt ta
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8.4. Chun complexon
85
9. u nhc im ca phng php phn tch th tch
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Cu hi n tp, bi tp
89
Chng IV: Phn tch cng c
91
1. Phn loi phng php
91
1.1. Nhm cc phng php quang hc
91
1.2. Nhm cc phng php in t
92
1.3. Nhm cc phng php tch
92
1.4. Nhm cc phng php nhit
92
2. Phng php quang ph hp th phn t vng t ngoi v nh sng nhn thy
92
2.1. C s l thuyt ca phng php so mu
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2.2. Yu cu i vi phc cht mu
95
2.3. Ph hp th v chn bc sng o
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2.4. o so mu
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3. Phng php o in th
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3.1. t vn
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3.2. in cc
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3.3. o in th
103
3.4. ng dng phng php o in th trong phn tch
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4. Phng php chit
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4.1. Khi nim
105
4.2. Chit cht rn bng cht lng
105
4.3. Chit cht lng bng cht lng
105
Cu hi n tp, bi tp
106
Chng V: Sai s trong Ho phn tch
108
1. Sai s
108
1.1. Phn loi sai s
108
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CHNG I
CC KHI NIM C BN CA HO PHN TCH
1. HO PHN TCH V VAI TR CA N
Ho phn tch l mn khoa hc ng dng s dng cc kin thc ca Ho v c,
Ho hu c, Ho l, Ho sinh, Vt l... nhm tr li cu hi vt cht nghin cu c cu
to t cc thnh phn no v hm lng ca tng thnh phn l bao nhiu.
Ho phn tch c s dng t rt lu trong Ho hc ni chung. Song, phi t
th k 17, vi nhng c s bt u t cc cng trnh ca R. Boyl v sau l ca M. V.
Lomonosov, A. L. Lavoisier v R. Fresen, Ha phn tch mi tr thnh mt ngnh khoa
hc ring bit. Trong nhng th k tip theo, cc nh khoa hc khng ngng pht trin
ngnh hc ny theo hng phn tch nhanh hn, chnh xc hn, t ng ho hn v gi
thnh r hn. Chnh v th, ngoi cc phng php phn tch ho hc thng thng, cc
phng php phn tch bng cng c pht trin mnh m v tr thnh b phn khng
th thiu ca phn tch hin i nh cc phng php: quang ph, sc k, cc ph
Trong thc t, Ho phn tch thm nhp vo nhiu lnh vc khoa hc v l cng
c nghin cu ca chng; ngoi ra, n cng chim mt v tr quan trng trong sn xut.
Ho phn tch thng c chia thnh hai phn Ho phn tch nh tnh v Ho
phn tch nh lng. Nhim v ca Ho phn tch nh tnh l xc nh vt cht nghin
cu c cu to t cc thnh phn no, cn ca Ho phn tch nh lng l xc nh
hm lng ca cc thnh phn cu to nn vt cht nghin cu.
2. PHN LOI PHNG PHP PHN TCH
C nhiu phng php phn tch, tin cho s chn la, trong Ho phn tch,
thng chia cc phng php phn tch theo hai cch: da trn bn cht ca phng php
phn tch v hm lng cht cn phn tch cha trong mu.
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S xut hin kt ta trng cho bit trong mu c ion clorua, cn khi lng kt
ta cho bit hm lng ca ion clorua trong mu. Phn ng trn c gi l phn ng
phn tch, dung dch AgNO3 c gi l dung dch thuc th.
Phng php phn tch ho hc c u im: c chnh xc cao, dng c phn
tch n gin. Tuy nhin, trong phn tch dng mt quan st cc hin tng xy ra,
nn phng php c nhy khng cao, ch c th phn tch c cc cht khi hm
lng ca n trong mu ln hn 10-2 % (bng B. I.1), ngoi ra khng th t ng ho
c qu trnh phn tch. Trong nhm cc phng php ho hc c cc phng php:
phng php phn tch khi lng (chng II) v phng php phn tch th tch
(chng III).
b. Phng php phn tch bng cng c
Cn c gi ngn gn l phn tch cng c (chng IV). Gm cc phng php
phn tch ho l v phn tch vt l.
*Phng php ho l
y, dng cc cng c o cc i lng vt l c lin quan n phn ng ho
hc xy ra. V d: dng in cc bc o in th dung dch ca phn ng gia ion
Cl- v AgNO3 ni trn, gip theo di c din bin ca phn ng Phng php ho l
c nhy kh cao, cho php xc nh c cc mu vi hm lng ca cht phn tch
nh ti 10-6 % (bng B.1.1). V d: phng php so mu, phng php cc ph
* Phng php vt l
y, s dng cc cng c o cc i lng vt l c lin quan n thnh phn
cn phn tch. Phng php c nhy rt cao, cho php phn tch cc thnh phn rt
nh trong mu, ch chim khong 10-8 - 10-9% (bng B.1.1).
Bng B. 1.1: Gii hn xc nh ca mt s phng php phn tch
Phng php
12
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2.2. Phn loi theo khi lng v lng cha ca cht phn tch trong
mu
Da vo khi lng mu ly phn tch v lng cha ca cht phn tch trong
mu, xy dng cc phng php ghi trong bng B.2.1.
Bng B.2.1: Phn loi cc phng php phn tch theo lng mu phn tch
Tn phng php
Lng
mu
(g)
Mi
Gram
Xentigram
Miligram
Microgram
C
Thng lng
Bn vi lung
Vi lng
Siu vi lng
10-1
10-2 - 10-1
10-4 - 10-2
10-4
Thnh phn
vi lng
0,01%
10-5
10-5
10-5
10-5
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4.1. Ly mu
Trong phn tch, rt t khi c th phn tch ton b vt th cn nghin cu. V d:
khi nghin cu tnh cht nng ho ca mt tha rung, thnh phn dinh dng ca mt
kho thc n gia sc khng th mang phn tch ton b t ca tha rung hoc c kho
thc n Do vy, kt qu phn tch c ngha thc tin cn tin hnh trn mu i
din (mu trung bnh). Mu i din l mu cha thnh phn v t l hm lng ging
nh vt th cn phn tch. Tuy nhin, kh c th ly c mu i din p ng yu
cu trn m ch c th ly c mu c tnh cht gn ng vi yu cu m thi.
Mu phn tch rt a dng v nhiu mt nh v trng thi tn ti, v ng nht,
cng nh khi lng ca mu. V th, ly c mu i din cn tun th mt s
nguyn tc ly mu cho tng loi i tng.
* Vt th phn tch c khi lng nh:
Vi vt th c khi lng nh, c th phn tch ton b, th mu ly l ton b vt
th. V d: Vt mu, mu bnh phm nh nc di ca vt nui
* Vt th ng tnh:
L cc vt th m mi im thnh phn v hm lng ca cht cn phn tch l
nh nhau. V d: vt th cn phn tch l ho cht sch, mu vt l dung dch Trong
trng hp ny, c th ly mu bt c im no ca vt th. V d: khi phn tch hm
lng axit HCl trong dung dch, c th dng pipet ht dung dch bt c v tr no trong
bnh cha.
* Vt th khng ng tnh:
Khi vt th cn phn tch c khi lng ln v khng ng tnh, th vic ly mu
da trn nguyn tc ly mu nhiu im ri trn li vi nhau c mu i din.
Tuy nhin, vic ly nhiu hay t im ph thuc vo trng thi ca vt cn phn tch.
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4.2. Lp h s mu
Sau khi ly xong, mu phn tch c chia t nht thnh hai phn: mt phn gi i
phn tch, cc phn cn li c lu gi phng khi mu b hng, b tht lc trn ng
vn chuyn hoc khi cn phn tch thm ch tiu hoc khi cn phn tch kim chng. Trn
c hai phn ca mu cn lm h s y v nh nhau. Trn h s phi ghi r: tn mu,
ngy ly mu, ngi ly mu, a im ly mu, cch ly mu, cch s ch mu (nu c)
v mc ch ca vic ly mu ( phn tch ch tiu no). Vic lp h s cn chnh xc
khng b nhm ln mu cng nh nhm ln kt qu phn tch. Cng vic ny cng quan
trng i vi cc vt th cn phn tch theo thi gian. V d: khi nh gi cht lng ca
mt ngun nc, phi phn tch nc theo ch thu vn v theo di trong nhiu nm,
do vic c nh thi im, v tr v cch thc ly mu l rt quan trng trong vic so
snh kt qu sau ny.
4.3. Khong ho mu
Khi phn tch, nht l vi cc mu rn, thng chuyn mu phn tch thnh dung
dch. Cng vic ny c gi l khong ho mu hay cn gi l cng ph mu.
Trong khong ho mu thng dng cc ho cht c tnh cht ho hc i khng
vi tnh cht ho hc ca mu cn khong ho. Mu cha thnh phn ch yu l cc cht
c tnh baz th dng cc axit mnh cng ph, v d, khong ho mu t dng axit
H2SO4 c phi hp vi cc axit HClO4 v HF; mu c tnh kh nh mu thc vt dng
cc cht c tnh oxi ho hay hn hp cc cht oxi ho nh H2SO4 + K2Cr2O7, H2SO4 +
HNO3 hay NaOH + NaNO3
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+ Tm ion NH4+:
Cho vo dung dch phn tch dung dch NaOH d, s xy ra phn ng:
NH4+ + OH- = NH4OH
Khi un nng dung dch NH4OH b phn hu:
to
NH4OH = NH3 + H2O
Amoniac bay ln gp giy qu tm t s lm cho mu ca giy qu chuyn
thnh mu xanh.
C th tm ion NH4+ bng thuc th Nestler (K2HgI4). Hi NH3 bay ln tc dng
vi thuc th cho kt ta nu:
NH3 + 2K2HgI4 + 3KOH = [Hg2ONH2]I + 7I- + 2H2O
nu
+ Tm ion K+:
Chnh pH dung dch phn tch v gi tr 5 7. Cho vo dung dch thuc th natri
cobantinitrit Na3[Co(NO2)6], nu c ion K+ trong dung dch xut hin kt ta mu vng:
2K+ + Na3[Co(NO2)6] = NaK2[Co(NO2)6] + 2Na+
vng
+
Khi c mt ion NH4 trong dung dch phn tch, phi ui hon ton n i trc
khi phn tch ion K+ bng cch cho vo dung dch phn tch NaOH d v un nng.
+ Tm ion Na+:
Trung ho dung dch phn tch v mi trng trung tnh ri cho vo dung dch vi
git thuc th km uranylaxetat (Zn(UO2)3(CH3COO)8), nu c ion Na+ s hnh thnh kt
ta mu vng:
Na+ + Zn(UO2)3(CH3COO)8 + CH3COO- = Na Zn(UO2)3(CH3COO)9
vng
C th nhn bit ion K+, Na+ bng cch quan st mu ngn la ca chng. Nhng
mt dy Pt sch vo dung dch phn tch ri t n trn ngn la khng mu, nu c ion
K+ s thy ngn la pht mu tm, cn nu c ion Na+ s thy ngn la mu vng. Nu
cng c c hai ion Na+ v K+, th mu vng s che lp mu tm v nn nhn thy mu
tm cn nhn n qua knh mu chm.
+ Tm ion Mg2+:
Cho vo dung dch phn tch cc dung dch (NH4)2CO3 v (NH4)2S kt ta tt
c cc ion kim loi tr cc ion kim loi kim, NH4+ v Mg2+. Tm ion Mg2+ trong dung
dch lc bng thuc th Na2HPO4 trong mi trng c NH4Cl v NH4OH:
Mg2+ + Na2HPO4 + NH4OH = MgNH4PO4 + 2Na+ + H2O
trng
3Nu mu cha ion PO4 th phi tch b n bng cch cho vo dung dch phn
tch mui Al(NO3)3 trc khi lm kt ta mu bng (NH4)2CO3 v (NH4)2S.
+ Tm ion Ca2+:
Cho vo dung dch phn tch dung dch K2SO4 6% kt ta cc ion Ba2+, Sr2+
(ion Ca2+ trong iu kin ny hu nh cha b kt ta). Lc tch kt ta, iu chnh pH
dung dch v pH = 4 bng dung dch m axetat v cho vo mt th tch tng ng
ca dinatri etylendiamintetraaxetat (Na2EDTA) 10% che cc ion gy nhiu. Sau ,
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cho vo dung dch Al(CH3COO)3 d che Na2EDTA v tm ion Ca2+ trong dung dch
bng (NH4)2C2O4:
Ca2+ + (NH4)2C2O4 = CaC2O4 + 2NH4+
trng
+ Tm ion Ba2+:
Cho vo dung dch trung tnh cn phn tch tun t cc dung dch Na2EDTA 10%
(ly d, che cc ion kim loi nng) v Mg(CH3COO)2 (ly d, che Na2EDTA d).
Sau , cho vo dung dch thuc th K2Cr2O7 v dung dch CH3COONa, nu c ion Ba2+
s xut hin kt ta mu vng BaCrO4:
K2Cr2O7 + 2OH- = 2CrO42- + 2K+ + H2O
Ba2+ + K2CrO4 = BaCrO4 + 2K+
vng
+ Tm ion Mn2+:
Cho vo dung dch phn tch dung dch K2S2O8, axit HNO3 v xc tc AgNO3.
un nng dung dch, nu dung dch chuyn sang mu tm, th trong mu c ion Mn2+:
2Mn2+ + 5S2O82- + 8H2O = 2MnO4- + 10SO42- + 16H+
tm
S gy nhiu ca ion Cl- c kh bng cch cho thm vo dung dch phn tch
dung dch AgNO3. S gy nhiu ca ion Fe3+ nng cao (mu vng ca ion Fe3+)
c kh bng s to phc cht khng mu [Fe(PO4)2 ]3- vi vic cho H3PO4 vo mu
phn tch.
+ Tm ion Fe3+:
Cho vo dung dch phn tch dung dch NaOH v NH4OH d. Tch kt ta hnh
thnh v ho tan n bng dung dch HCl, ri tm ion Fe3+ bng cc phn ng vi thuc
th KCNS hay K4[Fe(CN)6]:
Fe3+ + 6KCNS
= [Fe(CNS)6]3- + 6K+
mu
3+
4Fe + 3K4[Fe(CN)6] = Fe4[Fe(CN)6]3 + 12K+
xanh Berlin
2+
+ Tm ion Cu :
Cho vo dung dch phn tch NH4OH c d v un n si. Dung dch thu c
c trung ho bng axit CH3COOH n khi mt mu hng ca phenoltalein, ri cho vo
thuc th K4[Fe(CN)6]. Nu xut hin kt ta mu nu chng t dung dch cha
ion Cu2+ (vi hm lng Cu2+ nh ch nhn thy dung dch mu hng):
2Cu2+ + K4[Fe(CN)6] = Cu2[Fe(CN)6] + 4K+
nu
+ Tm ion Hg2+:
Cho vo dung dch phn tch axit HCl kt ta cc ion Hg22+, Ag+ v Pb2+. Dng
CH3COONa chnh pH dung dch v pH = 5 v cho vo dung dch SnCl2. Nu c ion
Hg2+, s xut hin kt ta en:
Hg2+ + Sn2+
= Hg + Sn4+
en
+ Tm ion SO42-:
Axit ho dung dch phn tch bng HNO3 long (nu c kt ta th lc b), thm
t t vo vi git Ba(NO3)2. Dung dch cha ion SO42- s cho kt ta trng:
Ba2+ + SO42- = BaSO4
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trng
-
+ Tm ion Cl :
Axit ha dung dch phn tch bng axit HNO3 (nu xut hin kt ta th lc b),
cho tip vi git dung dch AgNO3. Nu c kt ta hnh thnh chng t mu c th cha
cc ion Cl-, Br-, I- (X-):
AgNO3 + X- = AgX + NO3Li tm ly kt ta v cho vo hn hp gm 4 phn (NH4)2CO3 bo ho + 1
phn NH4OH (6M), th AgCl s tan ra:
AgCl + 2NH4OH = [Ag(NH3)2]+ + 2H2O + ClTch dung dch ra khi kt ta v cho vo HNO3, nu xut hin kt ta chng
t c ion Ag+ :
[Ag(NH3)2]Cl + 2HNO3 = AgCl + 2NH4NO3
trng
gin tip chng minh s tn ti ca ion Cl-.
+ Tm ion NO3-:
Cho vo dung dch phn tch dung dch FeSO4 d ri thm t t tng git H2SO4
c theo thnh ng nghim. Nu c ion NO3- th b mt tip xc gia hai lp dung dch
v H2SO4 c s c mt vnh mu nu:
2HNO3 + 8FeSO4 + 3H2SO4 = 3Fe2(SO4)3 + 2FeNOSO4 + 4H2O
nu
3+ Tm ion PO4 :
Cho vo dung dch phn tch axit HNO3 d lm mi trng, ri thm vo
thuc th amoni molypdat, nu c ion PO43- s xut hin kt ta mu vng (khi lng ion
PO43- t, ch nhn c dung dch mu vng):
PO43- + 3NH4+ + 12MoO42- + 24H+ = (NH4)3[P(Mo3O10)4] + 12H2O
vng
2+ Tm ion CO3 :
Cho vo dung dch phn tch mui Hg(II) v KMnO4 loi b cc gc mui ca
cc axit d bay hi khc. Sau , axit ho dung dch bng axit H2SO4 (1: 4) v dn kh
CO2 thot ra vo dung dch Ba(OH)2 , nu c CO2 s to thnh kt ta mu trng BaCO3 :
CO32- + H2SO4 = CO2 + H2O + SO42CO2 + Ba(OH)2
= BaCO3 + H2O
trng
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= PbS + 2NO3en
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- Loi hnh bu (hnh H.3b.1), loi ny ch cho ly chnh xc th tch dung dch
theo nh dung tch ghi trn pipet khi ly trn c bu.
Trong phn tch th tch thng dng pipet bu ly trn mt th tch dung dch
ch khng dng pipet thng v pipet bu c tit din phn vch c nh hn nn sai s
c nh hn.
Pipet cn c thnh 3 loi A, B, C theo chnh xc ca vch chia , trong
k hiu A c chnh xc cao nht, k hiu C c chnh xc thp nht. Trong Ho phn
tch, ch dng pipet c k hiu A.
Khi s dng pipet cn lu :
- V sai s khi ly trn th tch ca cc loi pipet l nh nhau nn ly pipet tng
ng ht lng dung dch cn thit. V d: cn ly 3 - 5ml dung dch dng pipet 5ml,
ly 6 - 10ml dung dch dng pipet 10ml. Trnh ht nhiu ln, sai s ly dung dch l
nh nht.
- Bao gi cng ly dung dch t vch xut pht.
* ng ong v cc chia
Sai s ca cc dng c ny l rt ln vt qu sai s phn tch cho php nn
khng dng chng ly th tch chnh xc dung dch, ch dng ly th tch gn ng.
7.2. Thit b o
a. Cn
Trong Ho phn tch, s dng cc loi cn c chnh xc khc nhau, v d: cn k thut
vi sai s cn 0,01g, 0,001g, cn phn tch vi sai s cn 0,0001g (dng cho phn
tch thng thng), 0,00001g (dng cho phn tch bn vi lng), 0,000001g (dng
cho phn tch vi lng) v vi cc gii hn khi lng c cn khc nhau. Tu theo
mc ch m s dng cn thch hp. Nguyn tc chung l:
- c k hng dn s dng cn v gii hn ti a ca khi lng c cn,
m bo sai s cn v an ton ca cn.
- Khi cn cn xc nh lng ti thiu cn cn m bo sai s cn khng ln
hn sai s phn tch cho php.
V d: vi sai s phn tch 0,1%, cn phi cn bao nhiu mg mu trn cn phn
tch 0,0001g, sai s cn khng vt qu sai s cho php?
Gii: Khi cn phi cn hai ln: cn b v cn b cng vi khi lng phi cn a,
nn mc hai ln sai s cn. Theo nguyn tc tnh sai s (mc 2 chng V), sai s tng
i e% = [(2. sai s cn)/a ].100, suy ra: a = 2.0,1. 100: 0,1 = 200mg. Vy phi cn t
nht 200mg mu.
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Hnh H.1.1
Bnh nh mc
Hnh H.2.1
Buret
Hnh H.3a.1
Pipet thng
Hnh H.3b.1
Pipet bu
Hnh H.4.1
ng ong
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Cu hi n tp
1. Nhim v ca Ho phn tch? Ho phn tch nh tnh v nh lng l g? Quan h
ca hai lnh vc ny.
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Bi tp
1. Ly chnh xc 100ml dung dch 0,2M H2SO4 cho vo bnh nh mc 250ml v in
nc ct ti vch. Hy tnh nng ng lng gam ca dung dch mi nhn c v
s gam H2SO4 c trong 100ml dung dch ny! (p s: 0,16N; 0,7846g).
2. Dung dch NH3 m c c nng 26% (d = 0,904). Dung dch ny c nng
mol/lt l bao nhiu? Nu ly 100 ml dung dch ny pha thnh dung dch NH3 1N th
th tch dung dch sau khi pha long l bao nhiu ml? (p s:13,8M; 1380ml).
3. Trn 500ml HCl 0,1N vi 250ml HCl 0,2N. Dung dch thu c c nng ng
lng gam l bao nhiu? (p s: 0,133N).
4. Trn 500ml HCl c pH = 1 vi 250ml HCl c pH = 2. Dung dch thu c c nng
mol/lt l bao nhiu? (p s: 0,07M).
5. Cn cn bao nhiu mg CuSO4.5H2O pha 100 ml dung dch 1000ppm Cu? (p s:
390,6 mg).
6. Ha tan 100mg CaCO3 bng axit HCl thnh 100ml dung dch. Nng ppm ca ion
Ca2+ l bao nhiu? (p s: 400ppm).
7. Cn ly bao nhiu ml dung dch Cd2+ 5ppm pha thnh 100ml dung dch Cd2+
500ppb? (p s: 10ml).
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Chng II
PHN TCH KHI LNG
1. CC KHI NIM C BN TRONG PHN TCH KHI LNG
y l phng php c lch s lu i nht trong cc phng php phn tch nh
lng. Phng php ny da trn khi lng cn chnh xc ca sn phm sch, c cng
thc ho hc xc nh cha nguyn t, ion, hoc thnh phn cn phn tch c
tch ra sau khi chuyn ho chng bng cc phn ng thch hp, t tnh ra lng
cht cn phn tch c trong mu.
V d: khi phn tch ion Fe3+ trong dung dch, lm kt ta n di dng Fe(OH)3
bng dung dch NH4OH. Lc ly kt ta v ra sch. Nung kt ta nhit 1000oC n
khi lng khng i, nhm chuyn kt ta thnh Fe2O3. ngui mu nung n nhit
phng, ri cn khi lng ca n bng cn phn tch. T khi lng cn tnh ra khi
lng ion Fe3+.
Da trn cch tin hnh khc nhau, c th chia cc phng php phn tch khi
lng thnh 4 nhm phng php chnh sau:
+ Phng php tch
+ Phng php chng ct hoc t chy
+ Phng php nhit phn
+ Phng php kt ta
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1.4. Phng php kt ta (Phng php phn tch khi lng kt ta)
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Sau khi lc, ra sch, kt ta c nung nhit 1000oC chuyn sang dng Al2O3:
1000oC
2Al(OH)3 =
Al2O3 + 3H2O
c thnh phn ho hc xc nh v cn. T lng cn Al2O3 tnh ra hm lng ion Al3+
trong mu.
Trong 4 phng php k trn, phng php kt ta thng c dng nhiu
nh lng cc cht nht l cc hp cht v c, v qu trnh chuyn thnh phn cn xc
nh vo mt hp cht kh tan d dng hn nhiu so vi qu trnh tch n di dng t
do, thm na, cng v cc phn ng to kt ta c th s dng trong phn tch c nhiu
hn nhiu so vi cc loi phn ng khc. Ngoi ra, phng php kt ta cn l mt trong
nhng phng php tch cht cn phn tch hay cht gy nhiu rt hiu qu.
Phng php kt ta thng c s dng trong phn tch nng nghip, do vy,
di y s tp trung trnh by v phng php ny.
2. PHNG PHP PHN TCH KHI LNG KT TA
Tin trnh ca phng php kt ta bao gm ln lt cc cng on sau:
Cn mu Dung dch Kt ta Lc, ra Sy hoc nung Cn Tnh ton.
Tt c cc cng on u c nh hng trc tip n chnh xc ca kt qu
phn tch. Song, cng on lm kt ta c nh hng ln nht n kt qu cng nh n
tc phn tch, v chnh xc ca php phn tch ph thuc rt nhiu vo vic chn
cht kt ta, vo lng kt ta, vo iu kin thc hin kt ta S dng phng php
kt ta ph hp s trnh c hoc lm gim cc nh hng xu nh: s tan ca kt ta,
s bn kt ta, cng nh gip cho qu trnh lc ra d dng v vic chuyn dng kt
ta sang dng cn c thun li.
2.1. Yu cu ca dng kt ta
Dng kt ta l hp cht t tan thu c khi cho thuc th thch hp tc dng vi
thnh phn cn xc nh trong dung dch.
V d: nh lng ion SO42-, c th dng thuc th Ba(NO3)2,v phn ng xy
ra nh sau:
Ba2+ + SO42- = BaSO4
Sn phm kt ta BaSO4 thu c, c gi l dng kt ta.
Trong ho hc, mt nguyn t hoc ion c th c chuyn vo nhiu dng kt
ta khc nhau. V d: ion SO42- c chuyn vo cc dng kt ta BaSO4, PbSO4, hoc
SrSO4; ion Fe3+ c th chuyn sang cc dng kt ta Fe(OH)3, FePO4, Fe(cuferon)3,
FeS Nhng, ch c dng kt ta p ng cc yu cu di y mi c dng trong
phn tch kt ta:
a. Dng kt ta phi t tan
Khi phn ng to kt ta MaXb t cc ion Mm+ v Xn- hon thnh, kt ta v
cc ion to ra n nm trong trng thi cn bng theo II- a:
MaXb aMm+ + bXn(II- a)
Do c trng thi cn bng m trong dung dch vn tn ti mt lng cht cn theo di
dng ho tan gy ra mt kt ta, hin tng ny c gi l s khng hon ton ca phn
ng. Lng kt ta b mt do cht cn phn tch khng i vo kt ta c tnh theo biu
thc II- 1:
w = M.C.V
(II- 1)
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2.2. Yu cu ca dng cn
Dng cn l dng kt ta sau khi em sy hoc nung n khi lng khng
i.
Tu theo bn cht ca kt ta, dng kt ta v dng cn c th c cng hoc
khng cng cng thc ho hc.
V d: kt ta BaSO4 cho dng kt ta v dng cn nh nhau, u l BaSO4. Vic
sy hoc nung, trong trng hp ny, ch lm mt i nc hp ph. Nhng, i vi dng
kt ta Fe(OH)3, khi nung s thu c dng cn l Fe2O3:
10000C
2Fe(OH)3 =
Fe2O3 + 3H2O
c th t khi lng dng cn tnh ton c hm lng ca thnh phn cn
phn tch, th dng cn cn phi m bo cc yu cu sau:
a. Dng cn phi c cng thc ho hc xc nh
c th tnh c kt qu phn tch bt buc dng cn phi c cng thc ho
hc xc nh, k c phn nc kt tinh.
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2.3. S gy bn kt ta
Kt ta thu c trong mi trng kt ta s tng tc vi cc ion c trong
mi trng v to nn s bn kt ta. C 2 nhm nguyn nhn chnh gy bn kt ta
l s cng kt v s kt ta theo.
a. S cng kt
Kt ta c hnh thnh trong qu trnh phn tch thng ko vo cu trc ca
mnh cc tp cht (cc ion l). Khi cc tp cht cng kt ta ng thi vi kt ta chnh
mc d nng ca chng cha t ti trng thi bo ho, th hin tng ny c gi l
s cng kt mt yu t gy nn sai s phn tch.
Cc nguyn nhn gy nn s cng kt l: s hp ph b mt, s kt vn, s to
tinh th hn hp.
*S cng kt do hp ph:
Xy ra khi kt ta chnh dng keo trong s d tha thuc th. Cc ht keo hp
ph ion hot ng ca thuc th s dn n s hp ph cc ion tri du. V d: kt ta
BaSO4 trong iu kin d ion SO42- s hp ph cc ion dng. Trong trng hp ny,
thc t cho thy ion gy nhiu no to mui vi thuc th c tan nh hn, s b hp
ph nhiu hn; vi kt ta BaSO4 ni trn, th s hp ph i vi cc cation nh sau: Na+
< K+ < Ca2+ < Pb2+.
Nhm khc phc s hp ph, nn tin hnh kt ta vi dung dch long thuc th
long, kt ta nng v khng nn kt ta qu lu trong dung dch.
*S cng kt do hin tng kt vn:
Gy bn c hc kt ta, bi khi tin hnh kt ta mt phn cht gy nhiu b
kt ta bao bc. Hin tng ny thng gp khi kt ta vi dung dch c, kt ta nhanh
v khuy khng tt. loi tr s cng kt ny, cn tin hnh kt ta vi dung dch
long nng, kt ta chm v khuy tt hoc lm kt ta ng tnh. Nu khng thnh cng,
th phi s dng bin php kt ta li.
*S cng kt do hin tng to tinh th hn hp:
Xy ra khi bn knh ion ca ion trong kt ta chnh v ion gy nhiu khng khc
nhau nhiu ( sai khc nh hn 10 15%). Lc ny cc ion gy nhiu c th thay th
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cho ion to kt ta chnh trong mng tinh th. V d: ion MnO4- c th thay th ion SO42-,
nn khi kt ta BaSO4 vi s c mt ca ion MnO4- s thu c tinh th kt ta c cha
ion MnO4-. S cng kt ny khng th loi b c bng cch ra hoc kt ta li m ch
c th loi b c bng cch che, kh cc ion gy nhiu i. Chng hn, v d trn, c
th loi nh hng ca ion MnO4- bng cch kh n v ion Mn2+ khi cho axit oxalic vo
dung dch phn tch trc khi lm kt ta.
Trong phn tch, s cng kt khng phi lc no cng gy hi m i khi li c
li. Khi phn tch hm lng nh cc cht, thng s dng s cng kt gom cc
cht cn phn tch. V d: khi xc nh ion Pb2+ t dung dch long, nng ca n nh
n mc m kt ta PbS, l kt ta t tan nht ca ion Pb2+, cng khng hnh thnh. Cho
vo dung dch phn tch ion Ca2+ v kt ta ion Ca2+ di dng CaCO3, trong iu kin
ny ion Pb2+ b cng kt theo. Sau , ho tan kt ta cacbonat vo axit axetic v phn
tch ion Pb2+ bng cc phng php thng thng. Mt v d khc, l s gom lng
nh cc ion kim loi ho tr 2 nh Cu2+, Cd2+, Mn2+, Zn2+ trn kt ta Fe(OH)3 hoc
Al(OH)3.. Bng s cng kt c th lm tng nng cc cht cn phn tch ln hng
ngn, hng vn ln.
b. S kt ta theo
Ngoi s cng kt, trong thc t cn gp hin tng kt ta theo lm cho kt ta
chnh b bn. Hin tng ny xy ra khi kt ta chnh kt ta xong v khng c tch
kp thi ra khi dung dch, th sau mt thi gian s hnh thnh trn kt ta chnh kt ta
ca cc cht bn mc d trong iu kin bnh thng n khng kt ta. V d: MgC2O4 l
cht tan, khng cng kt ta vi CaC2O4, nhng sau khi CaC2O4 kt ta ht v lu
trong dung dch (khong 2 gi), th MgC2O4 b kt ta theo. khc phc s kt ta theo
cn tch kp thi kt ta chnh trc khi kt ta theo xut hin.
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to
CO(NH2) 2 + 3H2O = 2NH4OH + CO2
v phn ng to kt ta Fe(OH)3 xy ra ti mi im cng mt lc. S kt ta ny gi l
kt ta ng tnh.
+ Dng mt lng thuc th d so vi l thuyt (thng dng d gp i), v
tan ca kt ta s gim i nhiu, khi trong dung dch c ion chung.
Tuy nhin, cn lu , mt s kt ta c th tan trong thuc th d. V d: cc kt
ta AgCl, HgI2 tan c trong thuc th d (Cl- , I-) do s to thnh cc phc cht tan
[AgCl2]- , [HgI4]2-, cc trng hp ny, phi tnh ton lng thuc th sao cho va
kt ta hon ton v trnh c s ho tan ca kt ta do s to phc cht tan.
b. Lm kt ta
Lm kt ta trong cc chu nhit. Khi lng kt ta cn nm trong khong
200mg, th tch khi kt thc lm kt ta khong 100 - 200ml. Tu theo bn cht ca kt
ta (dng tinh th, dng keo hay dng v nh hnh) m chn cch lm kt ta thch hp.
* Lm kt ta tinh th
S to thnh kt ta bao gm hai qa trnh: s pht sinh cc mm kt tinh l trung
tm ca s kt ta v cc mm tinh th ln dn ln.
+ S pht sinh cc mm kt tinh l trung tm ca s kt ta.
Cc mm kt tinh c th t hnh thnh trong qu trnh lm kt ta, cng c
trng hp to nn bng cc thao tc thch hp nh dng a thu tinh c vo thnh bnh
to mm tinh th (trng hp kt ta MgNH4PO4)
+ Cc mm tinh th ln dn ln.
tng cng qu trnh ny, thng yn kt ta trong vi gi hoc lu hn
(lm mui kt ta, kt ta). giai on ny, cc tinh th nh s tan ra, cn cc tinh th
ln s ln ln, v trong cng iu kin, dung dch s bo ho i vi tinh th ln nhng
c th cha bo ho i vi tinh th nh.
Nh vy, khi lm kt ta tinh th, c kt ta tinh th ht ln, phi hn ch qu
trnh to mm tinh th v phi c thi gian lm mui kt ta. hn ch s mm tinh th
cn lm kt ta chm bng cch kt ta vi dung dch long, thuc th long hoc lm
tng tan ca kt ta nh kt ta vi dung dch nng, thuc th nng hoc pH thch
hp Sau , s kt ta hon ton c m bo bng vic dng thuc th d hay bng
iu chnh pH hoc thnh phn dung mi
V d: kt ta ion Ca2+ di dng CaC2O4. u tin un nng dung dch phn tch
vi axit oxalic ( s mm tinh th c to thnh t do c t ion C2O42-), sau trung
ho mi trng bng NH4OH n pH 5 (tng lng ion C2O42-). yn kt ta khong
1 gi (lm mui), ri lc ly kt ta.
* Lm kt ta v nh hnh:
Ngc li vi vic lm kt ta tinh th, khi lm kt ta v nh hnh cn phi tin
hnh nhanh trong dung dch nng vi thuc th d v khuy tt, c thm cht in li
h thng keo nhanh b ng t v chng c s pepti ho. Nh vy, kt ta s dy c,
vng chc hn, b mt tip xc s b hn. Sau khi lm kt ta xong phi lc ngay, v
lu kt ta qunh li gy kh ra. Nu c th c, nn lm kt ta ng tnh.
T nhng phn tch trn c th thy nhng thao tc trong phn tch khng th tin
hnh mt cch tu m phi theo mt qui nh nghim ngt m bo cho vic phn
tch t kt qa chnh xc. Nng thuc th c, long, cho d nhiu hay t hoc lm
kt ta nhanh hay chm l nhng qui nh m mi ngi lm phn tch phi tun theo.
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c. Lc kt ta
lc kt ta thng dng 3 loi dng c lc: phu lc, cc lc bng gm v cc
lc bng thu tinh.
* Phu thu tinh:
c thi t thu tinh chu ho cht vi cc tiu chun: gc to bi hai ng
sinh bng 90o v chiu cao ca phu t 9 12cm. i vi phu lc phi dng giy lc
khng tn, tc loi giy khi t chy hon ton cho lng tro khng ng k (< 0,0001g,
sai s ca cn phn tch). Giy lc c chia lm 3 loi ty theo kch thc l ca giy:
- Loi l nh (giy lc bng xanh) dng lc gi cc kt ta c ht nh.
- Loi l trung bnh (giy lc bng vng, bng trng) dng lc gi c ht va.
- Loi l to (giy lc bng ) dng lc gi cc loi ht th.
Vic chn giy lc cho ph hp vi c ht l rt quan trng nhm loi tr vic kt ta
chui qua giy v to cho vic lc, ra c nhanh.
B lc ny c u im l rt ph bin trong phng th nghim. Tuy nhin, khi
chuyn sang dng cn nht thit phi nung kt ta v phi t chy giy lc. Ngoi ra,
khng th s dng k thut ht chn khng vi b lc ny, v vic ht chn khng s lm
thng giy lc, gy mt mu.
* Cc lc bng gm:
L loi cc lm bng gm c y l mng gm xp vi cc kch c ca cc l
hng khc nhau. K hiu cho tng loi cc ca cc nc c khc nhau, v d: A1, A2, A3
(c), trong A1 c kch thc l to nht, A3 c kch thc l b nht. u im ca
loi cc lc ny l cho php dng k thut lc chn khng v c th sy hoc nung
chuyn dng kt ta sang dng cn.
* Cc lc bng thu tinh:
L loi cc lm bng thu tinh c y l mng thu tinh xp vi cc kch c ca
cc l hng khc nhau. K hiu cho tng loi cc ca cc nc c khc nhau, v d: S1,
S2, S3, S4, (Sc), G1, G2, G3, G4 (c), trong S4, G4 c l hng ln nht v S1, G1
c l hng b nht, thng dng loi S2, S3 hay G2, G3. u im ca loi cc lc ny l
cho php dng k thut lc chn khng, song, ch c th sy chuyn dng kt ta sang
dng cn.
Khi lc thng kt hp gn ra v lc mau t c kt ta sch. Trc tin,
cht phn nc trong ln h thng lc, cho tip dung mi vo kt ta v khuy u ri
sa lng. Cht tip phn nc trong ln h thng lc. Qu trnh ny c lp li khong 3
ln, sau mi chuyn ton b kt ta ln h thng lc v tin hnh ra kt ta.
d. Ra kt ta
Mc ch ca s ra kt ta l loi cc tp cht hp ph trn kt ta. Trong khi
ra, cc kt ta thng tan ra cho nn cn chn dung dch ra, dung mi ra v cch ra
thch hp.
Thng chn dung dch ra nh sau:
- Dung dch ra c cha thuc th, nu thuc th l cht d bay hi hoc d b
phn hu khi sy v nung kt ta. Ra bng cch ny s hn ch c s tan ca kt ta.
V d: ra kt ta AgCl bng dung dch cha HCl long.
- Dung dch ra c cha cht in gii d b bay hi khi nung. Ra bng dung
dch ny s hn ch c hin tng keo tn (pepti ho) ca cc kt ta keo. V d: ra
kt ta Fe(OH)3, Al(OH)3 bng dung dch NH4Cl, NH4NO3.
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2.5. Mt s ng dng c th
ng dng ca phng php kt ta rt a dng v cho php phn tch hng lot
cc ion, cc hp cht (bng B.1.2).
Di y, ch trnh by nguyn tc cc phng php thng dng trong phn tch
mt s ion thng gp nng nghip:
* Xc nh ion SO42-:
Dng kt ta v dng cn u l BaSO4.
Mu phn tch c axit ho n pH = 4 bng axit HNO3 v lm kt ta ion SO42bng dung dch thuc th Ba(NO3)2 ly d. Trong iu kin ny, cc ion CO32-, PO43khng gy nh hng n kt qa phn tch. Kt ta BaSO4 sau khi c ra sch bng
nc ct, th em nung nhit 700oC n khi lng khng i v cn. H s chuyn
FSO42- = 0,4116.
Bng B.1.2: Mt s phng php phn tch khi lng kt ta
Nguyn t
c xc
nh
Ag
Al
Ba
Ca
Dng kt ta
AgCl
AgBr
AgI
Al(OH)3
AlPO4
BaCO3
BaCrO4
BaSO4
CaC2O4.H2O
CaC2O4.H2O
CaC2O4.H2O
CaSO4.H2O
Tch s
tan (T)
1,78.10-10
5,3.10-13
8,3.10-17
1.10-32
5,75.10-19
5,1.10-9
1,2.10-10
1,1.10-10
2,3.10-9
9,1.10-6
Nhit
sy, nung
(oC)
130
130
130
1000
1000
600
550
700
900
500
105
600
Dng cn
AgCl
AgBr
AgI
Al2O3
AlPO4
BaCO3
BaCrO4
BaSO4
CaO
CaCO3
CaC2O4.H2O
CaSO4
H s
chuyn
(F)
0,7526
0,5744
0,4594
0,5292
0,2212
0,6959
0,5421
0,5884
0,7147
0,4004
0,2743
0,2944
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900
AgCl
0,8141
AgCl
1,78.10-10
CoNH4PO4.H2O
1100
Co2P2O7
0,4039
BaCrO4
1,2.10-10
500
BaCrO4
0,2052
Cr(OH)3
1000
Cr2O3
6,3.10-31
0,6842
Cu
CuCNS
4,8.10-15
110
CuCNS
0,5225
F
CaF2
4,0.10-11
500
CaF2
0,4866
-38
Fe
Fe(OH)3
3,2.10
1000
Fe2O3
0,6994
I
AgI
8,3.10-17
130
AgI
0,5405
-13
Mg
MgNH4PO4.6H2O
2,5.10
1100
Mg2P2O7
0,2184
Mn
MgNH4PO4.H2O
1.10-12
1100
Mn2P2O7
0,3871
Ni
NiNH4PO4.6H2O
1100
Ni2P2O7
0,4030
-13
P
MgNH4PO4.6H2O
2,5.10
1100
Mg2P2O7
0,2790
Pb
PbCrO4
1,8.10-14
140
PbCrO4
0,6411
-8
PbSO4
550
PbSO4
1,6.10
0,6832
S
BaSO4
1,1.10-10
700
BaSO4
0,1374
Si
SiO2.xH2O
1000
SiO2
0,4674
Zn
ZnNH4PO4.6H2O
1100
Zn2P2O7
0,4291
* Xc nh ion Cl :
Dng kt ta v dng cn u l AgCl.
Mu phn tch c axit ho bng axit HNO3 n pH 1 v lm kt ta ion Clbng dung dch thuc th AgNO3. Kt ta AgCl sau khi c ra sch th sy nhit
130oC v cn. H s chuyn FCl- = 0,2474. Trong phng php ny, cc ion CO32-, PO43khng gy nh hng n kt qu phn tch.
* Xc nh ion PO43-:
Dng kt ta MgNH4PO4.6H20, dng cn Mg2P2O7.
Cho vo dung dch phn tch c axit ho bng axit HCl thuc th MgCl2 +
NH4Cl v sau dng NH4OH chnh pH mi trng n khi kt ta hon ton ion PO43di dng MgNH4PO4.6H2O. kt ta hon ton cn dng d NH4OH (khong 1/5 th
tch dung dch NH4OH 20%). Kt ta c ra bng dung dch NH4OH 5% v sau khi
sy kh th c nung nhit 1100oC chuyn hon ton sang dng cn Mg2P2O7.
H s chuyn FPO43- = 0,8535. Trong trng hp c cc ion Al3+, Fe3+ trong mu, cn lm
kt ta MgNH4PO4 trong mi trng cha ion xitrat ngn nga s to kt ta FePO4
hay AlPO4.
* Xc nh ion SiO32-:
Dng kt ta H4SiO4 (hay SiO2. 2H2O), dng cn SiO2.
Ion SiO32- c kt ta trong mi trng cha 20% axit HCl v 5% gelatin hay
agar. Mang nung kt ta thu c nhit 1000oC c khi lng a (g). Thng
trong kt ta c ln mt s tp cht, nn sau khi nung cho tip vo phn cht rn cn li
axit HF v axit H2SO4 c v nung tip ui ton b SiF4. Khi lng cht rn cn li
l b (g). T lng hao ht (a b) cho bit lng SiO2 cha trong mu. H s chuyn FSiO2
= 1,000, FSiO32- = 1,5333.
* Xc nh ion Fe3+:
Dng kt ta Fe(OH)3, dng cn Fe2O3.
Cho vo mu phn tch mui NH4Cl hay NH4NO3 ( lm cht in gii) v kt
ta ion Fe3+ t dung dch nng bng lng d dung dch thuc th NH3 long (1:3). Kt
ta Fe(OH)3 c lc v ra bng dung dch nng NH4NO3 hay NH4Cl 1% v sau
Cl
Co
Cr
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mang nung nhit 1000oC chuyn ton b Fe(OH)3 sang dng cn Fe2O3. H s
chuyn FFe = 0,6994.
* Xc nh ion Al3+:
Dng kt ta Al(OH)3, dng cn Al2O3.
Cho vo mu phn tch mui NH4Cl hay NH4NO3 ( lm cht in gii) ri kt
ta ion Al3+ t dung dch nng bng dung dch thuc th NH3 long (1:3). pH khi dng
kt ta: 5 6. Kt ta Al(OH)3 c lc v ra bng dung dch nng NH4Cl hay NH4NO3
1% v sau mang nung nhit 1000oC chuyn hon ton Al(OH)3 sang dng cn
Al2O3. H s chuyn FAl = 0,5293.
Phng php phn tch khi lng kt ta c nhng u nhc im chnh sau:
* u im:
- Trang thit b dng trong phn tch n gin v khng t tin nn c kh nng
ph cp cao.
- chnh xc rt cao, v khi phn tch tch c phn cn xc nh ra khi
hn hp, nn c dng lm phng php chun kim tra cc phng php khc v
kim tra cc dung dch m (l dung dch c nng 10-2M, khi s dng th pha
long thnh cc dung dch vi nng nh hn).
- C th dng phn tch hu ht cc ion v c.
- Phng php kt ta cn c s dng tch cc ion ra khi nhau.
* Nhc im:
- Tc phn tch chm.
- nhy thp nn khng th dng phn tch lng nh cht cn phn tch nu
khng lm giu mu trc khi phn tch.
- Khng th t ng ho c qu trnh phn tch. Do , ngy nay, trong phn
tch ng dng t s dng phng php ny.
Cu hi n tp
1. Trong cc cng on ca phng php phn tch khi lng kt ta, cng on no l
quan trng nht? Ti sao?
2. Dng kt ta cn phi tho mn nhng iu kin g? Ti sao?
3. Dng cn cn phi tho mn nhng iu kin g? Ti sao?
4. Cc yu t nh hng n tan ca kt ta?
5. S cng kt l g? Cch khc phc? v s dng hin tng ny?
6. Nguyn tc chon thuc th trong phng php phn tch khi lng kt ta
7. Hy nu cch lm kt ta.
8. Hy nu cch lc v ra kt ta.
9. Cch tnh ton kt qu phn tch.
10. ng dng phng php phn tch khi lng kt ta trong phn tch mt s i tng
nng nghip.
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Bi tp
1. Cn 0,400g mu cha SO42- ri ho tan thnh 200 ml dung dch. Ly 100ml dung dch
ny v lm kt ta bng Ba(NO3)2 ly d trong mi trng axit HNO3. Lc ly kt ta,
ra sch v sy kh c 0,1165g. Hy tnh thnh phn % SO42- trong mu. (p s:
24%).
2. Cn 0,500g mu cha Cu2+, Pb2+ v tp cht khng tham gia phn ng ri ho tan
thnh 250ml dung dch. Ly 100ml dung dch ny cho tc dng vi axit H2SO4 0,5M ly
d th thu c 0,151g kt ta. Mt khc, khi ly 100ml dung dch trn cho tc dng vi
H2S d th thu c 0,1675g kt ta. Hy tnh thnh phn % Cu2+ v Pb2+ trong mu.
(p s: 16,0%Cu2+, 51,6Pb2+).
3. Cn 0,500g mu cha CO32- v SO42- ri ho tan thnh 200ml dung dch. Ly100ml
dung dch ny lm kt ta vi Ba(NO3)2 ly d trong mi trng kim yu th thu
c 0,414g kt ta. Mt khc, khi lm kt ta dung dch trn pH = 4 vi Ba(NO3)2 ly
d th thu c 0,233g kt ta. Hy tnh thnh phn % ca hai ion trn trong mu. (p
s: 38,6%CO32-, 38,4%SO42-).
4. lng kt ta MXn mt do phn ng khng hon ton khng ln hn 0,1mg (sai s
cn), th TMXn l bao nhiu, nu th tch khi ngng lm kt ta l V lt? (p s: TMXn =
[10-4/(MMXn.V)]n+1.nn]).
5. Tnh khong pH kt ta hon ton ion Fe3+ (khi [Fe3+] <10-6M) trong hn hp vi
ion Mg2+. Gi thit nng ion Mg2+ khi dng kt ta ion Fe3+ l 0,01M. Cho TFe(OH)3 =
3,2.10-38, TMg(OH)2 = 6,0.10-10. (p s: 3,5 < pH <10,4).
6. Tnh nng AgNO3 d cn thit, khi kt ta ion Cl- th s mt Cl- do kt ta
khng hon ton khng vt qu sai s cn (0,1mg). Bit th tch khi dng kt ta l 0,2
lt, TAgCl = 1,78.10-10. (p s: [AgNO3] = 1,27.10-5).
7. Tnh lng CaC2O4 mt i khi ra n bng 100ml nc ct (gi thit b qua s thu
phn). Cho TCaC2O4 = 2,3.10-9. (p s: 0,0004g).
8. Cho dung dch NH3 d vo 25 ml dung dch FeCl3. Thu ly kt ta, ra sch, nung n
khi lng khng i c 0,1952 gam cht rn. Tnh nng mol/l ca FeCl3 trong
dung dch phn tch. (p s: 0,0976M).
9. Tnh lng AgCl b mt khi ra n bng: a- 200ml nc ct; b- 200ml HCl 0,01M.
Cho TAgCl = 1,78.10-10. (p s: a) 3,8.10-4g; b) 5,1.10-7g).
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CHNG II
PHN TCH TH TCH
1. NHNG KHI NIM C BN V PHN TCH TH TCH
Phng php phn tch th tch (phng php chun ) l phng php phn tch
nh lng da trn vic o chnh xc th tch dung dch thuc th c nng chnh xc
phn ng va vi dung dch phn tch. T lng thuc th tiu tn tnh ra hm lng
cht cn phn tch c trong mu phn tch.
Dung dch thuc th c nng chnh xc gi l dung dch tiu chun.
Tnh ton kt qu ca phng php ny l da vo nh lut ng lng: Cc
cht tham gia phn ng theo s ng lng gam bng nhau:
Vx.Nx = Vtc.Ntc
(III- 1)
(trong x l cht cn xc nh, tc l cht tiu chun).
Nh vy, nu bit th tch ca dung dch phn tch Vx ly, th tch dung dch
tiu chun Vtc c nng Ntc tiu tn, s d dng tnh c nng ca dung dch cn
xc nh Nx.
o chnh xc th tch dung dch tiu chun tham gia phn ng, s dng
dng c o chnh xc, l buret. Qu trnh a t t dung dch tiu chun t buret vo
dung dch phn tch gi l qu trnh chun hay qu trnh nh phn. Tuy vy, trong
thc t chun , nhiu khi cht cn phn tch trn buret.
im m ti dung dch tiu chun tc dng va vi dung dch phn tch gi
l im tng ng.
Trong nhiu phn ng khng th dng mt xc nh im tng ng. V d:
vi phn ng
HCl + NaOH = NaCl + H2O,
cc ho cht tham gia u khng c mu, nn khng th dng mt xc nh khi no
t n im tng ng. xc nh im tng ng, cn dng ch th cho vo bnh
phn ng. Ch th l ho cht hoc cng c o, n thay i tnh cht ca mnh nh mu
sc hoc tn hiu o ngay ti im tng ng, bo hiu s dng chun (kt thc
chun ). Song, trong thc t nhiu trng hp, ch th khng phn ng ng im
tng ng dn n sai s chun v c gi l sai s ch th. Sai s ch th mang
tnh cht sai s h thng do phng php (chng V).
V d: chun xc nh HCl bng NaOH vi vic NaOH trn buret, ti im
tng ng c pH = 7, nu dng ch th l qu tm (c pKa = 7) th phn ng ch th xy
ra ng im tng ng v chun c sai s bng 0, nu dng ch th l metyl (c
pKa = 5) th phn ng ch th xy ra trc im tng ng, nh vy khi kt thc chun
trong dung dch cn mt lng d axit HCl, dn n sai s ch th (sai s m), cn khi
s dng ch th phenophtalein (c pKa = 9) th phn ng ch th xy ra sau im tng
ng, nh vy khi kt thc chun trong dung dch cn mt lng d baz NaOH,
dn n sai s ch th (sai s dng).
Sai s ch th phn trm (ss%, e%) c tnh theo biu thc III- 2:
e% = [(Vkt - Vt)/Vt].100,
(III- 2)
trong , Vt l th tch dung dch tiu chun cn t im tng ng, Vkt l th tch
dung dch tiu chun dng khi kt thc chun .
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pH = 7
MnO4 + 3H2O + 3e
=
MnO(OH)2 + 4OH
pH > 10
MnO4- + e
=
MnO42Hay khi chun chun ion Cl- bng AgNO3. phi duy tr mi trng trung
tnh hoc axit yu, v trong mi trng kim xy ra phn ng:
2Ag+ + 2OH- = Ag2O + H2O
lm mt mt lng thuc th, gy nn sai s.
c. Phn ng phi chn lc trnh nh hng ca ion gy nhiu
Nu c cc ion gy nhiu th cn gii hn iu kin phn ng xy ra l chn
lc hoc phi tch, che ion gy nhiu.
V d:
- Chun complexon III xc nh ion Fe3+ trong iu kin c cc ion Al3+,
2+
Mg , Ca2+ cn chun ti pH = 2, lc ny ch c ion Fe3+ tham gia phn ng chun ,
cc ion khc khng tham gia nn khng gy nn sai s chun .
- Chun complexon III xc nh ion Ca2+ trong iu kin c ion Mg2+, cn
chun ti pH = 12, lc ny ch c ion Ca2+ tham gia phn ng chun ; cn ion Mg2+
b kt ta di dng Mg(OH)2 khng tham gia nn khng gy nn sai s chun .
- Chun complexon III xc nh ion Mg2+ trong iu kin c ion gy nhiu
Fe3+, Cu2+, c th che cc ion Fe3+, Cu2+ bng ion CN- di dng cc ion phc cht tan
[Fe(CN)6]3-, [Cu(CN)4]2-, lc ny ch c ion Mg2+ tham gia phn ng vi complexon III.
- Chun complexon III xc nh ion Mg2+ trong iu kin c ion gy nhiu
3+
Fe , Al3+, c th tch cc ion gy nhiu Fe3+, Al3+ di dng cc kt ta hydroxit
Fe(OH)3, Al(OH)3 ti pH = 5 - 6, lc b kt ta s thu c dung dch ch c ion Mg2+,
sau mi tin hnh chun .
d. Tc phn ng phi ln phn ng tc thi t cn bng
Nh vy, s trnh c s d thuc th do trng thi qu bo ho ca n ti im
tng ng, nguyn nhn gy nn sai s. Nu tc phn ng chm phi dng xc tc
tng tc hay chn cch chun ngc (mc 3.2 chung III).
V d 1: Dng xc tc tng tc ca phn ng chun xc nh H2C2O4
bng KMnO4 trong mi trng axit bng cch un nng dung dch n nhit 60 - 800C
hoc cho vo dung dch chun ion Mn2+.
V d 2: Chn cch chun ngc chun complexon III xc nh ion Al3+.
e. Phi c ch th xc nh im tng ng
Nu khng c th d phn ng tho mn cc iu kin trn cng khng s dng
c. V d: phn ng
Ca2+ + C2O42- = CaC2O4
tho mn tt c cc iu kin t a n d, song, khng dng c, v khng c ch th mu
thch hp xc nh im tng ng.
-
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3.2. Phn loi phng php theo cch tin hnh chun
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V d: chun xc nh ion Ca2+ bng dung dch tiu chun KMnO4. Cho ion
Ca phn ng vi dung dch tiu chun (NH4)2C2O4 ly d, lc b kt ta, dung dch thu
c c chun bng dung dch tiu chun KMnO4:
Ca2+ + (NH4)2C2O4 d = CaC2O4 + 2NH4+ (phn ng th)
5(NH4)2C2O4 d + 2KMnO4 + 16H+ = 10CO2 + 2Mn2+ + 2K+ + 10NH4+ + 8H2O (phn
ng chun )
Cc phn ng trn cho thy: 1 ion Ca2+ c th bi s mt i ca 1 ion C2O42-, 1
ion C2O42- khi tham gia phn ng chun nhng 2e, do , 1 ion Ca2+ tng ng
vi 2e, suy ra: Ca2+ = MCa2+/2. Cng theo cc phn ng trn c: VCa2+.NCa2+ =
V(NH4)2C2O4. N(NH4)2C2O4 - VKMnO4.NKMnO4.
2+
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Khi pha dung dch tiu chun t ho cht gc ch cn cn chnh xc lng tnh
ton bng cn phn tch v ho tan vo bnh nh mc c dung tch bng th tch cn pha
s c dung dch tiu chun c nng cn pha.
Nu ho cht dng pha khng phi l cht gc th ch cn cn tng i chnh
xc lng cn cn c tnh thm t 5 10% bng cn k thut v em pha. Dung
dch thu c c nng gn ng. Nng ng ca dung dch ny cn c xc nh
bng chun vi dung dch tiu chun khc. y, c 2 cch pha:
- Cch 1: Pha dung dch c nng chnh xc gn bng vi nng cn pha.
Lng cn tnh c pha vo trong cc hoc trong bnh nh mc thnh dung
dch c th tch cn pha, lc b kt ta nu c. Dung dch thu c c chun li
kim tra nng bng dung dch tiu chun khc.
V d: pha1 lt dung dch NaOH 0,1000N dng cho chun trung ho. V NaOH
rn d ht m nn n khng phi l cht gc. Do vy, khi cn cn cn tng khong 5
10% so vi lng phi cn, tc t 4g thnh khong 4,2g 4,4g, ri pha vo bnh nh
mc 1 lt. Dung dch thu c c chun li bng dung dch cht gc H2C2O4
0,1000N hoc dung dch HCl 0,1000N tiu chun xc nh chnh xc nng ca n.
- Cch 2: Pha dung dch c nng ng vi nng cn pha N.
Lng cn tnh c pha vo trong cc vi th tch dung mi chnh xc (Vml)
nh hn th tch cn pha, thu c dung dch c nng N cao hn nng cn pha
N. Dung dch thu c c chun li kim tra nng bng dung dch tiu chun
khc, ri t kt qu thu c tnh ra lng dung mi (VH2O) cn thm vo lng dung
dch cn (V1) li theo biu thc III- 5:
VH2O (ml) = [(N/N) 1]. V1 (ml)
(III- 5)
y: N nng dung dch pha.
N nng dung dch cn pha.
V1 th tch dung dch pha cn li cn pha long, bng th tch dung dch ban
u V tr i s ml dng cho chun kim tra.
V d: pha khong1 lt dung dch NaOH 0,1000N dng cho phn ng trung ho.
Cng nh cch 1, cn khong 4,2g 4,4g NaOH rn ri pha vo mt th tch chnh xc
b hn th tch cn pha, v d: 800 ml. T dung dch thu c ht 2 ln, mi ln 25 ml,
chun vi dung dch H2C2O4 0,1000N ht trung bnh, v d: 30,0 ml. Nh vy,
dung dch pha c nng 0,1200N cao hn nng cn pha. Do , cn thm nc ct
vo dung dch pha, lng nc c tnh theo biu thc III- 5: N = 0,1200 ; N =
0,1000; V = 800 (2 . 25) = 750 ml; VH2O cn thm = 150 ml. Nh vy, khi cho thm
150 ml H2O vo 750 ml dung dch pha cn li s c 900 ml dung dch NaOH vi nng
chnh xc 0,1000N.
Cch pha th 2 phc tp hn cch pha th 1, nhng rt thun tin cho vic tnh
ton, nht l trong phn tch hng lot mu, v y, tr s nng l nhng s chn.
Hin nay, vi s hon thin ca cng nghip ho cht, sn xut sn cc ng
chun (fixanan) nh: ng fixanan HCl 0,1N; KCNS 0,1N Vic pha dung dch tiu
chun t cc ng fixanan rt n gin: ch cn ho tan ton b lng cha trong ng
thnh mt th tch xc nh theo ch dn s c dung dch c nng chnh xc nh
ghi trn ng. V d: pha mt ng fixanan HCl 0,1N thnh mt lt dung dch s c dung
dch HCl c nng chnh xc 0,1N m khng cn chun li.
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6.1. nh ngha
Trong chun , nng ca cc cht trong dung dch lun thay i. S thay i
ny dn n hng lot cc i lng vt l, ho hc cng thay i tr s ca mnh. Do ,
theo di s thay i ca cc i lng vt l, ho hc c th cho bit nng cc cht
trong dung dch. V d: khi chun xc nh HCl bng NaOH th hng lot cc i
lng nh nng ca HCl, NaOH, H+, OH- thay i dn n pH dung dch thay i
hay cc i lng vt l khc nh dn in ca dung dch, in th dung dchthay
i ph thuc vo lng NaOH a vo h chun . Do c nhiu i lng vt l,
ho hc gn lin vi h chun , cho nn, tu tng phng php chun m s dng
i lng theo di thch hp. Thng thng, trong phng php trung ho dng i
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lng pH, trong phng php oxi ho kh dng i lng in th dung dch E, trong
phng php kt ta dng cc i lng pX (pX = -lg[Xn-]), pM (pM = -lg[Mm+]), trong
phng php to phc dng i lng pM, pX.
th biu din s ph thuc ca mt i lng vt l, ho hc no c lin
quan n nng cc cht tham gia phn ng chun ln th tch dung dch tiu chun
a vo c gi l ng chun . Tuy vy, tu theo loi phn ng chun m
chn mi quan h thch hp. Thng thng, trong phng php trung ho l ng
biu din ph thuc: pH = f(Vtc); trong phng php oxi ho kh: E = f(Vtc); trong
phng php kt ta, to phc: pM = f( Vtc), pX = f(Vtc). Cng c th biu din ng
chun di dng hm i lng o ph thuc ln % chun .
Tr s ca pH, E, pM, pX ti im tng ng c gi l ch s pT.
Vic nghin cu ng chun c ngha rt ln trong vic tin hnh chun ,
n gip cho vic xc nh t chnh xc cao v chn ch th thch hp cho chun .
Qu trnh chun tri qua 4 giai on: cha chun , chun trc im
tng ng, chun ti im tng ng, chun sau im tng ng. mi
giai on, thnh phn cc cht trong dung dch chun ging nhau, nn xy dng
ng chun chnh l thit lp cc biu thc ton biu din s ph thuc ca i
lng theo di ca tng giai on ln th tch dung dch tiu chun s dng hay ln %
chun . Vic tnh chi tit ch cn l s thay s vo cc biu thc ton c.
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HA = H+ + A-
CHA
(III- 8)
(III-
(III(III-
(III- 14)
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Nu coi [OH-] [H+], th CHA = [HA] + [H+] v thay n vo biu thc III- 15
[H+]2 + Ka[H+] - KaCHA = 0
(III- 16)
Khi s phn li ca HA l khng ng k (i vi axit yu v rt yu) v CHA
ln, c th coi [H+] CHA hay [HA] CHA, th biu thc III- 16 c n gin ho
thnh biu thc III- 17 v pH dung dch c xc nh bng biu thc III- 18:
[H+] = (Ka . CHA )1/2
(III- 17)
pH = (1/2)pKa - (1/2)lgCHA
(III- 18)
Khi o pH, thng mc sai s 5%, nn vic tnh pH theo biu thc III- 18 c
coi l ng, nu pH tnh c tho mn iu kin:
pH > pCHA + 1,3,
( y, pCHA = - lgCHA), nu khng, phi tnh [H+] theo biu thc III- 16 hoc biu thc
III- 15.
* pH dung dch baz trung bnh v yu:
Gi thit c baz BOH, theo Arrhenius, trong dung dch nc ca n c hai cn
bng:
BOH OH- + B+
CBOH
11)
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Nh ni trn, khi o pH, thng mc sai s 5%, nn vic tnh pOH theo biu
thc III- 24 c coi l ng, nu pOH tnh c tho mn iu kin:
pOH > pCBOH + 1,3,
( y, pCBOH = - lgCBOH)), nu khng, phi tnh [OH-] theo biu thc III- 21 hoc III- 20.
* pH dung dch cha cp axit baz lin hp ca axit hoc baz trung bnh v
yu:
Trong dung dch nc, theo Bronsted, cp axit baz lin hp ca axit hoc baz
trung bnh v yu vi nng ca axit l CHA v ca baz l CA- s to ra h m pH. S
tong tc gia chng vi nhau th hin qua cc phng trnh:
HA H+ + AA- + H+ HA
Cc mi quan h ny c thit lp bi hng s cn bng Ka (III- 14).
T mi quan h cn bng vt cht c:
CHA = [HA] + [A-] = [HA] + [H+] - [OH-] [HA] = CHA - [H+] + [OH-]
25)
(III- e1)
(III- e2)
(III-
(IIICA- = [A-] + [HA] = [A-] + [OH-] - [H+] [A-] = CA- - [OH-] + [H+]
26)
Do , phng trnh III- 14 c vit thnh:
[H+] = Ka{CHA - [H+] + [OH-]}/{CA- - [OH-] + [H+]}
(III27)
Nu [OH-] < 5% [H+], [H+] < 5% CHA v [H+] < 5% CA- (5% l sai s ca my o
pH), cc biu thc III- 25 v III- 26 c n gin ho thnh: [HA] = CHA v [A-] = CA-.
Thay cc gi tr ny vo biu thc III- 27 s c:
{[H+]
CA-}/CHA
Ka
=
(III- 28)
Log ho biu thc III- 28 v chuyn v s c:
pH = pKa - lg(CHA /CA- )
(III- 29)
* pH dung dch mui thu phn:
- Khi trong dung dch nc c mui BA to bi axit yu HA v baz mnh BOH.
Mui BA b thu phn:
BA + H2O = HA + B+ + OH(III- f)
Theo Bronsted, c th coi BA nh l mt baz yu. Do , c th s dng biu
thc III- 24 vi vic thay CBOH bng CBA v pKb = 14 - pKa tnh pH dung dch mui
BA (III- 27).
pH = 7 + (1/2)pKa + (1/2)lgCBA
(III- 30)
- Khi trong dung dch nc c mui BA to bi baz yu BOH v axit mnh HA.
Mui BA b thu phn:
BA + H2O = BOH + H+ + A(IIIg)
Theo Bronsted, c th coi BA nh l mt axit yu. Do , c th s dng biu
thc III- 18 vi vic thay CHA bng CBA v pKa = 14 - pKb tnh pH dung dch mui
BA:
pH = 7 - (1/2)pKb - (1/2)lgCBA
(III- 31)
* pH dung dch mui lng tnh:
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(III-
(III33)
Trong dung dch, nng [H+] s bng tng lng [H+] do HA- phn li ra (tc bng [A2-]
v nc phn li ra (tc bng [OH-] tr i lng [H+] tham gia phn ng vi HA- to
H2A (tc bng [H2A]):
[H+] = [A2-] - [H2A] + [OH-] = [A2-] - [H2A] + KH2O/[H+]
(III34)
Thay [A2-] v [H2A] t III- 30 vo III- 28 v III- 29 s c:
[H+] = {Ka1(Ka2[HA-] + KH2O)/(Ka1 + [HA-])}1/2
(III35)
Thng thng [HA-] KH2O, [HA-] Ka1, nn biu thc III- 35 c th rt gn
thnh: [H+] = (Ka1Ka2)1/2 . Nh vy:
pH = (pKa1 + pKa2)/2
(III- 36)
Vi trng hp tng qut ca ion HmAn-:
HmAn- Hm-1A(n+1)- + H+ v HmAn- + H+ Hm+1A(n-1)-, c th vit:
pH = (pKan + pKan+1)/2
(III37)
Trong : Kan l hng s axit phn li ra gc mui HmAn-, Kan+1 l hng s axit m gc
mui HmAn- s phn li c gc Hm-1A(n+1)-.
b. ng chun axit mnh bng baz mnh
Khi chun axit mnh HA c th tch dung dch VHA v nng NHA (CHA)
bng dung dch baz mnh BOH c nng NBOH (CBOH), v d, chun 100 ml HCl
0,1N bng dung dch NaOH 0,1N, ng chun c xc nh nh sau:
* pH khi cha chun :
Dung dch ch cha axit mnh HA phn li hon ton:
HA = H+ + A-,
nn s dng biu thc III- 10 tnh pH dung dch.
Thay s, theo v d nu trn, c:
pH = - lg [H+] = -lg CHA = -lg0,1 = 1
* pH trc im tng ng:
Vic a BOH vo dung dch HA dn n phn ng:
HA + BOH = BA + H2O
lm gim nng axit HA, nhng, axit vn cn d v n quyt nh pH dung dch. Nng
axit HA d s bng:
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38)
(III-
50
Trc im
90
tng
99
ng
99,9
Ti im
100
tng
ng
100,1
Sau im
101
tng
110
ng
150
Vn dng
biu thc
III- 10
III- 38
III- 39
HCl 0,1N
pH
HCl 0,01N
HCl 0,001N
1,00
1,48
2,30
3,30
4,30
2,00
2,30
3,04
4,04
5,04
3,00
3,30
4,00
5,00
6,00
7,00
7,00
7,00
9,70
10,70
11,70
12,30
8,96
9,96
10,96
11,70
8,00
9,00
10,00
10,69
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http://hoahocsp.tk
Trc im
tng ng
%
chun
0
50
90
99
99,9
Vn dng
biu thc
III- 13
III- 39
NaOH 0,1N
pH
NaOH 0,01N
NaOH 0,001N
13,00
12,52
11,70
10,70
9,70
12,00
11,70
10,96
9,96
8,96
11,00
10,69
10,00
9,00
8,00
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Ti im
tng ng
Sau im
tng ng
100
100,1
101
110
150
III- 38
7,00
4,30
3,30
2,30
1,48
7,00
5,04
4,04
3,04
2,30
7,00
6,00
5,00
4,00
3,30
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http://hoahocsp.tk
Bng B.3.3: S bin thin pH dung dch trong chun 100ml axit yu
CH3COOH (pKa = 4,76) nng 0,1N bng NaOH 0,1N
Trng thi chun
% chun
Cha chun
Trc im tng
ng
0
50
90
99
99,9
100
100,1
101
110
150
Ti im tng ng
Sau im tng ng
Vn dng biu
thc
III- 18
III- 40
III- 27
III- 41
III- 27
III- 39
pH
2,88
4,76
5,72
6,76
7,80
8,73
9,70
10,70
11,70
12,52
Hnh H.3..3: ng chun axit yu CH3COOH (pKa= 4,76) 0,1N bng baz
mnh NaOH 0,1N.
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http://hoahocsp.tk
% chun
Cha chun
Trc im tng
ng
0
50
90
99
99,9
100
100,1
101
110
150
Ti im tng ng
Sau im tng ng
Vn dng biu
thc
III- 24
III- 42
III- 27
III- 43
III- 27
III- 38
pH
11,13
9,26
8,31
7,26
6,22
5,28
4,31
3,32
2,38
1,70
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Hnh H.5..3: ng chun baz yu NH4OH (pKb = 4,74) 0,1N bng axit
mnh HCl 0,1N:
http://hoahocsp.tk
T cc hnh v H.3.3 - H.6.3 c nhn xt: Khi chun axit yu bng baz
mnh cng nh khi chun baz yu bng axit mnh, trc im tng ng, trong
dung dch u tn ti h m pH nn pH thay i chm. Do , d dng nhn thy rng
vic chun axit yu bng baz yu hoc ngc li s dn n ng cong chun
khng c bc nhy (v trc v sau im tng ng trong dung dch lun tn ti h
m pH lm pH thay i chm). Chnh v iu ny, nn trong thc t khi chun theo
phng php trung ho ch dng dung dch tiu chun l cc axit, baz mnh ng
chun c bc nhy ln.
e. ng chun hn hp nhiu axit n chc hoc axit a chc bng baz mnh
hoc chun hn hp nhiu baz n chc hoc baz a chc bng axit mnh
ng chun hn hp nhiu axit n chc cho bc nhy ring r gn im
tng ng ng vi vic chun ca tng axit ch khi cc axit ny c hng s axit
khc nhau r rt (vi sai s % = 0,1% th Ka1/Ka2 104), (v d: hn hp axit HCl (phn
li hon ton) v CH3COOH (Ka = 1,74.10-5)), nu cc hng s axit Ka1 khc nhau khng
nhiu (v d: cc axit hu c dy axit focmic nh HCOOH vi Ka = 1,8.10-4 v
CH3COOH vi Ka = 1,74.10-5) ), th ng chun c chung mt bc nhy. iu ny
cng ng cho chun axit a chc, bi v axit a chc phn li theo tng nc v mi
nc phn li khc nhau c th c coi l s phn li ca mt axit khc. V d:
Axit HnA phn li nh sau:
HnA
Hn-1A- + H+
2-
Hn-1A Hn-2A
+ H
(nc 1),
(nc 2),
HA(n-1)- An- + H+
(nc n)
pH ca dung dch axit HnA c tnh theo cc biu thc III- 10 (cho axit mnh) hoc cc
biu thc III- 16 v III- 18 (cho axit yu). Cc ion gc mui Hn-1A-, Hn-2A2-,.HA(n-1)c gi l cc gc mui lng tnh v pH ca cc dung dch cha cc ion ny c tnh
gn ng theo biu thc III- 37.
Vi baz a chc B cng c th vit tng t :
B + H+ BH+
+
BH
..
+ H
(nc 1)
BH2
2+
(nc 2)
BHn-1(n-1)+ + H+ BHnn+
(nc n)
pH ca dung dch baz B c tnh theo cc biu thc III- 13 (cho baz mnh) hoc cc
biu thc III- 21 v III- 24 (cho axit yu). Cc ion gc mui Hn-1A-, Hn-2A2-,.HA(n-1)c gi l cc gc mui lng tnh v pH ca cc dung dch cha cc ion ny c tnh
gn ng theo biu thc III- 37.
Vic xy dng ng chun cho c hai trng hp cng tng t nh khi xy
dng ng chun axit bng baz mnh hoc chun baz bng axit mnh, ch c
khc mt iu l i vi axit a chc c th coi y l hn hp ca nhiu axit n chc
c cng nng mol/lt v tng t i vi baz a chc c th coi nh chun hn
hp nhiu baz n chc c cng nng mol/lt.
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http://hoahocsp.tk
ng chun axit H3PO4 bng NaOH c biu din bng hnh v H.5.3.
ng ny c 3 im tng ng nhng ch c hai bc nhy ng vi vic chun
nc 1 v nc 2, cn chun nc 3 s khng c bc nhy v axit th 3 qu yu. Tng
t c th xy dng ng chun baz a chc bng axit mnh vi vic s dng biu
thc III- 48:
pKa + pKb = 14,
(III- 48)
trong Ka v Kb l cc hng s axit v baz ca mt cp axit baz lin hp.
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hoc vi a a, b b, v d:
2Na2S2O3 + I2 = 2NaI + Na2S4O6
S4O62- + 2e = 2S2O32I2 + 2e = 2I
- Phn ng oxi ho kh, trong cc cp oxi ho kh trao i s electron khng
nh nhau.
C th, i vi phn ng ring phn III- c1 v III- c2 vi m n, vi a = a, b = b,
v d:
5Fe2+ + KMnO4 + 8H+ = 5Fe3+ + K+ + Mn2+ + 4H2O
Fe3+ + e = Fe2+
MnO4- + 8H+ + 5e = Mn2+ + 4H2O
hoc vi a a, b b, v d:
6Fe2+ + K2Cr2O7 + 14H+ = 6Fe3+ + 2K+ + 2Cr3+ + 7H2O
Fe3+ + e = Fe2+
Cr2O72- + 6e + 14H+ = 2Cr3+ + 7H2O
ng chun ca mi nhm c nhng c im khc nhau.
Kh nng tham gia phn ng oxi ho kh ca cc cht ph thuc rt nhiu vo
iu kin mi trng, do , n gin cho vic xy dng ng chun , thng gii
hn iu kin phn ng chun lun c nh. V d: nu trong phn ng c s tham gia
ca ion H+, thng qui c [H+] = 1 iong/l.
a. ng chun oxi ho kh ca trng hp m = n, a = a, b = b
Nh vy, i vi h ny tn ti: a = a = b = b = 1. Chun xc nh cht kh 1
c th tch Vkh1, nng Nkh1 bng dung dch cht oxi ho 2 c nng Nox2 s theo
phng trnh:
kh1 + ox2 = ox1 + kh2
( III- d )
hoc
( III- 49 )
(III- 50)
E = E0ox2/kh2 + (0,059/n)lg([ox2]/[kh2])
Tuy nhin, cn chn la biu thc thch hp, c th d dng tnh c nng
ca cc cht trong biu thc t nhng d liu chun . Thng thng, da vo s d
tha ca cc cht tham gia phn ng chn. V d: vi chun xc nh cht kh 1
bng cht oxi ho 2, khi trong dung dch cn d cht kh 1, chn biu thc III- 49, khi
trong dung dch c d cht oxi ho 2, chn biu thc III- 50.
ng chun c xy dng nh sau:
* E khi cha chun :
Trong dung dch ch c cht kh 1, nn, E dung dch c tnh da vo nng
cc cht oxi ho kh ca cp 1 (biu thc III- 49). Thay s c:
E = E0ox1/kh1 + (0,059/m)lg[0/(Nkh1/m)]
(III- 51)
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% chun
0
1
Vn dng biu
thc
III- 51
E (V)
0,53
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Trc
ng
im
tng
Ti im tng ng
Sau im tng ng
hay
10
50
90
99
99,9
100
100,1
101
110
200
III- 52
III- 53
III- 54
0,71
0,77
0,83
0,89
0,95
1,10
1,26
1,32
1,38
1,44
Et = (mE0ox1/kh1 + nE0ox2/kh2)/(m + n)
(III- 55)
* E sau im tng ng:
Tng t nh phn 6.3.a trn, E c tnh theo biu thc III- 50. Thay d
liu s c:
(IIIE = E0ox2/kh2 + (0,059/n)lg{[(Vox2 . Nox2 Vkh1 . Nkh1)/n]/[(Vkh1 . Nkh1)/n]}
56)
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im
tng
Ti im tng ng
Sau
im
ng
tng
% chun
0
1
10
50
90
99
99,9
100
100,1
101
110
200
Vn dng biu
thc
III- 51
III- 52
III- 55
III- 56
E (V)
0,53
0,71
0,77
0,83
0,89
0,95
1,39
1,48
1,49
1,50
1,51
6.4. ng chun kt ta
Trong thc t s dng rt t cc phn ng kt ta tin hnh chun . Ph bin
nht l s dng cc phn ng to cc kt ta AgCl, AgBr, AgI, AgCNS v i khi
BaSO4, PbCrO4 trong vic xc nh cc ion to nhng mui trn. Nh vy, phng trnh
phn ng c th vit di dng tng qut:
Mn+ + Xn - = MX
(III- e)
vi tch s tan:
TMX = [Mn+] [Xn-]
ng chun kt ta l ng biu din s ph thuc pX = f(Vtc), hoc pM =
f(Vtc) hay pX = f(% chun ) hay pM = f(% chun ).
Khi chun xc nh ion Xn- c nng Nx, th tch Vx bng dung dch ion Mn+
c nng NM, ng chun c xy dng nh sau:
-----------------------------------------------------------------------------------------------------------* chnh th tiu chun ca hai cp oxi ho kh cng ln th hng s cn bng K ca
http://hoahocsp.tk
http://hoahocsp.tk
pX = (lgTMX)/2
(III- 59)
*pX sau im tng ng:
Vic a d dung dch tiu chun Mn+ vo dung dch chun lm cho cn bng
III- e chuyn dch sang bn phi, do nng ion Xn- tip tc gim. Nng ion Xnlc ny l:
[Xn-] = TMX/ [Mn+] = TMX/ [(VMm+ . NMm+ - VXn- . NXn-)/ n (VMm+ + VXn-)
tc
pX = - lg[TMX (VMm+ + VXn-).n/(VMm+ . NMm+ - VXn- . NXn-)]
(III60)
C th minh ho vic xy dng ng chun kt ta thng qua trng hp
chun 20 ml Cl- 0,1N bng dung dch AgNO3 0,1N (TAgCl = 1,78.10-10). Chun xy
ra theo phng trnh:
Cl- + AgNO3 = AgCl + NO3Cc s liu tnh ton c ghi trong bng B.7.3.
Bng B.7.3: pCl dung dch khi chun 20 ml Cl- 0,1N bng dung dch AgNO3
0,1N (TAgCl = 1,78.10-10)
Trng thi chun
% chun
pCl
Cha chun
0
10
50
90
99
99,9
100
100,1
101
110
150
III- 57
1,00
1,04
1,48
2,28
3,30
4,30
4,87
5,45
6,45
7,43
8,95
Trc im tng
ng
Ti im tng ng
Sau im tng
ng
III- 58
III- 59
III- 60
http://hoahocsp.tk
http://hoahocsp.tk
http://hoahocsp.tk
hay:
69)
(III-
%
chun
Vn dng
biu thc
III- 64
50
90
99
99,9
100
100,1
101
110
150
III- 65
III- 68
III- 69
1010
1012
1016
1020
2,00
2,00
2,00
2,00
2,00
2,48
3,28
4,30
-
2,48
3,28
4,30
5,30
2,48
3,28
4,30
5,30
2,48
3,28
4,30
5,30
2,48
3,28
4,30
5,30
5,15
6,15
7,15
9,15
11,15
6,00
7,00
7,70
7,00
8,00
9,00
9,70
9,00
10,00
11,00
11,70
13,00
14,00
15,00
15,70
17,00
18,00
19,00
19,70
http://hoahocsp.tk
http://hoahocsp.tk
bng baz mnh c bc nhy di hn chun axit yu bng baz mnh, chun kt
ta vi TMX cng nh th bc nhy cng di
4. Bc nhy ng chun ph thuc vo nng dung dch cc cht tham gia
phn ng, nng cng ln bc nhy cng di. Ring trong chun oxi ha kh th
bc nhy t ph thuc vo nng .
5. Khi chun hn hp nhiu cht th thu c ng chun vi nhiu bc
nhy tng ng vi tng cht, bc nhy trc l ca cht hot ng mnh hn. Tuy
vy, cc bc nhy ch r rng tch ra khi nhau khi hng s cn bng ca cc phn ng
m chng tham gia khc nhau r rt. V d: Vi sai s 0,1%, cc hng s cn bng ca
cc phn ng phi hn km nhau 104 ln.
b. ng dng ca ng chun
ng chun c nhiu ng dng trong thc t nh:
1. Xc nh sai s chun .
V d: khi chun trung ho dng chun ti mt gi tr pHkt no th sai
s chun l bao nhiu? xc nh sai s ch cn dng ng cong chun tng
ng. T trc tung (pH) xc nh pHkt v trn trc honh tm tr s phn trm chun
tng ng vi pHkt, cui cng l tnh sai s %: sai s% = % chun - 100.
2. Chn cht ch th thch hp m bo chun vi chnh xc cho trc.
Cht ch th mu c dng phi c khong i mu nm trong bc nhy ca ng
chun (mc 7.1 chng III) v c gng sao cho ch s chun pT nm gia khong
i mu.
3. Chn cch thao tc chun thch hp.
i vi ng cong chun i xng c th chun theo c 2 chiu m vn
t c chnh xc nh nhau nu cng dng mt tr s chun . V d: chun
axit mnh bng baz mnh hoc ngc li, nu dng chun pH = 5 th vic chun
theo chiu tng pH (a baz vo axit) hay chiu gim pH (a axit vo baz) u
cho kt qu nh nhau.
i vi ng cong bt i xng th ch c mt cch chun sao cho tr s i
lng o thay i t phn bin i chm sang phn bin i nhanh, v nh hng ca
git d l khc nhau mi phn ng cong. C th: khi chun axit yu bng baz
mnh th phi a baz mnh vo axit, chun baz yu bng axit mnh th phi a
axit mnh vo baz, hay, trong chun oxi ho kh b tr dung dch ca cp trao i
electron t hn trn buret, v d, chun xc nh ion Fe2+ bng K2Cr2O7 th a ion
Fe2+ vo dung dch K2Cr2O7).
4. Chn nng thch hp ca cc dung dch tham gia phn ng.
Bc nhy ng cong chun cng di khi nng cng ln, nn trnh s pha
long dung dch chun mt cch khng cn thit v nn s dng dung dch tiu chun
c nng cao. Song, khng nn dng nng qa cao ca dung dch tiu chun
trnh sai s git d (git d l git dung dch cht tham gia phn ng gy ra s i mu
ca ch th, v khng phi ton b git ny tham gia phn ng).
V d: chun xc nh NaOH bng HCl, nu dng HCl 0,1N ht 20 ml, cn
nu dng HCl 1N ht 2 ml, th sai s do git d (1 git tng ng vi 0,03 ml) gy nn
s l:
- Trong trng hp dng HCl 0,1N: e% = (0,03 . 100)/20 = 0,15 %
- Trong trng hp dng HCl 1N:
e% = (0,03 . 100)/2 = 1,5 %
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7. CH TH
C rt t cc phn ng chun , m , bn thn cc cht tham gia phn ng c
mu v t n ch th im tng ng nh s xut hin hoc s bin mt ca cht mu
ny. V d: chun cc cht kh bng dung dch tiu chun KMnO4, th li dng mu
tm ca KMnO4 lm ch th im tng ng, khi mu tm hng xut hin s dng
chun . Cc phn ng chun ny c gi l cc phn ng t ch th. Cc chun
loi ny c chnh xc rt cao, v sai s y ch l sai s git d.
Trong i b phn cc trng hp chun , nhm xc nh im tng ng
phi dng ch th. Ch th l mt hp cht hay mt dng c o c a vo dung dch
chun . Ti im tng ng hay xung quanh im tng ng, ch th bng s thay
i tnh cht ca mnh bo hiu im kt thc chun . Trong phn tch th tch hay
dng ch th l nhng cht mu hay cht to mu (gi chung l ch th mu).
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7.2. Khong i mu ca ch th
Khi chun , tr s chun lin tc thay i lm cho cc thnh phn ca ch th
thay i dn n mu sc thay i. Tuy vy, trong chun thng dng mt nhn
bit s thay i mu m kh nng ca mt ch c hn, n ch c th nhn c mu sc
trong nhng gii hn nht nh ca nng cht mu. Khong nng gii hn li
ph thuc vo tr s chun . Khong tr s chun m mu ca ch th thay i
mt con ngi nhn bit c, c gi l khong i mu ca ch th.
Khong i mu ca ch th ph thuc vo ch th mt mu hay hai mu.
a. i vi nhm ch th mt mu
Vi loi ch th ny, khng c s pha trn mu gia cc dng ca ch th, nn s
nhn c mu ca mt ph thuc vo nng ca dng mang mu. Thng mt nhn
c mu khi trong dung dch c nng ca dng mang mu khong 10-5 10- 6 mol/lt.
V d: vi ch th phenolphtalein ch nhn thy mu hng khi nng dng baz ca ch
th ny trong dung dch l > 10- 6M.
b. i vi nhm ch th hai mu
y, c s pha trn mu, nn, vic nhn thy thay i mu ca mt ph thuc
vo t l nng cc dng mang mu ca ch th.
Thng mt ch nhn thy mu ca mt dng no khi n chim khong 1/10
tng lng cht mu. V d: vi ch th axit baz:
HInd H+ + Ind
CInd = [HInd] + [Ind]
mt nhn thy mu chuyn sang mu ca dng [Ind-] khi: ([Ind-]/CInd ) 1/10 v khng
thy s chuyn na khi ([Ind-]/CInd ) 9/10 v t s ny thay i ph thuc vo pH dung
dch.
* Vi ch th axit baz:
Nu k hiu ch th axit baz c dng axit l HInd v dng baz l Ind-, c:
HInd H+ + Indvi hng s phn li:
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chng i bng cch cho vo dung dch NaOH, KOH mt t mui BaCl2 v lc ly dung
dch, sau mi xc nh nng ca cc dung dch ny.
c. Cc cht ch th thng dng trong chun trung ho
Thng dng ch th l cht hu c c tnh axit yu, baz yu v c mu dng axit
khc mu dng baz (bng B.9.3).
Bng B.9.3: Cc cht ch th thng dng trong chun trung ho
Tn ch th
Bromthymol
xanh
Metyl da cam
Metyl
Phenol
Phenolphtalein
pKaHInd
7,30
Khong
i mu
(pH)
6,2 7,6
0,1g trong nc
0,1g trong cn 60%
0,1g trong cn 20%
0,1g trong cn 50%
3,46
5,00
8,00
9,00
3,1 4,5
4,2 6,2
6,8 8,4
8,0 10,0
Mu ca cc dng
axit
baz
vng
xanh
vng
khng
mu
vng
chanh
vng
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Dung dch tiu chun thng dng l FeSO4, Ti2(SO4)3, Na2S2O3 t hnh
thnh cc phng php chun st (II), chun titan, chun thiosunphat
Cc cht gc thng dng K2Cr2O7, KIO3, Ce(SO4)2.
c. Ch th thng dng trong chun oxi ho kh
Trong chun oxi ho kh thng s dng 3 loi ch th: t ch th, ch th
khng lin quan n in th dung dch v ch th c lin quan n in th dung dch.
* T ch th:
l chun vi dung dch tiu chun KMnO4 trong mi trng axit. Mt git
d KMnO4 lm dung dch chuyn t khng mu sang mu hng, bo s kt thc ca
chun .
* Ch th khng lin quan n in th:
Cht ch th to phc mu vi mt dng oxi ha kh ca cht cn xc nh hoc
thuc th. Khi d mt git dung dch tiu chun s xy ra s chuyn mu. V d: chun
it vi ch th h tinh bt th s chuyn mu l do vic to ra hay mt i mu xanh tm
than ca phc cht it h tinh bt
* Ch th lin quan n in th:
l cc ch th c tnh oxi ho kh. S chuyn mu ca n lin quan cht n
th in cc ca dung dch. Tu theo tng phn ng chun m chn ch th thch hp.
Mt s ch th thng dng c nu bng B.10.3.
EoInd
S e
trao
i
1
Mu ca cc dng
oxi ho
kh
xanh
tm
khng
mu
khng
mu
khng
mu
Diphenylamin
1g trong H2SO4 c
0,76
tm
Axit N phenylanthranylic
0,2g trong nc
1,08
tm
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lm mi trng cho chun ny, dng axit H2SO4 m khng dng axit HCl.
Tng t, chun khng c tin hnh nu mu cha ion Cl-, bi v, th in cc ca
clo EOCl2 / 2Cl- = 1,36V, nh hn th in cc ca cp MnO4-/Mn2+, nn ion MnO4- oxi ho
c ion Cl-:
2MnO4- + 10Cl- + 16H+ = 5Cl2 + 2Mn2+ + 8H2O
Trong trng hp khng th loi tr c ion Cl-, th cho vo dung dch chun
MnSO4, hn ch nh hng ca ion Cl-.
Vi chun pemanganat khng cn dng cht ch th, v bn thn ion MnO4- c
mu tm hng, s xut hin hoc mt mu tm hng bo hiu im kt thc chun . Do
trong chun trc tip lun b tr KMnO4 trn buret.
Pemanganat l mt cht oxi ha mnh nn dng chun pemanganat c th xc
nh c nhiu cht bng nhng cch chun khc nhau:
+ Chun trc tip: Xc nh c nhng cht tham gia phn ng trc tip vi
ion MnO4- nh: Sn2+, Fe2+, AsO33-, Sb3+, Ti2+, Ti3+, [Fe(CN)6]4-, NO2-, H2O2, H2C2O4,
ancol
+ Chun ngc: Dng xc nh cc cht kh km bn trong mi trng
axit, do to cht bay hi, d phn hu, nh S2-, SO32-, I-. Trong trng hp ny, cho
KMnO4 d vo dung dch chun v lng d ca KMnO4 c xc nh li bng
dung dch tiu chun FeSO4.
Chun ngc cng cn dng xc nh cc cht oxi ha nh MnO2, PbO2,
K2Cr2O7, H2O2 Trc tin, cho cc cht ny phn ng vi dung dch tiu chun
H2C2O4 hay FeSO4 ly d, sau lng d ca H2C2O4 hay FeSO4 c xc nh bng
chun pemanganat.
+ Chun th: Cc ion kim loi Ca2+, Sr2+, Ni2+, Co2+, Mn2+, Cd2+, Cu2+
khng phn ng vi ion MnO4-, nhng li to kt ta hon ton vi ion C2O42-, thu ly
kt ta ri ho tan trong axit H2SO4 v chun lng axit H2C2O4 gii phng ra bng
KMnO4.
+ Cch pha dung dch tiu chun KMnO4: V KMnO4 rn d b phn hu bi nh
sng v nhit cao nn n khng phi l cht gc. Sau khi ho tan lng cn tnh
vo nc ct, yn trong bng ti v ni mt 72 gi ri cht ly phn dung dch trong
hoc lc dung dch bng phu lc s hoc thu tinh (khng lc qua giy lc). Dung dch
thu c mang chun li bng dung dch tiu chun gc H2C2O4 nhit 60 80oC
(v nhit thp, phn ng xy ra chm):
60oC 80oC
+
2KMnO4 + 5H2C2O4 + 6H
=
10CO2 + 2K+ + 2Mn2+ + 8H2O
v bo qun trong cc bnh mu nu ni ti v nhit thp.
* Chun bicromat (bicromatomet):
L php chun vi dung dch tiu chun K2Cr2O7 v tin hnh trong mi
trng axit (pH 0) theo phng trnh phn ng:
K2Cr2O7 + 6e + 14H+ = 2K+ + 2Cr3+ + 7H2O
EoCr2O72-/ 2Cr3+ = 1,36V,
([H+] = 1M)
K2Cr2O7 = MK2Cr2O7/ 6
Mi trng axit c duy tr bng axit H2SO4 hoc axit HCl. Khc vi phng
php chun pemanganat, trong chun ny ion Cl- khng gy nh hng n kt qu
phn tch. Nhng khi tin hnh chun nhit cao, th ion Cl- s gy nh hng, v
lc ny bicromat oxi ha c ion Cl-, gii phng Cl2.
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dch c xc nh bng dung dch tiu chun Na2S2O3. Dung dch c bo qun trong
bnh mu v ni ti, mt.
Trong trng hp chun ngc c th dng bin php iu ch trc tip I2
trong dung dch bng phn ng:
KIO3 + 5KI + 6H+ = 3I2 + 6K+ + 3H2O
KIO3 = MKIO3/6
y, ch cn ly chnh xc mt lng KIO3 (KIO3 l cht gc) tng ng vi lng
I2 cn c v cho tc dng vi dung dch KI d trong mi trng axit H2SO4 hoc axit
HCl.
Dung dch tiu chun Na2S2O3 c pha t Na2S2O3.5H2O. V Na2S2O3.5H2O
khng phi l cht gc nn dung dch sau khi pha cn c xc nh li nng bng
dung dch tiu chun gc K2Cr2O7, KBrO3 hay KIO3 bng cch cho cc dung dch tiu
chun gc K2Cr2O7, KBrO3, KIO3 phn ng vi KI d trong mi trng axit:
K2Cr2O7 + 6KI + 14H+ = 3I2 + 8K+ + 2Cr3+ + 7H2O
K2Cr2O7 = MK2Cr2O7/6
KBrO3 + 6KI + 6H+ = 7K+ + 3I2 + Br- + 3H2O
KBrO3 = MKBrO3/6
ri chun lng I2 gii phng ra bng dung dch Na2S2O3 vi ch th h tinh bt.
Dung dch Na2S2O3 sau khi pha xong c b sung vi git CHCl3 chng vi khun n
lu hunh.
Khi s dng phng php it - thiosunphat cn lu :
- Chun ch tin hnh pH = 0 8, bi v pH thp hn 0, axit HI c th t
phn hy to thnh I2 (2HI H2+I2), cn pH > 8 s xy ra phn ng:
I2 + 2OH- IO- + I- + H2O
gy mt it hoc cho phn ng ph bi kh nng oxi ha mnh ca IO-.
- Do phn ng ca I2 vi cht kh hoc ca I- vi cht oxi ha thng xy ra
chm, nn cn c thi gian cho phn ng xy ra hon ton.
- It d bay hi, nn khng chun vi dung dch nng v khi chun gin
tip, phi y kn bnh phn ng trong khi I2 phn ng vi cht kh hay khi iu ch I2.
- B mt mt s cht kt ta, cht keo c kh nng hp th I2,, nn khi chun
cn lc k, nht l gn im tng ng.
- Phc cht it h tinh bt ch thun nghch khi nng it thp, nn khi chun
gin tip phi chun khng c ch th n khi nng it cn rt thp (mu vng
nht) mi cho ch th vo v chun tip.
- Dung dch KI d b oxi khng kh oxi ha:
4I- + O2 + 2H2O I2 + 4OHnn trong chun th cn lm mu trng. Cng do phn ng ny, m trong chun
gin tip s mt mu ca ch th ch cn bn trong 30 giy, v sau , mu c th s ti
xut hin.
- Dung dch Na2S2O3 khng bn trong mi trng axit mnh:
Na2S2O3 + 2H+ = 2Na+ + S + SO2
nn n c b tr buret v nh t t vo bnh phn ng.
- Nng ca cc dung dch tiu chun I2 v Na2S2O3 cn c kim tra thng
xuyn.
* ng dng chun oxi ha kh:
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8.3. Chun kt ta
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N CH2 COOH
CH2 COOH
axit nitriltriaxetic (complexon I)
HOOC CH2
CH2 COOH
N CH2 CH2 N
HOOC CH2
CH2 COOH
axit etylendiamintetraaxetic (complexon II , EDTA)
HOOC CH2
CH2 COONa
N CH2 CH2 N
NaOOC CH2
CH2 COOH
dinatri etylendiamintetraaxetat (complexon III, Na2EDTA, Na2H2Y, Trilon B)
Cc hp cht complexon u to phc cht bn vi hng lot cc ion kim loi vi
thnh phn phn t 1:1, nn chng u c th s dng lm thuc th trong chun xc
nh cc ion kim loi. Song, hp cht complexon III c s dng nhiu nht, v phc
ca n vi ion kim loi rt bn (bng B.11.3), n d tan trong nc hn complexon II v
tinh th Na2EDTA. 2H2O c th c coi l cht gc. S to phc ca complexon III vi
cc ion kim loi c th hin qua phng trnh:
Na2H2Y + Mm+ = MY m-4 + 2H+ + 2Na+
y, quy nh: Na2EDTA = MNa2EDTA/2, nn Mm+ = MMm+/2.
EDTA l mt axit hu c 4 ln axit vi pKa1 = 2,0, pKa2 = 2,76, pKa3 = 6,16 v
pKa4 = 10,26, nn s to phc MYm-4 s ph thuc vo pH mi trng. Phc cht cng
bn th cng c kh nng hnh thnh pH thp hn. Da trn kh nng ny c th chia
cc phc cht thnh 3 nhm:
- Nhm phc cht hnh thnh mi trng axit mnh (pH 1 2): gm phc cht
ca i b phn cc ion kim loi nng ha tr +3, +4 nh Fe3+, Cr3+, Th4+
- Nhm phc cht hnh thnh mi trng pH > 4: gm phc cht ca i b
phn cc ion kim loi nng ha tr +2 nh: Zn2+, Pb2+, Cu2+, Co2+, Ni2+, Fe2+v ion
Al3+.
- Nhm cc phc cht hnh thnh mi trng pH 10: gm phc cht ca cc
2+
ion Ca , Mg2+, Ba2+, Sr2+.
y l c s ca vic chun phn on cc ion kim loi.
Bng B.11.3. Hng s bn phc cht ca mt s ion kim loi vi
axit etylendiamintetraaxetic
Cation
Ag+
Pb2+
Hg2+
Cu2+
Cd2+
Ni2+
Co2+
Fe2+
Fe3+
Phc cht
AgY 3PbY 2HgY 2CuY 2CdY 2NiY 2CoY 2FeY 2FeY -
lg KMYm-4
7,2
18,04
21,8
18,8
16,46
18,62
16,31
14,33
25,1
Cation
Mn2+
Al3+
Zn2+
Ca2+
Sr2+
Ba2+
Mg2+
Cr3+
Th4+
Phc cht
MnY 2AlY ZnY 2CaY 2SrY 2BaY 2MgY 2CrY ThY
lg KMYm-4
14,04
16,13
16,5
10,96
8,63
7,76
8,69
24,0
23,2
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pH mi trng
pH 12
10, m amoni
10, m amoni
13
56
12
2
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* Chun ngc:
Dng xc nh cc ion kim loi to phc chm vi complexon III nh Al3+,
Cr3+ hoc xc nh cc ion d b thu phn, hoc khng c ch th thch hp. Trong
trng hp ny, thng cho cc ion cn xc nh phn ng vi lng dung dch tiu
chun ly d, sau lng dung dch tiu chun d c chun bng MgSO4 vi ch
th eriocrom T en hoc bng cc dung dch tiu chun khc nh ZnSO4, Pb(NO3)2 nu
phc cht ca cc ion ny km bn hn phc cht ca cc cht cn xc nh.
* Chun th:
Dng xc nh mt s ion kim loi to phc cht MYm-4 bn hn phc cht ca
ion Mg2+ (MgY2-). y, cho ion cn xc nh phn ng vi phc cht MgY2-:
Mm+ + MgY2- = MYm-4 + Mg2+
2+
sau lng ion Mg gii phng ra c chun bng complexon III vi ch th
eriocrom T en.
Chun complexon III cho php xc nh nhiu ion trong hn hp da trn s
chun phn on v s che cc ion gy nhiu.
Chun phn on da trn s khc nhau v bn ca cc phc cht pH
khc nhau. Gi thit trong hn hp c nhiu ion th tin hnh chun xc nh cc ion
M4+ ti pH < 1 (Ti4+, Zr4+), chun cc ion M3+ ti pH 2 3 (Fe3+, Bi3+), sau
chun cc ion M2+, Al3+ ti pH 3 5, cn cc ion Ca2+, Mg2+, Sr2+ c chun cui
cng ti pH 10. V d: chun xc nh hn hp Fe3+, Mg2+, u tin chun xc
nh ion Fe3+ pH = 2 vi ch th axit sunphosalyxilic, sau chun tip ion Mg2+ ti
pH = 10 vi ch th eriocrom T en.
Chun vi s che cc ion gy nhiu l da trn s to phc cht bn ca cc
ion gy nhiu vi cc phi t khc nhau; cc phc cht ny bn hn phc cht MYm-4 nn
cc ion kim loi gy nhiu s khng tham gia phn ng vi complexon III. V d:
Dng KCN c th che: Fe3+, Cd2+, Hg2+, Cu2+, Zn2+, Ag+, Ni2+, Co2+.
Dng trietanolanmin che Fe3+, Al3+.
Dng F- che Al3+ , Ti4+, Fe3+, Zr4+
Tm li, chun complexon III vi cc cch thao tc khc nhau cho php xc
nh hng lot cc ion v phng php ny cng ngy cng c ng dng nhiu trong
phn tch nh lng. Di y l nguyn tc chun mt s ion thng gp trong nng
nghip.
+ Xc nh ion Fe3+:
Dung dch cha ion Fe3+ c trung ha v pH = 2 v un n nhit 60oC. Sau
khi cho vo dung dch vi tinh th axit sunphosalixylic, th chun ion st (III) bng
complexon III n khi mu dung dch chuyn t mu hng sang khng mu hoc mu
vng nht (mu ca phc cht FeY-). nh hng ca mu vng ca phc cht FeY- l
khng ng k, cn chun vi dung dch long ( 0,001M).
+ Xc nh cng ca nc (Xc nh ion canxi v ion magie):
Dung dch cha cc ion Ca2+ v Mg2+ th c iu chnh v pH 10 bng dung
dch m amoni v c chun bng complexon III vi ch th eriocrom T en (t
sang xanh).
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Cu hi n tp
1. Nhng yu cu ca phn ng chun ?
2. Phn loi cc phng php chun ? Cch tnh ng lng gam ca cc cht tham
gia phn ng chun ?
3. Cch pha ch dung dch tiu chun?
4. Cc loi nng thng dng trong phn tch th tch? Cch tnh kt qu phn tch?
5. ng chun l g? Cch xy dng ng chun ca tng phn ng chun ?
6. S i mu ca ch th dng trong chun ? Cch chn ch th?
7. ng dng ng chun trong vic chn ch th v trong xc nh sai s ch th?
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8. Cc php chun thng dng (chun trung ho, chun oxi ha kh, chun
kt ta, chun to phc), nguyn tc v phm vi ng dng ca chng?
Bi tp
1. Cn cn chnh xc bao nhiu gam H2C2O4.2H2O (TKPT) pha c 2 lt dung dch
tiu chun 0,1N dng trong chun xc nh KMnO4 trong mi trng axit. (p s:
12,6000gam).
2. Tnh s gam Na2CO3 (TKPT) pha 250 ml dung dch, bit rng chun 20 ml dung
dch ny th ht 30 ml dung dch HCl 0,05N nu kt thc chun ti pH = 8,3. Cho: cc
hng s axit ca H2CO3 l Ka1 = 4,5.10-7; Ka2 = 4,8.10-11. (p s: 1,9875gam).
3. Chun 20 ml dung dch hn hp hai axit H2SO4 v H3PO4. Nu kt thc chun
ti pH = 4,66 th ht 15 ml dung dch NaOH 0,1N. Nu kt thc chun ti pH = 9,8 th
ht 25 ml dung dch NaOH 0,1N. Tnh nng mol/l ca mi axit trong hn hp u.
Cho: cc pKa ca H3PO4 l pKa1 = 2,12; pKa2 = 7,21; pKa3 = 12,38; axit H2SO4 in li
hon ton. (p s: H2SO4 0,0125M, H3PO4 0,05M).
4. Chun 20 ml dung dch CH3COOH 0,1N bng dung dch NaOH 0,1N. Nu php
chun mc sai s: 1%, th khi kt thc chun pH ca dung dch bng bao nhiu?
Bit pKa ca CH3COOH = 4,76. (p s: pH 0,1% = 6,76, pH +0,1% = 10,7).
5. Cho 50ml dung dch NaOH 0,1N vo 90 ml dung dch CH3COOH 0,07N, tnh pH
dung dch sau phn ng! Cn thm vo bao nhiu ml dung dch NaOH 0,1N na th ti
im tng ng? Bit pKa ca CH3COOH = 4,76. (p s: pH = 5,34, 13ml NaOH
0,1N).
6. Cn 6 gam mu gm NaOH, Na2CO3 v H2O pha thnh 1 lt dung dch. Bit rng,
chun 25ml dung dch ny th ht 16,5 ml dung dch HCl 0,1N nu kt thc chun
ti pH 8,3 vi ch th phenolphtalein); cn khi cng chun lng trn, nhng kt thc
chun ti pH = 4 (ch th metyl da cam) th ht 20,5 ml dung dch HCl 0,1N. Tnh %
khi lng cc cht trong mu phn tch? Bit: H2CO3 c pKa1 = 6,35; pKa2 = 10,32.
(p s: 33,33% NaOH, 28,26% Na2CO3, 38,41% H2O).
7. T dung dch HCl 0,3 N v dung dch NH4OH 0,2N, tnh th tch mi dung dch cn
ly pha c 250 ml dung dch m c pH = 8,46. Bit: pKb ca NH4OH = 4,74. (p
s: 89,3ml HCl, 160,7ml NH4OH).
8. T dung dch CH3COOH 1M v dung dch CH3COONa 1M, hy tnh th tch cn ly
cc dung dch pha 250 ml dung dch m CH3COOH/CH3COONa 1M c pH = 5,08.
Bit: pKa ca CH3COOH = 4,76. (p s: 83,3ml CH3COOH, 166,7ml CH3COONa).
9. Cn 1,2 gam mu cha Na2CO3, NaHCO3 v tp cht tr ho thnh 250 ml dung dch.
Chun 50 ml dung dch ny, nu kt thc chun ti pH = 8,3 th ht 5,7 ml dung
dch HCl 0,2N, nu kt thc chun ti pH = 4 th ht 15,2 ml dung dch HCl 0,2 N.
Tnh % khi lng ca mi mui trong mu phn tch. Bit: H2CO3 c pKa1 = 6,35; pKa2
= 10,32. (p s: 50,35% Na2CO3, 26,6% NaHCO3).
10. Cn 0,588gam K2Cr2O7, ho thnh 300 ml dung dch. Cn bao nhiu ml dung dch
ny, khi thm KI d v H2SO4 long ri chun lng I2 gii phng ra ht 25,16 ml
dung dch Na2S2O3 0,1N. (p s: 62,9ml).
11. Ho tan 4,895 g mu ch cha KCl v NaCl thnh 500 ml dung dch. Chun 25 ml
dung dch ny ht 20 ml dung dch AgNO3 0,1N. Tnh % khi lng ca CaCl2 trong
mu. (p s: 76% KCl).
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11. Ho tan 2,062g mu ch cha CaCl2 v MgCl2 thnh 500 ml dung dch. Chun 25
ml dung dch ny ht 35 ml dung dch AgNO3 0,1N. Tnh % khi lng ca KCl trong
mu. (p s: 53,83% KCl).
12. Thm 40 ml dung dch (NH4)2C2O4 0,1N vo 25 ml dung dch cha ion Ca2+. Lc b
kt ta, ly phn dung dch. Tin hnh chun dung dch ny trong mi trng H2SO4
long ht 15 ml KMnO4 0,15N. Tnh s gam ion Ca2+ c trong 1 lt dung dch. (p s:
1,4g ion Ca2+).
13. Ho tan 5 gam mu cha ion Pb2+ thnh dung dch ri kt ta ton b lng ion Pb2+
di dng PbCrO4. Ho tan kt ta bng H2SO4 long v thm KI d. Chun lng I2
gii phng ra ht 25 ml dung dch Na2S2O3 0,2N. Tnh % khi lng Pb trong mu. (p
s: 6,9% Pb).
14. Ha tan hon ton 0,2425 gam mu ch cha mui ca cc ion Ca2+ v Mg2+ thnh
500 ml dung dch. Ly 20 ml dung dch ny v iu chnh pH n 10 ri chun ht
11,75ml dung dch complexon III 0,016N vi ch th eriocrom T en. Nu chun 10
ml dung dch ny pH = 12 vi ch th murexit ht 4,85 ml dung dch Trilon B ni trn.
Tnh % khi lng ca Ca v Mg trong vi. (p s: 32% Ca, 4,06% Mg).
15. Tnh s ml dung dch ch th K2CrO4 0,5M cho vo 20 ml dung dch NaCl 0,1N,
khi chun xc nh ion Cl- bng dung dch AgNO3 0,05N th mc sai s + 0,1%. Bit:
TAgCl = 1,78.10-10; T Ag2CrO4 = 1,1.10-12. (p s: 0,12ml).
16. Ho tan 0,0202 gam vi ri kt ta hon ton ion Ca2+ di dng CaC2O4. Ho tan
kt ta bng dung dch H2SO4 long d ri thm vo 35 ml dung dch KMnO4
0,0366N. Lng KMnO4 d c chun bng 9,57 ml dung dch FeSO4 0,1N. Tnh %
khi lng ca Ca trong mu phn tch. (p s:31,9%).
17. Mt mu nc khong ch cha mui hydrocacbonat v sunphat ca cc ion Ca2+ v
Mg2+. Chun 100ml nc ny vi ch th metyl da cam (pHkt = 4) ht 20,5 ml dung
dch HCl 0,04N. Mt khc, sau khi un nng ri chun 50 ml nc khong ny pH =
10 vi ch th eriocrom T en th ht 20 ml dung dch Trilon B 0,025N. Tnh cng
ton phn v cng vnh cu ca nc khong. (p s: cng tm thi K = 8,2,
cng vnh cu K = 10).
18. Ho tan 5 gam mu c cha ng thnh 250ml dung dch ion Cu2+. Ly 25 ml dung
dich ny cho tc dng vi dung dch KCNS v KI ly d. Chun lng I2 gii phng
ra ht 15 ml dung dch Na2S2O3 0,1N. Tnh % khi lng Cu trong mu. (p s:19,2%
Cu).
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Chng IV
PHN TCH CNG C
1. PHN LOI PHNG PHP
Phn tch cng c l cch thng gi ca phn tch bng cng c gm cc phng
php phn tch m dng cc my o nh gi v theo di cc i lng vt l, ho
hc lin quan n h phn tch. Phn tch cng c l lnh vc rt rng bao gm nhiu
phng php khc nhau, da vo tng tc ca cht cn phn tch vi cc tc nhn phn
tch v tnh cht c trng ca i lng o c th chia thnh cc nhm c bn sau: cc
phng php quang hc, cc phng php o in t, cc phng php tch, cc phng
php nhit.
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Nng lng ca tia t ngoi v nh sng nhn thy tng ng vi nng lng
Ee, nn n to nn s dch chuyn electron t orbian ny sang orbitan khc (thay i
trng thi orbitan) to nn quang ph. Khi vt cht hp th bc x in t c quang ph
hp th vng t ngoi v kh kin, thng c gi l quang ph hp th dch chuyn
electron. Vng nh sng t ngoi v nh sng nhn thy gm cc sng c bc sng t
200 800 nm (2000 8000 AO) c nng lng kch thch cc electron lin kt dch
chuyn t orbitan lin kt sang orbitan phn lin kt.
Vng nh sng ny c chia thnh 3 vng nh vi cc bc sng nh sng ( )
khc nhau:
- Bc sng <200nm - vng t ngoi chn khng
- Bc sng t 200 n 400nm - vng t ngoi gn
- Bc sng t 400 n 800nm - vng nh sng nhn thy.
Thng thng hay s dng vng nh sng t ngoi v nh sng nhn thy, v d
khng ch iu kin o. Phng php o vi di bc x in t c cc bc sng t 400
n 800nm cn c gi l phng php trc quang so mu hay ngn gn l phng
php so mu.
Phng php so mu da trn s chuyn thnh phn xc nh thnh hp cht hp
th nh sng vng nhn thy ri o lng hp th nh sng, t suy ra hm lng
thnh phn cn phn tch.
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1.l.C A2 = 2.l.C.
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a
b
Hnh H.1a.4, H.1b. 4: Mt s dng ng A = f(C)
+Dung dch mu l dung dch tht, tc trong dung dch khng c kt ta, huyn
ph hay nh tng, v cc ht ny tn x mnh nh sng v lm thay i cng nh
sng i ra khi cuvet chiu vo b phn o.
+ iu kin o l thng nht mi mu, v o so mu l php o so snh. Khi
iu kin o thay i c th dn n:
- Nng cht mu thay i. V d: Khi s dng dung mi l cc cht d bay
hi, nu thi gian o khng nh nhau, lng dung mi bay i khng nh nhau dn n
nng bin i khc nhau, to nn sai s phn tch.
- Thay i dng cht mu. V d: Khi o mu vng ca ion CrO42-, nu pH dung
dch thay i chuyn sang mi trng axit, trong dung dch hnh thnh ion Cr2O72- c
mu da cam:
2 CrO42- + 2H+ =
Cr2O72- + H2O,
vng
da cam
lm sai lch s o.
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+ Khng pha long dung dch mu, nht l i vi cc phc cht mu khng bn
v khi pha long phc cht mu b phn li, v d: ML M + L lm cho phc cht mu
thay i v cng mu cng nh dng mu (mu ca dng ML sang mu ca dng L)
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a
b
Hnh H.2a.4 v H.2b.4: ng biu din ph thuc A= f(t)
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Da trn s cng tnh ca nh lut Lambe - Bia (biu thc IV- 5), c th xc
nh n cht mu cng mt lc nu o hp th quang ca dung dch phn tch n bc
sng i ( i = 2, 3,, n) khc nhau. Nh vy, khi biu din hp th quang tng bc
sng s c n phng trnh th hin mi tng quan A 1, A 2, ., A n vi cc nng
ca n cht mu. Gii h phng trnh bc nht ny s thu c cc gi tr nng ca
cc cht mu. Thng thng hay chn cc bc sng ng vi s hp th cc i ca
tng cht mu. V d: Xc nh ng thi chlorophyl a v chlorophyl b trong dung dch
da vo vic o hp th quang 2 bc sng 662nm ( max ca chlorophyl a) v
644nm ( max ca chlorophyl b).
* To nh sng n sc:
Hin nay, c 3 phng php to nh sng n sc, l dng knh lc, dng lng
knh v dng mng. Ph bin nht l 2 phng php dng knh lc v dng lng knh, v
sn phm to ra c gi thnh r cho php sn xut cc my o vi gi thnh r.
+ Phng php dng knh lc:
l dng c lm bng knh trong ho tan nhng cht mu c th hp th
mt phn nh sng trng, do , ch cho phn nh sng cn thit i qua. B lc ny c
phn gii 20 100 nm tu theo tng knh lc, v th, khi cn o hp th quang mt
bc sng c th, khng th dng loi my o vi phng php to nh sng n sc
ny. Hin nay, thng cc my o c thit k vi 5 - 7 knh lc cho vng nh sng
nhn thy.
+ Phng php dng lng knh:
y l phng php tch nh sng da trn s khc x ca cc tia nh sng khi i
qua lng knh. nh sng trng khi i qua lng knh s b tch ra thnh cc nh sng mu
khc nhau. phn gii t 0,1 - 0,5nm, t chnh xc cn thit cho o hp th
quang ca mt bc sng c th.
2.4. o so mu
a. My so mu
My o c hai loi, loi 1 tia sng (H.4a.4) v loi hai tia sng (H.4b.4). Loi 1
tia sng n gin, r tin, song, khng th t ghi quang ph (ph hp th), thng dng
trong o ng dng, o phn tch nh lng. Loi 2 tia sng cho php t ghi quang ph,
song, t tin, thng dng trong nhng nghin cu c bn gm c nghin cu phn tch
nh tnh v phn tch nh lng. to nh sng trng dng n si t vonphram,
to nh sng t ngoi dng n thu ngn hoc n deuteri. Cuvet dng cho o vng
nh sng nhn thy c lm t thu tinh thng, song, cho o vng nh sng t ngoi
gn phi lm t thu tinh thch anh.
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b
Hnh H.4a.4, H.4b.4: S my o so mu: a- loi 1 tia sng, b- loi 2 tia sng
b. Cc phng php so mu
* Phng php so mu bng mt:
Mt c kh nng nh gi mc bng nhau ca hai cng nh sng, nn thc
cht phng php so mu bng mt l dng mt so snh cng mu ca dung dch
phn tch vi cng mu ca dung dich tiu chun. Thng phng php ny c
chch xc khng cao (sai s khong 5 - 10% hoc ln hn tu tng mu), song, tin hnh
n gin v nhanh, rt thch hp cho phn tch ti hin trng.
tin hnh xc nh cc cht c th s dng cc phng php sau:
+ Phng php dy tiu chun:
Ly 6 ng nghim ng nht, cho vo y dung dch tiu chun ca cht cn xc
nh vi lng tng dn. Sau , thm dung dch thuc th v cc ho cht cn thit
khc n th tch bng nhau s nhn c dy tiu chun vi cng mu tng dn
(c gi l dy mu chun). Cho mt lng dung dch phn tch vo ng nghim khc
(ging ng lm dy tiu chun) v cng tin hnh tng t nh lm vi ng tiu
chun. em so snh ng phn tch vi dy mu chun, nu mu ging mu ca ng tiu
chun no th hm lng cht phn tch bng hm lng ca cht c trong ng tiu
chun, nu mu ca ng phn tch nm gia mu ca hai ng tiu chun th hm lng
cht phn tch bng trung bnh cng lng cht c trong hai ng tiu chun.
+ Phng php pha long:
Ly 2 ng nghim nh nhau, cho vo ng 1 dung dch tiu chun v vo ng 2
dung dch phn tch. Tin hnh to mu nh nhau cho c hai ng. Nu mu ca hai ng
khng nh nhau, th cho thm dung mi vo ng c mu m hn n khi mu hai ng
bng nhau. Ghi th tch ca c hai ng. Lng cht phn tch c tnh theo biu thc
IV- 6:
wpt = wtc.Vpt/Vtc ,
(IV- 6)
Trong : wtc - l khi lng cht tiu chun, wpt - l khi lng cht phn tch, Vtc - l
th tch dung dch ca ng cha cht tiu chun, Vpt - l th tch dung dch ca ng cha
cht phn tch. Phng php ny ch dng cho phn tch cc cht mu bn, khng b
phn hu do s pha long.
+ Phng php chun so mu:
Ly hai ng nghim nh nhau. Cho vo ng th nht dung dch phn tch, cho
thm cc thuc th v ho cht khc to mu ri v ln th tch V. Cho vo ng th
hai ch c thuc th v cc ho cht khc v cng ln th tch V. Dng buret nh tng
git dung dch tiu chun nng cao ( cho s thay i th tch sau ny l khng ng
k, <10%) vo ng 2 cho n khi mu ca hai ng nh nhau. Da vo lng dung dch
tiu chun dng suy ra hm lng cht cn phn tch.
* Phng php so mu bng my:
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3.1. t vn
Phng php o in th l da trn vic o th in cc ca in cc nhng
trong dung dch phn tch, th ca in cc ny l hm ca nng cht cn phn tch:
E = f(C). Nh vy, t gi tr th o c ca in cc c th suy ra nng cht cn
phn tch. in cc ny c gi l in cc o (in cc lm vic, in cc ch th).
Phng php o in th c tin hnh theo cch o trc tip (tc thng qua
hiu in th o c tnh ra hm lng cht cn phn tch), v d: o pH, o cc ion
Ag+, Cl- v mt s ion khc hoc cch o gin tip, v d: chun vi vic s dng
phng php o hiu in th xc nh im tng ng. Cch o th hai c ng
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dng rng ri trong chun trung ho, chun kt ta, chun to phc v c bit
trong chun oxi ho kh.
3.2. in cc
C th chia in cc theo c ch hot ng lm hai nhm chnh: 1- nhm c th
in cc hnh thnh do xy ra s trao i e trn bn in cc, 2- nhm in cc c th
in cc hnh thnh do s trao i hoc khuch tn ion qua li bn in cc.
a. Nhm c th in cc hnh thnh do xy ra s trao i e trn bn in cc
y l cc in cc c th in cc c hnh thnh do phn ng trao i e xy
ra trn in cc. Th ny c xc nh bi cc phng trnh Nerst I:
(IVE = EOMm+/M + (0,059/m)lg[Mm+],
8)
cho phn ng: Mm+ + me = M, v phng trnh Nerst II hoc Nerst - Peterson:
E = EOox/kh + [0,059/(m-n)]lg([ox]a/[kh]a),
(IV9)
v d: cho phn ng: aMm+ + a(m-n)e = aMn+
Cc in cc loi ny li c chia thnh hai nhm nh: 1- in cc h ng tnh
v 2- in cc h khng ng tnh.
+ in cc h ng tnh:
Cc cht tham gia phn ng u tan trong dung dch. in cc c lm bng
kim loi tr nh Pt. Nhm in cc ny dng o in th ca h, , xy ra phn
ng oxi ho kh:
aox + ane akh
hoc
aox + amH+ + ane akh + (m/2)H2O
Th in cc ca in cc c xc nh bi phng trnh Nerst II (IV- 9). in cc loi
ny c dng o nng ca cc cht tham gia phn ng oxi ho kh trong dung
dch.
+ in cc h khng ng tnh:
Mt trong hai cht tham gia phn ng oxi ha kh nm trong dng rn. in cc
dng trong cc trng hp ny c lm t chnh cc kim loi hot ng M, hoc Pt ph
kim loi hot ng, hoc ph cht khng tan ca kim loi hot ng. (Khi nim kim loi
hot ng l kim loi c cc ion tham gia phn ng cn theo di). Nh vy, c cc dng
tng tc sau:
- Kim loi M v ion Mm+ hoc phc cht ca n. in cc c cu trc: Mm+ | M,
c gi l in cc loi I. Th in cc ca in cc c xc nh bi phng trnh
Nerst I (IV- 8). in cc loi ny c dng o nng ca cc ion Mm+.
- Kim loi M v mui khng tan MXm hoc cc hidroxit M(OH)m khng tan. in
cc c cu trc: MXm | M, M(OH)m | M, c gi l in cc loi II. Th in cc ca
in cc cng c xc nh bi phng trnh Nerst I, tuy nhin, c s tham gia ca cc
anion X hoc cc ion OH-:
E = EOMm+/M + (0,059/m)lg[Mm+], song, do c phn ng to kt ta, v d: MXn,
m+
nn [M ] = TMXm/[X-]m. Thay gi tr ny vo biu thc IV- 8 s c: E = EOMm+/M +
(0,059/m)lg TMXm/[X-]m. V TMXm l hng s, nn nhp lgTMXm vi EOMm+/M ri t thnh
hng s mi EoMm+/M v nh vy biu thc IV- 8 tr thnh:
10)
(IV-
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3.3. o in th
Khng th o trc tip c th n cc ca mt in cc no , v th, phi s
dng php o so snh vi mt in cc bit gi tr th ca n. in cc bit th ca
n c gi l in cc so snh. in cc ny phi c th n nh trong iu kin o.
Nh vy, thit b o in th gm: in cc lm vic, in cc so snh v dng c o
hiu in th.
a. in cc so snh
+ in cc so snh tiu chun l in cc hydro chun:
in cc c cu trc l mt thanh Pt c ph mt lp PtO2 nhng trong dung
dch c hot ca H+ = 1 (aH+ =1), c h ny c t trong bu kh quyn hydro vi
p sut 1atm (Pt(PtO2) | aH+, H2). nhit 20o C, th in cc ca in cc c qui
nh l bng 0.
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in cc tiu chun hydro rt cng knh, nn trong phn tch ng dng thng
dng cc in cc khc d ch to v bn hn nh in cc calomen v in cc bc bc clorua.
+ in cc calomen:
y l loi in cc so snh tt nht v c s dng nhiu nht. N thuc vo
in cc loi II, c cu trc l Hg2Cl2(bo ho),KCl | Hg(Pt). Phn ng ca in cc l:
Hg2Cl2(rn) + 2e = 2Hg + 2ClTu theo nng KCl np trong in cc m n c cc gi tr in th khc
nhau. Thng thng s dng cc nng ca KCl: bo ho, 1M v 0,1M, trong nng
bo ho c s dng nhiu nht. nhit 25o C, th in cc ca cc loi in cc
ny nh sau:
in cc calomen 0,1M KCl
+0,335V
in cc calomen 1M KCl
+0,280V
in cc calomen KCl bo ho
+0,241V
+ in cc bc-bc clorua:
Cng thuc vo nhm cc in cc loi II. in cc c cu trc AgCl(bo
ho),KCl | Ag, hoc AgCl(bo ho),KCl | Pt m bc. Phn ng ca in cc nh sau:
AgCl(rn) + e = Ag + ClTh in cc ca n cng ph thuc vo nng KCl np trong in cc Thng
s dng cc loi in cc vi nng ca KCl: 0,1M, 1M v bo ho. nhit 25o C,
th in cc ca cc loi in cc ny nh sau:
in cc bc - bc clorua 0,1M KCl
+0,290V
in cc bc - bc clorua 1M KCl
+0,236V
in cc bc - bc clorua KCl bo ho
+0,197V
b. in cc o
C th s dng cc loi in cc m t ti mc 3.2 chng IV n trn. Tuy vy,
tu theo phn ng cn theo di hoc cht cn xc nh m chn la loi in cc thch
hp. C th:
+ Theo di phn ng trung ho:
Thng s dng in cc thu tinh.
+ Theo di phn ng oxi ho kh:
Thng s dng in cc lm bng cc kim loi tr nh Pt, Au.
+ Theo di phn ng kt ta v to phc:
Thng s dng cc loi in cc loi II v loi III.
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pH 25O
1,085
2,075
3,567
3,719
4,010
4,714
6,855
9,180
11,82
12,45
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Cn gi l phng php trch li. y, thnh phn cht gy nhiu hoc thnh
phn cn phn tch c chit ra khi hn hp bng dung mi thch hp.
V d: khi phn tch ion Hg2+ di dng kt ta HgS vi thuc th H2S, th kt
ta thng b ln nguyn t S. lm sch kt ta, khng th lm cho S bay hi v HgS
b thng hoa theo, do , chit S bng CS2 hoc nitrobenzen. Khi phn tch cht bo
trong nng sn c th chit n bng petrolejete , sau phn tch cht bo. Khi phn
tch cc mui ho tan trong t th chit chng bng nuc ct
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Biu thc IV- 15 cho they, nu hng s phn b thc nghim K ln hoc th
tch dung mi hu c rt ln, th ch cn chit mt ln l c th t E% chit gn 100%.
Song trong thc t, hng s K v lng dung mi hu c khng ln cho php ch
chit mt ln, lc ny cn s dng phng php chit nhiu ln, nh vy, hiu qu ca
vic s dng dung mi chit s cao hn. V d: Khi chit bng n ln chit vi th tch
ca hai tng khng i s c :
E% = 100.{1 - [Vnc/(K Vhc+Vnc)]n}
(IV- 16)
T cho thy, khi chia dung mi chit thnh nhiu phn chit th hiu qu
chit s cao hn. iu ny rt c li khi s dng cc dung mi c t l phn b nh hoc
cc dung mi t tin.
Trong Ho phn tch thng chit tch cc cht v c ra khi nhau thng qua
vic chit cc phc cht dng ni phc (v d: [Al(8-hydroxiquinolin)3]) hoc cc hp
cht axociat (ht cng hp) (v d H[FeCl4]) khng mang in tch ca chng.
Do phn ng to phc cht thng gii phng ra ion H+, nn khi cc ion khc
nhau cng to phc vi mt phi t th bn ca phc cht cng khc nhau ph thuc
vo pH ca mi trng. V th, bng s iu tit pH mi trng c th tch chn lc cc
ion ra khi nhau. V d: vi hn hp ion Al3+ v Mn2+ c th cho chng to phc cht
vi 8-hydroxiquinolin, ri chit phc cht ca ion Al3+ trc pH 3 4 (lc ny s to
phc cht ca ion Mn2+ khng xy ra), sau chit phc cht ca ion Mn2+ pH 6 7.
Cu hi n tp
1. nh lut Bug - Lambe Bia? Phm vi ng dng ca chng?
2. Tnh cng tnh ca ca nh lut Bug - Lambe Bia? v ng dng tnh cht ny?
3. Ph hp th v ng dng ca n ?
4. Nguyn tc ca cc phng php so mu bng mt v bng my?
5. Cc loi in cc dng trong o in th dung dch?
6. Nguyn tc xc nh pH bng phng php o in th.
7. Hng s phn b, hng s phn b thc nghim, % chit l g? Biu thc tnh ca chng?
Bi tp
1. So mu bng mt xc nh cht X theo phng php pha long. Khi th tch ca ng
mu phn tch v ng mu chun l V1, th mu ca ng phn tch nht hn. Sau khi cho
thm V2 ml nc vo ng mu chun th mu ca hai ng l nh nhau. Hy tnh khi
lng cht mu X trong ng phn tch, nu bit khi lng cht mu X trong ng chun
l a mg. (p s: a.V1/(V1 + V2).
2. Xc nh h s hp th nh sng ca cht mu X, o hp th quang ca 2 dung
dch cht mu X: o mu dung dch 1 c nng C1 = 10-4M vi cuvet 5 cm c A =
0,60 v o mu dung dch 2 c nng C2 = 4. 10-4M vi cuvet 1cm c A = 0,48. Hi:
c ph thuc vo cuvet v nng cht mu khng? (p s: khng).
3. So mu bng mt xc nh cht X c khi lng mol phn t M theo phng php dy
tiu chun, c mu ca ng phn tch ging ng mu c cha V ml dung dch tiu chun
nng C mol/l. Nu th tch dung dch cht X ly phn tch l VX ml, th khi
lng cht X trong 1 lt dung dch l bao nhiu? (p s: a = M.(VC/VX).1).
Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch113
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Chng V
SAI S TRONG HO PHN TCH
1. SAI S
Trong Ho phn tch, thu c kt qu cui cng ngi phn tch phi tin hnh
rt nhiu thao tc v mi thao tc u c th mc sai st dn n s sai lch kt qu
phn tch so vi gi tr thc ca mu. Sai s phn tch chnh l s sai lch gia kt qu
thu c so vi gi tr thc. Sai s l s kin m ngay c ngi phn tch cn thn nht,
s dng phng tin, dng c cng nh my mc phn tch hon ho nht cng khng
th trnh c.
Sai s thng c ln khc nhau v do nhiu nguyn nhn khc nhau gy nn.
Khng th trnh c sai s nhng c th hn ch tc hi ca n nu nm c nguyn
nhn v qui lut pht sinh ca n chn gii php phn tch tt nht.
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khc phc loi sai s ny cn cn chnh dng c, thit b o, kim tra ho cht
trc khi tin hnh th nghim.
Nu sau khi lm th nghim mi pht hin ra sai s th:
- Tt nht l lm li phn tch.
- Trong trng hp khng th lm li phn tch, th c th hiu chnh kt qu bng
h s xc nh. Trong trng hp trn vi s sai s o ca bnh, kt qu phn tch thu
c c hiu chnh bng cch nhn vi h s 100/99,5.
* Do phng php:
Php o lun cho kt qu ln hn hoc nh hn gi tr thc.
V d: Dng phn ng khng hon ton s lun mc s m (-). khc phc loi
sai s ny cn chn li phng php phn tch, nu khng th chn li phng php, cn
tnh ton sai s ca phng php hoc lm mu kim tra vi i tng chun (cht
chun) v sau chnh l kt qa phn tch theo sai s tnh. V d: Khi phn tch N
trong cc hp cht hu c vi cc vng thm cha N bng phng php Kendan
(Kjeldahl); thng qu trnh cng ph mu khng chuyn ho 100% N v NH3, v th
phi s dng cc ho cht sch c tnh cht tng t cht cn phn tch lm mu chun.
Phn tch mu chun s cho h s hiu chnh hiu chnh kt qu phn tch trong thc
t.
* Do s thin lch ca ngi lm phn tch:
Sai s ny do c nhn ngi phn tch gy nn do thiu kinh nghim hoc c s
thin v khi quan st v tin hnh th nghim hoc tnh ton sai. V d: Khi chun
nhn bit sai v s chuyn mu ca ch th. khc phc loi sai s ny ngi phn tch
cn phi t sa mnh cho cc thao tc tht chun xc.
c. Sai s ng tic (sai s th)
Sai s ny thng ln, khng c qui lut v gy nh hng ln n kt qu cui
cng.
Nguyn nhn gy ra sai s ny l:
* Do chn phng php phn tch khng n nh:
V d: Khi so mu chn phn ng km bn vi thi gian hoc b tc ng ca
khng kh hoc khi phn tch theo phng php khi lng kt tu s dng kt ta c
kh nng hp th cht bn qa ln kh ra sch Cch khc phc l thay i phng
php hoc n nh iu kin o
* Do ngi lm phn tch cu th, khng cn thn:
Nh khi lm phn tch khng tun th qui trnh, khi lm th nghim nh ,
nhm ln ho cht; nhm ln khi tnh ton khc phc loi sai s ny ngi phn
tch cn phi t sa mnh cho cc thao tc tht chun xc.
Trn quan im thc tin sai s cng c th c chia thnh hai nhm: sai s
chnh l c v sai s khng chnh l c. Sai s h thng do dng c, thit b v ho
cht v sai s h thng do phng php l loi sai s chnh l c thng qua con ng
thc nghim hoc thng qua tnh ton. Sai s ngu nhin l loi sai s khch quan khng
chnh l c, song, n rt nh nn c chp nhn. Sai s th l sai s khng chnh l
c v phi c loi ra khi tnh ton kt qu.
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(V-1)
(V- 2)
(V- 3)
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(V- 5)
e% = (dx/x).100
Sai s tng i thng dng biu din chnh xc ca kt qu phn tch.
Trong v d 2 nu trn, sai s e% ca phn tch SiO2 l 0,083%, ca phn tch As l 50%,
nh vy, vic phn tch SiO2 l chnh xc hn phn tch As. Cn vi v d 3, c hai php
o u mc sai s tng i 0,25%, nh vy c chnh xc nh nhau.
Nh vy, tu theo yu cu m biu din kt qu phn tch vi sai s tuyt i
hoc sai s tng i.
2. L THUYT V SAI S
Vic tnh ton sai s phn tch theo cc biu thc V- 1 - V- 5, thng ch dng
cho tnh ton kt qu tng cng on phn tch. Trong thc t, khi tin hnh phn tch,
ngi phn tch trin khai rt nhiu thao tc lin tip nhau c kt qu cui cng. Mi
thao tc mc mt sai s nht nh v sai s ny th hin trong kt qu cui cng. S th
hin ca chng c xc lp bng l thuyt sai s.
Nu mi bc i trong phn tch cho kt qu x1, x2,,xn, sai s dx ca chng l
dx1, dx2,, dxn v sai s % ca chng l ex1, ex2,, exn , kt qu cui cng ca phn tch
l y c biu din nh l hm ca cc xi: y = f(x1, x2,, xn), l thuyt sai s ni nh
sau:
y = f(x1, x2,, xn]
dy = (y/x1).dx1 + (y/x2).dx2 + + (y/xn).dxn v
ey = (lny/x1).dx1 + (lny/x2).dx2 + + (lny/xn).dxn
Nh vy, nu qu trnh phn tch l tng i s cc cng on th:
y = x1 x2 dy = dx1 + dx2 v ey = dy/y
(V6)
Nu qu trnh phn tch l gi tr thu c nhn vi hng s th:
y = kx dy = kdx v ey = ex
(V- 7)
Nu qu trnh phn tch l tch hoc thng ca cc cng on th:
y = x1.x2 hoc y = x1/x2
dy = ey.y v
ey = ex1 + ex2
(V- 8)
Nu qu trnh phn tch l hm m, hm cn ca cc cng on th:
y = xn dy = n.xn-1.dx v ey = nex
(V- 9)
Vic p dng cng thc no hoc t hp cc nhm cng thc ph thuc vo vic
xc nh cc mi tng quan trong tin hnh phn tch. V d: khi cn mu, trc tin
phi cn b (x1) ri cn b + mu (x2), khi lng cn ca mu y = x2 x1. Nu sai s ca
cn l dx, p dng biu thc V- 6 s c: dy = dx + dx= 2dx, suy ra ey = [2dx/(x2 x1)]100.
ng dng l thuyt sai s c th tnh c sai s phn tch khi bit sai s ca tng
cng on v xc nh c cng on no gy ra sai s ln nht c bin php lm
gim sai s phn tch.
V d: pha1 lt dung dch tiu chun CuSO4.5H20 10-4M. Chn la cch pha
trong hai cch sau: 1 - pha trc tip t lng cn, 2- pha long t dung dch m c
nng 10-3M, vi vic s dng cn phn tch c chnh xc 0,1mg v cc dng c
thu tinh tiu chun, sai s cho php 0,1%.
Cch 1: Khi lng mol phn t ca CuSO4.5H20 l 249,685g, vy lng cn pha1 lt
dung dch tiu chun c nng 10-4M l: 249,685. 1. 10-4g tc 24,9685mg 25,0mg,
Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch118
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3.1. ng
Phn tch l ng khi kt qu thu c trng vi gi tr thc. S sai lch gia kt
qu thu c v gi tr thc th hin ng ca php phn tch, gi tr ny cng nh th
ng cng cao. Trong Ho phn tch thng sai lch ny cho php nh hn hay
bng 0,1%, nhng trng hp c th c th cho php cao hn.
3.2. chnh xc
Mt cch gi khc l lp li hay hi t. Khi tin hnh phn tch nhiu ln
lp li (i ln) mt mu vi mt phng php, cc kt qu phn tch thu c thng cng
khc nhau v khc vi gi tr thc mt tr s dxi. Khong gi tr m cc kt qu xi phn b
c gi l hi t ca php phn tch. Nu khong cng nh, th php phn tch c
hi t cng cao; cn khong cng ln, th hi t cng nh hay phn tn cao
(php phn tch c th mc sai s th).
3.3. tin cy
tin cy l tiu ch phi hp bi ng v hi t. Php phn tch c coi
l tin cy cao, khi va cho kt qu c ng cao v va c hi t cao ca cc gi tr
xi. Trong phn tch mu thc t, i b phn cc mu khng c trc gi tr thc cho
nn thng chn cc phng php c hi t cao mc d c th mc sai s h thng.
Cn phng php tuy cho kt qu ng, nhng, phn tn ln khng c chp nhn,
v kh c c s m bo rng ln phn tch lp li tip theo s vn cho ng nh c
(v thng ch c th lp li mt s ln rt hn ch).
ng, hi t v tin cy c ng dng trong vic xc nh s ln phn
tch nhc li ti thiu cn thc hin. Nu phng php phn tch c hi t cao th s
ln nhc li c th t cn nu c phn tn cao th s ln nhc li phi nhiu. Thng
thng, khi xy dng phng php phn tch mi cn nhc li t nht 7 ln, cn khi phn
tch vi phng php c xc nh (khi phn tch hng lot mu) c th gim s ln
nhc li xung 3 hoc 2, v ch trong nhng trng hp nu trn mi c th dng ton
thng k xc nh sai s th, sai s h thng.
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Hnh H.1..5 Minh ha ng, hi t: a- c ng v hi t cao, bkhng c ng nhng c hi t cao, c- c ng nhng khng c hi t.
4. TNH TON SAI S H THNG DO PHNG PHP
Nh trn ni: sai s h thng do phng php c th tnh c v c th s
dng kt qu sai s tnh c kim tra phng php phn tch hoc chnh l kt qu
phn tch, nn vic tnh ton sai s h thng l cn thit.
Trong phng php phn tch ho hc hoc ha l thng s dng cc phn ng
ho hc thch hp tch hoc chuyn ha cht cn phn tch, song, do cc phn ng ny
khng bao gi hon ton nn c nh hng n chnh xc ca php phn tch. Hai
nguyn nhn chnh gy sai s h thng do phng php thng gp trong Ha phn tch
l:
- Do s cn bng ca phn ng ho hc.
- Do kt thc phn ng khng ng im tng ng, v d: ch th phn ng
khng ng im tng ng.
a)
(V(V-
10)
(trong phn ng to kt ta BAn th K c thay bng T v c K = 1/T).
Do vy, sau phn ng lun c mt lng cht A d v y chnh l ngun sai s
v c gi l sai s do phng php. Sai s ny c th tnh l thuyt c t biu thc
V- 10. T biu thc V- 10 c:
[A]
=
[ABn]/K[B]n
(V- 11)
Nu gi nng phn tch ca cht A l CA, s c:
CA = [A] + [ABn]
thay biu thc ny vo biu thc V- 11 c:
[A] = (CA [A])/K.[B]n CA/K.[B]n
(V12)
nu coi [A] CA.
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100[A]/CA=
100/
K[B]n
(M)
tc [B] 5 . 10-5M
thay [B] 5 . 10-5M vo biu thc V- 13 c K 2 . 107.
V d 2: Khi lm kt ta 96 mg ion SO42- bng BaCl2 ti pH = 4, th sai s phn
tch do phn ng khng hon ton l bao nhiu? Nu [Ba2+]d = 10-5 M, V = 200ml,
TBaSO4 = 1,1.10-10.
Gii:
BaCl2 + SO42- = BaSO4 + 2Cl2+
TBaSO4 = [Ba ] [SO42-]. T c:
[SO42-] = TBaSO4/[Ba2+] = 1,1.10-10/ 10-5 10-5 . Do sai s e% l:
e% = 100{[SO42-].V.MSO42-}/wSO42- = 100.10-5. 0,2 . 96/ 96 . 10-3 = -0,2%
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c:
pHkt = 4 < pHt d HCl, kt thc sau im tng ng, vy sai s h thng +.
Bc 4: Tnh ln ca sai s:
a) Ti pHkt = 6: S dng biu thc III- 42:
pH = pKa lg{[NH4Cl]/[NH4OH]} = 14 4,74 lg[VHCl . NHCl/(VNH4OH . NNH4OH
VHCl . NHCl)] 6 = 9,26 + lg{[(VNH4OH . NNH4OH)/VHCl . NHCl] 1 ]}
Thay s vo tnh, c:
VHCl = 20/(1 + 5,5 . 10-4) e% = 100{[ 20/(1 + 5,5 . 10-4)] 20}/20 = 0,06 %
b) Ti pHkt = 4: S dng biu thc III- 38 :
pHkt = 4 = lg[(VHCl . NHCl VNH4OH . NNH4OH)/(VHCl + VNH4OH)], thay s vo s
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Cu hi n tp
1. Sai s phn tch l g? S phn loi sai s v cc cch biu din sai s?
2. L thuyt v sai s? ng dng l thuyt ny?
3. ng, chnh xc, tin cy ca kt qu phn tch? ng dng cc tiu chun ny
trong vic xc nh cch tin hnh phn tch?
4. Cch tnh sai s h thng?
Bi tp
1. Sau khi lm kt ta 80mg ion Ca2+ bng (NH4)2C2O4 ti pH = 10, kt ta c ra 5
ln mi ln 10ml nc. Hy tnh sai s phn tch ion Ca2+ do s ho tan ca kt ta khi
ra! Cho TCaC2O4 = 2,3.10-9. (p s: -0,12%).
2. Tnh sai s khi chun 20 ml dung dch CH3COOH 0,1N bng dung dch NaOH
0,1N vi vic s dng phenolphtalein (pKa = 9) lm ch th im kt thc chun . Cho
pKa ca CH3COOH = 4,76. (p s: ti pH 8: -4%, ti pH 10: +0,2%).
3. Tnh sai s khi chun 20 ml dung dch HCl 0,1N bng dung dch NaOH 0,1N khi
kt thc chun : a) pH = 4; b) pH = 10. (p s: -0,2%, +0,2%)
4. Chun 20 ml dung dch Fe2+ 0,1N bng dung dch tiu chun Ce4+ 0,1N vi ch th
benzidin (ox + e = kh) s mc sai s l bao nhiu? Bit: EoFe3+/Fe2+ = 0,77V, EoCe4+/Ce3+`=
1,44V, EoIndox/Indkh = 0,92. (p s: 1. 0,3%, 2. 0%)
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5. Chun 20 ml dung dch NaCl 0,1N bng dung dch tiu chun AgNO3 0,1N vi ch
th K2CrO4 c nng trong dung dch trc khi chun l 0,1 M th s mc sai s l
bao nhiu? Bit: TAgCl = 1,78. 10-10 ; T Ag2CrO4 = 1,1.10-12. (p s: 0,02%)
6. Nu chit 100mmol cht X t 200 ml dung dch nc bng 50ml dung mi hu c th
sai s thu hi cht X l bao nhiu? Bit hng s phn b thc nghim K = 10. (p s:
28,6%).
7. kim tra phng php Kejdal xc nh N cn 5 mu mi mu l 0,1320g
(NH4)2SO4 tinh khit v em phn tch. Kt qu thu c nh sau: 0,0275g, 0,0279g,
0,0281g, 0,0277g, 0,0275g. Hy tnh sai s tuyt i, sai s tng i ca phng php!
(p s: d = 0,0026g, sai s% 0,93%).
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Cc bng ph lc
Ph lc 1: Tch s tan ca mt s kt ta
Tn hp cht
AgBr
Ag2CO3
Ag2C2O4
AgCl
Ag2CrO4
AgI
Ag3PO4
Ag2SO4
Al(OH)3
AlPO4
BaCO3
BaC2O4
BaCrO4
BaF2
Ba3(PO4)2
Tch s tan
(T)
5,3.10-13
8,2.10-12
3,5.10-11
1,78.10-10
1,1.10-12
8,3.10-17
1,3.10-20
1,6.10-5
1,0.10-32
5,8.10-19
5,1.10-9
1,1.10-7
1,2.10-10
1,1.10-6
6,0.10-39
-lgT
12,28
11,09
10,46
9,75
11,95
16,08
19,89
4,80
32,00
18,24
8,29
6,96
9,93
5,98
38,22
Tn hp cht
CuCO3
CuC2O4
Cu(OH)2
CuS
FeCO3
FeC2O4
FeS
Fe(OH)3
FePO4
Hg2Cl2
HgO
HgS (en)
HgS ()
MgCO3
MgC2O4
Tch s tan
(T)
2,5.10-10
3,0.10-8
2,2.10-20
6,3.10-36
3,47.10-11
2,0.10-7
5,0.10-18
3,2.10-38
1,3.10-22
1,3.10-18
3,0.10-26
1,6.10-52
4,0.10-53
2,1.10-5
8,6.10-5
-lgT
9,60
7,50
19,66
35,20
10,46
6,70
17,3
37,50
21,89
17,88
25,52
51,80
52,40
4,67
4,10
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BaSO4
CaCO3
CaC2O4
CaCrO4
CaF2
Ca(OH)2
Ca3(PO4)2
CaSO4
CdCO3
CdC2O4
Cd(OH)2
CdS
CoCO3
CoC2O4
Co(OH)2
CoS
CoS
Cr(OH)3
CrPO4 (tm)
CrPO4 (lc)
1,1.10-10
4,8.10-9
2,3.10-9
7,1.10-4
4,0.10-11
5,5.10-6
2,0.10-29
9,1.10-6
5,2.10-12
1,5.10-8
5,9.10-15
7,9.10-27
1,4.10-13
6,3.10-8
2,0.10-15
4,0.10-21
2,0.10-25
6,3.10-31
1,0.10-17
2,4.10-23
9,97
8,32
8,64
3,15
10,40
5,26
28,70
5,04
11,30
7,80
14,23
26,10
12,84
7,20
14,80
20,4
24,70
30,20
17,00
22,62
MgF2
MgNH4PO4
Mg(OH)2
Mg3(PO4)2
MnCO3
MnC2O4
MnNH4PO4
Mn(OH)2
MnS
NiCO3
NiC2O4
Ni(OH)2
NiS
NiS
PbCO3
PbC2O4
PbCl2
PbCrO4
Pb(OH)2
PbS
6,5.10-9
2,5.10-13
6,0.10-10
1,0.10-13
1,8.10-11
5,0.10-6
1,0.10-12
1,9.10-13
2,5.10-10
1,3.10-7
4,0.10-10
2,0.10-15
3,2.10-19
1,1.10-24
7,4.10-14
4,8.10-10
1,6.10-5
1,8.10-14
1,1.10-20
2,5.10-27
8,19
12,60
9,22
13,00
10,74
5,30
12,00
12,72
9,60
6,87
9,40
14,70
18,50
24,00
13,13
9,32
4,79
13,75
19,96
26,60
Tch s tan
(T)
1,6.10-8
2,8.10-9
1,4.10-11
1,5.10-9
-lgT
7,80
8,55
10,84
8,80
Tn hp cht
Zn(OH)2
Zn3(PO4)2
ZnS
ZnS
Tch s tan
(T)
7,1.10-18
9,1.10-33
2,5.10-22
1,6.10-24
-lgT
17,15
32,04
21,60
23,80
Ka
1,74.10-5
6,2.10-5
Ka1 5,8.10-10
Ka1 4,5.10-7
Ka2 4,8.10-11
1,4.10-3
Ka1 1,0.10-2
Ka2 2,1.10-3
Ka3 5,4.10-7
pKa
4,76
4,21
9,24
6,35
10,32
2,86
1,99
2,67
6,27
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Ka4 1,1.10-11
1,8.10-4
Ka1 5,6.10-2
Ka2 5,4.10-5
1,0.10-15
Ka1 7,6.10-3
Ka2 6,2.10-8
Ka3 4,2.10-13
10,95
3,75
1,25
4,27
15,0
2,12
7,21
12,38
o- Phtalic C6H4(COOH)2
Ka1 1,1.10-3
Ka2 4,0.10-6
2,95
5,40
Salixylic C6H4(OH)COOH
Sunphuric H2SO4
Tartric
HOOCCH(OH)CH(OH)COOH
1,1.10-3
Ka2 1,2.10-2
Ka1 9,1.10-4
Ka2 4,3.10-5
2,95
1,94
3,04
4,37
Xitric
HOOCCH2C(OH)(COOH)CH2COOH
Ka1 7,4.10-4
Ka2 1,8.10-5
Ka3 4,0.10-7
3,13
4,76
6,40
Focmic H COOH
Oxalic H2C2O4
Phenol C6H5OH
Photphoric H3PO4
Kb
1,76.10-5
4,2.10-10
1,1.10-3
9,8.10-7
9,6.10-6
1,1.10-9
1,5.10-9
pKb
4,76
9,38
2,97
6,01
8,02
8,99
8,82
Al
Dng oxi ho
Ag
AgBr
Ag(CN)2AgCl
AgI
Al3+
+ne
+e
+e
+e
+e
+e
+3e
Dng kh
Ag
Ag + BrAg + 2CNAg + ClAg + IAl
Eo, V
+0,7994
+0,071
-0,29
+0,224
-0,152
-1,66
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AlF63Ba2+
Br2
Ca2+
Cd2+
Cd (CN)42Cd(NH3)42+
Ce(SO4)32Cl2
Co2+
Co(NH3)62+
Cr3+
Cr2O72- + 14H+
Cu2+
Cu2+
Cu+
Cu (CN)42Cu(NH3)42+
F2
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
+3e
+2e
+2e
+2e
+2e
+2e
+2e
+1e
+2e
+2e
+2e
+3e
+6e
+2e
+e
+e
+2e
+2e
+2e
Al + 6FBa
2BrCa
Cd
Cd + 4CNCd + 4NH3
Ce3+ + 3SO422ClCo
Co + 6NH3
Cr
2Cr3+ + 7H2O
Cu
Cu+
Cu
Cu + 4CNCu + 4NH3
2F-
-2,07
-2,90
+1,087
-2,87
-0,402
--1,09
-0,61
+1,44
+1,359
-0,28
-0,42
-0,41
+1,33
+0,337
+0,153
+0,521
-0,43
-0,07
+0,287
H
Hg
I
K
Mg
Mn
N
Na
Ni
Dng oxi ho
Fe3+
Fe3+
Fe2+
[Fe(CN)6 ]32H+
2Hg2+
Hg2+
Hg22+
Hg2Cl2
Hg(CN)42I2
I3K+
Mg2+
Mn2+
MnO4- + 8H+
NO3 - + 2H+
NO3 - + 4H+
NO3 - + 10H+
Na+
Ni2+
Ni(NH3)62+
+ne
+e
+3e
+2e
+e
+2e
+2e
+2e
+2e
+2e
+2e
+2e
+2e
+e
+2e
+2e
+5e
+e
+3e
+8e
+e
+2e
+2e
Dng kh
Fe2+
Fe
Fe
[Fe(CN)6 ]4H2
Hg22+
Hg
2Hg
2Hg + 2ClHg + 4CN2I3IK
Mg
Mn
Mn2+ + 4H2O
NO2 + H2O
NO + 2H2O
NH4+ + 3H2O
Na
Ni
Ni + 6NH3
Eo, V
+0,771
-0,036
-0,440
+0,356
0,0000
+0,907
+0,850
+0,792
+0,2680
-0,37
+0,536
+0,545
-2,925
-2,37
-1,19
+1,51
+0,80
+0,96
+0,87
-2,713
-0,23
-0,49
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O2 + 4H+
O2 +2H+
O2 + 2H2O
H2O2 + 2H+
O3 + H2O
Pb2+
PbBr2
PbCl2
PbI2
S
S + 2H+
S4O62SO42- + 8H+
SO42- + 4H2O
SO42- + 10H+
Sn2+
Sn4+
Pb
Sn
+4e
+2e
+2e
+2e
+2e
+2e
+2e
+2e
+2e
+2e
+2e
+2e
+6e
+6e
+8e
+2e
+e
2H2O
H2O2
4OH2H2O
O2 + 2OHPb
Pb + 2BrPb + 2ClPb + 2IS2H2S
2S2O32S + 4H2O
S + 8OHH2S + 4H2O
Sn
Sn2+
+1,229
+0,682
+0,401
+1,77
+1,24
-0,126
-0,274
-0,266
-0,0,346
-0,48
+0,14
+0,09
+0,36
-0,75
+0,31
-0,14
+0,15
Dng oxi ho
2+
Zn
Zn
Zn (CN)42Zn(NH3)42+
+ne
+2e
+2e
+2e
Eo, V
-0,763
--1,26
-1,04
Dng kh
Zn
Zn + 4CNZn + 4NH3
Mu sc nh sng b hp
th
Tm
Xanh
Xanh lc
Lc xanh
Lc
Vng lc
Vng
Da cam
nh sng b sung
Vng lc
Vng
Da cam
gch
Tm
Xanh
Xanh lc
Lc xanh
http://hoahocsp.tk
B GIO DC V O TO
TRNG I HC NNG NGHIP I H NI
NGUYN TRNG SN (Ch bin)
NGUYN TH HNG LINH, BI TH VNH
GIO TRNH
HO PHN TCH
http://hoahocsp.tk
B GIO DC V O TO
TRNG I HC NNG NGHIP I H NI
NGUYN TRNG SN (Ch bin)
NGUYN TH HNG LINH, BI TH VNH
GIO TRNH
HO PHN TCH
http://hoahocsp.tk
H NI - 2007
http://hoahocsp.tk