I HC NNG

TRNG HC S PHM
BOg

tu 0303

L TH MI

HA HC PHN TCH
Nng, 2006
(Gio trnh dng cho sinh vin chuyn ngnh Sinh Mi trng, Ha k thut)

LI M U
Ha hc phn tch l mn khoa hc v cc phng php xc nh thnh phn nh
tnh v nh lng ca cc cht v hn hp ca chng. Nh vy, ha phn tch bao gm
cc phng php pht hin, nhn bit cng nh cc phng php xc nh hm lng ca
cc cht trong cc mu cn phn tch.
Phn tch nh tnh nhm xc nh cht phn tch gm nhng nguyn t ha hc
no, nhng ion, nhng nhm nguyn t hoc cc phn t no c trong thnh phn cht
phn tch. Khi nghin cu thnh phn mt cht cha bit, phn tch nh tnh phi c
tin hnh trc phn tch nh lng v vic chn phng php nh lng cc hp phn
ca cht phn tch ph thuc vo cc d liu nhn c khi phn tch nh tnh cht .
Phn tch nh tnh da vo s chuyn cht phn tch thnh hp cht mi no c
nhng tnh cht c trng nh c mu, c trng thi vt l c trng, c cu trc tinh th
hay v nh hnh, ...
Phn tch nh lng cho php xc nh thnh phn v lng cc hp phn ca cht
cn phn tch.
Ni dung ca ha hc phn tch l gii quyt nhng vn chung v l thuyt ca
phn tch ha hc, hon thin nhng lun thuyt ring v cc phng php phn tch hin
c v s c xy dng.
Ha hc phn tch ng vai tr quan trng v c th ni ng vai tr sng cn i
vi s pht trin cc mn ha hc khc cng nh cc ngnh khoa hc khc nhau, cc lnh
vc ca cng ngh, sn xut v i sng x hi. Ch cn n c mt v d: Mun tng hp
mt cht mi ri nghin cu cc tnh cht cng nh nhng ng dng ca n nht thit
phi s dng cc phng php phn tch thch hp xc nh thnh phn nguyn t,
mc tinh khit, xc nh cu trc ca n. Chnh v th, Engel tng ni: "Khng c
phn tch th s khng c tng hp".
Do c tm quan trng nh vy nn mt lot cc chuyn ngnh ca khoa hc phn
tch ra i v ngy cng pht tri n mnh nh: Phn tch mi trng, Phn tch khong
liu, Phn tch hp kim, kim loi, Phn tch lm sng, Phn tch d c phm, Phn tch
thc phm, ...
Khi phn tch mt i tng no , nh phn tch phi thc hin cc bc sau
y:
a. Chn phng php phn tch thch hp v cc vn cn gii quyt. Khi thc hin
bc ny cn phi c bit ch n tm quan trng, ngha php l v kinh t ca cng
vic phn tch, ch n ng n, lp li v tnh kh thi ca phng php phn
tch.
b. Chn mu i din l mu c thnh phn phn nh ng nht cho thnh phn ca
i tng phn tch. T mu i din tin hnh chn v chun b mu th nghim l mu
dng tin hnh phn tch cht cn xc nh. Sau thc hin vic bin mu ny thnh
dung dch phn tch.
c. Tch cht: phn tch cc mu c thnh phn phc tp thng phi tch hoc l
cc cht l, cc cht ngn cn php xc nh cht cn phn tch hoc tch ring

cht cn phn tch ra khi hn hp vi cc cht khc.

d. Tin hnh nh lng cht cn phn tch, tc l thc hin cc thao tc, cc php o
c phn tch xc nh nng hoc hm lng cht cn phn tch trong dung dch
mu chun b trong bc trn.
e. Tnh ton kt qu phn tch, nh gi tin cy ca cc kt qu .
Tt c cc bc trn u c tm quan trng v lin quan mt thit vi nhau khng
th b qua v coi nh bc no c.
Ty thuc vo bn cht ca cc phng php phn tch m ngi ta chia chng
thnh cc nhm ch yu sau:
1. Cc phng php ha hc: Cc phng php ny ra i sm nht, nn n nay
ngi ta thng gi nhm phng php ny l nhm cc phng php phn tch c in.
phn tch nh lng mt cht no bng phng php ny, ngi ta ch dng cc
thit b v dng c n gin (nh buret, pipet, cn, ...) thc hin cc phn ng ha hc.
Nhm phng php ny ch dng nh lng cc cht c hm lng ln (a lng)
nhng chnh xc, cho nn n nay phng php ny vn c dng nhiu trong cc
phng th nghim phn tch.
2. Cc phng php phn tch vt l: l nhng phng php phn tch da trn
vic o cc tn hiu vt l ca cc cht phn tch nh ph pht x, phng x, ... cc
phng php ny cn dng nhng my o phc tp.
3. Cc phng php phn tch ha l: l nhng phng php kt hp vic thc
hin cc phn ng ha hc sau o cc tn hiu vt l ca h phn tch, nh s thay i
mu sc, c, pht quang, dn in, ...
Cc phng php phn tch ha l cng nh vt l i hi phi dng nhng my o
phc tp, v vy chng c tn chung l cc phng php phn tch cng c.
Cc phng php phn tch cng c ra i sau cc phng php phn tch ha hc,
chng cho php phn tch nhanh, c th xc nh lng nh cht phn tch kh chnh xc
nn c ng dng rt rng ri. Vi s pht trin v bo ca k ngh in t, cc ngnh
k thut mi v nhng yu cu ngy cng cao ca cc ngnh khoa hc v cng ngh sn
xut hin i i hi v thc y cc phng php phn tch cng c ngy cng c
pht trin v hon thin p ng cc nhim v ngy cng nng n ca ngnh phn tch
hin i.
C s l thuyt chung ca ha hc phn tch l l thuyt v cc phn ng ha hc
dng trong phn tch. Trong gio trnh ny ch cp n l thuyt ca cc loi phn ng
phn tch v cc phng php ha hc s dng cc loi phn ng .
Chng ti xin chn thnh cm n mi c gi gp kin ph bnh v ngh v
quyn sch ny.
Tc gi

CHNG

DUNG DCH CHT IN LY - CN BNG HA HC

4.

Cht in ly mnh v yu.

Cc cht in ly mnh trong dung dch thc t phn ly hon ton. a s cc mui
tan, kim v axt mnh u thuc nhm ny.
Trong dung dch, cc cht in ly yu phn ly khng hon ton. Cc axit yu, baz
yu v phc cht l cc cht in ly yu. c trng cho kh nng phn ly ca cc
cht trong dung dch, ngi ta dng hai i lng l in ly a v hng s in ly
(hng s cn bng).
in ly v hng s in ly lin h vi nhau theo h thc Ostvant nh sau:
K = C-----, trong c l nng ban u ca cht tan.
1 -a
5. Cn bng ha hc v hot . 1.2.1. Nhc
li mt s kin thc cn dng
Trong ha hc, khi tnh ton ngi ta hay dng nng mol/l, cn phn bit cc
khi nim:
Nng gc C0 l nng ca cht trc khi a vo hn hp phn ng.
Nng ban u C l nng ca cht trc khi tham gia phn ng. Nng
ban u khc vi nng gc l do s thay i th tch khi trn cc thuc th vi
CV
nhau: C = .
V
V l th tch thuc th i ly a vo hn hp phn ng. V l tng th
tch ca hn hp phn ng.
Khi mt phn ng t trng thi cn bng th nng cc cht tham gia phn ng
ti thi im c gi l nng cn bng. Nng cn bng thng c k hiu
trong ngoc vung [ ].
V d:
Trong dung dch HCl: HCl = H+ + Cl" th [HCl] = nn CHCI = [Cl-] Trong dung
i

CH COOH

dch CH3COOH: CH3COOH ^ CH3COO" + H+ C

=
3
[CH3COOH] + [CH3COO ]
Theo nh lut bo ton nng th nng ban u ca mt cu t no bng
tng nng cn bng ca cc dng tn ti ca cu t trong dung dch ti thi
im cn bng.
V d: Biu din nh lut bo ton nng ban u i vi ion PO 43- trong dung
dch Na3PO4 0,1 M.
Trong dung dch ta c Na3PO4 = 3Na+ + PO43- ; H2O ^ H+ + OH PO43- + H+ ^
HPO42-HPO4 + H+ ^ H2P04" H2P04" + H+ ^ H3PO4

= C = 01
C 0 = 0,1 = [PO4 ] + [HPO^ ] + [H2PO4 ] + [H3PO4 ]
Mt dng khc ca nh lut bo ton nng l nh lut bo ton in tch. Theo
nh lut ny th m bo tnh trung ha in ca dung dch cht in ly, tng in
tch m ca cc anion c mt trong dung dch phi bng tng in tch dng ca cc
cation c mt trong dung dch. S in tch tuyt i tng loi ion c c bng s ion
tng ng c mt trong dung dch nhn vi in tch ca n. Nh vy tng in tch q
m mi loi ion c bng tch nng cn bng ca ion vi s Avgar N v in
tch n ca mi ion.
q = N[ ]n
V d: Trong dung dch Na3P04 trn ta c:
N[Na+] + N[H+] = N[OH-] + NP2PO4 ] + N[HP042-].2 + N[P043-].3 V ta c:
[Na+] + [H+] = [OH-] + [H2P04 + 2[HP042] + 3[Po4 ].
p

3-

1.2.2. Cn bng v hng s cn bng.

Trong ha hc phn tch ta thng phi tnh nng cn bng ca cc cht tham
gia v c to thnh trong cc phn ng phn tch, tc l nng ca cht khi phn
ng t ti trng thi cn bng. tnh cc nng cn bng, ngi ta thng s dng
biu thc ca hng s cn bng c thit lp bng cch dng nh lut tc dng khi
lng. Gi s xt cn bng ha hc:
mA + nB + ... ^ pC + qD + ... trong A, B, C, D ... l
nhng cu t tham gia cn bng m chng khng tch in. p dng nh lut tc dng
khi lng, ta c:
r = K (1.1)
[A]m[B]trong [A], [B], [C], [D], ... l nng cn bng ca cc cht A, B, C, D, ... v
K l hng s cn bng, l i lng ch ph thuc vo nhit . Nu A, B, C, D, ... l
nhng ion th ta phi tnh n s tng tc gia chng vi nhau nn trong biu thc
(1.1) ta phi thay nng bng hot .
Hot a ca mt cht c xc nh bng h thc:
^
a = fC \ (1.2)
trong , C l nng ca ion; f l h s hot .
i lng f ph thuc vo lc ion ca dung dch. Lc ion biu th tng tc
tnh in gia cc ion trong dung dch.
Nu Z1s Z2, ... l in tch v C1s C2, ... l nng ca cc ion trong dung dch th
lc ion c xc nh bng h thc:
= -2(Z1n
2
C1 + Z2C2 +...) (1.3a) Hoc di dng tng qut:

= T2
2

Z C

(1.3b)

i=1

Nu gn bng 0 tc l dung dch rt long, tng tc tnh in gia cc ion

khng ng k, th f bng 1, hot bng nng .

*Khi < 0,02 th f c tnh bng h thc:

lgf = 4 Iz2V (1.4)
V d 1: Tnh hot ca cc ion trong dung dch hn hp KCl 10-3M, MgS04
10-3M.
Tnh lc ion ca dung dch:
= 0,50.10-3 + 1 10-3 + 22.10-3 + 22.10-3) = 5.10-3 A/ =
7.10 = 0,07
Tnh h s hot ca cc ion:
log f = lgf =-0,05.1.0,07 = -0,035
0,92
K+= Cl =logfMg2+ = logfso2 =-0,5.2
2
.0,07 = -0,14
Mg2 + = S02 - = Tnh hot cc ion:
aK = a = 0,92.10 0,72
= 9,2.10 4mol.l K Cl
aM 2+ = a 2 = 0,72.10
4
= 7,2.10 4mol.lMg4
2

Cl

Cl

S0

+ S04

*Khi 0,02 < <0,2 th f c tnh bng h thc:

logf = 40,5^4^ (1.5)
1
V d 2: Tnh hot ca cc ion trong dung dch KCl 0,1M.
Lc ion ca dung dch:
= 0,5(12.0,1 + 12.0,1) = 0,1.
v = 0,32 H s hot
ca cc ion:
logfK+=lgf"l
3
=f = 0,757 Hot
ca cc ion:
aK = a = 0,757.100,121
41
.mol.l K Cl
*Khi > 0,2 th h s hot f c tnh bng cng thc:

:S

Cl

logf = 40,52^ + h (1.6) 1 + V

trong h l h s thay i cng vi ion.
Thc nghim cho thy rng, trong dung dch long c lc ion gn ging nhau th
f ca cc ion c in tch bng nhau gn ging nhau (bng 1.1)

Lc ion ()
0,001
0,005
0,01
0,05
0,1

in tch 1
0,96
0,92
0,89
0,81
0,77

Bng 1.1 H s F
in tch 2
0,86
0,72
0,63
0,44
0,33

in tch 3
0,73
0,51
0,39
0,15
0,08

in tch 4
0,56
0,30
0,19
0,04
0,01

Nu A, B, C, D, ... trong h thc (1.1) l nhng ion, tc l nhng phn t tch in,
th biu thc hng s cn bng c dng sau:

CD

a(1.7)

a a
Trong trng hp ny, Ka c gi l hng s cn bng hot hay hng s cn
bng nhit ng, i lng ny ch ph thuc vo nhit (khng ph thuc vo hot
). Thay a = fC vo biu
thc (1.7):
q
Ka =
(1.8)
[C]
[A]m[Br...fAmfBtrong , Kc c
gi l hng s cn bng nng , i lng ny ph thuc vo nhit .
Cc hng s cn bng ca cc h khc nhau, v d hng s axit, hng s baz, tch
s ion ca nc, tch s tan ca cc cht kh tan, hng s bn v khng bn ca cc
phc cht ghi trong cc ti liu thng l cc hng s hot . Trong thc t, tnh
ton c n gin, khi tnh nng cc ion trong dung dch, hng s cn bng hot
thng c coi bng hng s cn bng nng , tc l ta b qua s tng tc tnh in
ca cc ion trong dung dch v coi h s hot bng 1. Kt qu tnh ton, nh vy s
thiu chnh xc. Nhng v ta thng dng cc dung dch long nn sai s c th nm
trong gii hn c th chp nhn c.
Trong cc chng sau, n gin ha vic tnh ton, h s hot thng c
coi bng 1.
Gi s chng ta phi xt cn bng trn m cc cht m, B, C, D, ... trong cn
tham gia vo cc phn ng ph khc (nh phn ng trao i proton, phn ng to phc
cht, phn ng to kt ta) th nng ca chng tham gia vo cn bng trn s gim i,
ngha l cc phn ng ph nh hng n cn bng . biu th nh hng ca
cc phn ng ph n cn bng , ngi ta thng dng mt dng hng s gi l hng s
iu kin. Gi [A'], [B'], [C'], [D'], ... l tng nng cn bng ca cc dng ca m, B,
C, D, ... trong dung dch th [A], [B], [C], [D] ch bng mt phn ca cc nng [A'],
[B'], [C'], [D'], tc l:
[A] = [A']am ; [B] = [B'] aB trong am, aB l cc h s nh
hn 1 l nhng i lng biu th nh hng ca cc phn ng ph ti nng ca m,
B, C, D, ... t do.
Thay cc nng cn bng [m], [B], ... trn vo h thc biu din hng s cn
bng nng ca cn bng trn, ta c:

= [C]
[D]q... = [C]p a C[D]q a D
= [C]p[D]q a C a D = K aCaD (19)
m
n
m m
n
m
n
[m] [B] ... [m'] a [B'] a B [m] [B] a aB a aB i lng K' trong h thc (1.9)
c gi l hng s cn bng iu kin, n khng nhng ph thuc vo nhit , vo
lc ion ca dung dch m cn ph thuc vo c nng ca cc cht khc tc l ph
thuc vo iu kin ca dung dch trong cn bng chnh (a) c thit lp. Cc v d
c th s c trnh by trong cc chng sau.
Trong cc phng php ha hc ni ring cng nh trong tt c cc phng php
ca phn tch ni chung, ngi ta thng nghin cu s dng cc loi cn bng chnh
sau y:
* Cn bng axit - baz (hoc cn bng trao i proton)
* Cn bng to phc.
* Cn bng kt ta.
* Cn bng oxy ha kh (hoc cn bng trao i electron).
Trc khi i vo xt c s l thuyt ca cc loi cn bng trn v ng dng ca
chng trong cc phng php ha hc cng nh ha l ca chng, chng ta hy cp
n nguyn tc ca cc phng php ha hc: phng php phn tch khi lng v
phn tch th tch.
K
p

TI LIU THAM KHO

6. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB
KH & KT, 2002.
7. L c, Ha hc phn tch. NXB H Quc Gia H Ni, 2002.
8. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000.
9. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002.

CHNG 2

I CNG V PHN TCH KHI LNG V

PHN TCH TH TCH
10. Nguyn tc chung ca phng php phn tch khi lng
Phng php phn tch khi lng l phng php phn tch nh lng c in.
Tuy phng php ny ra i lu nhng n nay n vn ng vai tr c lc trong cc
phng php xc nh, nht l xc nh cht c hm lng ln v trung bnh trong
mu phn tch. Phng php ny c th dng xc nh hu ht cc nguyn t c
chnh xc v tin cy cao.
y l phng php phn tch nh lng da vo kt qu cn khi lng ca sn
phm hnh thnh sau phn ng kt ta bng phng php ha hc hay phng php vt
l. Do cht phn tch chim mt t l xc nh trong sn phm em cn nn da vo khi
lng ca sn phm em cn d dng suy ra lng cht phn tch trong i tng phn
tch.
Qu trnh phn tch mt cht theo phng php khi lng:
* Chn v gia cng mu.
* a mu vo dung dch (ph mu) v tm cch tch cht nghin cu khi dung
dch (lm phn ng kt ta hay nh phn).
* X l sn phm tch ra bng cc bin php thch hp (ra, nung, sy, ...) ri
em cn tnh kt qu.
V d: xc nh magie, ngi ta tin hnh nh sau:
Ha tan mu phn tch trong dung mi thch hp chuyn ton b lng magie
vo dung dch di dng ion Mg
2
+. Ch ha dung dch bng cc thuc th thch hp kt ta hon ton v chn lc ion
Mg2+ di dng hp cht kh tan MgNH4P04. Lc, ra kt ta ri sy v nung n nhit
thch hp chuyn hon ton thnh hp cht Mg2P207. Cui cng cn xc nh
khi lng ca n. Da vo cng thc ca kt ta v khi lng va cn c s tnh
c hm lng Mg trong mu phn tch. Trong v d ny hp cht MgNH4P04 c kt
ta tch nh lng magie nn c gi l dng kt ta cn Mg2P207 l hp cht c
to thnh sau khi nung dng kt ta v c cn xc nh hm lng ca magie nn
c gi l dng cn. Phng php phn tch khi lng magie nh trn c gi l
phng php kt ta. Phng php kt ta l phng php c s dng ph bin nht
trong phn tch khi lng.
11. Gii thiu v cc phng php phn tch khi lng.
12. Phng php y.
Da vo vic tch thnh phn cn xc nh dng n cht ri cn.
V d: Xc nh lng vng trong mt hp kim nh sau: ha tan hp kim bng
nc cng toan thnh dung dch. em ch ha dung dch bng nhng thuc th thch
hp ri kh chn lc v nh lng vng (III) thnh vng kim lo i mu. em lc ra kt
ta mu ri sy v nung n khi lng khng i, lm ngui ri cn.
13. Phng php kt ta.
Trong phng php ny ta dng phn ng kt ta tch cht nghin cu ra khi
}

dung dch phn tch, thu ly kt ta, lc, ra, em nung ri cn kt qu.
V d: Khi cn phn tch lng st (Fe) trong mt dung dch ta c th dng phn
ng to kt ta Fe(0H) 3 bng thuc th nh NH 3, lc kt ta Fe(0H)3, nung v cn
dng Fe203, t khi lng Fe203 thu c ta d dng tnh c lng Fe trong dung dch
nghin cu.
14. Phng php in phn
Ngi ta in phn tch kim loi cn xc nh trn catt bch kim. Sau khi kt
thc in phn, em sy in cc ri cn v suy ra lng kim loi thot ra trn cc
bch kim. Phng php ny thng c dng xc nh cc kim loi trong mi
trng m pH = 7.
15. Phng php chng ct
Trong phng php ny cht em phn tch c chng ct trc tip hay gin tip.
Trong phng php chng ct trc tip, cht em phn tch c chuyn sang dng bay
hi ri hp th n vo cht hp th thch hp. Khi lng ca cht hp ph tng ln mt
lng tng ng vi cht hp th vo.
V d: Khi cn phn tch C02 trong vi ta c th phn hy lng cn mu trong
mt dng c ring bng axt ri hp th ton b kh C0 2 gii phng ra vo cht hp th
thch hp nh hn hp Ca0 v Na0H hay Ba(0H )2. Cn khi lng cht hp th trc v
sau khi hp th s tnh c lng C02 trong vi. Trong phng php chng ct gin
tip, ngi ta un cho bay hi ht cht cn phn tch. V d: C th xc nh hm lng
nc kt tinh trong cc loi mui bng cch sy di mt nhit xc nh.
Ni chung phng php chng ct khng phi l ph bin v n ch c p dng
khi mu phn tch c cha cht bay hi hoc d dng chuyn sang cht bay hi.
Sau y ta ch nghin cu 2 phng php chnh, l phng php kt ta v
phng php in phn.
2.3. Phng php kt ta.
2.3.1. Ni dung v yu cu ca kt ta trong phng php kt ta.
Phng php kt ta l phng php da vo vic cn sn phm tch ra bng phn
ng kt ta. Trong phng php ny ngi ta thc hin mt lot cc thao tc nh lc,
ra, sy, nung, ... Trong qu trnh nung, thnh phn ca kt ta c th thay i. V vy
ngi ta phn bit 2 dng: dng kt ta v dng cn. 2.3.1.1. Yu cu ca dng kt ta.
* Dng kt ta phi c tan nh th mi kt ta c hon ton cht cn xc
nh. Thc t cho thy rng i vi cc kt ta loi mB, v d: BaS04, mgCl, ... th tch
s tan phi b hn 10-8 mi s dng c cn tch s tan ln hn 10 -8 th khng s dng.
Cht phn tch c lm kt ta mt cch nh lng, v d kt ta ti 99,99%.
* Dng kt ta phi tinh khit, tinh th ht to khi lp l giy lc, gim bt
hin tng cng kt v d lc, ra c th tch ra khi dung dch mt cch nhanh
chng v thun li nht.
Kt ta v nh hnh v c bit l li ng t nh ml(0H)3 c b mt tip xc ln
nn hin tng cng kt y rt ln, kh ra v lc rt chm. Trong mt s trng
hp, ngi ta c th to iu kin thch hp thu nhn c kt ta tinh th ht ln.

* Dng kt ta phi d dng chuyn sang dng cn.

2.3.1.2. Yu cu ca dng cn
* Thnh phn kt ta sau khi sy hoc nung phi ng ng cng thc nh trc.
V d: ml(0H)3 c dng cn thng ngm mt s phn t nc nn mun chuyn
thnh dng ml203, ta phi nung n nhit trn 1100 0C. Trong trng hp ny ta c th
chn dng kt ta l cc mui baz ca nhm chuyn thnh ml 203 ngay nhit
6400C hn dng ml(0H)3.
* Kt ta thu c sau khi nung phi bn v t ht m, kh b oxy ha trong
khng kh. Yu cu ny cng nhm m bo cho cht sau khi nung ng vi cng thc
nh trc. V d: Kt ta Ca0 d dng hp ph H20 v C02 t khng kh, thng ngi
ta chuyn sang dng CaS04 bng cch cho tc dng vi axit sunfuaric.
* Hm lng ca cht cn phn tch trong dng cn cng t cng tt. Nh vy s
gim c sai s h thng ca kt qu phn tch. V d: Cng mt i lng v sai s
tuyt i, trong khi xc nh Cr di dng kt ta BaCr0 4 v Cr203 th sai s v lng Cr
tm c trong BaCr04 s b gp 3,5 ln khi tm Cr203. V d: Khi xc nh Cr, nu mt
i 1mg kt ta th i vi dng cn l Cr203 s mt i 0,7mg Cr cn vi dng BaCr04 ch
mt 0,2mg Cr.
2.3.2. iu kin tin hnh phn tch theo phng php kt ta. 2.3.2.1.
Thuc th.
Thuc th dng trong phn tch khi lng c th l thuc th hu c hay v c.
Trong qu trnh to kt ta hin tng cng kt xy ra rt mnh, trong s ion b cng kt
c c ion ca thuc kt ta m khi ra cng khng th sch hon ton c. V vy cn
chn thuc th d bay hi hoc d phn hy trong qu trnh nung sy. V d: khi kt ta
Fe3+ di dng Fe(0H)3 th dng NH40H ch khng dng K0H hay Na0H, kt ta Ba2+ th
dng H2S04 ch khng dng Na2S04 hay K2S04. mg+ th
dng HCl ch khng dng NaCl. Nhng nguyn tc ny khng phi dng lc no cng
c. V d: kt ta Cu(0H)2 ngi ta khng dng NH40H bi nu tha NH40H s to
phc [Cu(NH3)4] m phi dng K0H hay Na0H. Trong trng hp ny cn phi ra kt
ta cn thn.
Thuc th cng c chn lc cao cng tt. V nh vy s trnh c hin tng
cc kt ta khc cng kt ta theo kt ta chnh. V d: khi xc nh ion ml3+ bng
NH40H v cn di dng ml203. Nu c mt Fe3+ th cng to Fe203. Do trong trng
hp ny ngi ta dng Na2S203:
2ml3+ + 3S2O3 + 3H2O 2ml(0H)3 + 3S + 3SO2
Lc v ra kt ta (ml(0H)3 + S) ri nung th lu hunh chy ht cn ml203. Ion
3+
Fe trong trng hp ny khng kt ta m b kh ti Fe2+.
Lng thuc th cng ng vai tr rt quan trng trong phng php khi lng.
Thc t cho thy rng khng tn ti kt ta no m li hon ton khng tan trong nc.
Do vy tch s tan lun lun ln hn 0. T ta thy rng khng th kt ta hon ton
bt k mt cht t tan no t dung dch. Trong phn tch nh tnh ngi ta thy rng qu
trnh kt ta c coi l hon ton khi lng ion cn xc nh cn li trong dung dch t
n mc m khng th dng phn ng no nhn ra c. Tng t nh vy trong
phng php khi lng qu trnh kt ta c coi l
2+

2-

hon ton khi hm lng ion cn li trong dung dch khng vt qu 0,0002g. Thng
thng th i vi cc kt ta c tan b ta ch cn lng thuc kt ta tng ng vi
lng tnh theo phng trnh phn ng l thu c kt ta hon ton. Khi kt ta c
tan khng nh hoc cht phn tch trong dung dch kh long, m bo kt ta
hon ton ta cn tng lng thuc kt ta lm gim tan ca kt ta. C nhiu trng
hp vic tng lng thuc kt ta khng nhng lm gim tnh tan m cn lm t ng tnh
tan theo hiu ng mui, s to phc, mui axit tan, do kt ta l lng tnh ... Thng
ngi ta dng lng thuc th d gp 1,5 ln lng cn thit tnh theo phng trnh phn
ng. 2.3.2.2. Nng thuc th.
i vi kt ta l dng v nh hnh hay tinh th ta c yu cu v nng khc
nhau.
* Kt ta v nh hnh:
Vi kt ta v nh hnh th tt nht l kt ta t cc dung dch c, nng. Khi lm
kt ta v nh hnh ta cn ch n xu hng d to thnh dung dch keo ca chng.
Mun lm ng t keo th ngi ta cho thm cht in ly no c ion khc du vi ion
b hp ph: cc mui amonium hoc cc axit (nu axit khng lm tng ha tan ca kt
ta). Sau khi kt ta xong d lc v gim s nhim bn do hp ph, ta pha long dung
dch gp i bng nc ct nng. Lc ny cn bng hp ph s b ph v mt phn ion b
hp ph s li ri b mt kt ta i vo dung dch. Kt ta thu c s chc, t b nhim
bn. Sau khi lm kt ta phi lc v ra ngay ch khng nn lu, lu l bt li v
trong mt s kt ta c th b c qunh li khng ra sch c. Ngoi ra khi lm kt ta
v nh hnh ta thng dng cc dung dch kim cho nn kt ta s b nhim bn cc cht
kh bay hi. V d Si02 t thy tinh ln vo.
* Kt ta tinh th
Vi kt ta l tinh th, c kt ta ln ht ta phi lm gim qu bo ha ca
dung dch bng cch kt ta t dung dch long. tng tan S ca kt ta trong qu
trnh kt ta ngi ta tng nhit hay thm cht no tng tan. Sau khi kt ta
xong cn lm mui kt ta bng cch ngm mt thi gian kt ta vo trong nc ci
thu c kt ta c kch thc ln, ng u, d lc, d ra. Ni chung thu c kt ta
tinh th phi tun theo 5 nguyn tc (xem trang 129). C ch ca qu trnh lm mui kt
ta tinh th nh sau:
V tinh th ln c ha tan b nn dung dch bo ha i vi tinh th ln vn cha
bo ha i vi tinh th b nn tinh th b phi tan ra. Lc ny dung dch li thnh qu
bo ha i vi tinh th ln v cht tan li bm ln b mt tinh th ln. By gi dung dch
li thnh cha bo ha i vi tinh th b do tinh th b li tip tc tan ra. Nhit
tng s lm tng tc lm mui kt ta. Sau khi lm mui ta c khng nhng mt kt
ta d lc m cn tinh khit hn. i vi cc loi kt ta keo k nc th hiu qu ny
khng r lm v trong vi trng hp cn cho kt qu xu. V d ngi ta xc nh c
l lng cc ion Co2+, Ni2+, Zn2+ b kt ta Fe(0H)3 ko theo s tng dn theo thi gian.
iu c ngha l c s hnh thnh dn nhng hp cht ha hc (cc ferit) gia
hydroxyt st v cc cation k trn. gim s hao ht do tnh tan, trc khi lc ngi ta
thng lm lnh lm gim tnh

tan ca kt ta.
16.
Lng cht phn tch.
Lng cn cht ly phn tch phi khng qu nh hoc qu ln. Lng cn ln
qu s thu c qu nhiu kt ta v gy kh khn cho vic lc, ra, nung. Tri li
lng cn qu nh th dung dch sau khi ph mu kh long v c th kh tch hon
ton cht cn phn tch, do kt qu phn tch s kh chnh xc. Theo Tanan-aep lng
cn phi ly th no cho lng cn kt qu phn tch vo khong 0,01 ng lng
gam i vi kt ta l tinh th v 0,005 ng lng gam i vi kt ta l v nh
hnh.
17.
Nhit .
i vi kt ta tinh th th vic un nng c tc dng lm tng tan, lm gim
qu bo ha tng i v gim c s trung tm kt tinh ban u, to c kt ta tinh
th to ht.
i vi kt ta v nh hnh, vic un nng gip ng t v lm to ht.
i vi kt ta c tan tng khi un nng th trc khi lc phi lm ngui v
phi ra bng nc ra ngui. i vi kt ta keo c tan b nh Fe(0H)3 th phi lc
nng v ra bng nc ra nng trnh s pepti ha. 2.3.3. Lc, ra, lm kh v nung
kt ta.
18.
Lc kt ta.
Khi lc ngi ta thng dng giy lc khng tn l giy lc c lm sch gn
ht cc cht v c bng cch ra vi HCl v HF. Khi chy chng ch li mt lng
tro khng ng k, lng ny c ghi v bc cc gi giy lc khng tn. Giy lc
khng tn c nhiu loi dy mng khc nhau ng vi kch thc ca cc phn t kt ta
cn lc. V d mun lc cc kt ta keo v nh hnh rt kh lc th ta nn dng giy lc
mng nht, chy nhanh nh giy bng hay en. Mun lc a s cc kt ta khc th
dng loi giy trung bnh (bng trng) v cui cng mun lc nhng kt ta rt b ht
nh BaS04 hoc CaC204 th nn dng loi giy dy nht (bng xanh).
19.
Ra kt ta.
Mc ch ra kt ta l ui ht cht bn, k c dung dch nc ci dnh kt
ta.
Thnh phn nc ra: c 4 trng hp
* Ra bng dung dch thuc kt ta: Ch trong nhng trng hp him c khi
ha tan ca kt ta l rt b ta mi phi b qua bin php ny. Khi ra kt ta ta cn
phi cho thm vo nc ra mt ion ca kt ta, v d dng mt dung dch long ca
thuc kt ta ra. V tch s hot cc ion l hng s nn khi tng nng ca mt
ion trong dung dch th ha tan ca kt ta s gim n mc c th b qua c. Tt
nhin l ion thm vo (hoc mt cht in gii no khc c cha ion ca kt ta) phi
l mt cht d bay hi khi nung ta c th ui n ra ht khi kt ta.
* Ra bng dung dch cht in ly: Mun ngn nga hin tng ha keo ta
khng nn ra kt ta bng nc ct m nn dng dung dch long ca mt cht in ly
no . Lc by gi cc ion b hp ph trc s b ra sch v kt ta s li hp ph cc
ion ca cht in ly dng ra, y c s hp ph thay th. Cht in
N

ly phi d bay hi hay mui amnium.

* Ra bng cht ngn c kt ta khi thy phn: V d kt ta MgNH4P04 l
mt cht c sn phm thy phn l NH40H:
MgNH4P04 + H20 ^ MgHP04 + NH40H nn s
c ra bng mt dung dch amoniac long.
* Ra bng nc: Trong nhng trng hp kt ta khng b mt do ha tan
cng khng to c dung dch keo v khng b thy phn th c th dng nc ct
ra kt ta.
Trong a s trng hp nc ra cn phi c un nng v nh vy s lm gim c
h s nht v cc dung dch nng s lc nhanh hn. K thut ra:
Trc ht ra bng cch lng v ch khi gn sch ta mi ra kt ta trn giy lc.
Ci li ca cch ra ny l kt ta d trn ln vi nc ra v ng thi cc phn t kt
ta li khng bt l giy lc. Thng ta ra bng cch lng vi ln ri mi chuyn
ton b kt ta ln giy lc. y l lc quan trng nht: Nu nh mt mt git cht
lng l kt qu phn tch c th b hng.
2.3.3.3. Lm kh v nung kt ta.
Sau khi ra, y phu bng mt t giy lc gi cho kt ta trnh khi b bi v
trnh c chuyn ng ca khng kh, t phu vo t sy khong 20 - 30 pht nhit
khong 90 - 1050C. Sau em nung trong chn s hoc chn bch kim n khi
lng khng i.
K thut nung:
Dng a thy tinh c u nhn ko giy lc ra khi phu, gp mp giy th no
kt ta tn ra xung quanh giy ri em b vo chn, cho nh nhn quay ln trn v
nung cho n khi c trng lng khng i. Nu dng l in th trc ht phi t giy
lc n (hoc bp in) v ch sau khi ht khi mi b vo l nung. Sau khi nung
xong (khong 30 pht) cho chn vo bnh lm kh (bnh ht m) chn khi hp th
hi nc trong khng kh v khi tng trng lng. Khng nn y bnh ngay m phi
sau vi pht hy y v nu khng th khi chn ngui trong bnh s c khong chn
khng v ta kh m np bnh.
2.4. Phng php in phn.
20. Ni dung.
in phn l phng php da vo vic cn xc nh khi lng kim loi thot
ra trn in cc bch kim di tc dng ca dng in. Phng php in phn thng
dng xc nh mt s kim loi trong cc hp kim. Phng php ny c coi l
phng php chnh xc xc nh mt s nguyn t nh Ni, Cu, Zn, Cd, v Pb trong
hp kim.
21. Cc thit b.
2.4.2.1. in cc:
Thng l in cc bch kim c ch to theo nhiu kiu khc nhau. Catt
thng l li an bng si bch kim c hnh tr. mnt c th l li hoc dy xon
bch kim. Trong mt s trng hp ngi ta cn dng in cc bch kim dng bt a
bch kim. Ngoi ra cn dng cc in cc bng Ni, mg, AU, ... (hnh 2.1)

22.

Ngun in:
Ngun in thng dng khi in phn l cc c-qui kim hay axit c th khong
12V hay 36V. Ngi ta thng dng my pht in mt chiu hay chnh lu.
23.
Cc thit b o:
24.

Cc xon

Cc li

Cc bt

Ch yu l cc ng h o in nh vn k, ampe k.
Hnh 2.1: Cc loi in cc bch kim thng dng
2.4.2.4. Cc thit b khc:
Bin tr con chy, my khuy in th k. Ngy nay ngi ta ch to cc my in
phn chuyn dng trong phng th nghim.
25. ng dng ca phng php khi lng.
Khi lng cht phn tch ln th phng php khi lng l phng php tin
cy v chnh xc. Phng php ny cho php xc nh hu ht cc nguyn t cn gp
trong thin nhin. Nhc im ca phng php l mt nhiu thi gian, nhiu khi khng
p ng c nhu cu kim tra nhanh trong nghin cu v sn xut. Tuy vy v c tin
cy v chnh xc cao cho nn n nay phng php ny vn c coi l phng php
trng ti nh gi tnh ng n ca cc kt qu phn tch theo cc phng php khc
nhau.
26. Phng php phn tch th tch
27. i cng
Khc vi phng php khi lng, phng php phn tch th tch khng cn c
vo khi lng sn phm phn ng m cn c vo th tch thuc th em dng cho phn
ng suy ra lng cht cn xc nh. Thuc th y bit nng chnh xc. Gi
s cn phn tch mt dung dch cht m, ta phi dng thuc th l dung dch cht B
bit nng chnh xc ri cho tc dng theo phn ng:
m+B=C+D
Phi cho dung dch cht B vo tc dng vi cht m th no cho lng cht B tc
dng vi cht m va theo phng trnh phn ng trn. Theo nh lut ng lng
hoc nh lut hp thc, ta d dng tm ra nng cht m. Phng php ny nhanh hn
phng php khi lng. Ngi ta ch cn o chnh xc th tch ca thuc th em dng
m khng cn tch, ch ha kt ta v cn. Vn quan trng y l phi c bin php
bit lc no l phn ng hon thnh.
28. Mt s nh ngha v khi nim

+ Nh v d nu trn, qu trnh thm t t dung dch chun cht B t burt vo

dung dch cht xc nh m tin hnh phn ng phn tch gi l qu trnh nh phn
(s nh phn) hay s chun .
+ Thi im m cht B thm vo va tc dng ht vi cht m theo phng
trnh phn ng gi l im tng ng.
+ nhn bit c im tng ng thng ngi ta dng cht ch th. Cht ch
th c c tnh thay i mu ti im tng ng trong qu trnh nh phn. Thi im
m mu ca ch th thay i r rt da vo ta kt thc s nh phn c gi l
im kt thc s nh phn hay im cui.
+ Trong trng hp l tng th im kt thc nh phn trng vi im tng
ng. Nhng trong thc t im kt thc nh phn thng sai lch vi im tng
ng. iu ny gy ra sai s cho php nh phn.
+ Dung dch cht B bit nng chnh xc gi l dung dch chun (hay tiu
chun). C hai phng php pha dung dch chun:
* Cn trn cn phn tch (chnh xc n 0,0002g) mt lng cht no , sau
ha tan vo bnh nh mc. Bit c lng cht (g), th tch dung dch thu c, ta d
dng tnh chun ca n: T = g/ml.
* Trong thc t pha dung dch chun ngi ta thng dng cc ng chun
"ixanal". l nhng ng thy tinh c hn kn 2 u, trong c cha mt lng
cht kh no c cn chnh xc hoc mt th tch chnh xc ca dung dch chun
cn thit pha 1 lt dung dch vi nng bit chnh xc, v d: 0,1N; 0,05N ...
Dung dch chun bit nng chnh xc nh trong trng hp ny gi l dung
dch gc v cht tng ng gi l cht gc, dung dch gc cn gi l dung dch tiu
chun.
Yu cu ca cht gc
+ Phi tinh khit v mt ha hc, tp cht khng ln hn 0,05 - 0,1%, c th kt
tinh li c v sy kh mt nhit nht nh.
+ Thnh phn ha hc phi ng ng vi cng thc ha hc. V d cc tinh th
ngm nc phi ng vi s phn t theo cng thc ha hc.
+ Cht gc v dung dch tiu chun phi bn trong thi gian gi gn v nng
phi khng i theo thi gian.
+ Mol ng lng ca cht gc cng ln cng tt tng chnh xc khi xc
nh nng ca dung dch.
S d gi l dung dch tiu chun v n c s dng xc nh nng ca cc
cht khc.
Nhng trong thc t khng phi mi dung dch chun u p ng c yu cu
trn. V d HCl, Na0H . Do vy i vi loi cht ny ngi ta pha vi nng gn ng
(dng ng ong, cn k thut). Sau ngi ta dng dung dch chun gc xc nh
li nng ca dung dch trn. V d nng ca dung dch Na0H c th xc nh bng
dung dch gc l axit oxalic (H2C204.2H20). Dung dch chun m nng ca n ngi
ta xc nh c nh dung dch gc gi l dung dch c chun ha hay dung dch
chun.
Trong thc t nng ca dung dch chun khng phi lc no cng c xc
nh bng mt dung dch gc no . V d xc nh nng dung dch Na0H c

th dng dung dch chun HCl, nng ca dung dch ny li c xc nh bng dung
dch gc khc. V d: dung dch gc borat natri Na 2B407.10H20 hay Na2C03 khan. Bng
phng php ny c th tit kim c cht gc nhng li km chnh xc hn v sai s
s l tng sai s ca cc php chun .
C trng hp ngi ta xc nh nng bng phng php trng lng. V d
xc nh nng HCl c th theo mgCl bng cch cho dung dch HCl tc dng vi dung
dch mgN03.
Cui cng khi phn tch cc hp cht t nhin hay cc sn phm cng nghip
ngi ta dng cc mu tiu chun xc nh nng ca dung dch chun. Mu chun
l mu trong c cha nguyn t cn phn tch nhng bit nng chnh xc. V d
khi xc nh Mn trong thp, ngi ta dng dung dch chun l Na3ms03, nng ca n
c xc nh bng mu thp chun c cha mt hm lng Mn chnh xc bit trc,
hoc khi xc nh ng trong ng thau th xc nh nng ca dung dch chun
Na2S203 bng mu chun ng thau bit trc hm lng ng, v.v... Dng mu
chun c li ch l tt c cc thao tc v cc yu t nh hng n kt qu phn tch l
hon ton ging nhau khi xc nh nng dung dch chun cng nh khi thc hin
phn tch mu cha bit. V vy chnh xc tng ln. 2.6.3. Cc phn ng dng trong
phn tch th tch
Mt c im quan trng ca phng php phn tch th tch l khng s dng d
thuc th m lun theo ng phng trnh phn ng, tun theo nh lut ng lng.
Nh vy r rng l khi nh phn phi xc nh c im tng ng. Trong mt s
trng hp vic xc nh im tng ng rt d dng, da vo s thay i mu ca
dung dch trong qu trnh chun . V d nh phn dung dch FeS0 4 bng KMn04 trong
mi trng axit:
8H+ + 5Fe2+ + Mn04- -- 5Fe3+ + Mn2+ + 4H20
Mi ln thm 1 git KMn04 th mu bin mt rt nhanh v ion Fe 2+ kh mu tm
ca Mn04- n Mn2+. Nhng khi ton b Fe2+ b oxy ha ht th mt git tha KMn0 4 s
lm cho dung dch chuyn sang mu hng hoc tm nht. iu ny ni ln rng im
tng ng qu hay ni cch khc im kt thc nh phn xut hin. Nh vy r
rng l chng ta khng kt thc nh phn ti im tng ng m hi qu mt t v
do s xut hin sai s chun . V nng ca dung dch KMn0 4 rt long v lng
tha khng ti mt git do sai s rt nh v c th b qua.
Phn ng dng v d trn gi l phn ng t ch th. Nhng trong thc t phn
ln cc php nh phn phi dng ch th t ngoi vo, v d khi xc nh nng Cl dng dung dch chun l mgN03 vi ch th l K2Cr04, hoc trong phng php trung ha
ngi ta dng metyl da cam, phenolphtalein.
Tm li, nhng phn ng ha hc dng trong phn tch th tch phi tha mn cc
yu cu sau:
* Cht nh phn phi tc dng hon ton vi thuc th theo mt phng trnh
phn ng xc nh, ngha l theo mt h s t lng xc nh.
* Phn ng phi xy ra rt nhanh. i vi cc phn ng chm, cn lm tng tc
ca chng bng cch un nng hoc dng cht xc tc thch hp.
*Phn ng phi chn lc, ngha l thuc th ch tc dng vi cht nh phn

tch m khng phn ng vi bt k cht no khc.

* Phi c cht ch th thch hp xc nh im cui vi sai s chp nhn c
29. Phn loi cc phng php phn tch th tch.
* Phng php trung ha: Cc phng php ny da trn phn ng c bn l
phn ng trung ha (axit - baz).
* Phng php oxy ha - kh da trn phn ng oxy ha - kh.
* Phng php dng cc phn ng kt hp gm cc phng php sau: phng
php kt ta da vo phn ng kt ta, phng php to phc da vo phn ng to
phc, thuc th dng nhiu nht l cc complexon.
30. Cc phng php chun .
31.
Chun trc tip.
Thm t t dung dch chun vo dung dch nh phn (cn xc nh) hoc ngc
li.
32.
Chun ngc.
Thm mt lng d chnh xc dung dch chun vo dung dch nh phn. Sau
chun lng thuc th d bng mt thuc th thch hp khc. Phng php ny c
s dng khi khng c ch th thch hp hoc khi phn ng chnh xy ra chm. V d
xc nh CaC03 ngi ta cho mt lng tha dung dch chun HCl vo mt lng cn
chnh xc CaC03, sau lng tha HCl c chun bng dung
dch Na0H.
33.
Chun thay th.
Cho cht cn xc nh X tc dng vi mt cht MY no :
X + MY = MX + Y
Sau chun cht Y bng dung dch thuc th R thch hp. Phng php ny
c s dng khi kh xc nh c im tng ng hoc khi xc nh mt hp cht
ha hc no khng bn. V d Cr2+ d b oxy ca khng kh oxy ha v kh chun
trc tip bi mt cht oxy ha no nn ngi ta cho mt lng d Fe 3+ vo dung dch
cn xc nh Cr2+:
Cr2+ + Fe3+ - Cr3+ + Fe2+
Lng Fe2+ c gii phng ra tng ng vi hm lng Cr 2+ v ta chun
2+
Fe rt d dng.
34.
Phng php chun gin tip tc l chuyn cht cn xc nh sang mt cht
khc cha t nht mt nguyn t c th xc nh trc tip c bng mt thuc th v
ch th thch hp. V d xc nh ch trong qung, ngi ta ha tan qung ri lm kt
ta PbCr04, sau ha tan PbCr04 bng dung dch hn hp HCl + NaCl thm d KI v
chun lng I2 thot ra bng Na2S203.
35.
Phng php chun phn on c p dng khi chun mt s cht trong
cng mt dung dch bng mt hay hai dung dch chun.
D cho phng php no i chng na th cng phi:
* o chnh xc th tch ca 1 hay 2 dung dch phn ng.
* Phi c dung dch chun.
* Tnh ton kt qu.
2.6.6. Cch biu din nng trong phn tch
Nng l i lng dng ch hm lng ca mt cu t (phn t, ion)

trong dung dch.

Sau y l cc cch biu din nng trong ha phn tch:
Nng th tch: Nng th tch ca mt cht lng l t s th tch ca cht lng
v th tch ca dung mi (thng l nc). V d dung dch HCl 1:4 l dung dch
gm 1 th tch HCl c (c khi lng ring d = 1,185g/ml) v 4 th tch nc.
Nng phn trm khi lng: Nng phn trm khi lng ca mt cht
trong dung dch l s gam cht tan trong 100g dung dch. Th d dung dch NaOH
25% l dung dch cha 25g NaOH trong 100g, tc l dung dch gm 25g NaOH v 75g
nc.
V d 1: Cn ha tan bao nhiu gam NaCl vo 100g nc c dung dch nng
10%.
t a l s gam NaCl cn ha tan, ta c:
a.100 = 10; suy ra: a = 11,111g
a +100
V d 2: C bao nhiu gam H2SO4 nguyn cht trong 1 ml dung dch axit sunfu-ric c
98% c khi lng ring d = 1,84g/ml? t a l s gam H2SO4 cn tnh, ta c:
.100 = 98; suy ra: a = 1,803g.
1,84
Nng moi: Nng mol ca mt cht l s mol cht tan trong 1l dung dch.
Loi nng ny c k hiu bng ch M hoc mol/l hoc mol.l -1 t sau ch s ch s
mol. V d: dung dch NaOH 0,1M tc l dung dch cha 0,1mol NaOH hoc 0,1x40 =
4,0g NaOH trong 1l dung dch.
Nu a l s gam cht trong V lt dung dch v M l khi lng mol ca cht tan
th nng mol CM c tnh theo cng thc:
Nu V biu th theo ml th:
= a.1000
= M.V , ,
, , V d: Cn ly bao nhiu
gam H2C2O4.2H2O iu ch 250ml dung dch nng
mol l 0,025M?
t s gam tinh th ngm nc cn ly l a, ta c:
0.025 = a 1000 ; suy ra: a = 0,7880g.
126.250
tnh ton kt qu phn tch th tch, ngi ta thng da vo nh lut hp
thc: "Khi phn ng t ti mc hon ton th ta cc i ca mi cht
phn ng phi bng nhau". Ta cc i bng s mol ban u chia cho h s hp
thc ca mi cht.
Gi s ta c phn ng: aA + bB = cC + dD
Trong : a, b, c, d gi l cc h s hp thc ca A, B, C, D.
C V C V inh lut hp thc: A A = B a b
Nng ng lng: Trc kia trong ha hc ngi ta thng dng khi
C

nim ng lng v ng lng gm nn trong ha hc phn tch, c bit trong

phn tch th tch ngi ta thng dng loi nng ny, v da vo nh lut ng
lng th vic tnh ton kt qu phn tch rt thun li v d dng. Nhng ngy nay trn
th gii ngi ta khng dng n khi nim ng lng v mol ng lng na nn
cc nc t dng khi nim nng ng lng.
Nng ng lng ca mt cht l s mol ng lng () ca cht trong
mt lt dung dch hoc s milimol ng lng (m) ca cht trong 1 ml dung dch
v thng c k hiu bng ch N t sau ch s ch nng . V d, dung dch NaOH
0,1N l dung dch cha 0,1mol ng lng NaOH trong 1 lt dung dch ca n. Nu a
l s gam cht tan trong Vl dung dch (hoc a l s mg cht tan trong V ml dung dch)
v l khi lng mol ng lng (), (i lng ny trc kia c gi l ng
lng gam) th c th tnh nng ng lng theo
cng thc: CN =B
a
N .V
Nu a biu din theo gam cn V theo ml th: CN = a^000
N
.V
T cng thc ta suy ra, CN.V l s mol ng lng nu V tnh theo lt v l s
milimol ng lng nu V tnh theo mililit.
Khi lng mol ng lng ca mt s cht l s gam cht v mt ha hc
tng ng vi mt nguyn t hoc mt mol ion H+ hoc OH - hoc X mol oxy (O).
ng lng mol ca mt cht khng phi l mt hng s nh khi lng mol m thay
i ty theo phn ng n tham gia.
Mol phn t ca mt cht th khng thay i, nhng ng lng gam th thay i
theo tng phn ng ha hc. Ta xt ng lng gam ca cc cht trong cc
phn ng sau da trn cng thc tnh mol ng lng ca mt cht: =
n
Trong phn ng trao i:
V d 1: i vi mt axit, n l s ion H+ ca mt phn t axit tham gia vo phn
ng cho: H3PO4 + NaOH = NaH2PO4 + H2O

H3PO4

= M = 98H3PO4 + 2NaOH = Na2HPO4 + 2H2O

3 4 = M = V d 2: i vi mt baz, n l s ion OH4Qg.

H PO

ca phn t tham gia vo phn ng. Ca(OH)2 + 2HCl = CaCl2 + 2H2O

= M = 37

Ca(OH)
2 V d 3: i vi cc phn ng trao i, to phc n l s
in tch m hay dng ca mt phn t cht tham gia vo phn ng cho.
K4[Fe(CN)6] + 2CuSO4 = Cu2[Fe(CN)6] + 2K2SO4

= M = 378 = Q45

K [Fe(CN)6]

6KCl

= -4

4 2K4[Fe(CN)6] + 3ZnCl2 = Zn3K2[Fe(CN)6]2 +

M = 378 = 126

Q4,5g

~~ Trong phn ng oxy ha - kh, n l s e ca 1 phn t cht oxy ha

hay cht kh thu vo hay mt i trong phn ng cho. V d:
10FeSO4 + 2KMnO4 + 8H2O = 5Fe2(SO4)3 + 2MnSO4 + K2SO4 + H2O Fe126g
2
+ - e = Fe3+; MnO4- + 8H+ + 5e = Mn2+ + 4H2O
=M =M
v
K MnO
5
FeSO 1
nh lut ng lng:
"S ng lng ca cc cht tc dng vi nhau hon ton bao gi cng bng
nhau".
V d: A + B C + D th mun cho 2 cht A v B tc dng vi nhau hon ton,
s ng lng ca chng phi bng nhau. C cc biu thc ton hc sau:
*Nu gi VA l th tch dung dch cht A, N A l nng ca ng lng ca
dung dch A v VB, NB l th tch v nng ca dung dch B. Ta c: NAVA = NBVB
'
'
'
'
ag bg
*Nu ag cht A tc dng ht vi bg cht B th: = -^
*Nu VA l th tch dung dch cht A (tnh bng lt) vi NA l nng ng
bg
lng ca dung dch A tc dng ht vi bg cht B th: VANA =
chun.
chun l s gam (hoc miligam - mg) cht tan trong 1 ml dung dch. Nu a l s gam
cht tan trong V ml dung dch th chun T = a/V. chun theo cht nh phn.
chun theo cht cn nh phn l s gam cht cn nh phn (ion, phn t hoc
nguyn t) phn ng ng vi 1 ml dung dch chun v c k hiu l TR /X trong R
l thuc th, X l cht cn nh phn. Cch biu din nng loi ny rt thun tin cho
vic tnh ton kt qu phn tch, c bit khi phn tch hng lot mu ti cc phng th
nghim nghin cu v sn xut.
V d: Tnh chun ca dung dch chun KMnO 4 0,02M theo st, khi chun
Fe2+ theo phn ng:
MnO4- + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
Theo phng php phn ng chun trn, ta c: 1 mol MnO 4 phn ng vi 5 mol
2
Fe +. Trong 1 ml dung dch chun KMnO4 0,02M c cha 0,02/1000 = 2.10-5 mol MnO4v do 1ml MnO4- phn ng vi 5 x 2 x 10-5 = 10-4 mol Fe2+ hoc 10-4 x 56 = 5,6 x
10 g Fe. Do :
0,0056 g
KMnO 0,02M/ Fe =
Nng (hoc hm lng) phn triu v phn t.
i vi cc dung dch rt long hoc c hm lng rt nh ngi ta thng dng
cc khi nim ny.
Phn triu (thng c k hiu l ppm - parts per million) l s microgam

K4[Fe(CN)6]

cht tan c trong mt gm hoc 1 microgam cht tan trong 1 gm dung dch. Mt cch
tng qut ta c:
Khi lng cht tan (g) x10Fe.ml.
6
(ppm) Khi lng dung dch (g) V d: Dung dch Au3+ nng 1 ppm, tc l dung
dch c cha 1 g Au trong 1g hoc 1mg Au trong 1kg dung dch. i vi cc dung dch
nc rt long th c th coi gn ng khi lng ring ca nc bng 1g/ml hoc 1kg/l.
Do , 1ppm = 1 g/ml hoc l 1 mg/l.
i vi cc dung dch long hn, ngi ta dng phn t, k hiu ppb (parts per
billion)
Cppb ,Kh: lng, ch *:m (g) x109(ppb)
Khi lng dung dch (g)
2.6.7. Cch tnh kt qu trong phn tch th tch.
Vic tnh kt qu ph thuc vo cch biu din nng v cch phn tch. Nguyn
tc chung l da vo nh ngha nng , phng trnh phn ng chun , nh lut
hp thc hoc nh lut ng lng m tnh kt qu phn tch.
* Trng hp chun trc tip.
Cch tnh theo nh lut hp thc: Da vo th tch, nng dung dch chun v
phng trnh phn ng chun tnh c lng cht cn phn tch theo s milimol
hoc s mol.
V d 1: Tnh nng mol ca mt dung dch NaOH bit rng khi chun 20ml
dung dch th phi dng va ht 22,75 rnl dung dch HCl 0,1060M.
Phn ng chun : ^
NaOH + HCl NaCl + H2O
S milimol NaOH bng s milimol HCl:
CNaOH x 20 = 0,1060 x 22,75
Suy ra:
CNaOH = (0,1060 x 22,75) : 20 = 0,,1260 M
V d 2: Khi chun 0,2275g Na2CO3 tinh khit n CO2 phi dng va ht
22,35ml HCl. Tnh nng mol ca dung dch HCl .
Phn ng chun : Na2CO3 + 2HCl - 2NaCl + CO2 + H2O
S mol Na2CO3 bng 0,5 s mol HCl.
S mol HCl = (0,2275 : 106) x 2
Nng dung dch HCl = CHCl = (0,2275 : 106) x 2 : 0,02235 = 0,1920M. Cch
tnh theo nh lut ng lng:
Khi tnh theo nng ng lng th cn da vo nh lut v ng lng l:
S mili ng lng mol ca dung dch chun bng s mili ng lng mol cht cn
xc nh phn ng vi nhau. tnh c khi lng cc cht phn ng phi bit
khi lng mol ng lng ca cc cht .
V d 3: Tnh nng ng lng ca dung dch Na 2S2O3, bit rng khi thm
lng d dung dch KI tinh khit vo 20 ml dung dch K 2Cr2O7 0,05N cha axit sunfuric lm mi trng th chun lng I2 thot ra bng 19,80 ml dung dch Na2S2O3
.
Mili ng lng mol Na2S2O3 = 19,80 x NNaSO = s milimol ng lng K2&2O7
= 20 x 0,05. Do , NNa S O = (20 x 0,05) : 19,80 = 0,0506 N.

Cch tnh theo chun cht nh phn.

V d 4: Tnh hm lng phn trm st trong qung, bit rng sau khi ha tan
0,5170 g qung, kh hon ton Fe(III) thnh Fe(II) ri chun Fe(II) bng dung dch
chun KMnO4 c chun theo Fe l 5,620 mg/ml th dng va ht 57,20 ml dung dch
chun .
Theo nh ngha th 1 ml dung dch chun KMnO4 oxy ha c 5,620 ml Fe2+. Vy
lng Fe c trong qung l 5,620 x 37,20 mg.
Phn trm ca Fe l [(5,620 x 37,20) : 517] X 100 = 62,18%.
* Trng hp chun ngc.
V d 5: nh lng Cr trong thp, ngi ta phn hy 1,075 g mu thp thnh
dung dch ri oxy ha hon ton Cr3+ thnh CrO4 . Sau thm vo 25 ml dung dch
chun FeSO4 0,0410 M v lng dung dch axit sunfuric long lm mi trng. Lng
Fe(II) d c chun bng 3,70 ml dung dch KMnO4 0,0400M. hy tnh hm lng
theo % khi lng ca Cr trong thp.
tin li ta tnh theo nh lut ng lng.
Nng ng lng ca dung dch chun FeSO4 bng nng mol ca n, bng
0,0410N. Nng ng lng ca dung dch KMnO4bng 0,0400 x 5 = 0,2N. S mili
ng lng mol CrO4 tc dng vi Fe2+ l:
25 x 0,0410 - 3,7 x 0,2
S ng lng mol Cr trong mu thp bng:
2-

2-

25.0,0415 - 3,7.0,2
1000
Khi lng mol ng lng ca Cr l M:3. Phn trm Cr c trong thp l: 25 0.04103,7.02
. -100- = 0,4595%
1000
3 1,075

* Trng hp chun gin tip.

V d 6: nh lng ch (Pb) trong qung ngi ta phn hy 1,1050 g mu qung
thnh dung dch. T dung dch thc hin quy trnh lm kt ta nh lng ch trong
mu thnh PbCrO4. Sau ha tan PbCrO4 bng dung dch hn hp HCl + NaCl d.
Thm vo dung dch mt lng d KI v cui cng chun lng I2 thot ra bng 24,20
ml dung dch chun Na2S2O3 0,0962N. Tnh hm lng ch trong qung theo % khi
lng.
Cc phn ng chnh ca qu trnh nh lng: CrO4 + Pb2+
PbCrO4^ 2PbCrO4 + 2H+ + 8Cl- 2PbCl42- + Cr2O72- + H2O I2
+ 2S2O32- 2I- + S4O62-Tnh theo nh lut hp thc:
Theo cc phng trnh phn ng trn th 1 mol Pb2+ phn ng vi 3 mol S2O3 . S
mol Pb2+ trong mu l: (24,2 x 0,0962) / (100 x 3). V y hm lng % khi lng ch
trong qung l:
2-

2-

24,2.0,0962.207,2.100 = 14 55%
1000.3.1,105
'%

Tnh theo nh lut ng lng:

Trong trng hp ny khng cn phi vit cc phng trnh phn ng thc

hin vic tnh kt qu v theo nh lut v ng lng, cc cht phn ng vi nhau theo
nhng ng lng mol bng nhau, tc l s ng lng mol ca S 2O32- bng s
ng lng mol ca Pb2+. V mt ion Pb2+ to nn mt phn t PbCrO 4 m CrO4 b
kh thnh Cr3+ vi s nhn 3 electron, nn ng lng mol ca PbCrO 4 bng 1/3 khi
lng mol ca n, v vy cng thc tnh trng vi cng thc u tnh theo nng mol.
2-

BI TP

36.
xc nh hm lng ca CaCO3 trong vi ngi ta cn 0,2560g
mu, ha tan thnh dung dch v kt ta ion Ca2+ di dng CaC2O4. Sau khi lc, ra v
nung kt ta , cn c 0,216g CaO. Tnh hm lng CaCO3 trong mu. CaCO3 =
100, Cao = 56.
37.
Khi phn tch dung dch c chit ra t mt mu t, ngi ta tm c
cc kt qu sau:
Hp cht CaO SO3 MgO CO2 Hm lng %
7,59 5,61 2,20 5,29
T cc s liu trn, hy tnh hm lng ca cc mui MgCO 3, CaCO3, CaSO4 trong
mu t.
38.
Khi phn tch mt mu bari clorua ngi ta tm thy hm lng ca bari
l 56,22%, ca nc kt tinh l 14,73%. Tnh thnh phn % ca bari trong bari clorua
khan.
39.
Phi dng bao nhiu ml dung dch (NH4)2C2O4 4% thc t kt ta ht
canxi c trong 0,4154g vi c hm lng CaO l 43%. Th tch cui cng ca dung
dch khi kt ta l 250ml, canxi c coi nh kt ta hon ton nu lng CaC 2O4 tan
trong dung dch khng qu 10-4g/l. TCaC O = 2,57.10-9, CaC2O4 = 128,
Cao = 56, (M4)2C204 = 124.
40.
Phi thm bao nhiu ml H 2SO4 c 98% (d = 1,84) vo 300 ml nc
dng lng dung dch ra kt ta SrSO 4 v lng kt ta mt i khng qu 10 -4g
TaSO = 2,8J0-7, SrSO4 = 183,7.
41.
Hy tnh mt phn t Na2CrO4 ngm bao nhiu phn t nc, nu em
phn tch trng lng 0,4927g mui ngm nc th cn c 0,1095g Cr 2O3. Cr2O3 =
152; Na2CrO4 = 162; H2O = 18.
42.
xc nh hm lng bari trong mt mu BaCl 2.2H2O, ngi ta cn
0,6531g mu, ha tan thnh 250ml dung dch, ly ra 50ml kt ta ion bari di dng
BaSO4. Sau khi lc, ra, sy v nung kt ta thu c 0,1241g BaSO 4. Tnh hm
lng bari trong mu BaSO4 = 233, Ba = 137.

TI LIU THAM KHO

43. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB
KH & KT, 2002.
44. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000.
45. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002.
46. Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch, NXB
H&TH Chuyn nghip, 1984.
47. B.H.AneKceeB, KaniHecTBeHHbi aHani3, MocKBa, H3gaTej[bcTBo "XiMira",
1972
48. B.H.AneKceeB, KonecTBeHHMH aHani3, MocKBa, H3gaTej[bCTBo "XiMira",
1972

CHNG
CN BNG AXIT

- BAZ. CHUN AXIT - BAZ

3.1. ngha thc t cc quan nim v axit - baz.

49. Thuyt axit - baz ca Areniut.
Theo thuyt ny, axit l nhng cht trong dung dch nc phn ly cho ion hydro
(H+), cn baz l nhng cht phn ly cho ion hydroxyt (OH -). nh ngha ny khng
c tng qut v ch p dng c cho mt s rt hn ch v khi dung mi l nc.
Nhng kt qu nghin cu v dung dch cho thy rng: s phn ly ca cc cht l do
tng tc ha hc vi dung mi, trong dung dch nc ion H+ khng tn ti di dng
t do, n b dung mi ha v tn ti di dng ion hydroxoni (H 3O+), nhng tnh cht
axit - baz cng th hin trong cc dung mi khng nc.
50. Thuyt axit - baz ca Bronsted - Lauri.
3.1.2.1. Ni dung
Nm 1923 hai nh bc hc Bronsted (an Mch) v Lauri (Anh) cng ra mt
nh ngha mi v axit v baz nh sau:
Axit l nhng cht c kh nng cho proton v baz l nhng cht c kh nng
nhn proton.
Proton khng th tn ti trng thi t do, v vy mt cht ch th hin tnh axit
hay baz trong dung mi c kh nng nhn hay cho proton.
Mi axit sau khi cho proton i thnh mt baz lin hip vi axit . Mt cp axit
- baz lin hp c th biu din bng h thc:
Axit ^ Baz + H+ (proton)
Th d v cc cp axit - baz lin hp:

30
Axit

Baz

HF
CH3COOH
H2O
NH4
Al3+.H2O
NH3
SHOH
+

F
+ HCH3COO+
+ H+
OH- + H+ NH3 +
H+ Al(OH)2+ +
H+ NH2 + HS+
2+ H+
O2- +

31
H+
Baz
V d:+ S-H+ Axit
+ SH3O-

+ HS-NH3 + H3O+ CH3COOH + OH

Axit + S (dung mi)
Baz + S (dung mi)
H2S + H2O
NH4 + H2O
CH3C0O- + H2O
+

Khi ha tan mt axit hay mt baz vo mt dung mi th s c cc phn ng:

Theo thuyt ny th cc axit, baz c th l phn t, anion, cation (bng3.1)

32

Bng 3.1. Phn loi axit - baz

STT
Phn loi
12 3 Phn t khng tch in
Anion Cation

Axit
Baz
HCl, H2SO4, ...HSO4 , NH3, C6H5NH2, NaOH, ...0H-,
HCO3-, ... H3O+, NH4+, Cl--, ... NH2(CH2)2NH3+, ...
...
-

Ngoi ra cn c cc cht lng tnh ngha l va c kh nng nhn va c kh nng cho

proton. V d:
H2O ^ H+ + OHAxit Baz
H2O + H+ ^ H3O+
Baz Axit
3.1.2.2. Phn ng axit - baz (phn ng trung ha)
Theo Bronsted, phn ng axit - baz c biu din nh sau:
Axit (1) + Baz (2) ^ Axit (2) + Baz (1) (3.1)
V d:
HCH3COO + NH3 ^ NH4+ + CH3COO(3.2) HCl + NaOH ^ H2O + NaCl Thc t cc cht phn ng vi nhau u trong mt
dung mi nht nh, v d trong nc cc cn bng phi l:
CH3CO0H + H2O ^ CH3COO- + H3O+ NH3 + H2O ^ NH4+ + OH
_________________H2O + H2O ^ H3O+ + OH-

HCH3COO + NH3 + 4H2O=^CH3COO- + NH4+ + 2H3O+ + 2OH-Thc cht khi ha

tan mt axit hoc baz vo nc l ta thc hin phn ng axit - baz v bn thn
nc theo quan nim ca Bronsted cng l mt cht c th l axit hoc baz.
Nh vy trong phn ng axit - baz (hay phn ng trung ha) bao gi cng tn ti
2 cp axit - baz lin hp. Nh v d tng qut trn (3.1) ta c: cp axit - baz (1) v cp
axit - baz (2). Trong v d (3.2) th l 2 cp: CH3COOH/CH3COO- v
NH4+/NH3.
Nhn ra tng cp axit - baz lin hp trong trng hp c th l rt quan trng
hiu cch lp lun v tnh ton trong cc phn sau. Sau y l mt s phn ng axit baz v cp axit - baz lin hp trong nc: (Bng 3.2)
Bng 3.2. Mt s cp axt - baz lin hp

33

Axit
(1)
H2S
HClO4
H2O

N
H
4

Baz (2)
H2O
CH3OH
CO3

+
+

2-

NH2Axit
(2) H3O
-

+
+

CH3OH2
HCO3
NH3

Baz (1)
HSClO4
CHNH3
-

34

(Phn ng trung ha NaNH2 bi NH4Cl trong amni lng)

NH4+
+
OHg
H2O
+ NH3

35

51.

Cng ca axit v baz: hng s axit KA v hng s baz KB

Mt axit cng mnh khi n c kh nng nhng proton cho dung mi cng ln. V
d: Khi cho axit vo dung mi S ta c:
Axit + S ^ Baz + SH+ (3.3) Axit cng mnh ngha l cng
ln, th phn ng (3.3) cng chuyn dch

mnh v pha phi, ngha l hng s cn bng K = [Baz][SH ] ca phn ng trn

[Axit][S]
cng ln.
Trong trng hp dung mi l nc, v nng ca nc l 1000 = 55,5
18
mol/lit l kh ln nn c th coi nh khng i khi dung dch long v c th vit:
= M^XKA (3.4)
[Axit]
v KA c gi l hng s axit, n biu th cng axit.
thun tin cho vic tnh ton ngi ta thng dng gi tr PK A = -lgKA thay cho
KA. V d: HF c PKA = 3,2; mnh hn HCN c PK A = 9,4. i vi axit mnh trong
nc phn ly hon ton khi c K A = +00. Mt baz cng mnh cng c kh nng nhn
proton ca dung mi. C th vit phn ng sau:
Baz + S ^ Axit + S- (3.5)
Baz cng mnh th phn ng (3.5) cng chuyn mnh v pha phi tc l hng
b K=[Axit][s-] hy , ,
s cn bng: K = ^ _ ca phn ng cng ln.
[Baz][S]
-

L [Axit][OH ]

Vi dung mi l nc, ta c: K = --------;

[Baz][H2O]
= Axit]Hll = KB (3.6)
[Baz]
vi KB l hng s baz, n biu th cng baz.
Thng ngi ta dng PKB = -lgKB thay th cho KB.
V d: NH3 c PKB = 4,75 mnh hn CH3COO- c PKB = 9,25.
Vi baz mnh trong nc phn ly hon ton nn KB = 0 .
52.
Dung mi
Theo thuyt axit - baz ca Bronsted - Lauri dung mi c mt vai tr quan trng
quyt nh mnh yu ca axit hay baz tan trong . Sau y im qua mt s tnh
cht ca dung mi.
* Tnh axit, baz ca dung mi
Da vo kh nng cho v nhn proton ca dung mi, ta chia cc dung mi thnh
hai nhm: dung mi khng cha proton v dung mi c cha proton.
Dung mi khng cha proton l nhng hp cht c tnh tr, phn t ca n khng
c kh nng cho hay nhn proton. Phn t ca loi ion ny khng b ion ha. Cc dung
mi ny khng tham d vo qu trnh tng tc proton ca cht ha tan. V d: cc loi
cht nh hydrocacbua [benzen, toluen, ...] v cc dn xut halogenua ca chng

36

[tetracloruacacbon, clorofooc, ...].

37
Cc dung mi c cha proton gi l dung mi protolit, l nhng hp cht ha
hc c kh nng cho v nhn proton, cc dung mi ny tham gia trc tip vo qu trnh
tng tc proton ca phn ng axit - baz. Dung mi protolit chia lm 3 loi: dung mi
lng tnh, dung mi axit v dung mi baz. Cc dung mi protolit c kh nng t phn
ly thnh ion.
Dung mi lng tnh phn t ca chng va c kh nng cho va c kh nng
nhn proton. V d nh dung mi nc, ru, xtn, nitril, .
Dung mi axit l nhng hp cht m phn t ca chng c kh nng cho proton
mnh hn kh nng nhn proton. Loi dung mi ny ch th hin kh nng nhn pro-ton
i vi cc cht c kh nng cho proton mnh hn dung mi. V d: HCOOH,
HCH3COO, H2SO4, .. .
Dung mi baz l nhng hp cht m phn t ca chng c kh nng nhn pro-ton
mnh hn kh nng cho proton. Chng ch th hin kh nng cho proton i vi cc cht
c i lc vi proton mnh hn n. Cc cht nh amniac lng, piridin, hy-drozin v
nhiu loi amin thuc loi dung mi ny.
phn ly ca axit, baz ph thuc vo bn cht axit, baz v ph thuc vo bn
cht dung mi. Ngi ta ly dung mi khng phi l nc m l nhng cht c tnh
kim yu hn nc, v d dung mi l C2H5OH th axit nitric (HN03) tr nn hi yu i.
Trong axeton hay C6H5N02 tt c cc axit mnh trong nc tr HCl0 4 v H2S04 tr
nn mnh va phi.
i vi nhng dung mi c i lc i vi proton khng mnh lm c ngha l d
dng nhng proton, v d trong H2S04 khan th ch c HCl04 l cn c i lc i vi
proton, tc vn l axit mnh cn HN03 th hin tnh cht ca baz bi n ly proton ca
H2S04 to nn ion nitron [N03H2]+ nh l axit cation ging nh NH4+. Cc axit hu
c, ru, te v mt s cht khc trong dung mi ny u tr thnh baz.
i vi nhng dung mi c tnh cht kim mnh hn nc, v d NH3 lng th mt s
axit yu trong nc tr nn axit mnh. * S phn ly ca dung mi.
Hng s t phn ly: Cc dung mi protolit c kh nng t phn ly thnh ion. S
phn ly ca dung mi c o bng hng s t phn ly K S. Gi s c dung mi S c th
t phn ly thnh ion theo cn bng sau:
2S ^ SH+ + SHng s phn ly KS tnh nh sau: KS = aSH+ .as- (a: hot )
Vi dung mi nc, ta c: 2H20

H30+ + 0H-

do :

2 =

H 0

H30+ .a0H-

Trong cc php tnh, thng thng ta thay bng: KH = [H30+][0H-] = 10-14

0

25 C
S t phn ly nh trn ca dung mi thc cht l phn ng axit - baz, trong mt
phn t dung mi ng vai tr axit, cn phn t kia ng vai tr baz. Sau y nu mt
s hng s t phn ly ca mt s dung mi (bng 3.3).

38

Bng 3.3. Hng s t phn ly ca mt s dung mi

Dung mi
Amniac
Axetonitril
Hydrazin
Ru izopropylic
Axeton 90%
Ru propylic
Ru tylic
Dioxan 70%
Dimetyl sunfoxyt

PKS
32,32
26,50
24,70
20,84
20,30
19,33
18,95
17,86
17,30

Dung mi
Propylenglycol
Ru metylic
Etylenglycol
Anhydrit axetic
Nc
Axit axetic
Axit foocmic
Monoetanol amin
Axit sunfuric

PKS
16,76
16,70
15,60
14,50
14,00
12,60
6,30
5,14
3,62

S dung phn: S tham gia ca cc phn t dung mi vo phn ng vi cht ha

tan trong phn ng axit - baz cn gi l s dung phn. V d: khi ha tan mui
CH3C00Na vo nc s c phn ng sau:
CH3COON + H2O ^ CH3COOH + Na+ + 0HHoc ha tan vo ru, ta c:
CH3COON + C2H5OH ^ CH3COOH + Na+ + C2H5OMc ha tan cng ln nu
s phn ly ring ca dung mi cng mnh. V d: trong dung mi nc cc mui ca
axit nitric khng c tc dng vi nc (khng b dung mi phn), nhng trong mi
trng H2S04 khan th mui ny b dung phn nh sau: 2KNO3 + H2SO4 ^ 2HNO3 + 2K+
+ SO4Theo bng 3.3, ta thy a s cc dung mi hu c u c hng s t phn ly nh
hn nc, do c nhiu trng hp mt cht b dung phn trong mi trng nc s
khng b dung phn trong cc mi trng khng nc (khan) khc. iu ny rt quan
trng trong vic ng dng dung mi khng nc nh phn bng phng php axt baz.
3.2. Cn bng axit - baz trong mi trng nc. 3.2.1.
Tch s ion ca nc, ch s hydrogen.
Nc l mt cht lng tnh nn c th t ion ha theo phn ng: H20 + H20 ^ H30+ +
0H h b K = [H3O + ][0H2-

]
c hng s cn bng: K = _ :----------[H20]V trong dung dch long [H20] l mt hng s nn c th vit:
KH2O]2
2

H2O

= [H3O+HOH-] = K

KH gi l tch s ion ca nc. nhit 250C: KH = 10-14, PKH0 = 14.

0

-14

Khi nhit tng KH tng. V d 50 C th KH = 8.10 , iu c th gii

thch do s phn ly ca nc tng, ng thi khi nhit tng s trng hp ca cc
phn t nc b ph hy: [H20]n nH20
Trong cc dung dch nc nu [H30+] tng ln th [0H-] phi gim xung hoc
0

39

ngc li, tch s nng H30+ v 0H- phi lun bng 10-14. c thun tin biu
din axit ca dung dch, ngi ta dng khi nim ch s hydrogen - k hiu l

40

pH - v ch s hydroxyl - k hiu l pOH - l tr logarit nng ion H30+ v ion 0H-pH

= -lg[[H30+] pOH = -lg[0H-] Ta lun c: pH + poH = PKH 0 = 14
Mi trng trung tnh ng vi pH = pOH = 7 Mi
trng axit khi pH < 7 v baz khi pH > 7.
Thng ta dng thang pH = (0 -- 14) ng vi dung dch n axit mnh v kim c
nng 1M. Khi nng ln hn 1M th pH c gi tr m.
53. Quan h gia KA ca mt axit v KB ca mt baz lin hp vi n
Nhn 2 h thc (3.4) v (3.6) vi nhau ta c:
[Baz][H30+][0H-][Axit] +
KAKB =-------- r A . J
1 --------= [H30+][0H-]
A B
[Axit][Baz] Vy KAKB = [H3O+HOH3
]]
i vi mt cp axit - baz lin hp, nu KA cng ln, ngha l axit cng mnh, th
KB cng b, ngha l baz lin hp vi n cng yu.
V d: HCl l mt axit mnh (trong nc) c K A = +00 th baz lin hp Cl- l mt
baz rt yu c KB = 0; HCN l mt axit rt yu PK A = 9,4 th baz lin hp vi n l
mt baz mnh c PKB = 14 - 9,4 = 4,6.
54. Tnh gi tr pH ca mt axit, baz hoc mui trong nc.
Bt k axit hoc baz no khi cho vo dung dch l nc cng tc dng vi nc sinh ra
baz hoc axit lin hp nh sau: Axit + H20 ^ Baz + H30+ Baz + H20 ^ Axit + 0H-Do
tnh pH ca cc dung dch nh vy ta lp mt cng thc tng qut cho php tnh
pH mt dung dch hn hp axit v baz lin hp, sau ta suy ra cc trng hp ring.
3.2.3.1. Cng thc tng qut tnh pH ca dung dch hn hp axit v baz lin
hp.
-

Nu cho vo nc mt hn hp axit yu HA v baz lin hp vi n A- (l ananion ca

mui NaA chng hn) th trong dung dch s thnh lp hai cn bng: HA ^ H+ + A- (3.7)
H20 ^ H+ + 0H- (3.8) Nu nng ban u ca HA l CA v ca baz l CB, hng s axit
ca cp axit - baz lin hp l KA th gia cc nng cn bng ca H+, 0H-, HA, A- v
Na+ c cc h thc sau:

=K
[HA]

HO

(3.9)
v

'

[H+][0H-] = K 2
(3.10)
[HA]
+
[A ]
=
CA
+
CB
(3.11)
[Na+]
+
[H+]
=
[0H ]
+
[A ]
(3.12)
[Na+] = CB
^ (3.13)
9
Hai biu thc (3.9) v (3.10) biu din hai cn bng (3.7) v (3.8). H thc (3.11)
biu din nh lut bo ton khi lng i vi A-. H thc (3.12) biu din

41

tnh trung ha in ca dung dch. H thc (3.13) th hin mui NaA l mt cht in ly
mnh phn ly hon ton.AT 5 phng trnh trn vi 5 n s ta suy ra:
- [H
] = KA C
+ ] + [CH ] (3.14) A CB + [H + ] - [CH-]
55.
Tnh pH ca dung dch axit mnh.
Cc axit mnh thng gp u l n axit nh: HCl, HNO 3, HBr, HI, ... ch tr
H2SO4 l a axit c K1 = 00 v K2 = 10-2.
Axit mnh trong nc phn ly hon ton (ngha l cho proton hon ton) nn cn
bng (3.7) chuyn hon ton v pha phi:
HA H+ + A- [ do [HA] = 0. Nhng ta li bit nng [H+] do HA phn
ly ra theo (3.7) bng CA v nng [H+] do nc phn ly ra theo (3.8) bng [CH-].
Nng cn bng [H+] bng tng nng ca H+ do HA v H2O phn ly ra.
Vy:
[H+] = CA + [CH-] (3.15) Cng c th suy cng thc (3.15) t cng thc
tng qut (3.14) vit di dng:
[H
+ B +[H +] W ] ) = CA - [H+] + [CH-]
-

](C

v KA = +00 v [H+](CB + [H+] - [CH-]) * 0 nn CB - [H+] + [CH-] = 0, do :

[H+] = CA + [CH-]
Thay [CH-] bng vo biu thc (3.15) ta c phng trnh bc hai theo
[H+]:
[H+]2 - CA[H+] - KH2C = 0 (3.16)
Phng trnh (3.16) dng tnh chnh xc pH ca dung dch axit mnh. Ta c cc
trng hp sau:
* Nu CA tng i ln hn 1 0 7 th c th b qua gi tr [CH -] trong (3.15),
khi : [H+] = CA (3.17)
V d:
* CA = 10-6, nu cho l [H+] = CA ngha l [H+] = 10-6 v [CH-] = ^ = 10-8
( -8250C). Nh vy nu b qua gi tr [CH-] trong (3.15) th sai s ch bng
10 .100 = [H+]
-----6 = 1% ca
[H ].
* 10Nu CA > 10-6
-6
th sai s cn nh hn na nu dng cng thc 3.17.
* Nu CA < l 7 , ta phi tnh pH t phng trnh (3.16). V d ly dung dch HCl
c nng 10-8 M th pH khng bng 8 m bng 6,91.
* Nu CA << l 7 th c th b qua CA cnh [CH-] trong (3.15) v khi :
[H+] = [CH-] = (3.18)
56.

pH ca dung dch baz mnh.

Lp lun nh i vi dung dch axit mnh s c h thc: [CH-] = CB + [H+]. K
Thay [CH-] = ^ + ta c phng trnh: [H+]2 + CB[H+] - K H = 0 (3.19)
H

42

[H

+] Phng trnh (3.19) dng tnh chnh xc pH ca dung dch baz mnh. Nu
nng CB ca baz tng i ln hn 102
-7
th [OH-] = CB. Do :

[H+] = -K

-=K

(3.20) [OH ]

Nu CB < 10

-7 th tnh theo (3.19). Nu CB << 10-7 th: [OH-] = [H+] = a/K

H20

3.2.3.4. pH ca dung dch axit yu.

Nu c dung dch axit yu HA th nng ban u CB ca baz lin hp A- l
khng c th cng thc tnh pH s rt ra t cng thc tnh tng qut nh sau:
[H+ ] = KA CAR;!H; + g (3.21)
Ty tng trng hp c th ta c th n gin ha cng thc trn:
* Nu [OH-] << [H+] ngha l coi nh nc khng phn ly th c th n gin

ha cng thc (3.21) v cn li: [H + ] = KA C

- [H ]

(3.22)

Cng thc (3.22) cng p dng c khi [OH-] << [A-] v theo phng trnh phn
ly ca axit: HA r=s H+ + A-, nu [H+] >> [OH-] ngha l nc hu nh khng phn ly th
[H+] = [A-]. Cng thc (3.22) thng c p dng khi KA >> 10-7.
Nu [0H-] << [H+] v [H+] << CA th ta li c:
[H + ] = IH^ ; [H + ] = VKACT (3.23)
Cng thc (3.23) cng c p dng khi [OH-] << [H+] v [A-] << [HA] v nu
coi [H+] << CA tc l coi nh HA khng phn ly, ngha l [HA] = CA v v [OH-] <<
[H+] nn [A-] = [H+]. Vy iu kin [A_] << [HA] tng ng vi iu kin [H+] <<
CA. Cng thc (3.23) thng c p dng khi in ly a ca axit HA nh hn
Ca2 '
0,05. V theo nh lut pha long Ostvand th K =--------nu cht in ly yu l
dung
1-a
dch khng long lm c th n gin cng thc bng cch b qua gi tr in ly a bn
cnh s 1:
K

KC

K = Ca2; a = , ; a < 0,05 tc J < 0,05; < 0,025 hay > 400.
ve
ve
CK
C

i vi trng hp axit yu th ta c:

> 400 (3.24)

* Nu eA qu nh [A-] << [OH-] th [H+] trong dung dch l hu ht do nc

phn ly ra. Khi [H+] = [0H-] v [H+] = KH2O .
* Nu [OH-] << [H+] nhng [H+] - [OH -] << eA th cng thc (3.22) c th rt
gn li:
[H+] = ^KAA + KHO . (3.25)
p dng ng cc cng thc trn cn phi bit c tr s tng i ca nng

43

cn bng cc ion v cc phn t khc trong dung dch. C th dng iu kin (3.24),
nhng thun li nht l dng cch gii theo logarit nng . Tuy vy trong cc php tnh
gn ng ta c th dng cng thc (3.22) v (3.23).

44

V d 1:
Tnh pH ca dung dch axit axtic CH3COOH 10-2M vi KA = 1,75.10-5 (PKA =
4,75).
e
10V = - = 571 > 400 nn c th p dng cng
thc (3.23). Ta tnh
KA
1,75.10 c: [H+] = VKAcA = V1,75.102
5

-5

.10 = 4,18.10-4 ; pH = 3,4. V d 2:-3

Tnh pH ca dung dch HF 10 M c KA = 6,75.10e
10V = 4" =
1,48 < 400 nn ta phi dng cng thc (3.22). Gii ra ta KA 1,75.10
c: [H+] = 5,5.10-4
2

-4

v pH = 3,26. V d 3:
Tnh pH ca dung dch HCN 10-4M c KA = 4,8.10-10. Trng hp ny phi dng
cng thc (3.25) tnh [H+] = V48 10.10 4 + 10-14 = 10-6,62 ; pH = 6,62.
3.2.3.5. pH ca dung dch baz yu.
Nu cho mt baz yu vo nc th tnh pH ca dung dch ta c th p dng cng
thc tng qut vi iu kin eA = 0. Cng thc by gi c dng:
[H + ] = KA [OH ] - r[H +J (3.26) p dng cng thc ny ta c cc trng
hp sau:
-

* Nu [H+] << [OH-] th [H + ] = K

C^OH

[OH ]
Hoc 2- = KA
; [OH-]2 + KB[0H-] - KBCB = 0
[OH-]
eB - [OH-]
H

_
K + JKB +4K C
Gii ra ta c: [OH ] = ------------------------- (3.27)
B

* Nu [OH-] << CB th: [OH-] = VKBCB (3.28) Trng hp ny cng ging nh

i vi dung dch axit yu, c p dng khi t

s -C
K

> 400.

Ch :
Cng thc tnh pH ca mt dung dch baz yu c th thu c bng cch thay cc gi
tr eA, KA, [OH-]. [H+] trong cng thc tng qut (3.14). V d 1: Tnh pH ca dung dch
NH3 10-2M c PKB = 4,75. Theo cng thc (3.28) ta c th tnh c: [OH-] = ^KBCB
= 10-4,75.10-2; rt ra
pH = 10,62.
-5

45

V d 2: Tnh pH ca dung dch axetat natri 0,05M bit KA = 2.10-5. Ta bit axetat
natri l mt mui ha tan vo nc n phn ly hon ton cho 2 ion: NaCH3COO ^
Na+ + CH3COOAnion axetat l mt baz yu:
CH3COO" + H2O ^ CH3COOH + OH tnh pH ca dung dch baz yu ny ta dng cng thc
(3.28) vi ch
1
-14
4
K
10
, . _______ 10
rng: K
= ^ngha l K
= 270^. Do : [OH-] =
^270^0,05 = 5.10
pOH = 6 - lg5 = 5,3 ; pH = 14 - 5,3 = 8,7.
3.2.3.6. pH ca dung dch axit yu v baz lin hp vi n.
Nu ta cho vo nc mt axit A v mt baz B lin hp vi n th lng ion H+ c
th tng ln hoc gim i. Ty theo dung dch s tr nn axit hay baz, ta c th chia ra
2 trng hp sau:
-6
+ Khi dung dch l axit: ngha l [H+] >> [OH
] th t cng thc tng qut ta

B H,O _B

rt ra:

[H + ] = K

-[H

+] (3.29)

Nu CA v CB kh ln hn [H+] th biu thc ny s c n gin ha nh sau:

[H+ ] - K

A^ (3.30)

+ Khi dung dch l kim (baz): ngha l [H] << [OH-] th ta li c:

=

+[OH- ] (3.31)

CB - [OH- ]

V nu CA v CB kh ln hn [OH-] th ta li tm biu thc (3.30). V d 1: Tnh nng

ion hydro trong dung dch cha 0,1M axit HA v 0,02M baz A- nu KA = 10-5.
T biu thc (3.30) ta tm c: [H +
] = 10-5 = 5.100,02
V d 2: Tnh nng ion hydro trong dung dch cha 0,001M axit HA v 0,1M
baz A-4
nu KA = 1 0 .
T biu thc (3.30) ta c: [H + ] = 10-8-000- = 10-10. y l dung dch c tnh
0,1
kim, th p dng cng thc
(3.31) ta c: [H + ] = 10-8 0,001 +
0,0001
= 1,1.100,1 -0,0001
Ta thy hai kt qu tm c khc nhau rt t, c th b qua trong cc php tnh
thng thng.
Mt dung dch gm axit yu v baz lin hp vi n cn c gi l dung dch m.
S d nh vy v dung dch ny c kh nng thay i pH rt t khi thm mt lng axit
hay baz mnh vo. Ch :
Cng thc (3.30) ch p dng c khi [H+] v [OH-10

46

] khng ng k so vi CA v CB nn khng th p dng c khi dung dch kh long.

Khi CA v CB < 10-3M th khng th p dng c cng thc trn.
V d: Tng nng CA + CB = C t nht phi bng bao nhiu c th dng cng
thc (3.30) tnh pH ca dung dch m axit axetic-axetat c CA = CB.
Ta c KA = 1,75.10-5 nn [OH-] << [H+] do iu kin tnh pH theo cng

47

thc (2.30) ch cn l:
CB 100
CC
[H + ] = K
<

AA
C

-B
C

48

[H + ] = KACA < -CA

Nu gi thit l khi hai nng ln hn nhau 100 ln th c th b qua nng
C
C +C
nh. Cng 2 phng trnh trn ta c: 2KA <
A
CB 100
CC
y CA = CB nn 2KA <-hoc KA <- .
A
100
200
57.
pH ca dung dch a axit
a axit l loi axit m mt phn t hay ion ca n c th cho ln lt nhiu [H+] v s
tng ng vi cc hng s axit: K1S K2, ..., Kn. V d: Axit HnA
[H+] = K, ArTT +v (3.32)
HnA ^ Hn-1A- + H+ ng vi K1 Hn-1A ^ Hn-2A2- + H+ ng vi K2 HA(n-1) ^ An- + H+ ng
vi Kn. Thng th K1 >> K2 >> ... >> Kn nn t nc 2 tr i kh nng cho H+ ca a
axit rt yu, do mt cch gn ng [H+] c tnh theo nc 1, v nh vy c th p
dng cng thc tnh pH ca n axit. + Nu K1 > 10-4 p dng cng thc:
C
[H + ]
[H + ]
V d: H3PO4 1M:
H3PO4 ^ H2PO4- + H+ , K1 = 7,6.10-3 hay pK1 = 2,12 H2PO4- ^ HPO42- + H+ , K2 = 6,2.10-8
hay pK2 = 7,21. HPO42- ^ PO43- + H+ , K3 = 4,4.10-14 hay K1 = 7,6.10-3 > 10-4 nn c th
p dng cng thc (3.32).
[H+] + K1[H+] - K1CA = 0 thay vo: [H+]2 + 7,6.10-3[H+] - 7,6.10-4 = 0. Gii phng
trnh bc 2 ny ta s tm c 2 gi tr ca [H+], nhng ch dng c gi tr no m
[H+] > 0.

+ Nu K1 < 10-4 p dng cng thc: pH = -(PK -lgCA) (3.33) V d:

Tnh pH ca dung dch H2CO3 10-1M c K1 = 3.10-7 hay pK1 = 6,32; K2 = 4,8.10-11
hay pK2 = 10,32.
p dng cng thc (3.33) ta tnh c: pH = 2(6,32 - lg10-1) = 3,66.
58.

pH ca dung dch a baz.

a baz l mt baz m mt phn t hay ion ca n c th ln lt nhn nhiu

H+.
V d: Ca(OH)2, Na2CO3, Na3PO4

49

* a baz l ion-mui trung tnh ca a axit v baz mnh.

V d: Dung dch Na2CO3.
Trong dung dch N2C03: Na2CO3 CO3 + 2Na+ Na+ l
mt axit rt yu, coi nh trung tnh. CO3 l a baz
ca a axit tng ng H2CO3.
H
ng vi
H
ng vi
3 + + ^
3
2 HCO^/CO?- 3 + + ^ 2 3
2-

2-

CO 2-

HCO -

HCO -

H CO

2CO3 HCO-

1H

L lun tng t nh trng hp a axit nh sau:

Nh bit K1 >> K2 >> ... >> Kn ngha l KB1 << KB2 << ... << KBn.
* i vi a axit K1 ln nht nn nc 1 c kh nng cho H+ ln nht, trong khi
kh nng ly H+ ca baz s nh nht, ngha l K B1 b nht. L lun tng t, Kn nh
nht th KBn ln nht. Vy r rng tnh kim ca a baz loi ny do dng baz c K Bn
hay K cui cng ca a axit tng ng quyt nh. Do ta c th dng cng thc tnh
pH ca dung dch n baz trung bnh hay yu, ch khc l thay KA bng K cui cng
ca a axit tng ng.
* i vi a baz trung bnh:

H2O[H+] - K

CB[H+] - K

cui cng.

H 2O

= 0 (3.34)

* i vi a baz yu:
pH = 7 + i(pKcui cng + lgCB) (3.35)
V d: Tnh pH ca dung dch Na2CO3 0,1M. Bit rng H2CO3 c: pK1 = 6,32; pK2
= 10,3.
p dng cng thc (3.35) ta tnh c:
pH = 7 + -2(pK2 + lgCB) = 7 + -2(10,3 + lg10-1) = 11,65.
* a baz l phn t: Cch tnh pH cng tng t nh trn.
3.2.3.9. pH ca dung dch hn hp axit hay hn hp baz
Cch tnh pH ca cc hn hp axit hay hn hp baz kh phc tp. y chng ta
ch nghin cu trng hp n gin: Nu nng ca axit hay baz khng chnh lch
nhau nhiu lm tc l gn xp x nhau, ta c th tnh pH ca cc hn hp gn ng
nh sau:
Nghin cu cch tnh pH ca hn hp 2 axit A1 + A2 c hng s axit tng ng KA1,
KA2 v nng CA1, CA2 (t trng hp ny s suy ra mt cch tng t cch tnh pH
ca hn hp 2 baz).
C 2 trng hp:
* Nu KA1 > KA2: Trng hp ny gn ging nh mt a axit, ta s tnh pH ca
dung dch hn hp theo A1 (v A1 mnh hn A2) bng cch p dng 1 trong 3 cng thc:
*Nu A1 l axit mnh th: pH = -lgCA1
*Nu A1 l axit yu th: pH = -2 (pKA1 - lgCA1)
*Nu A1 l axit trung bnh th: [H+]2 + KA1[H+] - KA1CA1 = 0

50

V d: Tnh pH ca dung dch 2 axit CH3COOH + NH4Cl c cng nng

0,1M. Bit pK
= 4,8 v pK = 9,2.

'

CH3COOH/CH3COO-

NH /NH3 '

y KCH > KNH+ v CH3COOH l axit yu, vy dung dch hn hp c pH: 1

pH = ^(pK^COOH - lgCCH3COOH) = 2(4,8 - lg10-1) = 2,9.
* Nu K & K2 ngha l 2 axit mnh bng nhau hay gn bng nhau. Ta c th dng
1 trong 3 cng thc trn tnh pH, nhng CA l nng chung ca 2 axit.
COOH

3.2.3.10. pH ca hn hp axit yu ca cp ny v baz yu ca cp khc.

Gi s trong dung dch c 1 hn hp axit yu A1 ca cp A1/B1 v baz yu B2 ca
cp A2/B2. Tuy A1 v B2 u yu nhng chng vn tng tc vi nhau v tn ti cc
cn bng sau:
r * A1 + B2 ^ B1 + A2
i vi A1 ta c cn bng:
* A1 ^ B1 + H+ ng vi K1 do : pH1 = pK1 + lg^Ail
1i vi B2 ta c cn bng:
* B2 + H+ ^ A2 ng vi K2, do : pH2 = pK2 + lg-tA
2
!
2Khi t n cn bng th nht tc l phng trnh tng cng ca 2 phng trnh
sau, th dung dch s c pH = pH1 = pH2, do ta c th vit:
[A

[A

* 2pH = pK1 + pK + lgA

4 4
A

[A1], [A2], [B1], [B2]: nng ca cc axit, baz ca cp A1/B1, A2/B2 khi
trng thi cn bng.
Nu nng ban u ca A1 trc khi tng tc l CA1 v ca B2 l CB2 th khi t
n cn bng gi s c mt lng X ca A1 phn ng vi cng mt lng X ca
B2 to ra cng mt lng X ca B1 v A2. Ta c:
[B1] = [A2] = X; [A1] = CA1 - X v [B2] = CB2 - X.
[A ] [A

Do :

[B ] [B ]

= lg

lg

B2

-X

=C

B2

-X

[A1 ][A2 ]

A1-X

X CA1- X

V A1 v B2 u yu nn X nh v gi s CA1 v CB2 khng qu nh th khi CA1,

CB2 >> X, bi vy c th b qua gi tr ca X v tnh gn ng, ta c:
lgCB2 -X & l B!
C
XC
g

Vy : pH = 2(pK1 + pK2 + lg^CB2) (3.36)

C 2 trng hp xy ra:
Trng hp : CA1 = CB2
* Cch tnh pH:

51

'AI

Khi CAI = CB2 th lg-C^ = 0.

c
/
Vy (3.36) s l: pH = 2(pKi + PK2) (3.36a) * ng dng:
* Tnh pH ca dung dch mui ca n axit yu v n baz yu. V
d: Tnh pH ca dung dch CH3C00NH4.
Trong dung dch: CH3CO0NH4 = CH3COO + NH4+
r B2 Ai R rng CAI = CB2,
bit pKi = 9,2; pK2 = 4,8.
Vy p dng cng thc (3.36a) tnh c: pH = 2(9,2 + 4,8) = 7
* Tnh pH ca dung dch cht lng tnh: mui axit. V
d: Tnh pH ca dung dch NaHCO3
NHCO3 = Na+ + HCO3 Trong dung dch Na+ coi nh trung tnh, HCO3- l cht
lng tnh v: HCO3 ^ CO32- + H+
K2 = 4,8.10-i1; pK2 = 10,32 HCO3- + H+ 5=*
-7
H2CO3 Ki = 4,35.10 ; pK = 6,36 Do c th vit: HCO3 + HCO3 ^ CO3 +
H2CO3 Ai B2
Vy r rng CA1 = CHC0- = CB do ta p dng c cng thc (3.36a):
-

2-

PH = -2(pK1 + pK2) = -2(10,32 + 6,35) = 8,33

Trng hp 2: CA

CB

*Gi s CA = mCB thay vo (3.36):

pH = 1 (pKi + pK2 + lg ) hay pH = -(pKi + pK2 - lgm) (3.36b)
2
m2
*Nu mCA = CB th ta c:
pH = 2 (pKi + pK2 + lgm) (3.36c) Mt cch tng qut, khi CA

CB ta c

cng thc tnh pH dng sau:

pH = ^2 (pKi + pK2 lgm) (3.36d) V d:
*Thm 4 mol NH4Cl vo 1 lt dung dch CH3COONH4 IM, gi s th tch
khng
1, tnh pH ca dung dch h n hp Bit pK
C

?
+
= 9,2; pK^ /CH,COO =
4,8.
Trong dung dch M4Cl = NH4+ + ClCH3CO0NH4 =
M4+ + CH3COOAi B2
Cl

coi nh trung tnh.

NH

3COOH

52

Axit NH4+ ca cp NH4+/NH3 v baz CH3C00- ca cp CH3COOH/CH3COOquyt nh pH ca dung dch. Khi thm 4 mol NH 4Cl vo dung dch CH3C00NH4 th
nng ban u ca A1 s l CA = 5 mol/lit, ca B2: CH3C00- s l CB = 1
c1
mol/lit. Vy ta c: C = CA = 5CB
m = 5.
A1 Thay cc gi tr vo (3.36b) ta c: pH = -2 (9,2 + 4,8 - lg5) = 6,85.
B2

* Thm 4 mol CH3C00Na vo 1 lt dung dch CH 3C00NH4 1M, gi s th tch

khng i. Tnh pH ca dung dch ?
C^COON CH3CO05
+ Na+ CH3C00NH4 NH4+ + CH3COO-A1 B2
Theo trn ta c: CA = 1 mol/lit, CB = 5 mol/lit, m = 5.
Do :

pH = -2(9,2 + 4,8 + lg5) = 7,15.

3.3. Dung dch m.

59. Khi nim v dung dch m.
Dung dch m l dung dch c kh nng gi c pH ban u gn nh khng i
khi ta thm mt lng nh axit mnh hay baz mnh hoc pha long.
Thnh phn ca dung dch m thng l hn hp ca axit yu v baz lin hp
vi n.
Cng thc tnh pH ca dung dch m loi hn hp axit yu v baz lin
hp:
pH = PKA - lg-C^
Mi mt dung dch m c mt gi tr pH xc nh. V d:
* Dung dch m axetat: CH3COOH 0,1M + NaCH3C00 0,1M; PKA = 4,75 c
pH = 4,75.
* Dung dch m fomiat: HCOOH 0,1M + HCOONa 0,1M; PKA = 3,2 c pH =
3,2
* Dung dch m pht pht: NaH 2P04 0,1M + Na2HP04 0,1M; H3P04 c pK1 = 2,12;
pK2 = 7,21; pK = 12,36. Vy: pH = pK2 + lgC^ = 7,21.
60.

m dung
Kh nng m ca dung dch m khng phi l v hn v khi thm mt lng
tng i ln axit mnh hay baz mnh th pH s thay i kh nhiu. c trng cho
tc dng m ca dung dch, Vanslyko a ra khi nim m dung p (hay m nng),
l s mol baz mnh hay axit mnh c th cho vo 1 lit dung dch m pH ca
dung dch ch thay i 1 n v.

53

p = ^-

= -4^ (3.37)

v
dpH dpH
Trong :
da: s mol axit mnh cn thit thm vo 1 lt dung dch m pH ca dung dch
gim dpH (c du -).
db: s mol baz mnh cn thit thm vo 1 lt dung dch m pH ca dung dch
tng dpH (c du +).
Theo cng thc bit ta tnh pH ca dung dch m:

54

CB

A
B

C
pH = PKA + lg}
1 CA
ln[H
+
] d[H+]

2,30
3
1
pH = -lg[H+] pH =

-2,303[H ]

1
-2,303
dlnx = dpH = - _
db
x 2,303[H]
ddpH
ln[H ]
Do : p

db

db
d[H
]

[H+]
=KA(
3.38)

(3.3
9)

55

tnh p ta ch cn thay gi tr [H+] v tnh gi tr ca

db
d[H ]

56

Ta coi nng chung ca dung dch m l khng i ( cho):

c = CA + CB = const (3.40) CA, CB: nng ban u ca
axit A v baz B lin hp ca dung dch m. Vy:
dC = dC A + dCB = 0
dCA = -dCB (3.41)
T (3.38) ta ly vi phn d[H+] = d(KACA) theo c.
Ta c:
C
d[H+] = KAd (CA = KABdcA-

Theo (3.41) thay gi tr ca dCA ta c th

(3.42
)

vit: d[H+] = -KAcAdcB

DCB(CA

Khi thm db ptg baz mnh vo 1 lt dung dch m th s tng 1 lng

dCB ca nng baz B v lm gim cng 1 lng nh th nng axit A,
do :
db = dCB
(3.43
CB)
)
T (3.42) v (3.43) ta c:
d[H
d[H
Ca
+l = +l = KA
+
db
db
hay
_ __
(3.44
Cb
)
y
d[H] K (C
+
C )
T (3.38), (3.39) v (3.44) ta
c:
db
cB
A
2,303K
A
+
hay: p = dpH
2,303
db
2,303[H+]
db
c
d[H ]
c
dpH
2,30 c c
A
cc
2
AB
3
c
c
s t cc i khi CA = CB c + c
C
=c
2,303
v p
(3.4
4

A A

A(C
A+CB

5)

)
=> p
2,303-:
0,576C

(3.4
6)

57

3.3.3. ng dng ca dung dch m.

61.
Trong phn tch nh tnh.
* Tch Ba2+, Pb2+ ra khi hn hp Ba2+, Pb2+, Sr2+, v Ca2+ dng Crmt. Ngi
ta thy rng:
pH 5, BaCr04, PbCr04 kt ta hon ton.
pH > 5, SrCr04 bt u kt ta.
pH < 5, BaCr04, PbCr04 bt u tan.

c
Do tch Ba +, Pb + dng Crmt ta dng hn hp m axetat c 7^=1
th s c mi trng c pH 5.
* Pht hin ion bng phn ng c trng.
Tm Ni2+ bng dimetylglyoxym, phn ng ch xy ra pH 9 do ta dng dung
dch m amoni.
Tm Al3+ bng alizarln S to mui ni phc alizarlnt Al pH 9 dng hn hp
m amoni.
62.
Trong phn tch nh lng
* Trong phng php it xc nh nng AsO3 da vo phn ng:
2-

I2 + As032- + H20 ^ 2I- + As043- + 2H+ ch xy ra

pH 7, ta c th dng h m cacbonat.
- Trong phng php complexon: da vo phn ng to complexonat - l phn ng
to mui ni phc gia comnplexon v ion kim loi cn xc nh - v da vo phn ng
to mui ni phc gia thuc th hu c l cht ch th kim loi v ion kim loi cn xc
nh. C 2 phn ng ny ch xy ra tt pH nht nh, do phi dng nhng hn hp
m thch hp. Ngoi ra cn rt nhiu trng hp trong cc phng php nh lng
khc nhau: phng php trc quang, phng php cc ph ... cng cn phi dng hn hp
m.

3.4. Tnh nng cc thnh phn ca dung dch khi bit pH.
C nhiu trng hp cn tnh nng ca cc thnh phn trong dung dch khi
bit pH. V d nh tm nng tng i ca 2 dng mt cht ch th mt gi tr pH cho
trc, khi tnh lc ion ca dung dch m hay xc nh nng cht to phc trong dung
dch m . 3.4.1. Trng hp n axit HA.
Gi s axlt HA c nng l CA. HA ^ H+ +
A- (1) CA = [HA] + [A-] K = [H + ][A ] ^
[HA = IH+1
[HA]
[A-] K
t a 0
v a1 l phn nng ca HA v A :
0
= [HA] =
[HA] = 1 = 1 K
= [H + ] a
= ~C7 = [HA] + [A ] = 1 + [A ] = 1 +
= [H+]
+K
[HA]
[H + ]
A

58

Bit a 0 suy ra [HA].

1
=K
[HA] + [A ] [HAI +1 [H+ ] + K

[A ]

[A]

Bit a 1 suy ra [A-]. 3.4.2.

Trng hp a axit H2A:
H2A ^ H+ + HA
-

^ H+ + A

HA-

[H + ][HA
2-

K1 =

K2 =

] [H2A]
[H + ][A2 ]
[HA-]

59

CA = [H2A] + [HA-] + [A2-] Ta s tnh a 0, a 1, a 2 cho cc thnh

phn H2A, HA-, v A2- tng ng.
+ 2
[H1[H
K
] 2A] K1K2[H2A]

Thay cc gi tr tng ng rt
[H+]

T ta tnh c:
[H A]

0=

ra t hai cn bng trn ta c:

CA

[H+]
2
[H+] +K1[H+] + K1K

a1
=
a
=

[HA-]

[A2]

K1[H + ]
[H + ] + K1[H + ] + K1K2
2

= [H2A] +

60

3.4.3. Trng hp tng qut HnA.

K

. K

MS phng trnh phn ly v tnh a0, a1, ... an. Mu s s c nhiu s hng dng sau:
Ta vit
N
K1[H+]
K1K2[H+]N MS

N1

2
0

MS

Tng qut:
= K1K2...KL[H + ]N1 = KL[H + ]v i K0 = 1.
N1

K1K2.4H+ ]

Ki[H+ ]1=0 1=0

n

V d:
Tnh nng HPO4
trong dung dch m 0,1M vi pH = 7. Nu pK1 = 2,16; pK2 = 7,13; pK3 = 12,3. Gii:
Khi
pHrt
= ra:
7 ta2 c MS = 10-21 + 10-16,16 + 10-16,29 + 10-21,59 = 10100,0426 M.
T
: 10 = 10-15,92
n

2-

16,29

-037

= 0,426. Nng HPO4 bng 0,426.0,1 =

2-

61

3.5. Chun axit - baz.

3.5.1. Bn cht ca phng php.
Trong phng php ny ngi ta dng phn ng trung ho A1 + B2 B1 + A2 (A,B l
axlt, baz tng ng)
Nh vy v nguyn tc ta c th dng dung dch chun l mt axlt xc nh mt
baz v ngc li. Dng phng php ny c th xc nh mt s mui Na 2C03,
Na2B4O7, xc nh cng ca nc, mui amni, nit trong cc hp cht hu c .
Dung dch chun trong phng php ny l cc axlt nh HCl, H 2S04, hay kim nh
NaOH, KOH . . . Cc cht ny khng p ng c cc yu cu ca cht gc nn khng
phi dung dch chun gc. Do ngi ta ch chun b chng vi nng gn ng, sau
xc nh nng chnh xc ca chng bng cc dung dch gc khc. V d cn xc
nh nng ca dung dch axlt ta dng borc (Na 2B407.10H20) hay Na2C03 khan, cc
cht ny p ng cc yu cu ca cht gc v dung dch c tnh baz. V d khi ho tan
borc vo nc ta c phn ng:
B4072- + H20 ^ 2H2B03- + 2H3B03
Tc l dung dch borc lng c th c xem nh l dung dch H 3B03 , lon H2B03trong dung dch b phn hu :
H2BO3- + 20 ^ OH- + H3B03
hay tng qut li:
Na2B407 + 7H20 NaOH + 4H3B03
H3B03 l axlt yu nn dung dch borc c mi trng kim. Phn ng nh phn
bng borc thc cht l: NaOH + HCl = NaCl + H20
T trn, phn ng HCl tc dng vi dung dch Na2B407 l :
Na2B407 + 2HCl + 5H20 = 2NaCl + 4H3B03
Ti im tng ng trong dung dch s tn ti hn hp NaCl v H3B03, pH ca
dung dch s l pH ca dung dch axlt yu H3B03.
pH = ipKA - ilgCA Gi s nng ca borc l 0,1N v
khi nh phn khng tnh n s tng th
tch th pH = 5,12.
Trong qu trnh nh phn axit, baz khi thm dn thuc th vo dung dch cn
nh phn th khng km theo s thay i no m mt ta nhn thy c m ch mt ch
s c trng ca dung dch l pH s thay i. Do xc nh im tng ng
ngi ta phi thm vo dung dch mt ch th no .
3.5.2. Cht ch th trong phng php trung ha.
3.5.2.1. Khi nim.
cht ch th trong phng php trung ho l nhng cht m mu ca n thay i
cng vi s thay i ca pH, dung dch mu ca cht ch th thay i trong mt khong
gi tr pH hp, khong pH ny ph thuc vo tnh cht ca cht ch th ch khng ph
thuc vo cc cht phn ng vi nhau. Cc yu cu i vi cht ch th:
63. Mu ca cht ch th phi khc nhau r rt trong nhng gi tr pH gn nhau.
64. S thay i mu ca cht ch th cn phi xy ra r rng trong mt khong nh
pH.

62

65. Mu ca cht ch th cng m cng tt.

66. Lng kim hay axlt thm vo lm thay i mu ca cht ch th cng t cng
tt khi nh hng n kt qu nh phn.
67. S bin i mu phi thun nghch.
Do nhng yu cu trn nn ta hn ch vic s dng cht ch th axlt baz, s cht
ch th s dng rng ri nht hin nay khng qu 20. Vic la chn ng cht ch th c
ngha rt quan trng trong php nh phn. la chn chnh xc cht ch th phi bit
r l thuyt v cht ch th. 3.5.2.2. Thuyt ion.
Theo thuyt ny th cht ch th trong phng php trung ho l nhng axit hay
baz hu c yu c dng phn t khc mu vi dng ion.
V d qu c dng phn t mu , dng lon c mu xanh, n l mt axlt yu. Gi
s mi ch th axit u k hiu HInd v dng ion ca n -Ind - ta c s phn ly ca qu
c biu din nh sau:
Hlnd ^ H+ + Ind-
xanh
Khi ho tan qu vo trong nc th dng phn t v dng ion cng tn ti cho nn
s c mu tm, nu thm dung dch axt vo th dung dch qu tm s c mu , ngc
li nu thm baz vo th dung dch s c mu xanh. Loi ch th m c hai dng u c
mu ngi ta gi l ch th hai mu. Metyl da cam cng l ch th hai mu:
Trong mi trng axit th dung dch c mu , trong mi trng baz c mu
vng, pH = 4 c mu hn hp ca c hai mu l da cam.
Hlnd ^ H + + Ind-
vng
Ngoi ra cn c cht ch th mt mu tc l ch th m mt trong cc dng c mu
cn dng kia khng mu. V d phenolphtalein trong mi trng axit khng mu, trong
mi trng baz c mu , l mt axit yu, dng phn t tn ti trong mi trng
axit, dng ion tn ti trong mi trng baz:
Hlnd ^ H + + Ind -khng
mu
mu
Tng t nh vy ngi ta gii thch cho cc ch th l nhng baz hu c yu
bng cc k hiu l IndOH v dng lon l Ind+. Trong dung dch chng phn ly theo
phng trnh:
IndOH ^ Ind+ + OHNu thm kim vo dung dch th cn bng s chuyn sang tri
v dung dch s c mu ca dng phn t IndOH. Nu thm axlt vo th cn bng
chuyn dch sang phi v dung dch s c mu ca dng ion.
Tm li thuyt ion rt n gin v gii thch c nguyn nhn ca s thay i
mu l do s thay i pH nhng cha gii thch c ton b tnh cht ca cht ch th.
Do xut hin thuyt th hai - Thuyt nhm sinh mu.

63

3.5.2.3. Thuyt nhm sinh mu.

Theo thuyt ny th mu ca cht ch th axlt baz c quyt nh bi s c mt
trong phn t ca chng mt s nhm nguyn t c bit (thng cha ni i).
Cc nhm ny thng l: nltro O = N -* c th bin i sang nhm HO = N- ;
az: - N = N - bin i sang = N - NH -, quan trng l nhm quynol c to ra t
benzen chng c kh nng sinh mu gi l nhm sinh mu. Ngoi cc nhm trn cn c
loi nhm th hai tuy chng khng c kh nng to mu cho ch th nhng s c mt
ca chng cng vi cc nhm trn s tng cng v lm m mu hn cho ch
th. l cc nhm-OH, -NH2, -OCH3, -N(CH)2, -N(C2H5)2 .. .
Theo thuyt ny th s thay i mu ca cht ch th l do s bin i cu trc bn
trong ca phn t. Khi c s bin i cu trc bn trong ca phn t ch th th s xut
hin hoc bin mt cc nhm trn v dn n s thay i cu trc ca ch th, s bin i
ny l thun nghch. V d: i vi n-nltrophenol l ch th c cu trc n gin nht, s
bin i tng h s l:

64
O N = O

O Nli OH

65

OH
O
Khng mu
Mu vng
R rng l khi cho kim vo dung dch n-nltrophenol s xut hin nhm quynol v
ch th s c mu vng, nu axit ho dung dch ni trn th mu vng s bin mt. Thuyt
ny gii thch c nguyn nhn ca s thay i mu l do bin i cu trc trong phn
t cht ch th nhng khng gii thch c s thay i cu trc phn t ph thuc vo
pH ca dung dch. Do phi kt hp c hai thuyt trn .
3.5.2.4. Thuyt ion - nhm sinh mu.
Da vo thuyt ny ngi ta gii thch c hu ht s thay i mu ca cc cht
ch th axit - baz. Theo thuyt ny cht ch th axit - baz l nhng cht hu c, trong
dung dch chng tn ti hai dng h bin (tc l nhng ng phn c th chuyn ho
thun nghch ln nhau) c mu khc nhau, khi chng cho v nhn proton th cu trc ca
n ng thi cng thay i theo v dn n s thay i mu. Mt trong hai dng h bin
ca cht ch th c th l axit hu c yu hay mt baz hu c yu (cng c khi l mt
cht lng tnh)
Gi s mt trong hai dng h bin l mt axlt yu trong dung dch s tn ti mt
h 2 cn bng sau:
HIndHlnd M Ind- + H+
Cn bng (I) l cn bng h bin, cn bng (II) l cn bng axlt-baz. Mu ca ch
th trong dung dch do t s nng hai dng h bin quyt nh. Vy theo (1) khi pH
thay i th cn bng (I) v (II) s chuyn dch sang tri hay sang phi do c th l
thay i mu ca cht ch th.
V d: cht ch th phenolphtaleln c dng h bin l axlt yu, trong dung dch s
tn ti theo 2 dng cn bng:
0

66

O = CO
C00-OH COOPhn t
khng mu (A)
Khng mu (B)
lon c mu
(Dng lacton)
(dng quynol)
mi trng kim c pH > 9 ta thy dung dch phenolphtalein c mu
v khi cn bng () v (li) chuyn sang phi nn cht ch th cn bng nh dng
(C). Ngc li trong mi trng axit th cn bng chuyn sang tri, to ra dng A khng
mu.
Metyl l mt cht ch th baz, metyl da cam l cht ch th lng tnh bi v
phn t ca n va cha nhm axit S0 3H va cha nhm baz N(CH 3)2. Khi phn ly
phn t metyl da cam to ion lng tnh va mang in tch dng va mang in tch
m. Trong mi trng axit th c mu , trong mi trng baz c mu vng.
HC
(C)
)

67

N 0=N NH-O- SO3- + OHH3C

H C/ ^ \=/ - - \=/ "~ 3 ' "2 vng
3

>N

N = N-@- SO - + H O
3

68

T cc v d trn ta thy r l tu theo pH ca mi trng m cht ch th s tn ti

dng nht nh no c mu khc nhau tu theo cu trc ca dng . 3.5.2.5.
Khong i mu ca cht ch th axit - baz.
* Phng trnh c bn.
trn ta nghin cu mt cch nh tnh s i mu ca cht ch th theo pH ca
dung dch. By gi ta xt mt cch nh lng, tc l tm mi quan h nh lng gia
mu ca cht ch th tc l t s [Hlnd 0]/ [ind-] vi pH ca dung dch. Gi s ta c cn
bng trn:
Hlnd0 i Hlnd 5 Ind + H+ p dng nh lut tc dng khi
lng vo cn bng () v (li) ta c:
*T (): [HInd]/[HInd0] = Khb (hng so h bin) [Hlnd0] = [Hlnd]/ Khb.
* T (II): [Ind-][H+]/[HInd] = Kpl (hng s phn ly - nu ch th l axit th l K A)
[Ind ] = Kpl[HInd]/ [H+].
Vy: [HInd]/ Ind- = [H+]/ Khb.Kpl
Ta t Kct = Khb.Kpl. Ta c: [H+] = Kct[HInd0]/[Ind-]
=* PH = PKc t - lg^ [Ind ]
PKct = -lgKct gi l ch s cng ca cht ch th.
y l phng trnh c bn biu din s ph thuc mu ca cht ch th vi pH ca
dung dch. Thc vy khi ta thm vi git dung dch cht ch th no vo mt dung
dch c pH xc nh th ng vi pH trong dung dch s c t s

69

[HInd0]/[Ind-] nht nh, do dung dch s c mu xc nh. Tri li khi dung dch cht
ch th c mu xc nh no th s ng vi mt gi tr pH xc nh ca dung dch.
* Khong oi mu ca cht ch th.
Theo phng trnh trn, khi thay i pH ca dung dch t s [HInd0]/[Ind-] cng
thay i. Tuy nhin trong thc t ngi ta nhn thy rng khng phi mi s bin i
gi tr pH ca dung dch u a n s i mu ca cht ch th m mt thng c th
nhn thy c. S d nh vy v mt chng ta ch nhn thy cht ch th c mu ca mt
dng h bin khi nng ca dng ny ln hn nng ca dng kia mt s ln nht
nh (tu theo tng cht ch th).
V d: i vi metyl da cam, mt chng ta ch nhn thy cht ch th c :
* Mu ca dng HInd0 khi [HInd0]/[Ind-] > 4,5 ng vi gii hn pH < 3,1.
* Mu vng khi [Ind-]/[HInd0] > 4,5 ng vi gii hn pH > 4,4. Khi pH < 3,1 mt
chng ta thy metyl da cam khng i mu m ch vn gi nguyn mu . Khi pH > 4,4
ta cng thy metyl da cam vn gi nguyn mu vng.
Vy r rng khi thay i dn gi tr pH trong phm vi trn 3,1 n 4,4 hay ngc
li th mu ca metyl da cam s dn t sang vng hay ngc li (m mt ta nhn thy
c).
Khong gi tr pH t 3,1 n 4,4 hay t 4,4 n 3,1 ng vi s i mu gi l
khong i mu ca cht ch th axit - baz. i vi phenolphtalein th t s [HInd 0]/
[Ind-] = 10 m KA 10-9 nn khong i mu s l 8 -- 10. Trong trng hp ny khong
i mu pH = pKA 1.
Vy khong i mu (KM) ca cht ch th axit baz l khong gi tr pH trong
cht ch th thay i mu m mt ta c th nhn thy c.
* Ch s nh phn pT ca cht ch th.
Trong khong i mu ngi ta nhn thy c mt gi tr pH m ti mu ca
cht ch th bin i r nht. Gi tr pH gi l ch s nh phn ca cht ch th (pT).
V d trong khong i mu ca metyl da cam pH: 3,1 - 4,4. Ngi ta nhn thy ti pH
= 4 metyl da cam c mu da cam r nht. Vy metyl da cam c pT = 4. Vy ch s nh
phn ca cht ch th axit baz (pT) l mt gi tr pH nm trong khong i mu, ng
vi pH mu ca cht ch th bin i r nht .
Khi nh phn thng nh dn dn dung dch chun vo dung dch phn tch c
cha cht ch th v dng li khi dung dch i mu r nht.Vy r rng pT chnh l pH
ca dung dch im kt thc nh phn cho nn pT c gi l ch s nh phn.
Ch :
* Khong i mu cng nh pT, gi tr ca chng hon ton khng chnh xc, thng
sai lch 0,3 n v pH tu theo kh nng nhn mu ca mt i vi mi ngi v tu
theo iu kin pha ch.
* Mt s cht ch th l hai nc c hai khong i mu. V d thimol xanh c KM1:
1,2 - 2,8 ( - vng ) v KM2: 8 - 9,6 (vng - xanh).
* Trong thc t ngi ta nhn thy pT c gi tr gn vi pKHInd v nm gia
KM.
* i lng pT ca cht ch th hai mu thng ph thuc vo nng , v rng s

70

bin i mu l do s bin i t ngt ca t s nng 2 dng (phn t v ion)

[HInd0]/[Ind-] c mu khc nhau. Tuy nhin khi dng mt lng ln ch th mu ca
dung dch s m hn nhng li kh nhn s i mu.
- c bit i vi cht ch th mt mu, pT ph thuc kh nhiu vo nng .
V d: Phenolphtalein chng hn. Trong dung dch n tn ti theo hai cn bng:
HP ^ HP ^ H+ + P-ta c KA = [P- ]
-9
[H+]/ [HP] = 10 c th rt ra mt s kt lun sau:
+ Khi pH = 9 ngha l [H+] = 10 -9 phenolphtalein chuyn mt na thnh dng .
Bi vy khi nh phn thng thng ly mt lng nh (2 - 3 git) cht ch th th khi
pH = 9 ta nhn thy ngay s i mu r nht.
+ Tuy nhin nu ly mt lng ln cht ch th, v d 5 --10 git dung dch ru
phenolphtalein 0,1% hay 2^3 git 1% th khi pH = 8 ch c 10% cht ch th chuyn
sang dng nhng lc c th nhn c mu rt r ging nh trng hp trn. S
d nh vy v trong c hai trng hp phenolphtalein u c cng nng dng [P -]
nn c cng cng mu mc d pH ca n khc nhau. Nh vy trng hp ny
mu xut hin pH = 8 tc pT = 8. Trong bng 3.1 l mt s cht ch th axit-baz
thng dng.
Bng 3.1. Mt s cht ch th axit baz
Tn thng thng
Thimol xanh
Tropeolin oo
Metyl da cam
Metyl vng
Metyl
Bromfenol xanh
Bromcrezon xanh
Bromthimol xanh
Fenol
Fenolftalein

Tn ho hc
Thimol sunfonftalein
Axit 4' fennylaminoazo bezen-4-sunfonic
Axit 4' - dimetyllaminoazobenzen-4-sunfonic
n dimetylaminoazobenzen
Axit 4' - dimetylaminobenzen-2-cacboxylic
3,3'-5,5' - tetraboonfenol
Sunfoftalein
3,3'-5,5'-tetrabrom-mcrezonsunftalein
Fenolsunfoftalein
Di-p-dioxyfenylftalit

Mu ca dng Axit Nng

Baz
(%)

vng 0,04
vng
xanh 0,1

PKHInd

KM

1,65
1,86

1,2 - 2,8
8,0 - 9,6

3,46

3,1 - 4,4

vng

0,04

5,0

2,9 - 4,0
4,4 - 6,2

vng
vng

0,04
0,1

4,1

3,0 - 4,6

vng

4,9
7,3

4,0 - 5,6
6,2 - 7,6

vng
vng

8,0
9,2

6,4 - 8,0
vng
8,0 - 10,0 khng mu

xanh tm 0,1
xanh
xanh

0,1
0,1

xanh

0,1
0,1

3.5.2.6. Cc yu t nh hng n khong i mu ca cht ch th.

* Hiu ng mui ca cc cht in ly.
*Chng lm thay i cng mu (do hp th nh sng) ca mt hay hai dng
mu ca cht ch th.
*nh hng n cn bng ca cht ch th:
+ Khi lc ion ln th c nh hng ln n mu sc ca ch th, i vi cc cht
ch th khc nhau v cc mui khc nhau th rt khc nhau. V d hp th nh sng
ca dung dch cha ion dinitrophenolat kh tng khi c cc cation ha tr 2 hoc 3
nhng n li gim khi c cc cation ho tr 1. Cc anion v ngay c cc cht khng in
ly nh ur cng c nh hng n mu ca cht ch th.

71

+ Khi lc ion nh n th hin nh i vi cn bng ca cht in ly thng.

Trong thc t khi lc ion ln cn phi hiu chnh li gi tr pH i mu ca cht ch th.
*nh hng ca nhit .
Khi nhit thay i th hng s phn ly ca nc v cht ch th cng thay i. V
vy nh hng ca nhit khng ging nhau i vi cc cht ch th khc nhau. Tu
theo cu trc bn cht khc nhau ca cc cht ch th m mc nh hng ca nhit
th hin nhiu hay t. Hin nay cha tm c quy lut no chung cho tc dng ny m
ch da vo thc nghim. Cn ch mt iu l i vi cc cht ch th l axit yu th
khong i mu hu nh khng thay i v t thay i K HInd. Nhng i vi ch th l
baz yu th li ph thuc nhiu v khi nhit tng th K H O tng nn KH O /KIndOH tng.
Ch th l baz yu (IndOH) ta c phng trnh
phn ly:
IndOH ^ Ind+ + OH[IndOH] _ [OH- ] _ KH2G 1
h
[H+1 _ KindOH [IndOH]
= _2. v nh vy v [H+] _
.L
nn
[Ind+ ] KIndOH KIndOH [H+ ]
K^O [Ind+]
khong i mu b h xung.
*nh hng ca dung mi
Khi dng dung mi khc nc, v d ru, axeton, . . . c hng s in mi nh
hn nc th axit v baz s phn ly t hn, do nh hng n khong i mu ca
cht ch th (thng di ra).
*Th t chun :
Th t chun rt quan trng v nh hng n chnh xc ca php nh
phn. V d nh phn dung dch axit bng dung dch kim t burt dng metyl da cam
lm ch th th phi i mu t hng sang vng, s i mu ny thng l khng chnh
xc v kh xc nh do ngi ta nh phn theo th t ngc li, tc l nh phn
kim bng dung dch axit t burt v s i mu t vng sang hng nhn d hn. Nhng
i vi phenolphtalein l ch th mt mu th d dng nhn nn chun th no cng c.
Cn ch mt iu na l thay i th t nh phn cc cht cng lm thay i gi tr
pH khi kt thc nh phn. V d nh phn dung dch kim bng axit vi metyl da cam
th kt thc nh phn pH = 4, cn nh phn axit bng kim th li kt thc pH =
4,4. Nu c hai gi tr pH trn u nm trong bc nhy th khng sao, nhng nu nm
ngoi bc nhy th s nh hng n kt qu nh phn. Mun mu thay i r hn v
c KM hp hn ngi ta dng ch th hn hp.
Ngoi cc cht ch th c trnh by trong bng 3.1 cn c mt s loi ch th
sau:
Cht ch th hn hp:
nhn bit s i mu mt cch r rt v chnh xc, ngoi cch chn cht ch th
thch hp, ngi ta cn dng cht ch th hn hp. Nh dng cht ch th hn hp ngi
ta c th nhn bit c khong i mu rt nh (0,2 -- 0,5 n v pH). c bit khi
chun cc axit baz yu hay chun dung dch axit baz rt long ngi ta thng
dng ch th hn hp. C th lm nh sau:
* C th dng mt hn hp 2 cht ch th axit - baz c mu khc nhau v c
IndOH

72

khong i mu gn trng nhau. V d Crzol c khong i mu pH = 7,2 - 8,8 v

Thimol xanh c khong i mu pH = 8,0 9,6. Nu ta trn theo t l 1:3 (nng
0,1%) th s c mt dung dch ch th hn hp i mu r hn khi pH = 8,2 ng vi
mu thm v khi pH = 8,4 ng vi mu tm.
* Trn mt cht ch th axit baz vi mt cht mu m mu ca n khng ph
thuc vo pH ca dung dch. V d hn hp metyl da cam + metyl xanh. Metyl xanh
khng i mu khi pH thay i, nhng mu xanh ca n phi hp vi mu ca metyl da
cam v bin i nh sau:
* pH = 4,4 hn hp c mu xanh l cy (vng + xanh).
* pH = 4 s chuyn thnh mu xm nht.
* pH = 3,6 c mu tm. Cht
ch th tng hp:
Ch th tng hp l hn hp gm mt s cht ch th. Loi ch th ny i mu
nhiu ln cc gi tr pH khc nhau. V d: cht ch th tng hp gm 0,125g trinitrobenzen, 0,0355g phenolphtalein, 0,0300g cresolphtalein, 0,0085g metyl da cam v
0,0500g pentametoxy, c th dng xc nh gn ng pH trong khong pH t 1,2 n
12,7. Mu ca ch th tng hp chuyn t (pH=2) n da cam (pH = 4), vng (pH
= 6), lc (pH = 7), xanh lc (pH = 8), chm (pH = 9) v chm tm (pH =
10).
Ngi ta thng dng giy tm ch th tng hp. Khi dng giy tm ch th tng
hp, ta cn nh mt git dung dch cn xc nh pH ln giy v i chiu mu trn giy
vi thang mu ( ghi ch pH) l bit c pH ca dung dch.
Cht ch th hunh quang:
Loi ch th hunh quang thng dng khi chun cc dung dch c hoc dung
dch bn thn c mu. Khi chiu tia t ngoi vo dung dch c ch th hunh quang
th hoc hunh quang s xut hin hoc s mt hunh quang nhng gi tr pH nht
nh. V d: ch th - naphtylamin s mt hunh quang (mu xanh) pH t 3,4 n 4,8.
Khi dng ch th hunh quang nn tin hnh chun ch ti.
3.6. Cch xc nh dim tng ng trong phng php trung ha.
Khi chun mun xc nh im tng ng phi dng cht ch th. Trong
trng hp l tng, khi kt thc chun cht ch th phi i mu chnh im tng
ng, ngha l pT ca cht ch th phi trng vi pH ca dung dch im tng
ng. Nhng thc t pT khng trng vi pH im tng ong, hoc ln hn hoc
nh hn. Do ta s chun thiu hoc tha v dn n sai s. Nh vy php
chun t kt qu tt nht, sai s nm trong phm vi cho php ngi ta thng dng
hai phng php sau:
*Phng php v ng nh phn hay l phng php th.
*Phng php tnh sai s ch th
Khi chun c th tin hnh trong dung mi nc hay khng nc. y ta
nghin cu cc trng hp chun trong dung mi nc.
Sau y ta s xt qu trnh chun axit-baz trong dung dch nc dng phng
php th.
3.6.1. Khi nim ng nh phn - ng cong logarit
Khi nh phn mt dung dch axit AX1 bng mt baz BaZ2 hay ngc li s

73

xy ra phn ng Axit - Baz:

AX1 + BaZ2 = BaZ1 + AX2
Trong qu trnh nng axit, baz ca hai cp thay i. Do pH ca dung
dch cng thay i. Nu ta biu din s bin i trn mt h trc ta : trc tung
biu din pH = -lg[H+], cn trc honh biu din lng thuc th thm vo: % hay ml
th ta s c ng cong lin tc gi chung l ng cong logarit hay l ng nh
phn. Vy ng nh phn l th biu din s bin i tnh cht no ca dung
dch cht nghin cu theo lng thuc th thm vo trong qu trnh nh phn.
C th ng nh phn axit baz l mt ng cong logarit biu din s thay i
pH (trc tung) ca dung dch cht nghin cu (axit hay baz) theo lng (% hay Vml trc honh) thuc th (baz hay axit) thm vo trong qu trnh nh phn. 3.6.2. Nguyn
tc xy dng ng nh phn axit - baz.
Gi s dung dch cht nghin cu l axit hay baz v dung dch chun l baz hay
axit c cng nng xc nh, v d thng ly C = 0,1 v V = 100ml. Sau ta s tnh
c cc gi tr pH ca dung dch ng vi cc thi im nh phn:
* Trc khi chun : khi cha thm thuc th.
* Trc thi im tng ng: giai on nh phn khi thm thuc th cha
mt lng tng ng - gi s khi thm 50%, 90%, 99,9% lng cn thit.
* Ti im tng ng: khi thm ng 100% lng thuc th cn thit.
* Sau im tng ng: giai on thm tha thuc th: 100,1%, 101%, 110%,
200% ...
* Ni cc gi tr pH li ta s c mt ng cong gi l ng nh phn hay l
ng chun .
Bng tnh ton v thc nghim u * pH thy
rng pH ca dung dch trong qu trnh chun
gn im tng c s thay i t ngt, gi l
bc nhy pH ca ng nh phn, da vo
chn cht ch th.
Thng
ngi
ta
quy
c
bc
nhy
pH
l
on
pH
ng
vi
thi
im
cn 0,1% lng cht nghin cu (cht
Vdd n(ml)
xc nh) cha c chun v 0,1%
lng dung dch chun d so vi cht nghin cu, tc l khong pH ng vi F
0,999 v 1,001
chu

3.7. Cc trng hp chun . 3.7.1. Chun

axit mnh bng baz mnh.
Gi s chun 100 ml dung dch HCl 0,1M bng dung dch NaOH 0,1M. Phn
ng chun : HCl + NaOH = NaCl + H2O
Vtdtd =
0,1

.-,,,

= lOOml

,A. A.

^,,,^

s milimol baz

thm vo CV gi F l phn axt c chun , tc l: F

s milimol axt ban u C0V0

74

Trong :
* C0, V0 l nng v th tch ban u ca axt
* C, V l nng v th tch ca baz thm vo Ta
tnh pH ca dung dch trong qu trnh chun :
* Khi cha thm NaOH, phn axit chun (F): F = 0, trong dung dch
ch c: HCl pH = -lgcl = 1,0
* Khi thm 50 ml dung dch NaOH, trung ha c mt na lng HCl (F
c=
50 X
3,33.10-2 pH = 1,48
= 0,5):
100 + 50
[H]+
Khi thm 90 ml dung dch NaOH, trung ha c 90% HCl (F = 0,9):
10 X 0,1
5,26.10-3 pH = 2,28
100 + 90
[H]+
- Khi thm 99 ml dung dch NaOH, trung ha c 99% HCl (F=0,99) nh vy,
cn 1% HCl:
1 X 0,1
5.10-4 pH = 3,3
100 + 99
- Khi thm 99,9 ml NaOH, trung ha c 99,9% HCl (F = 0,999) nh vy
[H]+
cn li 0,1% HCl cha b trung ha:
0,1 X 0,1
5.10-5 pH = 4,3
100 +99,9
* Khi thm 100 ml NaoH, trung ha ht HCl (F = 1) trong dung dch ch c
NaCl pH = 7.
* Khi thm 100,1 ml NaOH, lng NaOH d 0,1 ml (F = 1,001).
[OH]- = 0,1 X 0,1 = 10 4,3 pOH = 4,3 pH = 9,7
100 +100,1
* Khi thm 101 ml NaOH, d 1 ml NaOH (F = 1,01)
[OH]- = 1x 0,1 = 10-3 3 pOH = 3,3 pH = 10,7
[OH]100 +101
* Khi thm 110 ml NaOH, d 10 ml NaOH (F = 1,1)
10 X 0,1 , 0 -2,32
= 10-232 pOH = 2,32 pH = 11,58
100+110
Ghi cc kt qu trn vo bng 3.1 th hin mi quan h gia phn axit HCl
c chun v pH ca dung dch. Biu din ln th ta c ng chun trn
hnh 3.1.
Bng 3.1. Gi tr pH khi chun 100ml dung dch HCl 0,1M bng dung dch
NaOH 0,1M
Phn axit c chun (F)
pH ca dung dch
0,00
1,0
0,50
1,48
0,90
2,28
0,99
3,30

75

1,000
1,001
1,01
1,10

7,0
9,7
10,7
11,68

Qua bng trn v ng chun , ta thy khi axit cha b chun (F = 0) cho
n khi c chun 99,90% (F = 0,999) pH ca dung dch ch bin i 3,4 n v.
Nhng khong chun thiu v tha 0,1% (F t 0,999 n 1,001) th pH thay i 5,4
n v, s thay i rt t ngt to nn bc nhy pH quanh im tng ng ng
nh phn. Nu ta dng cht ch th c phn pT nm trong khong bc nhy trn (4,3 9,7) th kt thc chun khi cht ch th i mu th sai s ca php chun ch nm
trong khong 0,1%

76
o f-

pH

68.

ng tng ng
th metyl da cam(3,1 -

B
c
nh

69.

Kho
V ng chuyn mu ca cht ch

70.
5,4

71.

72.
-

4,4) /Khong chuyn mu ca

cht ch th metyl (4,4 6,2) ^. im tng
ng ^
trung
ha

im trung ha
Khong chuyn mu ca cht
ch th phenolphtalein(8,0
-10,0)

73.
-

74.
-

75.
-

76.
-

77.
-

78.
-

79.
-

80.
-

81.
L0, 9.

....................................................................___> F
1,0 1,1

Hnh 3.1: ng cong chun dung dch HCl

0,1M bng dung dch NaOH 0,1M

77

Bc nhy pH trn ng chun ph thuc vo nng ca dung dch chun

NaOH v nng ca dung dch axit cn chun HCl. Nng cng ln th bc
nhy cng di.
tin so snh, trong bng 3.2 trnh by s thay i pH khi trung ha 100 mi dung
dch HCl 1M; 0,1M v 0,01M bng dung dch NaOH c cng nng , khi tnh c th
k n s tng th tch dung dch khi chun .

78

Bng 3.2. Gi tr pH khi chun 100ml dung dch HCl IM; 0,1M v 0,01M bng
dung dch NaOH cng nhit
Phn axit c chun (F)
0
0,05
0,9
0,99
0,999
1,000
1,001
1,01
1,1

pH ca dung dch
1M
0,1M
0,01M
0
1
2
0,5
1,5
2,5
1,3
2,3
3,3
2,3
3,3
4,3
3,3
4,3
5,3
7,0
7,0
7,0
10,7
9,7
8,7
11,7
10,7
9,7
12,7
11,7
10,7

Biu din d kin ca bng ny ln th c hnh 3.2

79

1,1
* Khong chuyn mu ca cht

ng tng ng

ch
th metyl da cam(3,4 - 4,4)
/Khong chuyn mu ca cht
ch th meyl (4,4 - 6,2) L,
im lng ong ng
\ im trung ha ****** chuyn mu
ca cht ch
enolphtalein(8,0 -10,0)

(a) Bc nhy
7,4
nhy

(a)
5,4

Bc
(a)

Bc nhy 3,4

80

Hnh 3.2 : nh hng nng ca dung dch axit v baz n tnh cht ca
ng cong chun
1. Dung dch HCl IM; 2. Dung dch Hci 0,1M; 3. Dung dch HCl 0,01M
Sai s ch th
Sai s ch th l sai s gy ra do im cui ca s chun (tc pT ca cht ch
th) khng trng vi pH im tng ng. Sai s thng tnh theo sai s tng
i: S% = G ^ X100 D
G l gi tr gn ng; D l gi tr ng.

81

Th d 1: Tnh sai s ch th mc phi khi chun dung dch HCl 0,1M bng dung dch
NaOH 0,1M nu dng cht ch th c pT = 5 v pT = 9. Phng trnh chun :
HCl + NaOH = NaCl + H2O
pHt = 7.
1. Khi dng cht ch th c pT = 5 tc l kt thc chun pH = 5, vic chun
kt thc trc im tng ng.
S% = G-Dx 100 = CV CV X100 I D C0V0
Lng axit cha chun
X100
Lng axit ban du
Trong :
* C, VC: nng v th tch ca dung dch NaOH thm vo
* C0, V0: nng v th tch ca dung dch HCl
(Du tr (-) v chun kt thc trc im tng ng nn lng axit chun
(VCC) < lng axit ban u (V0C0))
c

S% = - 1tr < 0 + C> X100

10-1V
V kt thc chun gn im tng ng nn VC V0. Do :
V

S% =--------1. X 100 = -0,02%

10V
,,
2. Khi dng ch th c pT = 9, tc l kt thc chun pH = 9, vic chun
kt thc sau im tng tc l d NaOH.
d
S% = ----------------Lng
, X 100
Lng kim cn chun
(Du cng (+) v chun tha, tc l lng NaOH dng (VCC) > lng kim
d cn chun V0C0).
Kt thc pH = 9 [H+] = 10-9 [OH-] = 10S% = >H 1 K
VC ] = 1^ X100 = +0,02%
CV
01V

-5

0 00

Th d 2: Nu chun dung dch HCl 0,1M bng dung dch NaOH 0,1M th cn
kt thc chun pH bng bao nhiu (hay dng cc cht ch th c pT bng bao nhiu)
sai s cho php chun khng qu 0,1%.
Sai s khng qu 0,1% tc l sai s trong khong t -0,1% n 0,1%.
- Khi sai s -0,1% S = -0,001 hay 10-3, vic chun kt thc trc im tng
ng nn:
VC
C V
- 10 => +
) (vi V . Ve )
0-1 0
10 .V0
10-3 I" [H+]=-1
3

82

pH

,10 4
+ lg2 =
4,3

83

-4

- Khi sai s bng +0,1% S = 0,001 = 1010-4

-3

, vic chun kt thc sau im tng, d NaOH nn:

S = >H |(V , + Vc ) (v Vo . Ve )
CV
o

84

10-3=

[OH
]2Vo 10-

.Vo

[OH-]
2
1

85

0pOH = 4,3 pH = 14-4,3 = 9,7 Vy, php chun c sai s 0,1% th kt thc
chun trong khong pH: 4,3 - 9,7. Tc l php chun c th dng cc cht ch th
c pT nm trong khong gi tr 4,3 - 9,7.
3.7.2. Chun axt yu bng baz mnh hoc baz yu bng axit mnh. 3.7.2.1. Chun
CH3COOH bng dung dch chun NaOH.
Gi s chun " 100ml dung dch CH3COOH 0,1M bng dung dch NaOH 0,1M.
pKcH3C00H = 4,75. Phn ng chun :
CH3COOH + NaOH = CH3C00Na + H2O
- Khi cha thm NaOH, trong dung dch ch c CH 3COOH 0,1M (C0) pH ca dung
dch tnh theo cng thc:
[H + ]=vKACA pH = ^2pKA -"2lgCA
- Khi thm NaOH nhng cha trung ha ht, trong dung dch c
CH3COOH/CH3COO-, pH ca dung dch c tnh theo cng thc:

86

pH
pKA

,
C
lg
C

87

- Khi thm NaOH va trung ha ht CH 3COOH, trong dung dch ch c

CH3COO- l mt baz yu, pH ca dung dch c tnh theo cng thc:

88

[H + ]

AKH2O

Co
+C
C0C

89

Hay tnh: pOH = ^KCH3COO- -C

ri tnh pH = 14 - pOH

- Khi thm d NaOH, trong dung dch c NaOH d v CH3COO-. V CH3COOl mt

baz yu bn cnh NaOH l mt baz mnh nn pH ca dung dch c tnh
theo NaOH d.
Tnh theo cng thc trn ta c cc gi tr pH bin i theo lng CH 3COOH
c chun (F) nh sau:

90

Phn axit chun (F)

0
0,
2
0,
5

PH ca dung dch
2,88
4,20 4,81

91

0,9
0,99
0,999
1,00 (im tng ng)
1,001
1,01
1,1
2,0

5,80
6,80
7,8
8,87
9,7
10,68
11,62
12,52

Biu din cc d kin ca bng trn ln th,

ta c hnh 3.3
pH
Hnh 3.3. ng nh phn
ng tng ng

HCl 0,1M

F
0

1
100ml dung
dch
CH3COOH
0,1M bang
dung dch
NaoH 0,1M

Nhn vo hnh 3.3 v so snh vi hnh 3.1 ta

thy:
82.
im tng ng khi chun axit
yu bng baz mnh khng trng vi im trung ha
(c pH = 7) m nm min kim (pHt = 8,87).
83.
ng cong chun trong chun
axit yu bng baz mnh khng i xng so vi im
tng ng (khc vi hnh 3.1).
84.
Bc nhy khi chun axit yu bng
baz mnh (7,8 - 9,7) nh hn rt nhiu so vi bc

92

nhy khi chun axit mnh vi cng khong sai s

0,1% (4,3 9,7).
85.
Cng nh trng hp chun axit
mnh bng baz mnh th bc nhy ca ng
chun cng ph thuc vo nng . Nng cng
ln th bc nhy cng di. V d: chun dung
dch CH3COOH bng dung dch NaOH c cng nng
, bc nhy t F = 0,998 n F = 1,002 c pH
nh sau:
Nng CH3COOH C0
1M
0,1M
0,01M
0,001M

pH khi F = 0,998
7,45
7,45
7,44
7,37

pH khi F = 1,002
11,0
10,0
9,0
7,8

Bc nhy ca ng cong nh phn cng

ngn khi axit cng yu.
5. T nhn xt trn ta thy r rng bc nhy
pH ca ng nh phn axit di

ApH
3,55
2,55
1,56
0,43

hay ngn ph thuc vo mnh hay yu ca axit m ta nh phn, ngha l ph thuc

vo hng s axit KA, KA cng ln bc nhy pH cng di, KA cng nh bc nhy pH
cng ngn v tt nhin KA nh n mc no th s khng c bc nhy pH.
3.7.2.2. Chun dung dch NH3 bng dung dch HCl.
Gi s chun 100ml (V 0ml) dung dch NH3 0,1M (C0) bng dung dch HCl
0,1M (C); cho PK
3 = 4,75.
Phn ng chun : NH3 + HCl = NH4Cl
*Khi cha thm HCl trong dung dch ch c NH3 l mt baz yu, vy pH ca
dung dch c tnh theo cng thc:
[OH] = JKBCB ri tnh pH = 14 - pOH.
*Khi chun , trc im tng ng trong dung dch c NH4 + NH3, l h
m nn:
pH = pKA - lg-C^ vi pKa = 14 - pKB

NH

CA l nng ca NH4 ; CB l nng ca NH3.

- Ti im tng ng, trong dung dch ch c NH4Cl l mt axit yu nn:
+

[H +] = VKAC;vi: KA = ^ = 10-925
K

NH3

Vi CA l nng ca NH4 .
*Khi thm HCl d, trong dung dch c HCl d v NH4 . V NH4 l mt axit yu
bn cnh HCl l mt axit mnh, nn pH ca dung dch c tnh theo HCl d.
Tnh theo cng thc trn, ta c cc gi tr pH bin i theo lng NH3 c
chun (F) nh sau (vi quy c chun thiu v tha 0,2% lng baz)
+

Phn NH3 chun (F)

0
0,5
0,9
0,99
0,998
1,00 (im tng ng)
1,002
1,01
1,10

pH ca dung dch
11,13
9,26
8,36
7,26
6,56
5,13
3,7
3,0
2,0

Biu din cc d kin ca bng ln th ta c hnh 3.4.

pH

NaOH 0,1M
^ NH4OH 0,1M
--------------14 1i'
I Bc nhy pH
-----------------------------1
10
--------------- 1-----------------------1---------------
61
20

10
200 VHCl
0
Hnh 3.4. ng nh phn dung dch NH4OH
0,1M bng dung dch Hci 0,1M
Ging trng hp chun axit yu bng baz mnh, ng cong chun baz
yu bng axit mnh cng cho thy:
86.
im tng ng khng trng vi im trung ha, m min axit (pH t
= 5,13). Bc nhy pH: 6,5 - 3,7. ng cong chun khng i xng so vi im
trung ha.
87.
Bc nhy ca ng chun cng ph thuc vo nng v hng s
phn li ca baz yu.
Sai s ch th.
Th d 1: Tnh sai s mc phi khi chun CH 3COOH 0,1M (pKA = 4,74) bng
dung dch NaOH 0,1M nu dng cht ch th metyl da cam (pT = 4), pH t = 8,87 (xem
cch tnh trn).
Dng ch th c pT = 4, ngha l kt thc chun pH = 4, ngng chun
trc im tng, v vy trong dung dch cn CH3COOH cha c chun .
Ta c:
CH3COOH ^ H+ + CH3COO"
A [H+ |CH3COO
] [CH3COOH] = [H + ] [CH3COOH] ~* [CH3COO-] ~ KA
_, , CH3COOH Lng axit cha bi chun
T s :--- -3-------- =- - - --------" -;
5,5
CH3COO
L ng axit bi chun
K

1Q-=- ^ = 1Q4
0,74

=
5,5 4'X 1QQ
1QS% Lng axit cha bi chun
-85%
1 + 5,5
Lng axit ban du
Ngha l c 85% axit cha c chun .
Th d 2: Tnh sai s mc phi khi chun dung dch NH 3 0,1M (pKb = 4,74)
bng dung dch HCl 0,1M nu dng ch th c pT = 9 v pT = 4; pH t = 5,13 (xem cch

tnh trn).
* Dng ch th c pT = 9, ngha l kt thc chun pH = 9, ngng chun
trc im tng ng (v chun kim bng axit th trong qu trnh chun

96

pH gim dn), v vy, trong dung dch cn NH3 cha b chun . Ta

[NH+OH ] [NH3 ] = [OH ]

97

74

T s NH+

NH4 .
Lng kim cha b chun
NH3 c chun

: -
- = 10- = 0,55
1
10
0

-5

0,26

98

0-

4,74

_ - Lng NH3 cha chun . ^

S% =---------- -----------------------------X 100
Lng NH3 ban du
:

,'X = =
+[ 3 +

-^1]

^055-

100

-35%

[NH+]
NH
] 1
0,55
Sai s ln, vy khng dng phenol phtalein lm ch th chun dung dch
NH3 bng HCl c.
* Dng cht ch th c pT = 4, vic chun kt thc sau im tng
ng:
S% = +-------------Lng axitd
X 100
Lng axit dng chun
Axit d l axit mnh HCl nn nng axit d chnh l [H+] = 10-4. Do :
S0%

=+
+
)X
[H

+](v

Vc

100

-1

10 .V0
S%

=+

1.

X100 =

0,2%

3.7.3. Chun axit yu bng baz yu hay ngc li.

nh phn 100ml dung dch CH3COOH bng dung dch NH3 cng nng C =
0,1M.
3.7.3.1. Kho st ng nh phn.
* Trc khi chun :
Ta c dung dch axit yu CH3COOH 0,1M, tnh pH theo cng thc (2.5):
pK

CH3COOH

-1

= =
pH

(PK

- =
lgCA )

2(4,75

lg104,75

2,87

* Trong qu trnh chun :

Khi nh dn dung dch NH3 vo dung dch CH3COOH s c phn ng xy ra:
CH3 COOH + NH 3 ^ CH 3COO - +
NH+4
Ax1
Baz2
Baz1 Ax2
C pKA1 = 4,75 ; pKA2 = 9,25.
V CH3COOH v NH3 u yu nn lun lun tn ti trong dung dch 2 cp axitbaz: CH3COOH/CH3COO- v NH4+/NH3
n gin v tnh gn ng ta p dng cng thc (2.16) tnh pH ca dung

100

pH 1
2

C
pKA1 + pKA2 C
+ lg

B2
A1 J

101

B2

A2

-'CH3COOH

CNH : Nng NH3 lc bt u trn (nng ban u).

: Nng ca CH3COOH lc bt u trn (nng ban u)

102

CB
Trc im tng ng:
C

V d khi thm 99,9m1 NH3 ta c:

<1

103

C=
B2

0,1.

99,9
100

C
C

B2

99,9
100

99 9 ,
100
I 4,73 + 9,25 + lg^^
1 6,99

pH

105

Sau im tng ng:

C
>
C
1

107

C
B2

100
B2

C
CA

100
,1
10
0

pH

4,73

9,25 + Ig1001
100

6,99

109

13

10

axit d 0 kim d 10 %

111

dng cht ch th axit - baz th mt trong hai cht tc dng (axit hay baz) phi l axit
mnh hay baz mnh.
3.7.4. Chun a axit (hay a baz), hn hp axit (hn hp baz).
3.7.4.1. Chun a axit bng baz mnh.
Cc a axt mnh nh H2SO4 c K1 = 00, K2 = 10-2. V vy, vic chun H2SO4
bng NaOH cng nh chun HCl. Cn cc a axt yu th khi chun s xy ra theo
nhiu nc.
V d nh phn 100= ml H 3PO4 0,1M bng dung dch NaOH 0,1 M. Trong dung
dch H3PO4 l axit 3 nc tn ti theo 3 cn bng :
H3PO4 ^ H+ + H2PO4- ng vi K1 = 7,51.10-3 pK1 = 2,12.
H2PO4- ^ H+ + HPO42- ng vi K2 = 6,23.10-8 pK2= 7,21.
HPO42- == H+ + PO43ng vi K3 = 2,2.10-13 pK = 12,67.
Theo 3 phn ng trn, dung dch H3PO4 c coi nh hn hp 3 axit: H 3PO4 +
H2PO4- + HPO42- vi cc nng C1, C2, C3 v K1 >> K2 >> K3, do khi dng dung
dch NaOH chun th H3PO4 s c trung ha gn nh hon ton ln lt ht tng
nc:
nc 1: H3PO4 + NaOH ==== NaH2PO4 + H2O ng vi im tng ng 1. nc 2:
H2PO4- + NaOH ==== Na2HPO4 + H2O ng vi im tng ng 2. nc 3:
HPO42- + NaOH ==* Na3PO4 + H2O ng vi im tng ng 3. * Tnh pH ca
dung dch trong qu trnh chun :
* Trc chun : Ta c dung dch axit: H3PO4 c th tnh theo cng thc:
pH =

2(pK -lgCA) = (2,1 -lg10 1 )= 1,55

* im tng ng 1: khi chun H3PO4 n H2PO4 , ta c dung dch

lng tnh (mui axit NaH2PO4), c th tnh pH theo:
-

pH =

2 (pK1 + pK2) = (2,1 + 7,2) = 4,6

* im tng ng 2: khi chun n HPO4 , ta c dung dch lng tnh

(mui axit Na2HPO4), c th tnh pH theo:
pH =1 (pK2 + pK3) = 2 (7,2 +12,6) = 9,9
* im tng ng 3: khi chun n PO 4 , ta c dung dch baz (Na3PO4),
c th tnh pH theo :
pH = 7 + -2 (pK3 + lgCB ) = 7 + -2 (12,6 + lg10-1 ) = 12,8
2-

3-

* Cch xc nh cc im tng ng: Xc nh cc im tng ng 1, 2 tc l

cc im tng ng trc im tng ng cui cng: Trc ht chng ta phi tnh
bc nhy pH gn cc im tng ng 1, 2 theo nguyn tc sau:
* Mun nh phn t chnh xc 1% khi pK > 3,6 th s kt thc nh phn
trong khong pH sau:
ApK = 4 th pK2 - 1,8 > pH > pK1 + 1,8.
ApK > 4 th pK2 - 2 > pH > pK1 + 2.
- Mun nh phn t chnh xc 0,1% khi pK > 5,6 th s kt thc nh

112

phn trong khong bc nhy pH sau:

pK = 6 th pK2 - 2,8 > pH > pK + 2,8.
ApK > 6 th pK2 - 3 > pH > pK + 3.
Theo nguyn tc ny ta s tnh c nh sau:
* im tng ng 1: ta c pK = pK2 - pK = 7,2 - 2,1 = 5,1. Vy mun t
chnh xc 1% ta c th kt thc nh phn trong khong bc nhy pH:
7,2 - 2 > pH > 2,1 + 2
tc 5,2 > pH > 4,1
* im tng ng 2: Ta c pK = 12,67 - 7,21 = 5,46 bc nhy pH s l:
12,67 - 2 > pH > 7,21 + 2
tc 10,67 > pH > 9,21
- im tng ng 3: v K3 = 2,2.10-13 < 10-7 nn s khng c bc nhy. Nh
vy im tng ng I nm gn khong i mu ca metyl da cam (3,1
pH
4,4), nu dng metyl da cam th ta c th nh phn H3PO4 nh mt n axt, tc H3PO4
+ OH- =F=* H2PO4- + H2O, ng lng gam ca H3PO4 y bng chnh phn t gam
ca n. Vi ch th phenolphtalein (chnh xc hn l thimolphtalein) (9,4 -10,6) c th
nh phn H3PO4 nh l a axt hai nc H3PO4 + 2OH- ^ HPO42- + H2O. ng lng
gam ca H3PO4 bng mt na phn t gam. Khng th nh phn trc tip H3PO4 n
nc 3 v khng c bc nhy pH. ng nh phn c hnh dng nh hnh v 3.6.
S mol
NaOH
Hnh
3.6. ng nh phn 0,1M dung dch
H3PO4 bng dUng dch NaOH 0,1M
Trong thc t ngi ta c
th nh phn H3PO4 n nc th 3
bng cch gin tip nh sau: Cho
CaCl2 tc dng vi H3PO4, mt
lng tng ng HCl c gii
phng ra v ngi ta nh phn
lng HCl bng
NaOH:

Na3PO4

13
12 3

2H3PO4 + 3Ca2+ -> Ca3(PO4)2 + 6H+

6H+ + 6OH- -> 6H2O ng lng gam ca H3PO4 trong trng hp ny bng
1/3 phn t gam ca
n.
3.7.4.2. Chun a baz bng axit mnh.
HO
vb1pK
b2 = 10Ta xt s chun dung dch Na2CO3 (hay K2CO3) bng dung dch chun
K
=
HCl,
(
K>
2(H CO
K
CO3-7,68
2l mt a baz c pKb1 = 1
-4,65
0
theo 2 nc:
HO
K
b2 - '
2

3 ) )

1(H2 C

O3

) )

113

Cn c vo 2 gi tr pK ta thy c th chun CO32- bng HCl

* Nc 1: CO32- + H+ = HCO3pHtd1 - 2 (pKa1 + pKa2) -

(6,62 +10,35)-8,34

pH ny nm trong khong chuyn mu ca phenol phtalein. V vy, c th dng n

lm cht ch th chun CO3 bng HCl theo nc th nht.
* Nc 2: HCO3- + H+ = CO2 + H2O
pHtd2 l pH ca dung dch bo ha CO2 v khi d 1 git dung dch axit chun, pH
khong bng 4 nm trong khong i mu ca metyl da cam. V vy c th dng cht
ch th ny chun CO3 ti nc th hai. 3.7.4.3. Chun hn hp axt (hn hp
baz).
Trong thc t thng hay phi chun hn hp axt, c cc trng hp sau: nh
phn hn hp axt mnh v axt yu, nh phn hn hp axt yu. Gi s ta phi nh
phn hn hp axt A1, A2, A3 c nng ban u tng ng CA1, CA2, CA3 v cc hng s
axit tng ng KA1, KA2, KA3 ta xt hai trng hp thng gp sau:
Trng hp KA1 KA2 KA3. Trong trng hp ny ta ch xc nh c nng
tng cng ca 3 axit CA1 + CA2 + CA3 v ty theo gi tr ca KA s ri vo trng hp nh
phn axit mnh hay nh phn axit yu.
Trng hp KA1 >> KA2 >> KA3: trng hp ny ging nh nh phn axit. Qu
trnh nh phn s xy ra ln lt theo 3 phn ng sau:
A1 + NaOH ==== B1 + Na+.H2O ng vi im tng ng I A2 +
NaOH ==== B2 + Na+.H2O ng vi im tng ng II A3 +
NaOH ==* B3 + Na+.H2O ng vi im tng ng III Ch :
Chun dung dch hn hp baz cng tng t nh chun dung dch hn hp
axit.
3.7.5. Mt s th d v phng php chun axit - baz.
3.7.5.1. Pha ch dung dch chun HO, NaOH.
NaOH v HCl u khng phi l cht gc nn:
* pha dung dch NaOH nng khong 0,1M ta cn trn cn k thut khong
4,1g NaOH loi tinh khit phn tch v pha thnh 1 lt dung dch bng nc ct mi un
si ngui. Dung dch mi pha ng trong bnh polyetylen.
xc nh chnh xc nng dung dch NaOH trc khi dng ta cn chun
bng dung dch chun axit oxalic 0,05M vi cht ch th l phenolphtalein.
Axit oxalic l cht gc c cng thc l H2C2O4.2H2O (M=126,066). Dng cn phn
tch cn 6,3033 (g) tinh th H2C2O4.2H2O (tkpt), chuyn vo bnh nh mc sch 1 lt,
ha tan bng nc ri nh mc ti vch mc. Dung dch ng trong bnh polyetylen
hoc bnh thy tinh nt nhm.
Dng pipet ly 25 ml dung dch H2C2O4 0,05M va pha cho vo bnh nn dung
tch 250 ml ra sch v trng 3 ln bng nc ct. Thm vo 2 git cht ch th
phenol phtalein. T buret dung tch 50ml (hay 25ml) ng dung dch NaOH cn xc
nh nng , nh t t dung dch NaOH vo bnh nn, va nh va lc u cho ti khi
dung dch chuyn sang mu hng nht bn trong vi giy. Tin hnh chun 3 ln ly
kt qu trung bnh. Gi s th tch trung bnh NaOH ca 3 ln th nghim l V NaOH nng
chnh xc ca dung dch NaOH s l:
2-

2-

25.0,05
CNaOH -^V^- x 2(mol/l) NaOH
* pha dung dch HCl c nng khong 0,1M, ta ly khong 8,3 -8,5 ml dung
dch HCl c (c nng khong 35 - 38%, D = 1,174 - 1,185 g/cm 3) cho vo bnh
ra sch, thm nc thnh 1 lt, lc u. ng dung dch trong bnh polyety-len hay
bng bnh thy tinh c nt mi nhm.
xc nh chnh xc nng dung dch va pha, ta cho n vo burt, ly 25 ml
dung dch chun NaOH vo bnh nn ra, trng sch. Thm 1 - 2 git cht ch th
phenolphtalein. Chun dung dch bng dung dch HCl t buret n khi dung dch
chuyn t mu sang khng mu. Lm th nghim ba ln ri ly kt qu trung bnh v
tnh nng dung dch HCl.
CHcl - C .V (mol/l)
V

NaOH

88.

NaOH

Xc nh nng dung dch CH3COOH v dung dch NH3.

* Chun dung dch CH3COOH bng dung dch chun NaOH.
Cch tin hnh: Ly dung dch chun NaOH vo buret sch. Dng pipet ly 25ml
dung dch CH3COOH cho vo bnh nn sch, thm vo 2 git phenolphtal-ein. Tin
hnh chun bng dung dch NaOH n khi dung dch chuyn t khng mu sang mu
hng bn trong vi giy. Lm 3 ln th nghim v ly kt qu trung bnh ri tnh kt qu.
V nng dung dch CH3COOH cha bit nn trc khi chun chnh xc ta
nn lm th nghim thm d, nu nng dung dch CH 3COOH c qu hoc long qu
th phi pha long hoc ly tng th tch ln th tch dung dch chun tiu tn ht t
nht trn 20 ml.
* Chun dung dch NH3 bng dung dch chun HCl. Cch tin hnh th
nghim tng t nh chun CH3COOH bng NaOH. Ch
khc l ly 25 ml dung dch NH 3 cn chun cho vo bnh nn, cht ch th dng l
metyl da cam, cn buret ng dung dch chun HCl. Vic chun kt thc khi dung
dch chuyn t mu vng sang mu . Cng tin hnh chun 3 ln ly kt qu trung
bnh ri tnh kt qu.
89.
Xc nh nng dung dch H3PO4 bng dung dch NaOH.
Gi s ta cn xc nh nng ca H3PO4 c.
Cch tin hnh: Dng cc cn sch kh, cn trc khi lng. Dng pipet ly vo
cc cn 5ml H3PO4 c cn xc nh nng . Cn trn cn phn tch. Gi s khi
lng ca 5 ml axit l 8,3000 (g). Chuyn ton b lng axit va cn vo bnh nh mc
100 ml ra sch, trng ton b lng axit trong cc cn vo bnh nh mc, thm
nc ct ti vch nh mc, y nt lc k. Dng pipet sch v trng nhiu ln bng
dung dch H3PO4 va pha, ly 25 ml dung dch H3PO4 va pha cho vo bnh nn dung
tch 250 ml ra sch. Thm vo 2 git phenol phtalein. Chun bng dung dch
NaOH 1M n khi dung dch chuyn t khng mu sang mu hng bn trong vi giy.
Tin hnh chun 3 ln ly kt qu trung bnh. Gi s VNaOH = 41,0 ml.
Hm lng % theo khi lng ca H3PO4 l:

41 1x100

X X

98

; =
100

1000
25
8,300
chun ti nc th hai, do lgH =
3

96

2 V dng ch th phenol phtalein nn

PO

98/2.
90.

Xc nh Na2CO3 trong xt k thut.

Xt k thut lun lun cha mt lng Na2CO3 do NaOH hp th kh CO2 trong
khng kh.
Cch tin hnh: Cn a (g) xt k thut, ha tan trong nc ct un si ngui cho
vo bnh nh mc 100ml. Dng pipet (th d 25 ml) ly mt th tch chnh xc dung
dch ny cho vo bnh nn sch, dung tch 250 ml. Thm vo 1 - 2 git phenolphtalein, dung dch s c mu . Chun bng dung dch chun HCl bit chnh
xc nng n khi dung dch va mt mu hng. Khi xy ra 2 phn ng.
NaOH + HCl = NaCl + H2O Na2CO3 +
HCl = NaHCO3 + NaCl
(v pH ca dung dch lc l pH ca dung dch NaHCO3, pH =1 (pK1 + pK2) nm
trong khong i mu ca phenolphtalein). c v ghi th tch dung dch HCl tiu
tn, gi s ht V1 ml dung dch HCl. Thm tip vo bnh nn 2 -3 git metyl da cam,
dung dch c mu vng. Tip tc chun n khi dung dch chuyn t mu vng sang
mu da cam. Ngng chun v ghi th tch V 2 trn buret. Lm th nghim 3 ln v
ly kt qu trung bnh (th tch V2 tnh t vch 0 ca buret).
Nh vy, V2 -V1 l th tch dung dch HCl cn dng chun NaHCO 3. V V1 l
th tch dung dch chun HCl dng chun NaOH v nc 1 ca Na2CO3
thnh NaHCO3 nn V1 - (V2 - V1) = 2V1 - V2 l th tch dung dch HCl cn dng
chun NaOH. Hm lng % ca NaOH v Na2CO3 c a (g) xt k thut l:
%NaOH

(2V1

-V )

.C

40

1000
%Na2CO3

HCI
1a

%~V).C

X
1000

HCI X

MNa

CO3

100
2

Xc nh magi (Mg2+) hoc phtpht (PO43-)

Trong mi trng NH3 + NH4Cl, ion Mg2+ kt ta vi ion HPO42\
Mg2+ + NH4+ + HPO4 = MgNH4PO4 + H+ Lc v ra sch kt ta, ha tan kt
ta bng mt lng d chnh xc dung dch chun HCl, sau chun lng HCl d
bng dung dch chun NaOH vi ch th metyl da cam.
MgNH4PO4 + 2H+ = Mg2+ + NH4+ + H2PO4-H+(d)
91.

+ OH- = H2O
Theo cc phn ng trn 2+ = Mv , = ^ 0
2

2
% Mg
1000

(VHCl.

C HCl

2a

Mg

VNaOH .CNaOH

MMg

%PO = V HCl HCl NaOH NaOH 7 X

4X
% 100
4
~
1000 2 a
Cch tin hnh: Dung dch cha Mg2+ cho vo cc 200ml, thm 4 - 6 git
dung dch HCl 1M, 10 ml dung dch Na2HPO4 10% (nu xc nh PO43- th thm
lng d dung dch MgCl2 5%), 2 - 3 git metyl da cam, pha long bng H2O n
khong 80 ml, nu dung dch b c th thm vi git HCl n tan, sau thm tip 5 ml
HCl na. un nng dung dch NH3 5% va thm va khuy, ti khi dung dch chuyn
sang mu vng. Thm tip 3ml NH3 na. yn cc 2 - 3 gi. Lc kt ta bng giy lc
bng xanh. Ra kt ta bng nc ti khi nc ra chy ra khng c ion Cl - (th bng
dung dch AgNO3). Sau ra kt ta 3 ln bng dung dch ru etylic 5 0. Chuyn ton
b kt ta v giy lc vo cc sch. Thm vo mt lng d chnh xc dung dch
chun HCl. Khuy cho kt ta tan ht. Chun lng HCl bng dung dch chun
NaOH dng cht ch th metyl da cam. Ch chung:
92.
Tt c cc trng hp nh phn nghin cu trn u kho st
nhit trong phng th nghim thng khong t (20 -- 25)0C. Nu ta kho st nhit
khc th cc gi tr pH tnh c trong qu trnh nh phn c khc i mt t. Tuy
nhin s sai khc c thc t khng dng k, nu khi tin hnh nh phn nhit
khng khc vi nhit 220C nhiu lm.
93.
Cc trng hp nh phn axit - baz va nghin cu u tin hnh trong
dung mi nc, ngoi ra ngi ta cn thng nh phn axit - baz trong dung mi khc
khng phi l nc.
Trong nhiu trng hp nh phn axit - baz trong dung mi khng nc t ra u
vit hn l nh phn axit - baz trong dung mi nc v rng trong mt s trng hp
axit hay baz trong nc l dung dch axit hay baz qu yu khng th nh phn chnh
xc c, tri li nu chn dung mi khng nc thch hp th axit hay baz tr nn
mnh iu kin nh phn chnh xc c. Bi vy ngy nay phng php nh
phn axit - baz trong dung mi khng phi l nc ngy cng c p dng rng ri.
PO

BI TP
94.
Cc cht v ion sau y, cht no l axt, baz hoc lng tnh: HClO4, NH3,
CO32-, HCO3-, H2CO3, S2-, NNH4+, CH3COO-.
95.
Hi phi thm vo dung dch c pH = 0 thuc th no sau y c mi trng
axt yu: NH3, NaOH, CH3COONa, HCl, CH3COOH, NH4Cl.
96.
Tnh pH ca cc dung dch sau:
a. 0,1M HCl v 0,1M CH3COOH.
b. Dung dch 5% HCl v 5% CH3COOH; ddd = 1,1 g/ml. c.
Dung dch cha 7 g/l HCl v 7g/l CH3COOH.
97.
Tnh pH ca dung dch thu c khi thm 0,102g CH3COONa vo 100ml dung
dch 0,0375M CH3COOH. Bit pKCH COOH = 4,75.
98.
Tnh pH ca dung dch thu c khi trn ln:

a. 50ml 0,1M KH2PO4 v 25ml 0,2M K2HPO4. Bit H3PO4 c pK1 = 2,16; pK2 =
7,13; pK3 = 12,3.
b. 30ml 0,1M Na2CO3 v 15ml 0,1M NaHCO3. Bit H2CO3 c pK1 = 6,32; pK2 =
10,32.
99.
Phi thm vo 100ml 0,2M HCOOH bao nhiu gam natri foocmat rn HCOONa
c dung dch m vi pH = 4,3. Bit pKHCOOH = 3,77.
100. Cn bao nhiu gam CH3COONa ha tan trong 50ml dung dch CH3COOH
0,04M c pH = 5,43.
101. Tnh pH ca dung dch cha NH4Cl 0,01M v NH3 0,1M. Bit KNH = 1,75.10-5.
102. Nng M v N ca dung dch H2SO4 l bao nhiu nu dung dch H2SO4 c
TH2SO4 = 0,005122?
10. Nng N ca dung dch Ba(OH)2 l bao nhiu nu dung dch c
T = 00121?
103. Ba(OH) /CH COOH
?G
a. Hy tnh THCl/NH ca dung dch HCl 0,1125N ?
b. Hy tnh nng M, THCl, THCl/CaO ca dung dch HCl 0,1122N?
104. Cn bao nhiu ml dung dch HCl bc khi (axt c) c t trng 1,19 chun b
1.500ml dung dch HCl 0,2N. Bit rng dung dch HCI c t trng bng 1,19 th tng
ng vi 38,32% (phn trm theo trng lng).
105. Hi phi pha long 1 lt dung dch HCl 0,2N n th tch l bao nhiu thu
c dung dch c chun theo cht xc nh CaO l 0,005?
106. Tnh THCl/CaO ca dung dch HCl nu nh nh phn 0,104g Na2CO3 vi ch th
metyl da cam (pT = 4) th tn mt 25,14ml dung dch HCl .
107. Khi nh phn 20ml dung dch HCl c chun T = 0,003512 th tn mt
21,12ml dung dch NaOH. Hy tnh
TNaOH/HCl, TNaOH, TNaOH/H SO ca dung dch NaOH
trn.
108. trung ha 0,5g hn hp Na2CO3 v K2CO3 ti CO2 cn 39,5ml dung dch HCl
0,2N. Xc nh % Na2CO3 trong hn hp. Bit rng trong hn hp khng cha cc
cht khc na.
109. Trung ha 0,2g axt hu c th rn cn 31,7ml dung dch KOH 0,1N. Tnh
ng lng gam ca axt v xc nh l cht g?
2

TI LIU THAM KHO

110.
Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn
tch, NXB KH & KT, 2002.
111.
Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc,
2000.
112.
Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002.
113.
Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn
tch, NXB H&TH Chuyn nghip, 1984
114.
H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v
Nguyn Huyn dch. NXB KH & KT, 1976.

CHNG 4

CN BNG OXY HA

- KH. CHUN OXY HA - KH

4.1. Cn bng oxy ho - kh.

4.1.1. Phn ng phn ng oxy ho - kh v cch thnh lp cc phng trnh oxy ha kh theo phng php ion - electron.
115.
nh ngha phn ng oxy ha - kh.
Cc phn ng oxy ho - kh l cc phn ng xy ra c km theo s trao i
electron gia cc cht tham gia phn ng. Mt phn ng oxy ha - kh bao gi cng bao
gm 2 qu trnh : cho v nhn electron.
Cht oxy ha l cht c kh nng nhn electron .
Cht kh l cht c kh nng cho electron.
Mi cht oxy ha sau khi nhn electron tr thnh dng kh lin hp vi n v
ngc li, khi cht kh cho electron th n s chuyn thnh dng oxy ha lin hp.
Qu trnh cht kh cho electron l qu trnh oxy ha v qu trnh cht oxy ha
nhn electron l qu trnh kh. Nh vy mt phn ng oxy ha - kh y bao gm
hai na phn ng v ta c th biu din bng s n gin sau:
OX1 + ne ^ Kh1 Kh2 - ne ^ OX2 r OX1 + Kh2 ^ Kh1 + OX2 (4.1) Trong thc t phn tch
chng ta thng s dng cc phn ng oxy ha - kh tch v nhn ra cc ion. V d
v cp oxy ho - kh lin hp: Cht oxy ha Cht kh
T7 3+ ,
T 2+
Fe + e 5=i Fe Zn
2
+ + 2e Zno Cl2 + 2e ^ 2Cl [Fe(CN)6] + e ^ [Fe(CN)6] MnO-4 + 8H+ + 5e Mn2+ +
4H2O. Electron khng tn ti trng thi t do trong dung dch. Mt cht ch th hin
tnh kh khi c cht oxy ha nhn electron ca n.
Vic tnh ton trc cn bng oxy ha - kh s gip la chn d dng cc iu
kin th nghim. Tuy vy cn ch rng khng phi tt c cc qu trnh oxy ha -kh
u l nhng qu trnh thun nghch, trong cc phn ng thun v nghch xy ra v
cng nhanh t ti trng thi cn bng, m trong thc t ta gp nhiu trng hp
phn ng oxy ha - kh theo tnh ton cn bng th c kh nng xy ra, nhng thc t
th khng xy ra, v tc phn ng v cng b. Trong nhng trng hp nh vy cc
yu t lm tng tc phn ng nh tng nhit , dng cht xc tc ... l cn thit.
116.
Cch thnh lp cc phng trnh oxy ha - kh theo phng php ion -electron.
Phng php ion - electron da trn s cn bng khi lng v cn bng in tch
cc cu t tham gia phn ng trng thi tn ti ch yu ca chng trong dung
;

3-

4-

dch. C th cc cht in ly mnh th vit di dng ion, cc cht in ly yu v cc cht

kh th vit di dng phn t, cc cht rn th vit di dng phn t hay nguyn t.
Cc bc tin hnh:
+ Xc nh cc cht oxy ho, kh u v cui.
+ Vit tng na phn ng oxy ha - kh, thot u vit di dng oxy ha v dng
kh lin hp, sau cn bng khi lng, ngha l lm cho s nguyn t ca cc nguyn
t hai v ca phn ng phi bng nhau.
Thng thng y phi thm bt cc cht ph nh H+, OH-, H2O . Khi thm bt
nh vy phi ht sc ch n mi trng thc hin phn ng v khng c thay i
trng thi oxy ho - kh ca cc nguyn t. V d, nu phn ng thc hin trong mi
trng axit v sn phm phn ng li cha O2, m v tri khng c. Tt nhin, cn
bng cn thm O2 vo v tri. y c th ly O2 dng hp cht l H2O. Trong trng
hp phn ng tin hnh trong mi trng kim th phi thm ion OH- thay cho nc.
+ Sau khi cn bng khi lng th chuyn sang cn bng in tch, ngha l lm
cho tng s in tch hai v phi bng nhau. y ta dng cch thm hoc bt electron
thay i in tch. V d khi cn thm in tch m hoc bt in tch dng ta cng
thm mt s electron, cn khi cn thm in tch dng hoc bt in tch m th ta phi
tr mt s electron tng ng.
+ Sau khi vit xong cc na phn ng cn tng hp li thnh phng trnh y
. Trc ht cn lm cho s electron tham gia trong cc na phn ng phi bng nhau,
bng cch nhn na phn ng ny vi s electron tham gia trong na kia, sau cng
chng li theo tng v.
kim tra phng trnh phn ng vit ng cha, trc ht cn kim tra cn
bng khi lng, bng cch cng cc nguyn t ca mi loi trong tng v xem
bng nhau hay cha. Sau kim tra tng in tch mi v .
V d 1: Cn bng phng trnh: CrO2- + H2O2 CrO4 + H2O CrO2- +
2-

20H- - 3e CrO42- + 2H+

H2O2 + 2e - 2OHTrong phn ng th 2 cn bng khi lng ta phi thm vo v tri 2 oxy
ly ion OH(v phn ng tin hnh trong mi trng kim). Kt qu t hp cho ta: 2CrO 2- + 4OH- +
3H2O2 =F 2CrO42- + 4H+ + 6OHv 4H+

+ 4OH- = 4H2-O

- 2-

nn cui cng ta c: 2CrO2- + 2OH- + 3H2O2 = 2CrO42- + 4H2O

Trong trng hp phi thit lp phng trnh di dng phn t th vn ly c
s l phng trnh ion - electron v thm bt cc cht ph mt cch hp l. V d 2: Vit
phng trnh ha tan Ag2S trong axit nitric.

Ag2S + HNO3 - AgNO3 + S + NO + H2O Ag2S 2e 2Ag+ + S

NO3- + 4H+ + 3e
NO + 2H2O
3Ag2S + 8NO3- + 8H+ = 6AgNO3 + 3S + 2NO + 4H2O 4.1.2.

Cng cht oxy ho - kh. Th oxy ho - kh.

Mt cht nhn electron cng d, c tnh oxy ha cng mnh, v nhng electron

cng d, th c tnh kh cng mnh.

Trong mt cp oxy ho - kh lin hp, nu cht oxy ha mnh th cht kh yu v
ngc li. Kh nng oxy ho - kh ca cc cht c nh gi bng i lng th oxy
ho - kh, l i lng o cng ca cht oxy ha v cht kh ca cc cp oxy ho kh. Th ca cp cng cao cht oxy ha ca cp cng mnh v cht kh ca cc cp oxy
ho - kh lin hp cng yu. tin so snh th ca cc cp oxy ho - kh lin hp th
phi o th ca chng trong iu kin ging nhau.
Th ca mt cp oxy ho - kh lin hp: OX + ne Kh (thng gi l
th oxy ho - kh) c xc nh bng cng thc Nec:
E

- E

RT

ln-aX

(4 2)

Mt cch tng qut hn, nu cht oxy ha v cht kh tham gia vo cc phn
ng khc nh phn ng kt ta, to phc ... th cng thc Nec c dng sau:
V d vi trng hp : aA + bB + cC + ne ^ mM + nN ...
_ _ RT, a A a C _ x E = E
ln^--^ (4.3)
nF

MAN

+3-

Hot ca cht rn B c xem bng 1, nn khng c trong cng thc. Trong E: l

th oxy ho - kh R: l hng s kh R = 8,314J/mol.K T: l nhit tuyt i F: l s
Faraday F = 96.500c n: l s electron trao i. aA, aC, aM, aN l hot ca cc cht
tham gia v sn phm ca phn ng Nu thay R, F bng cc tr s ca chng v i
logarit t nhin sang logarit thp phn, th phng trnh Nec nhit 250C c dng:
E = E0 + ^lg^Xm (4.4)
n

M NE
A

...

: l mt hng s v c gi l th tiu chun. E0 ch ph thuc vo bn cht ca cp

oxy ho - kh lin hp.
Biu din hot qua nng ta c:
E = E0 + ^lg^!" + ^lg (4.5) n 5[M]m[N]n...
n X^N...
Phng trnh (3.5) cho thy th in cc khng nhng ph thuc nng cc
dng oxy ha v kh trong dung dch, m cn ph thuc vo lc ion ca dung dch.
Trong phn tch thng dng dung dch long nn c th chp nhn fox/fkh = 1 th ta
c phng trnh n gin, trong th ch ph thuc nng :
E = E0 + M^lg'*^ (4.6)
n [M]m[N]n...
E0 l th thc ch dng c trong tng mi trng c th. V d, th tiu chun
thc ca cp Fe3+/Fe2+ trong dung dch HCl 0,1M l 0,73V, ' trong dung dch HCl 0,5M
l 0,72V, trong dung dch HCl 1M l 0,7V v trong dung dch H2SO4 0,1M l
0,68V,.

Trong thc t, khng th xc nh c gi tr tuyt i th ca mt cp oxy ha kh lin hp, m ch xc nh c gi tr tng i ca n so vi cc cp khc. c

th so snh th ca cc cp oxy ho - kh lin hp vi nhau th cn phi xc nh gi tr
tng i th ca cc cp y so vi th ca 1 cp oxy ha - kh lin hp quy c bng 0
khi aox = akh. Trong thc t thng so snh vi th tiu chun ca cp 2H+/H 2 quy c
bng 0.
Sau y cho n gin hot c thay bng nng . V d, mun xc nh
th tiu chun E0 ca cp Fe3+/Fe2+ th o th hiu gia cc platin nhng vo dung dch
hn hp FeCl3, FeCl2 c nng bng nhau, bng 1 v cc hydrro tiu chun.
Hiu th tiu chun gia cp Fe3+/ Fe2+ v cp 2H+/H2 bng
EFe 3+ '/Fe
, 2 + - E +
= +0,77V
+
2H+ /H '
3

V E + quy c bng 0 nn th tiu chun ca cp Fe3+/Fe2+ bng +0,77V,

du "+" ch ra rng th cp Fe3+/Fe2+ ln hn th cp 2H+/H2 v trong qu trnh Fe3+
oxy ha H2 theo phn ng: 2Fe3+ + H2 ^ 2Fe+ + 2H+
Dng electron di chuyn t cc bn cp 2H+/H2 sang cc bn cp Fe3+/Fe2+ Th
tiu chun ca cp: Zn2+/Zn = - 0,76V, du " - " ch rng th ca cp ny
b hn th ca cp 2H+/H2, hay ni mt cch khc cc nhng trong cp Zn2+/Zn l
cc m, v trong phn ng Zn kh H+ theo phn ng: 2H+ + Zn 5=^ H 2 + Zn2+ Dng
electron di chuyn t cc bn cp Zn2+/Zn sang cc bn cp 2H+/H2 Trong cc
sch ch ghi th tiu chun ca cc cp oxy ha - kh lin hp khi
cht oxy ha v cht kh ca cp khng tham gia vo cc phn ng khc ngoi
phn ng trao i electron (bng 1 - Phn ph lc).
Khi biu din th in cc theo hot trong cc phn ng th phc tp hn
cn ch y tt c cc cu t tham gia vo na phn ng oxy ha - kh, v
y cng p dng cch ghi tng t nh khi vit theo nh lut khi lng. i vi
trng hp tng qut:
aOX + mH+ + ne ^ bKh + pH2O
0
25 C ta c: Eox/kh = Ex.h + ^lg^
/

kh

V d: Vi na phn ng : PbO2(r) + 4H+ + 2e ^ Pb2+ + 2H2O.

E
= 0 0,059, [H + ]
T
Ta c : E
2+ = E
2+ +---------lg-
PbO /Pb +
PbO /Pb +
2
[Pb2+ ]
Trong thc t cht oxy ha v cht kh ca mt cp lin hp thng tham gia vo
nhng phn ng khc, nh phn ng axt - baz, phn ng to phc, phn ng kt ta...
Di y ta s ln lt kho st nh hng ca cc yu t khc nhau ti in th
oxy ha - kh ca mt bn phn ng.
4.1.3. Nhng yu t nh hng n th oxy ha - kh. Th oxy ha - kh iu kin.
4.1.3.1. Anh hng ca pH
Th tiu chun E0 ghi trong cc ti liu chuyn kho thng l th c xc
4

nh khi nng H+ bng IM tc l khi pH = 0. T gi tr E 0 c th suy ra th tiu

chun cc pH khc, gi l th tiu chun iu kin E0'.
Chng ta phn chia nh hng ca pH ti in th oxy ha - kh lm hai trng
hp:
Trng hp 1: ion H+ (hoc OH-) trc tip tham gia vo cc bn phn ng oxy
ha - kh, v d i vi bn phn ng: MnO4- + 8H+ + 5e 5=* Mn2+ + 4H2O
0
, 0,059 [MnO-][H + ]Ta c: E = E
0
+11 l i
~ 4 JL^
8

aw.

MnO-/Mn2+

MnO-/Mn2+

[M 2+ ]
n

R rng l khi [H+] thay i E ca h s thay i theo

V d:
Tnh th oxy ha - kh tiu chun iu kin ca cp MnO -4/Mn2+ trong dung dch
c pH = 5, bit EMM
trong dung dch c pH = 0 l 1,51V.
nO-/Mn2+

Ta c:

lg

, 0,059, JMnO-][H + ]
[M 2+ ]

MnO /Mn +
MnO /Mn ++
5
10Th tiu chun iu kin E-5
0'
khi pH = 5 l th khi [MnO-4] = [Mn2+] v [H+] =
E

E' = E + ^^Igao-5 )8 = 1,04 V Vy khi

pH tng th th tiu chun cng gim.
Cn ch l c i khi in th oxy ho - kh ca mt cp no gn gi tr pH
ny th E khng ph thuc vo pH, cn khong gi tr pH khc th E li ph thuc. V
d, trong mi trng axit: Zn2+ + 2e *=* Zn.
E ca h khng ph thuc pH, tri li trong mi trng kim:
ZnO22- + 4H+ + 2e **=* Zn + 2H2O. th E ca n li ph thuc pH.
Trng hp 2: i vi loi ny th khi pH thay i th s lm thay i dng tn ti
ca dng oxy ha hoc kh, lm nh hng n nng ca cc dng v do th
ca h cng b bin i theo. lm v d, chng ta kho st nh hng ca pH n
tnh cht kh ca ion S2-.
Ta bit : S2- - 2e ^ S
^ 0,059, 1
n r 0,059, rri n
0

y ta ly nhit l 250C. Trong dung dch : S2- + H+ 5=* HS- ng vi K2 phn ly

HS- + H+ **** H2S ng vi K1 phn ly. Nh ta bit (xem chng 3, phn tnh nng
cc thnh phn dung dch khi
-1
[H + ] , [H + ]1 + +
2
K

K K

1 2

bit pH): [S2- ] = CH

y

Trong C

H2S

H2S

= [S2-] + [HS] + [H2S]

1

rrM

2^^

R(1

1^0

,59 ,

+ [H+] + [H+r
K, K,K 2

Thay gi tr [S ] vo biu thc trn ta c: E = E +

lg---------------- ------- 1

H2S

2 C

126

0,059,
2 ~\
0,059
+H+1+H+i!.'
V

H2S

K K

1 2

[H + ] [H + ]2 ^
K

E=E +
E = EX

K K

1 2

lgl 1 +
+
lgCH s ; EX = E0 +

I----lgC

2
0,059lgC

0 = E0

-W7~

, 0,059 2

""N*

127

Trong : EX gi l in th tiu chun iu kin, n l mt hng s mt gi

tr pH khng i (v nu ti hot th phi c iu kin lc ion khng i).
Tng qut ha, i vi trng hp c ion H+ (hoc OH -) ca mi trng tham gia
phn ng v cc cht kh hoc oxy ha c th tn ti di dng khc nhau, in th oxy
ho - kh c tnh theo cng thc sau:
E = E + ,059! [tt c cc dng OX]
(4 7)
n
[tt c cc dng Kh]
117.
Anh hng ca s to phc
in th oxy ho - kh b thay i khi t s nng ca dng oxy ha v dng
kh thay i. Nu trong dung dch c cht to phc vi dng kh hoc dng oxy ha
hoc c hai dng nhng vi mt mc khng ng nht th t l nng gia dng
oxy ha v dng kh b thay i, kt qu l in th oxy ha ca cp oxy ho - kh b
thay i. Nu nng ca dng oxy ha b gim (nng ion t do) th in th oxy
ha ca h b gim, ngc li nu nng ca dng kh b gim th in th ca h
tng.
V d in th oxy ha - kh tiu chun ca h Fe 3+/Fe2+ bng 0,77V, nu thm
H3PO4 vo dung dch th H3PO4 to vi Fe3+ phc [FeHPO4 ] lm cho [Fe3+] b gim
xung. Cn khi ta thm KCN vo dung dch th in th ca h Fe 3+/Fe2+ cng b gim
xung v phc [Fe(CN)6]3- bn vng hn phc [Fe(CN)6]4-. Tri li nu thm H2P2O7 vo
h V5+/V4+ th in th oxy ha - kh ca h tng v phc ion H 2P2O7 vi V4+ bn vng
hn so vi V5+.
118.
Anh hng ca s to thnh kt ta.
Khi mt trong hai dng oxy ha hoc kh l pha rn, lc in th oxy ha-kh
ch ph thuc vo nng dng nm trong dung dch, v hot (nng ) ca cht rn
trong dung dch l mt i lng khng i v c a vo in th tiu chun.
V d 1: i vi h Ag+ + e ^ Ag
E = E0 + 0,059lg[Ag+] V d 2: i vi h MnO4- + 4H+ +
3e ^ MnO2 + 2H2O E = 0 + 0,059lg[MnO-][H + ] 3 [MnO2]
Trong E0 l th tiu chun ca h. Trong dung dch lun lun bo ha MnO 2,
ngha l nng ca n l i lng khng i, do ta c:
E = E0 ' + 0,359lg[MnO-][H + ]Trong E
0
l in th tiu chun vi gi thit trong dung dch bo ha MnO2.
119.
Anh hng ca s to kh.
Nu trong bn phn ng oxy ha - kh c s tham gia ca kh t tan.
+

2-

2-

128

V d:
O2 + 4H+ + 4e 5=* 2H2O th in th oxy ha ca h bng:
E = Eo + M^lg^HH + ]Trong E
0
l th tiu chun ca h. Nu trong dung dch bo ha oxy p sut 1 atm, nhit
2980K ngha l [O2] l mt i lng khng i, lc :
E = E0 + 0,059lg[H + ] trong E0 gi l th tiu chun
iu kin ca h trong dung dch bo ha oxy mt p sut nht nh. 4.1.3.5. Anh
hng ca lc ion.
Nh trn ni, v n gin cho vic lp lun, nn chng ta dng nng thay
cho hot . S tht in th oxy ha - kh phi tnh theo hot . Nhng chng ta bit,
khi lc ion ca dung dch thay i, hot ca cc ion cng thay i theo. S thay i
hot ca dng kh v dng oxy ha lc khng ng nht, do t s hot ca
chng thay i v kt qu in th ca h thay i.
V d: E0 ca cp [e(CN)6]3-/[e(CN)6]4- = 0 0,4V; khi c mt dung dch KCl 2M
th in th ca h tng ln ti 0,55V. S d th v s c mt ca KCl lm tng lc ion
ca dung dch v lm gim hot ca hai ion [Fe(CN)6]3+ v [Fe(CN)6]4+, trong ion
c in tch cao hn, hot b gim mnh hn. Qua y ta thy r nh hng ca lc
ion, tuy nhin n gin cho tnh ton, ta vn dng nng thay cho hot .
4.1.4. Chiu ca phn ng oxy ha - kh v cc yu t nh hng. 4.1.4.1.
Chiu ca phn ng oxy ha - kh
Gi tr th tiu chun E0 ca cc cp oxy ho - kh cng ln th kh nng oxy ha
ca cht oxy ha cng mnh, v ngc li gi tr E 0 cng nh th kh nng kh ca dng
kh cng ln. Trong bng 4.1 th cc cht oxy ha mnh nht nm pha trn, cn cc
cht kh mnh nht nm pha di.
V d: Cht oxy ha mnh nht F2 c E0 ln nht (+2,87V), sau n zn
O3(+2,07V), pesulphat amni (+2,0V)....Cc cht kh mnh nht l kim loi kim sau
n kim loi kim th Mg, Al, Zn ...
Nu bit c gi tr E0 ca cp oxy ha - kh ta c th on bit c chiu ca
phn ng oxy ho - kh.
V d: Xt phn ng sau: 2Fe3+ + Sn2+ ^ Sn4+ + 2Fe2+
4

l+ /Fe
; n /Sn R rng E + + > E
+ s + do Fe + s l cht oxy ha v Sn2+ l cht kh.
Vy phn ng s xy ra theo chiu thun
2e3+ + Sn2+ - Sn4+ + 2e2+
Sn phm ca bt k phn ng oxy ha - kh no cng l nhng cht kh v oxy
ha mi, tuy nhin chng s yu hn nhng cht oxy ha v cht kh ban u. V d i
vi phn ng trn th cht oxy ha Sn4+ v cht kh e2+ yu hn nhng cht ban u l
e3+ v Sn2+.
Cn ch rng mi cht oxy ha c th oxy ha c nhng cht c gi tr E 0 nh
hn v ngc li mi cht kh ch c th kh c nhng cht c gi tr E0 ln
0

2+=+

0 , 7 7 V

4+

2+=+

0 , 1 5 V

129

hn n.
Mt s v d minh ha cho quy tc trn:
V d 1:
T bng 5 ta thy
- 0,76V,
Zn2+ /Zn =
Pb2+ /
= - 0,126V Cu2+,Cu = Nh vy nu cho km kim
loi vo dung dch mui ca ch v ng, th s c phn ng sau:
Pb0,337V
2
+ + Zn Pbi + Zn2+
Cu2+ + Zn Cui + Zn2+ Sn phm ca hai phn ng trn l Pb
v Cu, l nhng cht kh yu hn Zn v khng th kh c ion Zn2+ n km kim
loi. V d 2:
E ' = + 1,359V; E0
= +1,087.
E

Cl2/2Cl-

'

'

pb

Br2/2Br '

Vy phn ng s l: Cl2 + 2Br- 2Cl- + Br2

E - > E , nn s c phn ng: 2e2+ + Br2 2e3+ + 2BrBr /2Br
e
2
+ /e +
r
B Vy Cl2 c th oxy ha c ion Br
nhng e3+ khng oxy ha c Br-V d 3:
Trong phn tch nh tnh thng gp hn hp cht kh m cc cht ny u phn
ng vi cng mt cht oxy ha khc, v d hn hp Br - v I- u tc dng vi Cl2. Xut
hin cu hi y l cht no s b oxy ha trc. Nhn vo bng 5 ta thy I - s b oxy
ha trc, sau mi n Br -. Tht vy gi s Br- b oxy ha bi Cl2 trc th khi xut
hin phn t Br2 lp tc n oxy ha ion I- n I2 v tr li Br-. Qu trnh ny tip tc cho
n lc tt c ion I- b oxy ha ht.
T cc v d trn ta rt ra kt lun:
Trong iu kin cho ca cc qu trnh oxy ha - kh, qu trnh no c hiu s
cc th in cc tiu chun ln nht th s xy ra trc tin.
V d 4: Cho st kim loi tc dng vi axit nitric long. y c hai cht oxy ha
l H+ v NO3-, nhng v E -, > E2 +, do theo quy tc trn th NO3- s
/2

3+ 2+

NO3 / NO

2H / H2

tham gia vo phn ng ch khng phi H . Vn y t ra l st b oxy ha n e 2+

hay e3+. Gi s e2+ c to thnh th theo bng 4.1 lp tc n li b oxy ha n e 3+
di tc dng ca axit nitric tha. Do phn ng s l:
ei + 4H+ + NO3- e3+ + Nt + 2H20 4.1.4.2. Cc yu t nh hng n
chiu ca phn ng oxy ho - kh. * Anh hng ca nng .
Theo phng trnh Nernst gi tr in th oxy ho - kh ca mi cp ph thuc
vo t s nng ca cc dng oxy ha v dng kh, ng thi ph thuc vo mi
trng. Do khi thay i t s nng v gi tr pH ca mi trng th in th s
thay i v dn n thay i chiu ca phn ng oxy ho - kh.
V d: Theo gi tr E ca cp Sn2+/Sn (-0,14V) v cp Pb2+/Pb (-0,13V) trong iu
kin tiu chun, nng ca cc dng bng nhau v bng 1M, th s c phn ng: Pb i +
Sn2+ Sn + Pb2+
Hiu s cc in th tiu chun ca hai cp trn (E0 = 0,01V, do vy ch cn thay
i rt t nng ca mt trong cc ion th chiu ca phn ng s thay i.

130

Nhng i vi phn ng:

2Ag+ + H2 2H+ + 2Ag th E = 0,8V nn mun thay
i chiu ca phn ng th phi gim nng Ag+ xung mt lng ln. C th thc
hin iu ny bng cch to mui kh tan ca Ag+ hoc a v phc bn. V d cho bc
kim loi tc dng vi dung dch HI 1M. V tch s tan ca AgI bng 10 -16 m nng
ca ion I- l 1M, do nng ca ion Ag+ khng vt qu 10 -16M. Trong trng hp
ny in th ca cp bc l:
EA ~A = 0,8 + 0,05lg10-16 = -0,13V.
+

Do vy phn ng trn xy ra theo chiu ngc li, tc l phi sang tri. Tm li

bc kim loi tc dng c vi HI (cng nh vi H 2S) gii phng H2 mc du n ng
sau hyr trong dy hot ng ha hc ca Bktp.
* nh hng ca mi trng.
Nu trong phn ng c s tham gia ca ion H + th nng ca n cng nh hng
nhiu n i lng in th oxy ha - kh, thay i nng ca n th chiu phn ng
s thay i.
V d: E ca cp H3AsO4/HAsO2 l +0,56V, cn ca cp I2/2I- l +0,536V, phn
ng s l: H3AsO4 + 2I- + 2H+ HAsO2 + I2 + 2H2O
Trong iu kin [H3AsO4] = [HAsO2] v [H+] = 1. Nhng nu cho vo phn ng 1
lng tha NaHCO3, dung dch ca n c pH 8 th lc ny [H+] = 10-8 M:

0,56 + ^lg^A^P +] 2
'
2 * [HAsO2]
-8
Khi [H3AsO4] = [HAsO2] v [H+] = 10 ta c :
EH AsO /HAsO = 0,56 + ^lgK8 ) = 0,068V
Nh vy 0,068V < 0,54V v phn ng trn s xy ra theo chiu ngc li.
T v d trn y ta thy, nu trong phn ng c ion H+ tham gia th cn phi thc
hin trong mi trng axit, cn nu ion H+ c to ra trong phn ng th cn phi
trung ha n bng cch cho thm NaHCO3 chng hn.
Khi xc nh chiu ca cc phn ng oxy ho - kh c s tham gia ca ion H+ th
ngi ta thng da vo cc gi tr E 0 ca cc cp oxy ho - kh tng ng trong iu
kin [H+] = 1M. Nu nng ca cc ion H+ thay i th dn n cc gi tr E 0 v chiu
ca phn ng cng thay i theo.
E

H ASO /HASO
3

V d 1: Cho hai dung dch KI v KNO2 tc dng vi nhau, mc du EHNO /NO =

0,99V v E0 / = 0,54V nhng phn ng vn khng xy ra. Nhng nu cho mt t
axit H2SO4 hay HCl thm ch c CH 3COOH th lp tc phn ng xy ra mnh lit gii
phng kh NO v kt ta mu nu en I2.
2I- + 2NO2- + 4H+ 2NOT + 2H2O + I2
Tng t nh vy, trong mi trng trung tnh hay baz th cc ion H+ khng tc
dng vi phn ln cc ion oxy ha nh: CrO 42-, IO3-, BrO3-, ClO3-, AsO43- ... nhng trong
mi trng axit th li xy ra phn ng.
V d 2: Nu trn hai dung dch K2CrO4 v Na2S th s khng c phn ng g,
nhng nu axit ha mi trng th phn ng xy ra ngay:
_

131

3S2" + 2CrO42" + 16H+ -> 3S + 2Cr3+ + 8H2O Cng ging nh trn ion
CrO42- ch tc dng vi ion c tnh kh nh Cl-, Br-, I-, SO32-, S2O32-, SCN-, C2O42- ...
trong mi trng axit.
Khc vi cc ion c tnh oxy ha nh NO 3-, CrO42- ... ion MnO4- c kh nng oxy
ha khng ch trong mi trng axit, m cn c trong mi trng baz. Trong mi
trng axit, ion MnO4- nhn 5 electron v b kh n ion Mn2+. Trong mi trng baz
th ion MnO4- ch nhn 3e v b kh n MnO 2 hay chnh xc hn n MnO(OH)2 di
dng kt ta mu nu. V gi tr E
= 1,51V v E MnO /MnO
MnO4 /Mn
-

0,6V nn tnh oxy ha ca MnO4 trong mi trng axit v baz khc bit nhau, c th l
trong mi trng axit mnh hn.
4.1.5. Hng s cn bng v vn tc ca phn ng oxy ho - kh.
4.1.5.1. Hng s cn bng ca phn ng oxy ha kh.
Nh ni trn, mt phn ng oxy ho - kh bao gm hai bn phn ng: OX1 + n1e ^
Kh1 (4.8) Kh2 + ne ^ OX2 (4.9) trong OX1 v Kh2 l nhng cht u, cn Kh1 v
OX2 l cc sn phm to thnh, n1 v n2 l s electron nhn v cho ca mt phn t cht
oxy ha 1 v cht kh 2. Ta s c c phng trnh phn ng oxy ho - kh y
bng cch gp hai bn phn ng (4.8) v (4.9), v i vi mt bn phn ng phi nhn
vi mt h s tng ng cho s electron cho, nhn phi bng nhau. V d i vi
phng trnh (4.8) ta nhn vi p v (3.9) vi q, lc p.n1 = q.n2.
p.OX1 + q.Kh2 u p.Kh1 + q.OX2 r (4.10) ( y cn ni thm
rng c mt s trng hp h s ca OX1 v Kh2 khng bng nhau).
Nh chng ta bit, da vo hng s cn bng ta c th bit c phn ng din
ra chiu ny hay chiu khc. y cng vy, hng s cn bng ca phn ng oxy ho kh cho ta kh nng on c phn ng (4.10) xy ra theo chiu no. Ni cch khc,
khi ta trn hai cht OX1 v Kh2 vi nhau, phn ng c din ra hay khng.
Hng s cn bng ca phn ng (4.10):
[Kh1 NOX2 ] _ f [Kh!
q

[OX2 p

K
(4.11)
[OX1 ]p.[Kh2] UOX1 ]J \[Kh2]. Hng s ny c th tnh theo in
th oxy ho - kh ca hai cp oxy ho - kh lin hp trong phn ng :
q

/[OX p
0,059
[Kh1

] p.n1

E _ E +

(4.12)
(4.13)

0,059lglOXil
2
^ 2
Gi s cc cht u ta ly OX
1 v Kh2 nh vy trong qu trnh phn ng [OX 1]
gim v [Kh2] tng dn, do E1 gim dn, tri li v [Kh1] gim v [OX2] tng dn nn
E2 tng dn, cui cng khi E1 = E2 h thng t ti cn bng :
q.n

0q2

Kh

132

E0 + M59,

QX

[Kh1 ]J

]
2

E2 +

0,059 r[OX2]
lg

\[Kh2

(4.14)

133

t n = p.n1 = q.n2 l s electron tham gia cho nhn, th n vo phng trnh

(4.14) v sau mt vi php bin i n gin ta c:
q

_ n.(E - 2 ) (415)
[Kh2 ] .[OX1 ] 0,059
v (4.15) ta c: lgK _ J
(4.16)
[OX

2 ]q.[Kh1

n(E -E2)

T (4.11)

0,059
0

Hoc:

lgK _ 16,9.n(E - E2 )

(4.17)

T :

K _ 1016,9n(E0-e2)

(4.18)

Ch :
Trong trng hp chung n l bi s chung nh nht ca ni v n2. Cho nn, xc
nh K cn phi xc nh nj v n2, phi vit phng trnh cn bng ca phn ng xy ra
v phi tm bi s chung nh nht ca ni v n2 trc khi p dng biu thc (4.18).
By gi ta ly vi v d lm sng t nhng iu trn V
d i: Tnh hng s cn bng ca phn ng:
Fe2+ + Ce4+ u Fe3+ + Ce3+
0,77V ;
Fe /Fe =
Ce /Ce = Ta c n = 1; lgK = 16,9.1.(1,45 - 0,77) = 11,5 T : K =
10 bit c th hn mc hon ton ca cc phn ng trn, ta tnh t s Fe1,45V
E

3+

2+

4+

3+

11,5
3

+/Fe2+ trong dung dch hn hp Fe2+ v Ce4+ pH = 0 ([H+] = 1) khi nng ng

lng ban u ca cht oxy ha v cht kh bng nhau. trng thi cn bng:
[Ce3+] = [Fe3+] v [Fe2+] = [Ce4+].
Vy K _ !F ^ _ 10[Fe ]
11,5
Do : [Fe
3
+]/[Fe2+] = V"7 = 10Nh vy sau khi phn ng hon ton lng Fe5,75
2+
cn li rt t, coi nh khng ng k v phn ng xy ra n cng t tri qua phi.
V d 2: Tnh hng s cn bng ca phn ng: Ag+ + Fe2+ Ag + Fe3+
Bit EA + = 0,80V v EF
= 0,77V
e3

3+ / , 2 +

/ A

Ag+ /Ag

Fe3+ /Fe '

'

Ta c: lgK = 16,9.1.(0,80 - 0,77) = 0,507 v K = 3,21

V hng s cn bng ca phn ng khng ln nn phn ng c th din ra theo
chiu ny hay chiu khc, ty theo nng ca cc dng ion trong dung dch, ngha l
nu [Fe2+] ln th Fe2+ c th kh Ag+, ngc li nu d [Fe3+] th Fe c th oxy ha Ag.
V d 3: Tnh hng s cn bng ca phn ng:
2
3
3
Cr2Oy + 6Fe + + 14H+ ^= 2Cr + + 6Fe + + 7H2O
Bit EF = 0,77V v EC
= 1,33V
3+ /Fe2+

r O

2-

/Cr

3+

134

Trong trng hp ny n = 6 v lgK = 56,8 K = 1056'8

(K rt ln, phn ng din ra hon ton ) V d 4: Tnh
tch s ha tan ca AgCl, cho bit h:
0
AgCl + e ^ Ag + Cl c E = 0,222V
Ag0 - e Ag+ c EAg+ /Ag = 0,8V
S dng phng trnh (4.17) ta c :
LgT = 16,9 1.(0,222 =- 0,8) = -9,75 v T =1,7.10-10 = [Ag+][Cl-] = T cng thc
(4.16) ta thy hiu cc th tiu chun cng ln th hng s cn bng ca phn ng oxy ho
- kh cng ln, phn ng cng xy ra hon ton theo chiu thun. Nu E0 nh th phi
chn iu kin thch hp phn ng xy ra hon ton.
V d i vi phn ng: HAsO42- + 2I- + 3H+ ^ As02- + 2H2O + I2 c K 10 tng
i b nn phn ng xy ra theo chiu thun th phi thc hin trong mi trng axit
mnh v tha nng I-. Ni chung vi n = 1, khi AE0 = 0,25V ta c K = 1,5.104 v K >
104: phn ng xy ra theo chiu thun.
*1 < K < 103 phn ng xy ra theo chiu thun nghch.
*K < 1 phn ng khng xy ra hoc xy ra theo chiu ngc li.
Cui cng cn ni thm rng, da vo in th tiu chun v hng s cn bng
trong mt s trng hp cha c th kt lun c phn ng c th xy ra hay khng, m
ch cho bit kh nng xy ra phn ng, cn phn ng xy ra nhanh n mc no l ty
thuc vo tc ca n. 4.1.5.2. Vn tc ca phn ng oxy ha - kh.
Cc phn ng oxy ha kh c mt s c im gy kh khn cho vic ng dng
chng trong phn tch th tch. V d nh tnh thun nghch nh trnh by trn, trong
mt s trng hp c bit khi phn tch phi khc phc tnh thun nghch .
Mt c im na l vn tc ca nhiu qu trnh phn ng oxy ho - kh khng
ln.
Nh ta bit, nhng phn ng tin trin chm khng c li cho vic chun , v
trong trng hp vic chun khng nhng phi ko di m cn khng th hon
ton chnh xc. Bi th nn mun dng nhng phn ng nh th trong phn tch th tch
th cn tng vn tc phn ng. Vic lm tng vn tc phn ng nhng phn ng tin trin
chm c th t c bng nhiu cch, ln lt ta s nghin cu nhng cch .
* Tng nhit
nh hng ca nhit i vi vn tc phn ng rt ln, c tng nhit ln 100C
th vn tc phn ng tng 2 - 3 ln, iu thnh nh qui lut. Do khi tng nhit
theo cp s cng, vn tc phn ng tng theo cp s nhn.
V vy ngi ta gp nhiu trng hp m phn ng thc t khng xy ra nhit
ca phng, nhng khi un nng li xy ra vi vn tc kh ln.Ta c th ly v d nh
phn ng:
5H2C2O4 + 2KMnO4 + 3H2SO4 = 2MnSO4 + K2SO4 + 8H2O + 10CO2 xy ra khi
nh phn axit oxalic bng permanganat, vic nh phn phi tin hnh
nhit 700C - 800C.
Tuy nhin khng phi lc no cng c th lm phn ng tin trin nhanh bng

135

cch un nng dung dch, v nu lm phn ng tin trin nhanh bng cch un nng
dung dch th c th hoc lm bay hi mt trong cc cht tc dng (V d I2 khi xc nh
theo phng php it) hoc cc cht b oxy ha bi oxygen khng kh (s oxy ha
Fe2+ khi nh phn dung dch FeSO4 bng permanganat).
* Tng nng ca cc cht tc dng v thay oi [H+]
V d phn ng tin trin chm:
6KI + KC^O? + 7H2SO4 = 3I2 + 4K2SO4 + Cr2(SO4)3 + 7H2O c th lm
tng vn tc bng cch tng nng ion H+ hoc I- trong dung dch.
Nh ta bit, theo nh lut tc dng khi lng, vn tc ca nhng phn ng
trong mi trng ng th t l thun vi tch s nng ca cc cht tc dng, nng
ca cc cht ny c ly tha bng cc h s tng ng. V d nh vn tc
ca phn ng: 2I- + H2O2 + 2H+ = I2 + H2O
Theo nh lut tc dng khi lng phi bng:
v = K.[I-]2'[H2O2].[H+]2 Nu nng ca c ba cht bng
nhau v bng C th ta c: v = K.C5 Tuy nhin, th nghim chng t rng trong thc t
vn tc ca phn ng ny khng t l vi ly tha 5 ca nng , m t l vi bnh
phng ca nng , ngha
l: v = K.CNhng s sai lch vi nh lut khi lng tng t nh th cn thy
trong nhiu phn ng oxy ho - kh khc. Nguyn nhn ca s sai lch l do nhng tnh
cht phc tp trong tin trnh ca cc phn ng oxy ho - kh y. S trao i cc in
tch thng xy ra thnh mt vi giai on k tc nhau, i hi c mt thi gian lu
hn.Cht oxy ha khng th nhn mt lc tt c s electron c th nhn m ch mt
phn thi, chuyn v gi tr trng thi thp hn v sau li nhn tip electron tr v
trng thi ha tr thp hn na ...
V d: Ion MnO42
khng nhn mt lc 5 electron b kh v Mn2+, m nhn qua cc giai on sau:
Mn7+ - +-Mn +-i^vin3 +e >Mn2+
Cht kh cng c th khng cho cc electron tt c m cho tng phn. Trong mt
vi trng hp cht kh lc u cho qu s electron bnh thng cn cho, v sau ly
phn electron cho tha tr li.
V d: S oxy ha Fe2+ bng MnO4- c th din ra nh sau: Fe2+
- 3e Fe5+ Fe5+ + 2e Fe3+
Vn tc ca ton b qu trnh ph thuc cht ch vo vn tc ca cc giai on
trung gian ca n, v v th d on vn tc y da vo phng trnh tng cng ca
phn ng.
Thng ta khng bit c mt cch chnh xc cc giai on trung gian. Tuy nhin
trong mt s trng hp c bit ngi ta cng kho st c s tin trin thc t ca
qu trnh.
V d: Cho phn ng: 2I- + H2O2 + 2H+ = I2 + 2H2O
Theo phng trnh tng cng trn l phn ng "Ng phn t". Thc nghim
chng minh rng mt trong nhng giai on trung gian ca n l to thnh cc anion ca
axit hypoiodit theo phng trnh:
I- + H2O2 = IO- + H2O (*)
4

136

Sau cc ion IO- va to thnh kt hp vi cc ion H+:

IO- + H+ ^ HIO
V sau ht HIO l cht oxy ha mnh oxy ha I- theo phng trnh: HIO + I- + H+ ^ I2 +
H2O ^ Cng cc phng trnh trn theo tng v ta c phng trnh tng cng.
Tt nhin vn tc ca cc phn ng phc tp trn xc nh bng vn tc ca giai
on trung gian tin trin chm nht ca n.
Giai on trung gian tin trin chm nht trong qu trnh oxy ho - kh trn l
phn ng (*), v n l phn ng lng phn t nn vn tc ca ton b qu trnh phi t
l vi bnh phng nng nh c xc nh bi thc nghim.
Do , kt qu s sai lch i vi nh lut tc dng khi lng ta nhn thy khi
nghin cu vn tc ca cc phn ng oxy ho - kh ch l s sai lch biu kin, v ngi
ta gii thch bng s tn ti ca cc giai on trung gian cha bit ca qu trnh oxy ho
- kh.
* Cht xc tc:
Cht xc tc l nhng cht lm thay i tc ca phn ng nhng khng c mt
sn phm cui cng v n tham gia vo cc giai on trung gian v li c ti sinh
trong nhng giai on cui.
V d, mc d th tiu chun ca cp S2O82-/2SO42- = +2,0V, ln hn th tiu chun
ca cp MnO4- + 8H+/Mn2+ (+1,51V) kh nhiu song nu trong dung dch ch c cc ion
S2O8 v Mn2+ th phn ng gia chng rt chm, thc t gn nh khng xy ra. Nu
thm vo dung dch mt lng nh mui bc lm cht xc tc th phn ng s xy ra
rt nhanh. Phn ng xy ra theo cc giai on sau:
S2O82- + 2H+ ^ H2S2O8 2H2S2O8 + 2H2O ^ 4H2S4 + 2O 2Ag+ + O + H2O
Ag2O2 + 2H+ 5Ag2O2 + 2Mn2+ + 4H+ 2MnO4- + 10Ag+ + 2H2O Phn ng gia oxalat
C2O42- v MnO4- trong mi trng axit thng c biu din bng phng trnh:
2MnO4 + 5C2O42- + 16H+ = Mn2+ + 10CO2 + 8H2O
Nhng thc ra phng trnh ch l phng trnh tng cng nhiu phn ng ch
hon ton khng ni ln c c ch ca phn ng . Nu trong dung dch ban u ch
c cc ion MnO4 , C2O4 v H+ th phn ng gia chng xy ra rt chm. Nu thm vo
dung dch mt lng nh mui Mn 2+ (MnSO4) th phn ng xy ra rt nhanh v ion
Mn2+ xc tc lm tng tc ca phn ng . Phn ng ny xy ra theo nhng giai
on sau:
2MnO4- + 3Mn2+ + 16H+ 5Mn4+ + 8H2O (Phn ng nhanh) Mn4+ + Mn2+ ^
2Mn3+ (Phn ng nhanh, thun nghch) Tip theo, cc ion Mn3+ v Mn4+ phn ng
vi ion C2O4 theo cc giai on
sau:
Mn4+ + C2O42- Mn3+ + CO2 + CO2-Mn4+
+ CO2- Mn3+ + CO2 (Phn ng nhanh)
2-

2-

2-

137

Mn3+ + C2042-=^ Mn(C2O4)+

(Phn ng nhanh, thun nghch)
Mn3+ + C2O42- Mn2+ + C02 + CO2Mn3
+ + C02" Mn2+ + C02 Nu trong dung dch ban u c ion Mn2+ th ion Mn4+ c to
thnh s b kh nhanh xung Mn3+, sau Mn3+ s to phc vi ion oxalat v ri phc
b phn hy.
Trong thc t cc cht xc tc thng c chn bng con ng thc nghim
theo quy tc sau:
Th tiu chun ca cht xc tc phi gia th tiu chun ca cht oxy ha v cht
kh, tuy nhin cng ch l iu kin cn ch khng phi l iu kin m chng ta
phi dng thc nghim nghin cu chn cht xc tc thch hp t nhng cht tha
mn iu kin .
* Phn ng cm ng.
Phn ng cm ng l phn ng mt mnh th xy ra rt chm, nhng tc ca n
c tng ln khi ng thi c mt phn ng nhanh khc xy ra.
Nguyn nhn, c ch ca hin tng ny cha c gii thch mt cch thng
nht. Tuy vy ngi ta thng cho rng trong qu trnh phn ng c to nn nhng cht
trung gian c tnh oxy ha hoc kh mnh hn cc cht ban u.
V d: Cromat CrO42- oxy ha Mn(II) rt chm, nhng nu c ng thi H3AsO3
th phn ng gia CrO42- v Mn2+ xy ra kh nhanh, v phn ng oxy ha H3AsO3 bng
cromat lm tng tc phn ng gia cromat v Mn 2+. Hin tng c gii thch
nh sau:
Cr042- + H3As03 H3As04 + Cr032-(Phn ng nhanh) tip theo
CrO32- c to thnh s oxy ha Mn(II) thnh Mn(III).
Cr032- + Mn2+ + 6H+ Mn3++ Cr3+ + 3H20 Mt trng hp rt thng
gp trong thc tin phn tch l khi chun st (II) bng pemanganat MnO4-, trong
mi trng axit HCl th lng pemanganat dng thng ln hn so vi lng tng
ng vi lng st (II). Nguyn nhn ca sai s ny l tuy axit HCl l long v khi c
mt mnh thc t n rt kh b pemanganat oxy ha, nhng nu trong dung dch ng
thi c c st (II) th HCl b oxy ha bi pe-manganat di dng phn ng cm ng.
Nguyn nhn c l l u tin Fe(II) b pe-manganat oxy ha thnh Fe(V), ri Fe(V)
oxy ha Fe(II) thnh Fe(III).
2Fe2+ + Fe5+ 3Fe3+
v ng thi cng oxy ha Cl- thnh Cl2
Fe5+ 2Cl- Fe3+ + Cl2 Cl2 sinh ra li oxy ha Fe(II): Cl 2
2
3
+ 2Fe + 2Cl + 2Fe + Nu tt c lng Cl2 u cn c trong dung dch th lng Fe 3+
sinh ra s tng ng vi lng pemanganat tc dng vi Cl - to nn Cl2 v nh
vy khng gy nn sai s. Nhng v c mt lng kh clo no bay ra khi dung
dch nn phi dng d pemanganat. Kinh nghim cho thy l nu thm vo dung dch
mt lng nh mui mangan (II) th s khng gy sai s v Mn(II) s d b Fe(V) oxy
ha hn: Fe5+ + 2Mn2+ Fe3+ + 2Mn3+

138

Mn3+ sinh ra s oxy ha Fe2+: Fe2+ + Mn3+ Fe3+ +

Mn2+ Mn3+ khng b mt i nh Cl2 do khng b mc sai
s.
Nhng khi nh phn H202 bng pemanganat hoc nh phn st (II) bng Ce(IV)
th c th dng HCl lm mi trng axit m khng gy sai s nh trn. Do , cha c
quy lut chc chn d on cc phn ng cm ng no s xy ra. Thng c th d
on cc phn ng cm ng bng quy tc thc nghim sau:
* Nu trong dung dch c hai cht kh Akh v Bkh c th oxy ha khc nhau nhiu
th thng Bkh b oxy ha mt phn do hin tng cm ng. Nhng nu phn ng: B ox +
Akh Bkh + Aox xy ra nhanh th s cm ng khng gy sai s, v Bkh s c ti sinh
li hon ton. Nu phn ng trn chm hoc mt phn Box b thot ra khi dung dch th
s mc sai s.
* Nu mt cht oxy ha b kh chm bi mt thuc th th tc phn ng s tng
ln khi xy ra phn ng ng thi gia thuc th v mt cht khc.
V d ion PO33- khng lm mt mu dung dch kali pemanganat trong mi trng
axit, nhng nu c ion Fe2+ trong dung dch th PO33- s kh MnO4-.
Oxy c trong khng kh c kh nng tham gia vo mt s phn ng cm ng v
y l nguyn nhn gy ra sai s khi tin hnh phn tch cc cht bng phn ng oxy ha
- kh. V d khi chun Sn2+ bng dung dch chun kali penmanganat hoc kali
bicromat th Sn2+ b oxy ha mt phn bi oxy khng kh trong phn ng cm ng. Khi
tin hnh phn ng trung ha ion HS0 3- bng dung dch chun kim th n rt d b oxy
ca khng kh oxy ha thnh sunfat trong phn ng cm ng.
4.2. Chun oxy ha-kh.
Trong cc phng php chun oxy ha - kh ngi ta thng tin hnh phn
ng chun , l phn ng trao i e gia dung dch chun cha cht oxy ha (hoc
kh) vi dung dch phn tch cha cht kh (hoc cht oxy ha). nhn ra im tng
ng ca phn ng chun , ngi ta cng dng cc cht ch th. 4.2.1. Ch th trong
phng php oxy ha - kh.
Khc vi phng php trung ha, trong phng php oxy ha-kh c th xc nh
im tng ng bng cch dng cc cht ch th sau:
120.
Khng dng cht ch th t ngoi a vo.
Trong trng hp ny, thuc th l mt cht c mu ring r rt m ta s kt thc
chun khi dung dch i mu.
V d: Khi chun dung dch H2C204 bng dung dch KMn04 trong mi trng
axit theo phn ng:
5H2C204 + 2KMn04 + 8H20 = K2S04 + 2MnS04 + 10C02 + 8H20 khi cho tha
mt git KMn04 th dung dch phn tch s c mu hng r rt. Loi phn ng ny ngi
ta gi l phn ng t ch th.
121. Dng cht ch th t ngoi a vo *
Cht ch th c bit
Loi cht ch th ny dng nhn lng thuc th tha ra mt t (1 - 2 git) trong
qu trnh chun .
V d: H tinh bt dng lm ch th nhn ra it khi c mt lng nh trong
dung dch. Lc dung dch c mu xanh hoc dung dch s mt mu xanh khi it b tc
dng ht. Chng hn khi nh phn dung dch it bng Na2S203 theo phn ng:

139

I2 + 2Na2S2O3 2NaI + Na2S4O6

9
n im tng ng va ht it th dung dch s ht mu xanh.
Hoc c th dng sunfoxyanua lm ch th nhn ra Fe3+.
* Cht ch th bt thun nghch.
Loi cht ch th ny c c tnh l 2 dng oxy ha v kh ca n (c mu khc
nhau) khng bin i thun nghch c.
V d: metyl da cam hay metyl trong mi trng axit c mu , khi b oxy ha
chng s chuyn thnh dng oxy ha khng mu nhng dng oxy ha ny khng th b
kh tr li dng kh ban u c. Gi s ta chun dung dch Sb 3+ bng dung
dch KBrO3 trong mi trng axit c metyl da cam hay metyl lm ch th:
3Sb3+ + BrO3- + 6H+ ^ 3Sb5+ + Br- + 3H2O dung dch s c mu , nu cho tha 1-2
git KBrO3 s c phn ng tip theo: BrO3- + 5 Br- + 6H+ ^ 3Br2 + 3H2O
Lc Br2 c to ra s oxy ha metyl da cam hay metyl to thnh mt hp
cht khng mu, ta kt thc nh phn.
* Cht ch th oxy ha-kh
Cht ch th oxy ha-kh l cht ch th i mu theo in th oxy ha-kh, chng
l nhng cht oxy ha hoc kh m dng oxy ha (Ind ox) v dng kh (Indkh) c mu
khc nhau, tn ti trong dung dch theo cn bng: Indox + ne Indkh
T l nng 2 dng [Ind ] trong dung dch quyt nh mu ca dung dch v
khlin h vi nhau theo cng thc Nec: EId
= E0 +
0,059
[Ind ]
lg
.
x k h
n [Indkh]
Theo biu thc trn, r rng khi in th ca dung dch thay i s lm bin i t s
nng ca 2 dng v c th a n s i mu ca dung dch. Cng tng t nh s
bin mu ca cht ch th axit baz:
* Mt ta ch nhn c mu ca mt dng khi [d ^ ln hn hay nh hn mt
khs ln nht nh, thng thng khong 10 ln.
* Mt ch nhn thy mu ca Indox khi
[Ind ]
> 10 ng vi dung dch c
t

ox

[Ind

/ I d

ox

ox

[Ind

ox

140

[Ind

kh]

E1 > 0 , 0,059
E0 +

141

n
- Mt ch nhn thy mu ca Indkh khi [Ind ] > 10 ng vi dung dch c
E2 < E
0 0,059
v mu ca cht ch th trong dung dch s bin i t mu ca n
dng Indox sang mu ca dng Indkh (m mt ta c th nhn thy c) ng vi E
,
r, ,
.,_ , 0,059
. ,. 0,059 ,.
ca dung dch thay i t E---------- n E +-------, ngha l trong gii hn:
nn
ox

[Ind

kh

T 0

142

0,059

< Edd < E0

+

0,059

143

n
n
khong
E gii hn gi l khong i mu ca cht ch th oxy ha-kh.
Vy, khong i mu ca cht ch th oxy ha-kh l khong gi tr in th E m
trong khong khi E ca dung dch thay i th mu ca cht ch th thay i (mt ta c
th nhn thy c).
Ch : V gi tr 0,059/n rt nh nn khong i mu dao ng thc t rt gn vi
gi tr E0 ca cht ch th oxy ha-kh, cho nn thng ngi ta ch quan tm n gi tr E 0
ca ch th. Mt s cht ch th thng dng c k bng 4.2
Bng 4.2. Mt s cht ch th oxy ha-kh thng dng
Ch th
Mu dng oxy ha Mu dng kh
Diphenyllamin
Xanh tm tm Khng mu
Axit diphenylazosulphonic
tm Xanh

Axit phenylantranilic
nht Xanh tm
Khng mu
Pheroin
Axit o,o'diphenylamin dicacbonic

E0 khi [H+] = 1
+0,76 +0,84
+1,08 +1,06
+1,26

4.2.2. ng nh phn trong phng php oxy ha-kh.

Trong qu trnh chun theo phng php oxy ha-kh, nng ca cc dng oxy
ha v kh ca cc cp thay i. Biu din th oxy ha-kh ca dung dch (E dd) theo lng
thuc th thm vo trong qu trnh chun ln trc ta ta c ng nh phn oxy
ha-kh.
Xt mt trng hp c th, qua ta s suy ra cc trng hp chung ca phng php
oxy ha-kh.
V C

00

V d ta kho st ng nh phn ca qu trnh chun V0 ml dung dch FeC

c nng C0 mol/l bng dung dch Ce2+
4
+ c nng C mol/l. Vt
4.2.2.1. Tnh th oxy ha-kh ca dung dch (Edd) trong qu trnh chun .
Khi chun , phn ng s xy ra: Ce4+ + Fe2+5=t Ce3+ + Fe3+
0
E
c:
+1,45V
n(E
o1
E- E;o2)E
= +0,77V 1,45 - 0,77
Ce + /Fe
Fe
/Ce ++
34

23

0,059 0,059
+ /Fe +
KCB ca phn ng trn kh ln (1011'35) nn phn
ng ;xy
nh hon ton. (v
= 11,35
KCBra= gn
10Fe11,35
mi mt thi im chun , phn ng s t n mt trng thi cn bng
khi

mi, do trong cng mt dung dch E Ce + /ce +

vn tc phn ng
ca 2 chiu nh nhau) v chnh l in th ca dung dch ti thi im :
3

Edd

Ce4+ /ce3+

Fe3+ /Fe2+

144

c th vit:
ECe + 0,059lg
E =E=
^dd - -C/Ce4+ /Ce3+ ~
"Ce

Edd

E
EF
0,059lg
=

3+

2+

[Ce4+ ] [Ce3+ ] [Fe3+ ] [Fe2+ ]

145
Bi vy mun tnh in th Edd ca dung dch trong qu trnh chun ta c th
tnh theo in th ca 1 trong 2 cp. Tuy nhin thun li, trc im tng ng
ta thng tnh in th Edd theo EFe3+ /Fe2+ v sau im tng ng tnh Edd
theo E
Ce4+ /Ce3+

(v d tnh c nng ca cc dng).

Nng [ox], [kh] tnh bng n v mol/l (trong trng hp ny, nng ng
lng bng nng mol/l).
* in th ca dung dch trc im tng ng
Ta
dd E tnh theo:
E

+ /Fe2+

Fe=

[Fe2+]
[Fe3+]
+0,77 + 0,059lg

146
V+V
C
CV

Fe -

[Fe

C
V

Trong : [Fe
3+
]

=
C V

0 0-

CV

C V

0 0

V+VV+V

[Fe2+]
Vy E

= 0'77+0-059lgcY,-cv

0
Ce4+
/Ce3+

Ta tnh theo:
E
* in th ca dung dch sau im tng ng.
Edd =
[Ce4+ ]
= 1,45 + 0,059lg
[Ce3+ ]

C V

0+

147
V

Trong , [Ce4+]

V0 + V
CV - CVtd
V0 + V

C V

C(V - Vtd) cBn [Ce +

]

CVtd 0 0
V0 + V V0 + V

148
Vy, Edd = 1,45 + 0,059lg

C(V - Vtd)
C V

0 0

* in th im tng ng
Khi cho 100ml Ce4+ th ton b
Fe2+ thnh Fe3+ v ton b Ce4+
s thnh Ce[Fe3+
+

] [Ce4 ]

nn ta khng d dng tnh c gi tr ca 1 hay

khng th tnh
[Fe2+] [Ce3+]
c Edd theo cc phng trnh trn. Ta c th tnh Edd theo
cch sau: Khi phn ng t n cn bng, ta c th vit:
dd [Fe
E

bi

vy

2+

] [Ce4+] [Ce3+]

[Fe3+ ]
Edd = 1,45 + 0,059lg
0,77 + 0,059lg-L
J

0,77 +1,45 + 0,059lg

[Fe3+] [Ce4+]

T phng trnh
phn ng :
2E

dd

[Fe ] [Ce ]
do
Ce
4
+ + Fe2+ 5 Ce3+ + Fe3+, im tng ng khi t n cn bng th:
[Fe3+ ] = [Ce3+ ] [Fe3+ ] = [Ce4+ ]
[Fe2+ ] = [Ce4+ ] [Fe2+ ] [Ce3+ ]
=

149

{^1 = 1^ = 1 bi vy: 2Edd = 0,77 + 1,45 => Edd = 0,77 1,45 = 1,110V [Fe2+ ] [Ce3 ] 2
p dng cc cng thc tnh ton trn, ta tnh s bin i th E ca dung dch khi
chun 100ml dung dch Fe2+ 0,1M bng dung dch Ce4+ 0,1M. Cc kt qu tnh ton
c trnh by trong bng 4.3.
Bng 4.3. S thay i gi tr in th E ca dung dch trong qu trnh chun
VC 4+ thm
(ml)
V < Vt
10
50
90
99
99,9
V = Vt
100
V > Vt
100,1
101
110
220

Phn c
chun (F)

[Fe3+ ]
[Fe2+ ]

0,1
0,5
0,9
0,99
0,999

- 10-1
-1
- 10
- 102
- 103

[Ce4+ ]
[Ce3+ ]

Th E (V)
0,71
0,77
0,83
0,89
0,95

1,0

1,11
- 10-3
- 10-2
- 10-1
1

1,001
1,01
1,1
2,0

1,27
1,33
1,39
1,45

4.2.2.2. V ng nh phn v nhn xt.

T cc s liu trong bng 4.3 ta v ng nh phn (hnh 4.1) v c nhngnhn
xt sau:
* Tng t nh trong phng php trung ha: khi tha 0,1% Fe 2+ n lc tha
0,1% Ce4+ ng nh phn c dng gn nh thng ng, ngha l E dd thay i t ngt
(0,947V -- 1,273V) tc l y c bc nhy E trn ng nh phn ( gn im
tng ng). Ngoi khong ra th Edd bin i t t (hnh 4.1)
T cch tnh ton Edd u v cui bc nhy, trong trng hp chung ngi ta
nhn thy rng: AE0 ca 2 cp ox/kh cng ln th bc nhy E cng di.
Trong mt s trng hp, ta c th ko di bc nhy E bng cch gim E dd u
bc nhy hoc tng Edd cui bc nhy.
V d trng hp nh phn trn, u bc nhy ta tnh c:
+

[Fe3 ]

Edd = 0,77 0,059lg^+i = 0,77 0,059lg103 = 0,947V

[Fe ]
, s
[Fe32+ ]_\ i th Edd s nh i. Gi s
bng
cch
no

m
gim
c
t
6lng thchNu
6
V
J
[Fe + ] lc ta cho thm mt
hp H3PO4 hay NaF th lm cho [Fe
3+
] gim i
dd

150

= 10 1 ;

[Fe3+ ] 10

rt

nhiu, gi s b gim i 10 ln, ngha l u bc nhy:

[Fe2+ ] 104 do Edd
-1

= 0,77 + 0,059lg10 = 0,711V

Vy by gi bc nhy E ca ng nh phn s l (0,711 - 1,273)V ngha l
c ko di hn trc (bc nhy E c: 0,947 + 1,273 V) 0,236V.
E (mV)
1500'
1400f
1300
1200
1100 1000
900f
800

ng tng ng

100

110

VCe4+ (mi)

Hnh 4.1. ng nh phn dung dch FeSO4 0,1N bng

dung dch Ce(S4)2 0,1N
* Trong trng hp phn ng dng trong chun c pH ca dung dch khng
i, h s ca 2 dng ox v kh ca 2 cp bng nhau (nh trng hp trn) th khi pha
long dung dch, nng ca 2 dng ox, kh cng gim nh nhau nhng t s [kh]
trong biu thc Nec vn khng thay i, do Edd vn khng thay i ngha l di
bc nhy E khng thay i. Tri li nu h s ca 2 dng ox/kh ca 2 cp khc nhau th
s pha long dung dch c nh hng n di bc nhy E.
* Trong trng hp tng qut ta c phn ng:
n1 (kh1) + n2 (ox2) n1 (ox1) + n2 (kh2) th ta tnh in th im tng
ng nh sau:

151

Etd =

n2Ek + n.E"
h

2__kh_ 1 ox

n1 + n2

152

E[ox]
, E = 0,771 + 5.1,51 = 1387
c: Etd =---------:----------= 1,387 ;
0

.=
Fe3+ /Fe2+

E0.
V d phn ng: 5Fe2+ + MnO4- + 8H+ ^ Fe3+ + Mn2+ + 4H2O
1+5
0.771V
= 1,51V

153

4.2.2.3. Chn cht ch th xc nh dim tng ng

Cng tng t nh trong trng hp trung ha ta s kt thc nh phn khi cht
ch th oxy ha-kh i mu trong khong bc nhy E ca ng nh phn th ch
mc sai s khng qu 0,1%.
l EVy: xc nh im tng ng vi chnh xc cho php (thng l 0,1%)
Nh trng hp trn ta c th chn c cc cht ch th c:

154

0,95V < Elnd /Ind < 1,27V

V d c th dng axit phenylantranilic c E0
0
= 1,08V lm ch th hoc pheroin c E0 = 1,06V.
Nu gi thit mun dng diphenylamin c E0 = 0,76V th phi ko di bc nhy
th no Edd u bc nhy phi: Edd u < 0,76V
Gi s ko di bc nhy bng cch thm H 3PO4 hay NaF chng hn (xem cch
tnh trn)
4.2.3. Mt s phng php oxy ha kh thng dng.
4.2.3.1. Phng php pemanganat.
c im chung ca phng php: Phng php pemanganat da trn phn ng
oxy ha ca ion MnO4-. Kh nng oxy ha ca ion MnO 4- ph thuc nhiu vo axit
ca mi trng phn ng.
*Trong mi trng axit mnh MnO4- b kh v Mn2+:
MnO4- + 5e + 8H+ ^ Mn2+ + 4H2O V d: MnO4- +
2
5Fe + + 8H+ ^ Mn2+ + 5Fe3+ + 4H2O
*Trong mi trng axit yu, trung tnh hay kim th MnO4- ch b kh ti
MnO2.
MnO4- + 3e + 4H+ ^ MnO2 + 2H2O E,
, , = 1,67(V)
ox

kh

MnO-/MnO2

'

c nh y

'

MnO4 + 3e + 2H2O ^ MnO2 + 4OHE,

= 0,57(V)
MnO4+H2O /MnO2

'

'

C th gii thch kh nng oxy ha khc nhau ca MnO4 trong mi trng axit v mi
trng kim bng s chuyn ha gia MnO2 v ion Mn2+ nh sau: MnO2 + 2e + 4H+
^ Mn2+ + 2H2O (*)
Trong mi tng axit, cn bng (*) s chuyn dch v pha phi to thnh Mn 2+.
Nh vy, c th coi rng trong mi trng axit MnO4- trc tin b kh thnh MnO2 sau
v nng ion H+ trong dung dch cao nn lp tc MnO2 b kh tip xung
Mn2+.
Trong mi trng trung tnh hay kim th MnO4 b kh ti MnO2 v khng b kh
tip na v trong mi trng ny cn bng (*) chuyn dch sang tri, to thnh
MnO2.
Nh vy, kh nng oxy ha ca MnO4- trong mi trng axit ln hn rt nhiu so
vi mi trng kim. Hn na trong mi trng axit, sn phm b kh l Mn 2+ khng
mu, nn chnh KMnO4 cng l cht ch th cho qu trnh chun , v sau im tng
ng 1 git dung dch KMnO4 d cng lm cho dung dch chuyn t khng mu
sang mu hng. Trong khi nu tin hnh chun trong mi trng kim hoc trung
tnh hay axit yu th sn phm kh l MnO 2 l cht kt ta mu nu sm, nh hng n
vic xc nh im cui ca qu trnh chun . V vy, trong thc t ngi ta ch dng
phng php pemanganat chun cc cht kh trong mi trng axit mnh.
iu chnh mi trng axit, dng H2SO4 ch khng dng HCl (v Cl- kh c MnO4- v
bin thnh Cl2) v cng khng dng HNO3 v HNO3 l cht oxy ha mnh, n s oxy ha
cht kh lm kt qu chun s sai.
Kali pemanganat (KMnO4) khng phi l cht gc v n thng khng tinh
-

155

khit, bao gi cng cha tp cht l sn phm kh MnO 2. Ngoi ra KMnO4 l cht oxy
ha mnh, d b kh bi cc cht hu c c ln trong nc, trong bi khngkh, b phn
hy bi nh sng... Do dung dch KMnO 4 pha xong phi ng trong l c mu nu,
y kn v yn mt thi gian mi c dng, trc khi dng phi xc nh li nng
bng dung dch chun l axit oxalic.
Dng phng php pemanganat c th xc nh c nhiu cht v c v hu c
khc nhau bng cch chun khc nhau.
* Cc cht kh: cc kim loi (Fe, Bi, Ag, Cd, Zn, kim loi t him v.v...) cc phi
kim (Sb, As, P v.v...) cc ion ha tr thp c kh nng cho hp cht ca nguyn t ha
tr cao (Fe2+, Cr2+, Mn2+, Sn2+, Cu+, Ti3+, V(III), V(IV), Mo(IIIX U(IV), W(IV);
As(III) v.v...) ion phi kim nh Cl-, Br-, I-, S2- v.v... cc cht l nhng ion phc tp (SO32-,
S2O32-, TeO32-, SeO32-, SCN-, CN-, NO2-, [Fe(CN)6]4-: cc axit poli v oxycacboxylic
(H2C2O4, HOOC-CH2-COOH, v.v...) cc andehyt, cc axit focmit, uric, ascobic,
sunfonic, ng, poliphenol, cc hp cht khng no v nhiu sn phm khc.
* Cc cht oxy ha: Fe3+, Ce(IV), U(VI), Mo(VI), W(VI), Cr(VI), MnO2,
PbO2, NO3 , BrO3 , ClO3 , IO3 v.v...
Phng php pemanganat c cc u im sau:
*Khng phi dng cht ch th.
*Pemanganat c th oxy ha kh cao E0
+ = 1,51(V) nn c th xc nh
-

MnO-/Mn2+

'

'

c nhiu cht khi chng khng th chun c bng cc cht oxy ha yu.
*Pemanganat d kim, r tin, dng KMnO4 c th chun c c nhng cht
khng c tnh oxy ha kh, v d xc nh c Ca 2+ bng cch kt ta vi ox-alat sau
chun lng cht kh d hoc ha tan kt ta s tnh c lng canxi, xc nh
anhiric axetic da trn phn ng ca n vi axit oxalic sau chun lng d axit
oxalic bng KMnO4 .
(CH3CO)2O + 11H2C2O4 -> 2CH3COOH + CO2 + CO + (n-1)H2C2O4 anhiric
axetic
H2C2O4 (d) +MnC+ > 2CO2T + 2H+
4.2.3.2. Phng php dicromat
c im chung ca phng php dicromat l da trn phn ng oxy ha ca ion
dicromat (Cr2O7 ) trong mi trng axit.
Cr2O72- + 6e + 14H+ 2Cr3+ + 7H2O
2-

TH oxy ha ca h Cr207- /Cr 1,36(V)

+ cng ph thuc rt nhiu vo nng ca ion
H+. K2Cr2O7 oxy ha yu hn KMnO4. Phng php dicromat c mt s u im sau:
*K2Cr2O7 d iu ch c tinh khit, K2Cr2O7 l cht gc nn dung dch chun
K2Cr2O7 d iu ch, d bo qun v bn lu.
*Tin hnh chun trong mi trng axit H2SO4, H3PO4 v c HCl (v EC - + =
1,36(V)cng bng E -). Tuy vy khng c tin hnh chun
E

Cr2O7-/2Cr3+=

2 ;

/ l

Cr2O7 / 2Cr

Cl2 / Cl

trong mi trng HCl > 2M v trong iu kin , nng Cl- rt ln nn lm gim

156

th ca cp Cl2/2Cr, do Cr2O72- s oxy ha c mt phn Cl- thnh Cl2.

Sn phm ca phn ng kh Cr 2O72- l ion Cr3+ c mu xanh. im cui ca qu
trnh chun khng th nhn ra c mu da cam do mt git dung dch K 2Cr2O7 d,
do vy xc nh im cui ca qu trnh chun ta phi dng cht ch th oxy ha
kh. Cht ch th thng dng trong phng php icromat l di-phenylamin (c E0 =
0,76V), mui natri (hay bari) diphenylaminsunfonat (c E0 = 0,84V), ch th ny d tan
trong nc hn diphenylamin v s i mu r rt hn (t khng mu sang mu tm ).
Cng c th dng axit phenylantranilic (E 0 = 1,08V dng oxy ha c mu tm, cn dng
kh khng mu).
Kali dicromat c kh nng oxy ha c nhiu cht v c v hu c: Fe(II),
Mn(III), Ti(III), SO32-, [Fe(CN)6]4-, AsO33-, I-, ru, hiroquinol, glixrin, axit ascobic, thioure v.v...
Di y l mt vi phn ng oxy ha c trng ca dicromat dng trong phn
tch chun .
* Oxy ha hexaxianoferat (II):
&2O72- + 6[Fe(CN)6]4- + 14H+ 2Cr3+ + 6[Fe(CN)6]3- + 7H2O
* Oxy ha Fe(II):
&2O72- + 6Fe2+ + 14H+ HPO* 2Cr3+ + 6Fe3+ + 7H2O
3 4
* Oxy ha ru metylic:
Cr2O7 + CH3OH + 8H+ - 2Cr3+ + CO2 + 6H2O
* Oxy ha hiroquinol:
Cr2O7 + C6H4(OH)2 + 12H+ - 2Cr3+ + C6H4O2 + 7H2O
4.2.3.3. Phng php iot - thiosunfat.
c im chung ca phng php iot - thiosunfat.
- Phng php ny da trn phn ng oxy ha ca I2 v phn ng kh ca I-I2 + 2e
^ 2I
CN c vo gi tr E
54V
0E2 /2I - '
ta thy I2 l cht oxy ha yu hn KMnO4, K2Cr2O7 nhng I- li l cht kh mnh.
Nhiu cht kh c th b I2 oxy ha, nhng cng c nhiu cht oxy ha b I- kh. Cho
nn trong phn tch, ngi ta thng dng c hai tnh cht oxy ha v kh ca I2 v I-
xc nh c cht kh v cht oxy ha. Trong phng php ny, ngi ta thng dng
phn ng ca thiosunfat (S2O3 ) vi it, v th phng php ny thng c tn gi ghp
li l phng php iot - thiosunfat phn ng gia iot v thiosunfat xy ra theo phng
trnh: 2S2O32- + I2 2I- + S4O62-ion thiosunfat
ion - tetrathionat
^Ur / 2S2O2- =
2-

2-

2-

2S2O31V
- 2e ^ S4O62- S2O3- = M 2- nhn ra im cui ca qu trnh chun ngi ta
thng dng cht ch th
2-

S2O

157

l h tinh bt. H tinh bt khng phi l cht ch th oxy ha kh m n c tnh cht hp

ph I2, c mu xanh m. Khi s dng cht ch th h tinh bt, ta phi lu , nu dng
dung dch I2 chun dung dch Na2S2O3 th ta c th thm cht ch th h tinh bt
ngay t u, trong qu trnh chun d dung dch khng mu, sau im tng ng c
d mt git dung dch I2 dung dch s c mu xanh. Nhng khi chun I2 bng dung
dch Na2S2O3 th khng c cho ch th h tinh bt ngay t u, bi v nu thm h tinh
bt t u n s hp ph I2, I2 b hp ph ln h tinh bt b gii hp rt chm nn khi
chun lng Na2S2O3 d m mu xanh vn cha mt, do chun s qu im
tng ng rt nhiu nn kt qu b sai. Bi vy, khi chun I 2 bng dung dch
Na2S2O3 ch c thm h tinh bt khi qu trnh chun gn kt thc ngha l khi dung
dch cn li rt t I2 (dung dch lc c mu vng rt nht, nh mu ca rm nn gi l
mu vng rm) , dung dch lc c mu xanh, nh t t tng git dung dch Na 2S2O3
va nh va lc mnh n khi dung dch mt mu xanh th l im cui ca s chun
.
* Xc nh cht kh:
Ta c th dng I2 xc nh nhiu cht kh bng phng php chun ngc,
nguyn tc nh sau: thm mt lng d xc nh dung dch I 2 bit nng vo dung
dch cht kh, sau khi phn ng xy ra hon ton, ta chun lng I 2 d bng dung
dch chun Na2S2O3.
* Th d xc nh SO32-, AsO>33\ H2S, Sn2+... SO32- + I2 + H2O ^ SO42- + 2I- +
2H+ AsO33- + I2 + H2O ^ AsO43- + 2I- + 2H+ H2S + I2 ^ Si + 2I- + 2H+ sn+ + I2 ^
Sn4+ + 2IXc nh cht oxy ha:
xc nh cht oxy ha bng phng php ny ta lm nh sau. Thm vo dung
dch cht oxy ha mt lng d KI ri to iu kin thch hp cho phn ng gia Iv cht oxy ha xy ra hon ton. Khi o I- b oxy ha thnh I2, m I2 l cht t tan
trong nc nn ta phi dng d nhiu KI I2 tch ra s kt hp vi I- to thnh I3tan: I2 + I- 5=* I3Sau chun lng I2 thot ra ( dng I3) bng dung dch chun Na2S2O3.
Bng cch ny ta c th xc nh c cht oxy ha: Br 2, MnO4 , Cr2O7 , ClO3 ,
H2O2, Fe3+ v.v. ..
Br2 + 2I- = 2Br- + I2
2MnO4- + 10I- + 16H+ = 2Mn2+ + 5I2 + 8H2O
Cr2O7 + 6I- + 14H+ = 2Cr3+ + 3I2 + 7H2O ClO3 +
6I- + 6H+ = Cl- + 3I2 + 3H2O
4NO2- + 4I- + 8H+ = 4NOT + 2I2 + 4H2O
* H2O2 + 2I- + 2H+ = I2 + 2H2O 2Fe3+ + 2I- = I2 + 2FeNgoi vic xc nh cc cht
kh v cht oxy ha, phng php iot-thiosunfat cn c dng xc nh axit. Iodua
phn ng vi iodat khi c axit theo phng trnh sau:
5I2+
+ IO3- + 6H+ 3I2 + 3H2O
-

2-

2-

158

T phng trnh trn ta thy lng ion H + tham gia phn ng tng ng vi
lng I2 thot ra. Do , sau khi phn ng trn xy ra hon ton, ta chun lng I 2
thot ra bng dung dch chun Na2S2O3. Da vo lng Na2S2O3 tiu tn ta s tnh
c lng ion H+ trong dung dch. Nh vy, dng phng php iot - thiosunfat ta c
th xc nh c axit. Phng php ny c tn gi l phng php iot - thi-osunfat xc
nh axit.
Ch :
* Natri thiosunfat c th kt tinh tinh khit, ng ng vi cng thc
Na2S2O3.5H2O nhng n vn khng phi l cht gc bi l dung dch Na 2S2O3 khng
bn, nng ca n b thay i theo thi gian do tc dng ca CO2 v O2 ca khng
kh.
Na2S2O3 + CO2 + H2O = NaHCO3 + NHSO3 + si
Na2s2o3 + O2 = Na2SO4 + si Ngoi ra dung dch Na2S2O3 cn d b cc vi sinh vt
trong khng kh phn hy. ngn cn s phn hy ny, ngi ta thm vo mt lt dung
dch Na2S2O3 10mg HgI2 lm cht st trng.
* Khi s dng phng php iot - thiosunfat cn ch my im sau:
* Vic chun phi tin hnh trong mi trng kim yu c pH < 9. Khng c
thc hin phn ng trong mi trng kim mnh bi v n c phn ng.
I2 + 2OH- = IO- + I- + H2O
Ion IO to thnh c tnh oxy ha mnh, n oxy ha mt phn S2O32- thnh
SO4S2O3
+ 4IO + 2OH = 4I + 2SO4 + H2O
Nng OH- trong dung dch cng ln th lng S2O32- chuyn thnh SO42-cng
nhiu. Do c phn ng ph ny m khng th tnh chnh xc kt qu phn tch c; ni
khc i phn ng chun khng xy ra theo mt h s t lng xc nh nn khng
dng c.
Nu phn ng sinh ra H + s lm pH ca dung dch gim khng m bo mi
trng kim yu, th ta phi dng NaHCO3 lm cht m ly bt H+ trong dung dch
i: HCO3- + H+ = CO2T + H2O
Khi pH ca dung dch oc gi gn nh khng i (pH = 8), khng cn tr vic
chun .
* V it l cht d b thng hoa v kh nng hp th ca h tinh bt i vi I 2 gim,
khi nhit tng. V vy, php chun iot - thiosunfat khng c tin hnh khi un
nng.
* V iot t tan trong nc, nhng tan nhiu trong dung dch c d I - do c phn
ng: I- + I2 5=* I3Nn khi xc nh cht oxy ha bng php o iot phi dng d KI. Phn ng to
thnh ion I3- l phn ng thun nghch v ion I3- rt km bn nn khi chun I2 bng
Na2S2O3 cn bng b ph v v chuyn dch hon ton v pha tri, ton b lng I 2 thot
ra c chun nh lng bng Na2S2O3.
* Phn ng gia I- vi cc cht oxy ha v phn ng gia I2 vi cht kh thng
xy ra chm, do sau khi thm I - hay I2 vo ta phi ch mt thi gian (khong 5 pht)
cho phn ng xy ra hon ton ri mi tin hnh chun . Khi
-

2-

2-

2-

2-

2- 2-

159

yn dung dch phi y kn v t ch ti v nh sng lm tng phn ng oxy ha I thnh I2 bi oxy khng kh.
I- + 4H+ + O2 =as= 2I2 + H2O
4.2.3.4. Phng php bromat - bromua.
Phng php ny da trn phn ng oxy ha kh, dng cht oxy ha l ion
BrO3 .
-

BrO3- + 6e + 6H+ = Br- + 3H2O Er , - = 1,44V; - = BrOM

/Br
'
'
BrO 6
Phn ng c s tham gia ca H+ nn phi tin hnh chun trong mi trng
axit. Mc d BrO3- l cht oxy ha mnh nhng tc phn ng oxy ha bng BrO 3-xy
ra chm. tng tc ca phn ng cn tin hnh phn ng trong dung dch nng v
mi trng axit mnh.
Sau im tng ng khi d 1 git BrO3- th xy ra phn ng: BrO3+ 5Br- + 6H+ = 3Br2 + H2O
Br2 t do sinh ra khng nhn ra mu. Do vy, nhn ra im cui ca qu
trnh chun ngi ta thng dng cc cht mu hu c nh metyl da cam, metyl
... lm ch th. Sau im tng ng BrO 3- d s phn ng vi Br- c sn trong
dung dch sinh ra Br2 n s oxy ha cht mu hu c nn s mt mu.
Cc cht mu hu c dng lm ch th cho php o ny khng phi l cht ch th
oxy ha kh, qu trnh Br2 oxy ha chng l qu trnh bt thun nghch. Do khi chun
cn lu khng c thuc th d tng vng, trong qu trnh chun , mun
vy phi chun t t v phi lc u. Do tnh cht bt thun nghch ca phn ng oxy
ha cht ch th bi Br2, khi chun mu c th mt trc im tng ng v th
trc khi kt thc chun cn thm vi git cht ch th na.
Phng php bromat - bromua c dng chun trc tip mt s cht
kh, v d As (III), Sb (III), v.v...
Ngoi ra phng php ny cn cho php xc nh c mt s cht hu c c kh
nng b brom ha, khi ta tin hnh chun cht hu c bng dung dch chun
KBrO3 khi c mt mt lng d KBr trong mi trng axit.
Ngoi cc phng php trn, ngi ta dng mt s phng php khc nh phng php
xri da trn phn ng oxy ha ca ion Ce4+. Ce4+ + e 5=55 Ce3+
Ce4+ /Ce3 + = v phng php vanadat da trn phn ng oxy ha
VO2
2
0
: VO2+ + e + 2H+ ^5 V0 + + 2H2O E = 1,0V v.v...
cc php o ny t dng trong thc t v cc thuc th Ce4+ v VO2 tng i t.
r

1,45V

160

BI TP
122. axit ca mi trng nh hng nh th no n th oxy ha ca h:
123. a. Cr2072-/Cr3+ b. Mn04-/Mn2+ c. SO4 /H2S d. N03 /NO e. As043-/AsO3in th oxy
ha ca cp Mn32
+/Mn bng bao nhiu khi cc nng Mn2+ bng:
a. 2 mol/l
b. 0.005 mol/l
124. in th oxy ha ca cp Sn4+/Sn2+ bng bao nhiu khi cc nng ca Sn4+ l
0,1M, ca ion Sn2+ l 0,0001M.
125. Mt pin gm c in cc tiu chun hydro ni vi cc Ni nhng trong dung dch
cha Ni2+, khi nng ca ion Ni 2+ bng 0,01M th pin c sc in ng l 0,172V. Tm
in th ha oxy ha tiu chun ca cp Ni2+/Ni.
126. Tnh theo tr s in th oxy ha tiu chun ca cp Mn0 2/Mn2+ v Cl2/2Cl- th
phn ng gia chng phi xy ra theo chiu nh th no? Hy gii thch hin tng l
trong phng th nghim ngi ta iu ch Cl2 bng tc dng ca HCl c vi
MnO2.
6.Lp cng thc tnh hng s cn bng ca cc phn ng:
a. Sn2+ + I2
Sn4+ + 2Ib. Mn04+ 8H+ + 5Fe2+ Mn2+ + 5Fe3+ + 4H20 v tnh ra tr s hng s. Trong cc phn ng
trn th phn ng no tin hnh hon ton hn?
127.Tnh nng N ca dung dch K2CrO4 trong phn ng oxy ha-kh, nu nh
trong phn ng kt ta dung dch ny c nng N bng 0,1.
128.Tnh nng ng lng ca dung dch KMnO 4 khi nh phn trong mi
trng kim (kh ti Mn02) nu nh khi xc nh nng ca n ngi ta tin hnh
trong mi trng axit v bit c nng ca n bng 0,1.
129.Khi chun 0,1133g Na2C2O4 sch trong mi trng axit th tn mt 20,75ml
dung dch KMn04. Tnh nng N v TKM ca dung dch KMn04 trn.
130.Tnh hm lng Mn2+ trong dung dch nu khi chun dung dch ny tn mt
21,5ml dung dch KMn04 0,02M. Khi chun Mn2+ cng nh KMn04 u bin thnh
Mn02: Mn2+ + 2Mn04- + 2H20 = 5Mn02 + 4H+.
131.Cn bao nhiu gam qung c cha gn 70% Fe 203 sau khi ch ha ri nh
phn Fe2+ to ra th tn mt 20 - 30 ml dung dch KMnO4 0,1N.
132.Lng qung (gam) cn phi ly l bao nhiu khi xc nh Fe trong th c
1ml dung dch K2Cr2O7 0,1N tng ng vi 2% Fe2O3.
133.Ha tan 0,16g vi trong HCl sau kt ta Ca2+ di dng CaC204 ri ha
tan kt ta c ra sch trong dung dch H2SO4 long v nh phn dung dch thu
c bng dung dch KMn04 c TKM
= 0,006. Tnh % CaC03 trong
vi bit rng lng KMnO4 tiu tn cho nh phn l 20,75ml.
-

O /F

O /CCO

161

14. nh phn dung dch Fe2+ thu c t 0,2g qung Fe bng dung dch chun
K2Cr2O7 0,02M. Lng K2Cr2O7 tiu tn cho nh phn l 20,5ml. M t qu trnh
xc nh bng cc phn ng ha hc v tnh % Fe trong qung.

TI LIU THAM KHO

134.
Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch,
NXB KH & KT, 2002.
135.

L c, Ha hc phn tch. NXB H Quc Gia H Ni, 2002.

136.

Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc,

2000.
137.

Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002.

138.
Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch,
NXB H&TH Chuyn nghip, 1984.
139.
H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v
Nguyn Huyn dch. NXB KH & KT, 1976.
140.
B.H.AneKceeB, KaniHecTBeHHbi aHani3, MocKBa, H3gaTej[bcTBo
"XiMira",
1972
141.
B.H.AneKceeB, KonecTBeHHMH aHani3, MocKBa, H3gaTej[bCTBo
"XiMira",
1972

162

CHNG 5

PHC CHT V THUC TH HU C TRONG HA PHN TCH.

CHUN COMPLEXON
5.1. Phc cht.
142. nh ngha.
Phc cht l loi cht sinh ra do ion n (thng l ion kim loi) gi l ion trung
tm kt hp vi phn t hoc ion khc gi l phi t. Trong dung dch, ion trung tm,
phi t v phc cht u c kh nng tn ti ring r.
Trong ha hc phn tch, nhng phc cht c nhng ng dng phong ph thng l
nhng phc cht phn ly c ti mc sn phm ca s phn ly c th ha hp vi
cc cht khc.
V dd:
[Ag(NH3)2]+ ^ Ag+ + 2NH3
Nng NH3 ln NH3 c th ha hp c vi H+.
NH3 + H+ 5=5= NH4+
HgCl2 - HgCl+ + Cl5
HgCl+ ^ Hg2+ + ClHg2+
nhiu c th ha hp c vi S2- to thnh kt ta Hg2S mu en.
y chng ta phi phn bit phc cht vi mui kp. Tri vi phc cht, mui kp
khng tn ti trong dung dch m chng phn ly thnh cc ion n gin.
V d:
Mui Mo:
(NH4)2Fe(SO4)2 = 2NH4+ + Fe2+ + 2SO4Phn nhm:
KAl(S04)2 = K+ + Al23
+ + 2SO42-Nhng ion nh SO42-, ClO3-, NO3- tuy c cu to ging phc cht nhng
phn ly qu b nn khng gi l ion phc m thng coi nh cc ion n.
143. Phn loi cc phc cht
Da vo cu to ta c th chia phc cht ra lm 2 loi: phc cht cng v ni
phc.
5.1.2.1. Phc cht cng
Trong dung dch chng phn ly thnh cc ion n gin v ion phc, tc l ngoi
cu v ni cu c in tch ngc du nhau, ni cu thng c vit trong ngoc [].
[Cu(NH3)4]Cl2 = [Cu(NH3)4]2+ + 2Clni cu ngoi cu
Trong ni cu (ion phc) ion kim loi lm nhn trung tm kt hp vi cc phi t
theo lin kt phi tr khng to vng, cc phi t c th l phn t hay anion v c hoc
phn t cht hu c.
Phi t l phn t, thng hay gp l hydrat hay amnic.

163

M3
H3N->Cu-NH3

V d:
3

; [Al(H20)6]-

NH3
Phi t l anion v c nh Cl-, F-, S042-, S2032-, CN-, ... V
d:
CN- CN\

NC -> Fe <- CN-

; AgCl2 , [Ca(S04)2] t \
-

2-

CN CN
Phi t l anion hoc phn t cht hu c. V d: [Fe(C204)3]3. 5.1.2.2. Ni phc.
Ni phc l nhng phc cht m nhn trung tm l nhng ion kim loi kt hp vi
cc phi t l nhng phn t cht hu c bng lin kt phi tr hay va bng lin kt
phi tr va bng lin kt ha tr to thnh mt hay nhiu vng.
V d:
COO OOC
2

\/ \/
NH2

NH2

Glycocolat Cu

1I
CH2 -NH 2

NH2 - CH2

Etylendiamin Cu (II)

Da vo cu to v c tnh ca lin kt trong ni cu c th chia lm 3 loi ni

phc:
* Mui ni phc khng c ngoi cu, ch c ni cu
Trong ni cu ion trung tm kt hp vi lin kt phi t va bng lin kt ha tr
va bng lin kt phi tr to thnh mt hay nhiu vng. V d nh mui ni phc
glycocolat Cu tan ( trn) hay dimetylglyoxim Ni t tan.
Cc ni phc phn ln t tan trong nc v tan nhiu hay tan hon ton trong dung
mi hu c.

0 ... H -O

\ CN==N C- Ni
C vng
H3C - C = N
- CH3 2= vng
1
*
O - H ... O

164

* Ni phc m ni cu l anion
y l mt phc cht c ngoi cu l cation v ni cu l anion. Trong ni cu ion
trung tm kt hp vi cc phi t va bng lin kt ha tr va bng lin kt phi tr
to thnh mt hay nhiu vng.
Axit ferisalixilic: H3[Fe(C6^OCOO)3] 3H+ + [Fe(C6H ^
O
CO
O

COO
=== )3]3

Cromooxalat Kali: K3[(C2O4)3Cr]

3K+ + [( I
* )3Cr]COO

V d:
* Ni phc m ni cu l cation
y l mt phc cht c ngoi cu l anion v ni cu l cation. Trong ni cu ion
trung tm kt hp vi cc phi tr ch bng lin kt phi tr to mt hay nhiu vng.
V d: Clorua etylendiamino Cu (II)

165

2^

CH, NH
I,
CH2 M/'

J2

Cu

C12

2C1" +

2 - NH2 s

Cu

J2

2+

166

Hay a, a'dipiridilo Fe (II):

167

\ /

Fe
NH4C5

2+

168

C5H4N ^

^ NH4C

Ni phc c mt s c tnh sau:

* Phn ln t tan trong nc, tan nhiu trong dung mi hu c.
* C bn ln.
* C mu khc vi mu ca ion trung tm v m.
5.1.3. bn ca phc cht.
5.1.3.1. Hng s bn v hng s khng bn ca phc cht.
Trong dung dch, phc cht c cn bng thun nghch: phn ly v to thnh
3
phc

cht.

phn ly
MnLmmL
-to
= -thnh
= -= nM +

Hng s cn bng i vi qu trnh phn ly phc th gi l hng s khng bn (K kb)

ca phc; trong cn bng trn th:
MnMm (5.1)
Kkb =
[M L ]
L

mJ

Hng s cn bng i vi qu trnh to thnh phc cht th gi l hng s bn

ca phc, trong cn bng trn th:

(P)

169

p=

T^LmI (5.2)

[M]n [L]So snh (5.1) v (5.2) ta thy hng s bn (P) l nghch

o ca hng s khng

bn v ngc li:

0 = (5.3)

V d, trong cn bng sau:

[Cd(M3)4m
2
2
+]
Cd + + 4NH3
0 Nyl
cn Kkb =
= 2,5.10p
[Cd2+][NH3 ]
[Cd(NH3 ) + ] '
[Cu(NH3)42+]
Cu2+ + 4NH3
[NH ]
cn Kb =
p0 =
] = 4,6.10
u ]|N" ]
[Cu(NH3 ) + ] '
Hng s khng bn cng nh th hng s bn cng ln tc l phc cng bn hay
phc phn ly cng t. Trong hai phc trn th phc [Cu(NH3)4]2+ bn hn.
7

kb

Ngyd
T

14

kb

P1

Cng ging nh cc a axit, a baz, i vi phc c nhiu phi t th qu trnh hnh

thnh hay phn ly ca phc cng xy ra tng nc. V d, phc [Zn(NH3)4]2+ xy ra 4 cn
bng sau: Zn2+ + NH3 =^ = [Zn(NH3)2+] Zn(NH3) +]]= 18 Z n2+] [INH ]]
[Zn(NH3) +]] + NH3 ^ [Zn(NH3)2 +]
2

0 2=

'S] ] 10
2
[Zn(NH ) +H NH ]

[Zn(N
3

1,25

[Zn(NH32 +] + NH3 ^ [Zn(NH3)3 +]

2

03

[ Zn(N

]]

",

2,31
] 10

[Zn(NH3)2+][NH3 ]
[Zn(NH332+] + NH3 ^ [Zn(NH3)42+]
[ZN(NH )2 ]
0 =
3 +
= 101,96
[Zn(N";);+][N"; ]
cho tin vic tnh ton, thng cn dng hng s bn tng cng ca nhiu cn bng
trn. V d, cng hai cn bng u trong 4 cn bng trn ta c cn bng: Zn2+ + 2M3
^= [Zn(M3)22+] Hng s cn bng bn s l:
1

=T

012

1,2

Zn(N"34

=P1P 2=

[Zn2+][NH3 ] Tng t ta c: PM = P1P2P3P4 = u "2+7r^

2

103,43

n4
=
107'[Zn(NH3)
2

7
+] [Zn +][NH3 ]Da vo hng s khng bn ta c th tnh nng cn bng ca ion
2

170

hoc phn t do phc cht phn ly ra tm cch tng hay gim cc nng n mc cn
thit

171

cho vic phn tch.

V d: Tnh nng cn bng ca cc ion trong dung dch diamino bc (II) ni-trat
[AgNH3)2]NO3 0,01M c KK = 6,8.10Gii: Trong dung dch, phc cht ny phn
ly hon ton theo phn ng:
[Ag(NH3)2]NO3 [Ag(NH3)2]+ + NO3
4

-8
-

Nng lc ban u:

0,01M

0,01M 0,01M

Nhng: [Ag(NH3)2]+ ^ Ag+ + 2NH3 (5.4) KKb = 6,8.10Vy khi cn bng ta c: -8

[Ag ][N"3] = KKb = 6,8.10-8 (5.5)
[AG(NH )
3 2
Theo phng trnh phn ly (5.4) ta c: [NH3] = 2[Ag+] (5.6) Theo nh lut bo
ton khi lng ta c:
[Ag(NH3)2]+ + [Ag+] = 0,01 (5.7) Gii phng trnh c 3 n s (5.5), (5.6),
(5.7) ta s tnh c gi tr ca [Ag+],
[NH3], [Ag(NH3)2]+.
W- = 6,8.10 8 0,01 [Ag+]
v ion phc phn ly yu (KKb = 6,8.10-8) nn: [Ag+] << 0,01M. Do
: 0,01 -- [Ag+] 0,01. ' Vy rt ra c:
[Ag+] =
5,5.10[NH3]] = 1,1.10[Ag(NH3)2]-4
-3
+

= 9,45.105.1.3.2. Cc yu t nh hng n bn ca phc cht. S phn hy phc

cht.
Ni cu ca phc cht l nhng cht in ly yu, trong dung dch n phn ly mt
phn thnh nhn trung tm (ion kim loi) v cc phi t (phn t hay ion).
V d: [Ag(M3)2]+ Ag+ + 2NH3 ,(5.8)
Mun phc cht bn ngha l t phn ly th phi chuyn dch cn bng (5.8) t phi
sang tri c th bng cch cho thm NH3, hay ni cch khc phc cht trn bn trong
mi trng NH3.
Ngc li nu ta gim nng ca cu t to ra ni cu nh NH3, Ag-3
+
ca phc cht [Ag(NH3)2]+ th phc cht s km bn v c th b phn hy hon ton.
Ta nghin cu mt s yu t trong mt s trng hp lm cho phc cht b phn
hy.
* Anh hng ca pH:
Ni cu do ion kim loi lm ion trung tm v cc phi t l phn t hay ion to
thnh. C 2 trng hp cn xt:

172

- lon kim loi trung tm thng l nhng nguyn t kim loi nng, theo thuyt
Bronsted chnh l nhng axit c kh nng nhng H+, ngha l c th kt hp vi OHca nc to thnh cc baz lin hp tng ng yu t tan, bi vy mi trng pH
cao - mi trng kim - phc cht c th b phn hy. V d: Na3[Co(NO2)6] 3Na+ +
[Co(NO2)6][Co(NO2)6]3
^ 6NO2 + Co3+ Co3+ + 3OH- ^ Co(OH3) Do cn bng (II) chuyn dch t tri sang phi
ko theo cn bng (I) chuyn dch t tri sang phi.
- Mt khc cc phi t l phn t hay anion, theo thuyt Bronsted c th l nhng
baz c kh nng nhn H+ to thnh axit lin hp tng ng yu. Bi vy trong mi
trng axit phc cht c th b phn hy.
V d:
[Ag(M3)2]+ Ag+ + 2NNH3
^ 2NH3 + 2H+ p 2NH+
9 ^
Do cn bng (IV) chuyn dch t tri sang phi ko theo chuyn dch cn bng (III)
t tri sang phi.
Qua s kho st trn r rng mi phc cht ch tn ti v bn trong dung dch mt
khong gi tr pH xc nh.
* Cu t ca ni cu kt hp vi mt cht khc to thnh mt hp cht t
tan.
Trong trng hp ny nu mt cht c tc dng kt hp vi ion trung tm hay vi
cc phi t to thnh mt cht t tan, nu cho mt lng ln th phc cht c th b
phn hy hon ton.
V d:
- Phc cht [Ag(NH3)2]+ s b phn hy nu cho mt lng KI ln v:
[Ag(NH)2]+ s 2NH3 + Ag+ r
Ag+ + ^ Agl
V I- kt hp Ag+ to thnh Agl t tan lm cn bng (II) chuyn dch sang phi ko
theo cn bng (I) chuyn dch t tri sang phi.
3- Phc cht [Fe(SCN6)] s b phn hy nu cho mt lng AgNO3 ln:
[Fe(sCN)]3- Fe3+ + 6SCN-6AgNO3 6NO3- + 6Ag+ 6Ag+ + 6SCN- ^ 6AgSCN ^ V
Ag+ kt hp vi CNS- to thnh AgSCN t tan lm cho cn bng (IV) chuyn sang
phi ko theo cn bng (III) chuyn dch t tri sang phi.
* Cu t ca ni cu kt hp vi mt cht khc to thnh mt phc cht khc
bn hn.
Nu cho mt cht vi mt lng ln c th kt hp vi ion trung tm hay vi cc
phi t to thnh mt phc cht khc bn hn th phc cht trc c th b phn hy.
V d: Nu cho mt lng ln KCN vo dung dch [Cu(NH3)4]2+ th phc
s b phn hy hon ton do to ra phc cht mi [Cu(CN)4] bn hn.
2[Cu(NH3)4] + + 10CN- u 2[Cu(CN)4] + (CN)2 + 8NH3
3-

3-

-14

Kkb = 4,6.10
dch phc cht [Cd(NH3)4]-28

Kkb = 5.0Nu cho mt lng CuSO4 ln vo dung

173

+ th
phc cht s b phn hy to thnh phc cht [Cu(NH3)4] bn hn.
[Cd(M3)4] + + Cu2+ ^ [Cu(NH3)4] + + Cd2+
Kkb = 8,96.10-8 Kkb = 4,6.105.2. Thuc th hu c.
2+

Thuc th hu c u tin c tm ra do Ilinsky vo nm 1884 l cht nitrozonaphtol xc nh Co-14

2
+, n tc dng vi Co2+ cho ta mui ni phc c mu nu c trng. Sau vo
nm 1905 Sugaep tm ra imetylglioxim lm thuc th pht hin Ni2+ m ngy nay
cn ng dng xc nh nh tnh v nh lng niken.
Do s pht trin ca l thuyt ha hc hu c, ngy nay ngi ta hiu c c
ch nhiu phn ng c s tham gia ca cht hu c v dn dn tng hp c nhiu
thuc th c nhiu c tnh qu bu, p dng c hiu qu vo ha hc phn tch. Vic s
dng thuc th hu c tr thnh ph bin v khng th thiu i vi ngnh ha hc
phn tch hin i.
Theo nh ngha ph bin nht th:
Tt c cc cht hu c ng dng trong ha phn tch nh tnh cng nh nh
lng tm hay xc nh, phn chia hay lm giu cc nguyn t gi l thuc th
hu c.
a s cc thuc th hu c dng trong ha hc phn tch l nhng cht in ly yu
v do phn ng gia chng vi cc ion kim loi cng l cc phn ng thuc loi ion.
Ta thng gp cc loi phn ng sau: 5.2.1. Cc phn ng ca thuc th hu c.
144.
Phn ng to cc hydroxyt hoc cc mui kh tan.
V d cc baz hu c nh piridin C5H5N, a-picolin C6H7N trong nc c phn ng
baz: C5H5N + H2O ^ C5H5NH+ + OHDo khi tc dng vi mt s ion kim loi th
cho kt ta hydroxyt. Cc anion ca mt s axit hu c nh oxalat C2O42, tatrat to c mui t tan vi mt s ion kim loi. V d: C2O42- cho kt ta CaC2O4:
Ca2+ + C2O42- ^ CaC2O4
145.
Cc phn ng to thnh sn phm oxy ha - kh.
tm mt s ion kim loi, i khi ngi ta dng mt s thuc th hu c c kh
nng tham gia phn ng oxy ha - kh vi cc ion to nn cc sn phm c mu
c trng. V d nhn ra ion Fe3+ c th dng phn ng vi benzidin l mt baz hu
c, n c th b ion Fe3+ oxy ha to thnh diphenylbenzidin tm.
146.
Phn ng to phc.
y l loi phn ng c nhiu ng dng quan trng nht. C th chia cc phn ng
to phc gia thuc th hu c v ion kim loi thnh 2 loi:
* Phn ng to phc thng.
* Phn ng to thnh ni phc. y l nhm thuc th hu c ln nht v
quan trng nht.
V d:
- Phn ng to cc ni phc khc:
- Phn ng Sugaep tm Ni2+ bng dimetylglyoxim to mui ni phc dimetylNiCl2 + 2NH3 + 2
glyoximat Ni:

174

CH - NH2
2 1 C H - NH 2
etylendiamin
3CgH4

H3

COOH OH
axit salixilic
+ C0CI2 ->

+ Fe3+

CI
2

2
1

Co
CH2 -NH 2
'/2

Cloruaetylendi
amino Co (II)
3Fe
COO
CH,
O
axit
ferisalixilic

+
3H+

175

5.2.2. c tnh ca thuc th hu c

Khi chn thuc th hu c dng vo mc ch phn tch, ngi ta ch n cc c
tnh sau:
147.
Tnh ring bit ca thuc th
C nhiu thuc th hu c khi tc dng vi cc ion v c trong iu kin nh nhau
u cho phn ng gn nh nhau. V d: 8-oxy quinlin, piridin, loi nh vy gi l thuc
th khng c tnh ring bit. Tri li c mt s thuc th c tnh ring bit cao, n c kh
nng cho phn ng c trng vi mt hay mt s nguyn t khi c mt cc nguyn t
khc. V d: tinh bt pht hin it (cho mu xanh c trng). Tuy nhin loi thuc th
c tnh ring bit cao ny kh him.
Ngi ta c th chn iu kin thch hp s dng thuc th hu c c tnh ring
bit thp hn nhm xc nh mt s cht khi c mt mt s cht khc. Cch lm nh vy
gi l s dng tnh chn lc ca thuc th hu c.
148.
nhy
nhy ca thuc th hu c th hin hiu qu phn tch ca thuc th, trong iu
kin tin hnh phn ng thuc th hu c thng c nhy cao hn hn so vi cc thuc
th khc. V vy mc d mt thuc th c chn lc km nhng nhy cao cng c
s dng tt cho mc ch phn tch. Ngi ta thng dng khi nim nng tm c
ti thiu v pha long gii hn c trng cho nhy ca thuc th hay ca phn
ng.
Ta gi lng ti thiu tm c l lng nh nht ca cht nghin cu (cn pht
hin) c th pht hin c bng thuc th tng ng iu kin phn ng ti u v c
o bng microgam (1|J, = 10-6gam). Cn nng pha long gii hn l t l gia khi
lng ca cht ha tan trn khi lng dung mi nh nht cn c th pht hin c bng
thuc th tng ng trong iu kin ti u.
V d: Thuc th albrn tm brili c pha long gii hn l 4.10-7, ngha l
nu pha long 1gam brili trong 107 gam nc vn cn pht hin c bng thuc ny.
5.2.3. C ch tng tc ca thuc th hu c
y chng ta nghin cu ch yu c ch tng tc ca nhm thuc th hu c to
cc ni phc, c bit i vi thuc th hu c to mui ni phc.
Khi nghin cu ngi ta thy rng mt thuc th hu c phn ng c vi mt s
ion nht nh to mui ni phc l do cu to phn t ca thuc th hu c v iu
kin tin hnh phn ng.

176

5.2.3.1. Cu to ca thuc th hu c.
Kt qu tng tc ca thuc th hu c vi cc ion c quyt nh bi 2 phn
trong phn t ca chng:
* Mt phn ca phn t quyt nh s tng tc vi ion ny hay ion khc gi l
nhm chc phn tch (hay nhm nguyn t c trng).
* Mt phn khc c nh hng n sn phm phn ng gi l phn gy hiu ng
phn tch (nhm hot phn tch).
*Nhm chc phn tch
Khi gn thm vo trong phn t ca mt hp cht hu c (khng c kh nng phn
ng vi ion cho) mt nhm nguyn t "c bit" th c th lm cho cht tr nn c
kh nng phn ng. S c mt ca nhm l "nhm chc phn tch". Trong nhm
chc phn tch c hai nhm nguyn t nm cnh nhau.
- Nhm to mui: trong nguyn t H c th cho cation kim loi thay th c
to lin kt ha tr nh nhm cacboxyl -COOH, nhm oxym =NOH, nhm nol
R
hydrxyl -OH, nhm sunfo -SO3H. nhm amin bc 1 -NH2, bc 2 -NC" , ...
H
- Nhm to lin kt phi tr: Trong nguyn t N nh trong =NOH, -NH2,
, -Ne ,N ^ ... nguyn t O nh trong -OH, = CO, ... c th to lin kt phi tr v H
cc nguyn t cn tha mt hay nhiu cp e - t do, lin kt ny thng c biu
din bng mi tn hoc ng chm.
V d nhm chc phn tch i vi Ni2+
-C=NOH -C=NH
v
C NOH
C NH
V d: CH3 _ C =^^1
O
H ^\/phi tr
OH

_ 7CH3-C"N(XA 1 +
L

I2
ti OH

*Nhm hot tnh phn tch: C cc nhm ch yu sau:

- Hiu ng trng lng: Lm cho mui ni phc c to t tan hn. V d:
+ Cupferon (phenyl-nitrozo-hydroxyl amin) v nes-cupferon u to c mui
ni phc t tan vi Cu2+ v Fe3+ nhng nes-cupferon lm kt ta hon ton hn v nhn
naphtalen gy nn hiu ng trng lng.
ONH
(Q)-N- O - NH4
4
NO
nes-cupferon
N
NO
cupferon

+ Alizarin v alizarin S u to mui ni phc t tan vi Al3+ nhng Alizarin S lm

kt ta hon ton hn v n c gn thm nhm -SO3Na.
O OH

AVV
O

O OH

OH

rnVSr

OH
SO3Na

alizarin S

alizarin O

* Hiu ng tr mu: Nu a vo phn t thuc th hu c khng mu no mt

nhm mang mu th phn t thuc th hu c tr thnh c mu v sn phm ca n
cng mang mu.
V d: nhm (CH3)2N-C6H4- lm tng hiu ng mu cho thuc th nhn piridin,
quinolin.
* Hiu ng chn lc: Nu gn thm vo phn nhn nhng nhm th mi c th gy
ra nhng hiu ng lm thay i tnh chn lc ca thuc th.
V d: Trong mi trng axit v c, axit phenylarsonic (C6H5 -AsO3H2) kt ta
c vi Zr4+, Sn4+, Hf4+, Nb5+, Ta5+, Ti4+ nhng nu gn vo v tr octo mt nhm
-NO2 to thnh axit Octonitro phenylarsonic th ch kt ta c vi Sn4+.
OH OH I I H()-As= O H()-As=()

rN
Axit phenylarsonic

Axit Octonitrophenylarsonic
5.2.3.2. nh hng ca iu kin tin hnh phn ng.
iu kin tin hnh phn ng c nh hng ln n tnh chn lc, quan trng nht
l iu kin pH ca mi trng.
C nhng thuc th hu c c kh nng tc dng c vi rt nhiu ion to thnh
mui ni phc, nhng khi thay i mi trng thch hp th kh nng b hn ch. Do
, c th chn mi trng thch hp lm tng tnh chn lc ca thuc th hu c.
V d: Dimetylglyoxim trong mi trng amoniac th phn ng c vi niken,
vanadi nhng trong HCl 2N th ch tc dng vi vanadi. 5.2.4. Mt vi loi thuc th
hu c thng gp trong ha phn tch.
Cc thuc th hu c l dn xut ca amoniac c tnh cht gn nh amoniac c
dng iu chnh pH, lm cht che. Cc cht thng dng l piridin C5H5N, pycolin
C6H7N. Cc cht ny c tnh baz yu hn amoniac nhiu. Cng nh amo-niac, chng
to c phc bn vi nhiu kim loi, v d: Ag+, Cd2+, Ni2+, Co2+, ...
- Axit etylendiamintetraaxetic (EDTA thng c gi l complexon II) l mt axit 4
chc:
HOOC CH2
> N - O2 - O2 - N\
HOOC - CH2

O2 COOH
N

O2 - COOH

no
Thuc th ny c kh nng to phc bn vi hu ht cc ion kim loi theo t l
1:1.
* Ditizon:
S=C

/ NH - NH- CH
x

N = N- CH
to phc vi mt s ion kim loi nh: Pb2+, Cu2+, Zn2+, ...
* Dimetylglyoxim cha 2 nhm oxim:
CH3- C . C- CH3 li
li
HON NOH
l axit yu, to kt ta kh tan vi ion Ni2+, Pb2+, to phc mu tan trong nc
vi ion Fe2+.
* Oxim (8 oxyquinolin) C9H6NOH:

OH
Oxim (8-oxyquinolin) C9H6NOH c tnh lng tnh, to c hp cht ni phc
kh tan vi nhiu ion kim loi. Bng cch iu chnh mi trng pH thch hp, dng
cht to phc ph c th dng oxim tch c nhiu kim loi khc nhau.
* Thuc th to thnh "sn" mu: Mt s thuc th hu c b hp ph vo b mt
cc hydroxit kim loi t tan v thay i mu. Bn cht ca s hp ph ny l s to phc
cng cua gia thuc th v ion kim loi nm trong hydroxit.
V d: Alizarin S to vi nhm "sn" mu do hnh thnh hp cht ni phc
c cu to:
OH OH \ /
AI
/
O O

l VOH
T.
KJSO3Na
Rodamin B to phc SbCl6-HR+ mu tm vi Sb(V) chit c bi benzen:
(C2H5)2N^vV-|= N+(C2H5)2C

rrO

* Nes-Cupferon to phc t tan vi Cu

2

OH

+ v Fe +:
N=O
U-N-ONH

5.3. ng dng ca phc cht v thuc th hu c trong ha phn tch.

149. Pht hin v xc nh ion.
V d: Khi phn tch nh tnh h thng cation nh:
* Tm Al3+ bng alizarin S trong mi trng kim (pH = 9).
* Tm Sb5+ bng rdamin B trong mi trng HCl m c dng mui ni phc
mu tm hoa sen.
* Tm Ni2+ bng dimetylglyoxim trong mi trng dung dch NH3 dng mui ni
phc mu ti ...
Dng iu ch dung dch m, v d hn hp m formiat biphtalat.
Nhiu ion n gin khng c tnh c trng r rt, v vy t c ng dng phn tch.
Tuy vy khi chuyn thnh phc thch hp th li rt c trng v c th s dng nhn
ra ion . Chng hn nh ion Cu2+ c mu xanh nht v khng th nhn ra c khi c
nng thp, tuy vy khi chuyn thnh phc [Cu(NH 3)4]2+ th n s c mu xanh m
v c th pht hin ra d dng hn.
Trong phn tch nh lng dng lm cht kt ta trong phn tch khi lng. V
d xc nh Ni2+ bng dimetylglyoxim, Al3+ bng 8-oxyquinolin ... Dng lm cht gc
trong phn tch th tch, v d H2C2O4.2H2O c lm cht gc cho phng php trung
ha v oxy ha-kh ... Dng iu ch dung dch chun nh trilon B.
150. Che du.
Trong thc t rt t thuc th hon ton chn lc, ngha l ch tc dng vi mt ion
nht nh m thi m thng cho phn ng ng thi vi mt s ion kim loi. Ta ni
rng cc ion ny cn tr ln nhau. V vy tm mt ion no trong dung dch c cc
ion cn tr khc cn phi "che" chng li bng mt phn ng to phc bn c trng.
V d, phn ng tm Co2+ bng thuc th NH4SCN to thnh phc [Co(SCN)4]2mu xanh trong axeton hoc te b cn tr mnh bi ion Fe 3+ v ion ny to c phc
mu m vi ion sunfoxyanat (Fe(SCN)3). Do nhn ra ion Co2+ cn phi "che"
ion Fe3+, chng hn bng cch thm vo dung dch mt lng ln H3PO4 hay F- th
Fe3+ s dng phc bn [Fe(HPO4)+] hay [FeF6]3- khng mu. Cht c a vo trong
mi trng phn ng nhm mc ch lm trit tiu hoc km hm mt phn ng khc
no c gi l "cht che". Cht che em s dng phi l cht c kh nng to c
vi cc ion cn tr phc c bn ln cc ion khng cn tc dng vi thuc
th s dng cho ion cn xc nh, ngc li bn ca phc gia ion cn xc nh vi
cht che (nu c) phi tng i b ion ny cn kh nng tham gia phn ng c
trng vi thuc th s dng. Ngoi ra cng cn phi ch ti iu kin l phc to
thnh gia cht che vi ion cn tr khng c gy kh khn cho vic phn ng gia
ion cn xc nh vi thuc th c trng s dng.
Bi ton gii quyt vn chn iu kin che ti u cho mt phn ng no

180

l kh phc tp. y phi gii quyt mt lot cc mi quan h gia cc bn ca cc

phc khc nhau vi pH, vi nng ca cc cu t trong dung dch.
V d: Khng th dng ion oxalat che ion Fe 3+ trong phn ng tm ion Co2+ di
dng phc sunfoxyanat bi v theo kt qu tnh ton th phc st (III) sun-foxyanat b
ph hy gn nh hon ton khi c ion C2O4 . Khi c mt ca C2O4 th ch cn 6% phc
coban sunfoxyanat tn ti trong dung dch, cn 94% lng ca n b phn hy v
chuyn thnh phc oxalat. Trong thc t ngi ta thng dng NaF lm cht che v ion
F- to phc kh mnh vi ion Fe3+ trong khi phc ca n vi ion Co2+ li rt t bn.
151. Thay i cng cc cht.
Cn phi k n s nh hng ca s to phc ln tnh axit baz v tnh oxy hakh ca hp cht. Nu anion ca mt axit yu no m to phc vi cation khc th s
lin kt gia n v ion H+ s yu i, v nh vy ta s c axit mnh hn axit u.
V d: Tnh axit ca axit oxalic (H 2C2O4) s tng ln nu c Mg2+ v ion ny to
phc vi C2O4 .
Axit borc s mnh ln nu c mt cc ru a chc nh glyxrin hoc manit bi
axt borc to nhng axt phc vi chng l axt manitoborc HBO 2[C6H8(OH)6]2 hay
glyxrinoborc HBO2[C3H5(OH)3]2. Cc axt ny mnh hn axt borc nhiu.
V vy trong phn tch nh lng, khi nh phn hn hp HCl v H 3BO3 thng
ngi ta cho vo mt t glyxrin v chun vi ch th phenolphtalein.
i vi cht oxy ha v cht kh th thng thng yu i khi c s to phc bi
v nng ca chng b gim i. V d ion Fe 3+ mt hn kh nng oxy ha ion I -n I2
khi c ion F-. H2C2O4 b gim kh nng kh xung khi c tha axit molipden v MnO 4
khng oxy ha c n.
152. Ha tan v tch.
S to phc c th c s dng chuyn kt ta vo trong dung dch:
HgI2 + 2I- = iHgI2]2" Hoc s dng tch. V d tch Cu2+
2+
v Ni nhm V ra khi nhm IV trong hn hp.
2-

2-

2-

181

Kt ta hydroxyt
nhm V, IV v
MnO2

Kt ta nhm
. +

NH4O^ IV v

MnO

Dung dch [Me(NH3)4]

ca nhm V

2+

182

Me : cation ca nhm V: Cu2+, Ni

Theo phn ng: Cu(OH)2 + 4NH3 ^ [Cu(M3)4] + + OH-5.4.
Chun to phc
Phng php chun phc cht l mt phng php phn tch th tch da vo
phn ng to phc bn. Yu cu ca cc phn ng to phc:
* Phn ng phi nhanh v hon ton.
* Phn ng phi xy ra theo ng t lng nht nh.
* Phi c kh nng xc nh c im tng ng.
V vy ch c mt s phng php ch yu sau:
2

183

153. Phng php thy ngn

Da vo phn ng to phc cht gia Hg 2] vi cc anion halogenua, CN-, CNSv.v... vi ch th diphenylcacbazit hay diphenylcacbazon trong mi trng pH thch hp.
V d:
Hg2+ + Cl- ^ HgCl+
K1 = 5,5.106
Hgcl+ + Cl ^ HgCl2 K2 = 3,0.106
Hgcl2 + Cl- ^ HgClV K3 = 7 HgCl3- +
Cl- ^ HgCl42- K4 = 10
Hai phn ng sau khng c gi tr nh lng v yu m thc t ch da vo 2 phn
ng u m thi.
154. Phng php xyanua
Da vo s chun dung dch xyanua bng dung dch AgNO3 to phc cht
[Ag(CN)2 ]: '
2CN- + A Ag+ ^ [Ag(CN)2 ]
Nu tha Ag] th li to ra kt ta:
Ag(CN)2- + Ag+ ^ Ag[Ag(CN)2]l c T = 10-12 9 Nh vy ta s kt
thc chun khi bt u thy dung dch vn c kt ta
Ag[Ag(CN)2].
C th da vo phng php ny chun gin tip mt s ion kim loi, c
bit l Ni2], Co2], Cu2] v Zn2] v chng c th to c vi CN- nhng phc cht bn hn
Ag(CN)2 v phn ng xy ra theo mt quan h t lng xc nh. V d nu cho d CNvo dung dch Ni2] trong amoniac th ton b Ni2] s dng phc cht [Ni(CN)4] bn hn
Ag(CN)2 do c th chun lng tha CN- bng phng php trn.
155. Phng php complexon
Da vo phn ng to mui ni phc gi l complexonat xy ra gia com-plexon
v hu ht cc ion kim loi. Phng php ny c phm vi ng dng rng ri, c nhy
v chnh xc rt cao. Hin nay n l phng php ph bin nht.
5.4.3.1. Cu to ca cc loi complexon.
Complexon l nhng dn xut ca axit aminopolycacboxylic, c 3 complexon
quan trng thng dng nht l:
Complexon I: l axit nitriltriaxetic (NTA), k hiu H3Y cn gi l trilon A
-

2-

CH2 COOH
N^-CH2 COOH c M = 191,1
CH2 COOH
Complexon II: l axit etylendiamin tetraaxetic (EDTA) k hiu l H 4Y c M =
292,1, t tan trong nc.

c _____

^ NCH2 CH2 N
HOOC CH 2
CH2 COOH
Complexon III: (vn quen quy c l EDTA) l mui dinatri ca axit H4Y, k
hiu Na2H2Y, tn k thut l trilon B c M = 336,2.

184

HOOC CH2

CH COONa

^>N CH2 CH 2NC ____________

NaOOC CH2 CH2COOH
Trong phn t ca cc complexon u c:
* Nhiu nhm -COOH: C tnh axit nn cc complexon l cc a axit. Cc hng s
axit KA ca chng nc u thng ln v gn nhau nn dung dch ca chng c tnh
axit mnh. Cn cc KA cc nc sau nh nn trong dung dch thng c pH cao mi tn
ti c cc ion cui. V d EDTA c K 1 = 10-2, K2 = 10-2,76, K3 = 10-6,16, K4 = 10-10,26,
pH = 2,2 tn ti dng H 3Y-; pH = 4,3 tn ti dng H 2Y ; pH = 8,3 tn ti HY 3-; pH =
12,4 tn ti Y
* Nguyn t O trong nhm COOH c kh nng to lin kt cng ha tr vi ion
kim loi: Nguyn t N trong nhm amin c kh nng to lin kt phi tr i vi ion
kim loi. Do complexon c kh nng to mui ni phc vi hu ht cc ion kim loi.
V d vi Ca2+ complexonat Ca
^2^Y + Ca2+ ^ Na2CaY + 2H+
Na2H2Y c cu to:

NaOOC CH2
CH2 COO
<rN CH2 CH2 N\
OOC CH2
CH2 COONa
2

t
Ca
5.4.3.2. S to thnh cc complexonat.
V d phn ng gia complexon III v ion kim loi Men+
Me2+ + H2Y2^ MeY2- + 2H+
Me3+ + H2Y2 MeY- + 2H+
Me4+ + H2Y^ MeY + 2H+ T cc phng
trnh trn, ta thy ni bt ln 2 c im:
* Phn ng theo t l 1:1 tc l 1 ion kim loi (bt k ha tr my) kt hp vi 1
ion complexon to thnh 1 ion complexonat nht nh - iu ny rt c bit khc vi
phn ln cc phn ng to phc cht khc. T t l 1:1 cho php ta xc nh lng ion
kim loi mt cch chnh xc.
* Trong cc phn ng trn, ta thy lun gii phng ra H + nn s lm cho mi
trng thnh axit mnh, nh hng n bn ca complexonat c to ra. Do ta
phi duy tr phn ng trong mi trng dung dch m.
Tnh cht qu gi nht ca cc complexon l kh nng to complexonat ngay c
vi cc ion kim loi kim th: Mg, Ca, Ba, ... Cc kim loi ny nh ta bit rt kh
hoc khng th chuyn thnh hp cht phc bng cc cch khc c. Phn ln cc
complexonat kim loi thng rt bn, tc l hng s to thnh kh ln. Thng bn
ca complexonat tng theo in tch ca ion kim loi: Me+ < Me 2+ < Me3+ < Me4+ th
hin ch complexonat Me4+ c th tn ti pH = 1, Me 3+ -- pH = 1^-2, Me2+ ch tn
ti trong mi trng kim. Ni chung cc complexonat thng bn

185

trong mi trng c pH cao v xc nh, nhng vi pH cao qu th complexonat b phn

hy to thnh hydroxyt t tan:
Me+ + nOH- ^ Me(OH)n B i
vy phi tin hnh phn ng trong mi trng m.
Cc complexonat d tan trong nc hn complexon tng ng. Trong cc complexonat kim loi th Na2CaY l t tan nht.
Complexonat ca ion kim loi mu th s c mu m hn, ca ion kim loi khng
mu th s khng mu. 5.4.3.3. Chun bng complexon
* Cht ch th trong phng php complexon
xc nh im tng ng trong phng php ny ngi ta dng cc ch th
nh oxy ha - kh, axit - baz, ch th kim loi nhng ph bin nht l ch th mu kim
loi. l nhng cht hu c c mu c th kt hp vi ion kim loi to thnh mui ni
phc kh bn, tan trong nc, c mu khc vi mu ca cht ch th kim loi dng t
do. Cc cht ch th mu kim loi thng l nhng axt hu c yu hoc baz yu, phn
t ca chng cha nhng nhm mang mu v tr mu nn cng l nhng cht ch th
pH. Do c im k trn, mu ca cht ch th loi ny bin i theo pH ca dung dch.
Cc cht ch th kim loi phi t c cc yu cu sau :
* Phi nhy v kh chn lc, nng ca cht ch th em dng phi nh nht c
th c.
* Phc cht c to ra gia cht ch th v ion kim loi phi kh bn nhng km
bn hn complexonat kim loi (t nht l 104 ln).
* Phn ng to phc gia cht ch th v ion kim loi (cn xc nh) phi kh nhanh
v thun nghch.
- S i mu ca cht ch th phi kh r c th nhn ra c bng mt. V d:
nh phn dung dch Me2+ bng Na2H2Y dng ch th kim loi Ind- (mu A).
+ Trc nh phn: Ta cho mt lng nh cht ch th, s c phn ng:
Me2+ + Ind- ^ [MeInd]+ dung dch c mu B phn ln
2+
Me trng thi t do v lng cht ch th cho vo rt nh.
+ Khi nh phn th Me2+ (t do) s kt hp vi thuc th Na2H2Y:
Me2+ (t do) + H2Y2- ^ MeY2- + 2H+ + Kt thc nh phn th nh
mt git cui cng Na2H2Y phn hy [MeInd]+ gii phng ra Ind-, theo phn ng:
[MeInd]+ + H2Y2- ^ MeY2- + 2H+ + Ind-mu
A
* Cc cht ch th quan trng thng dng trong chun complexon.
+ Eriocrmen T (ET.OO): c ng dng nhiu nht, v n c th xc nh trc
tip phn ln cation thng thng v mt s anion. y l cht mu az, l mui natri
ca axit H3Ind:

186

OH

187

OH

HO3 S"ON = N~f|p]

(H3
nd)

188

NO2 Trong dung dch n tn ti dng anion, k hiu: H2Ind-ET.OO c

tnh cht ca mt cht ch th axit - baz 3 mu, theo s sau:
pKi = 6,3

pK2 = 11,5 _

H2In- ^ HInd-2 ^ Ind-3

xanh
a cam
pH = 6: ch th c mu dng H2Ind pH = 7 - 11: ch th c mu xanh dng HInd-2
pH > 11,5: ch th c mu vng dng Ind-3 mi trng kim yu pH = 7 -- 11, ET.OO
c th kt hp vi Mg2+ v mt s cation kim loi khc to thnh ni phc c mu
mn theo phn ng:
Mg2+ + HInd2- MgInd- + H+
Ch :
2+

2+

2+ 3+

* Mt s ion kim loi nh Co , Ni , Cu , Al , ... kt hp vi ET.OO to thnh phc

cht bn hn complexonat tng ng nn khng nh phn trc tip c. S c mt
ca chng s lm cn tr vic nh phn trc tip cc ion khc, ch c Fe 3+, In3+, Se3+,
Sn4+, Th4+ c chun trong mi trng axit v to phc bn vi com-plexon.
* Mt s ion kim loi nh Pb, Hg, In, Ga, ... kt hp vi ET.OO to phc cht mu
qu nht nn cng khng chun trc tip c.
* Ion Fe3+ lm cn tr php chun bng complexon.
* Ion Mn2+ trong mi trng kim d b oxy ha thnh Mn3+ v Mn4+ s phn hy
cht ch th. Tuy nhin, c th thm cht ch th thch hp (nh axit ascobic, hydroxylamin) ngn chn s oxy ha Mn2+ v c th chun gin tip c.
+ Murext l mui amoni ca axit pupuric C8H5O6N5, c k hiu l H4Ind-.
Trong mi trng c 0 < pH < 9 murext c mu tm dng H3Ind2-; pH > 11 murext
c mu xanh dng H2Ind3-. Trong mi trng kim mnh (pH > 12) murext kt hp vi
Ca2+ to thnh phc mu theo s :
2+

Ca + murexit 5=* [Ca - murexit]

xanh tm
Ch :
Murexit l ch th kim loi thng dng xc nh Ca 2+ trong dung dch NaOH,
xc nh Cu2+, Ni2+, Co2+ trong mi trng amoniac. Cn cc ion kim loi khc to vi
murexit thnh nhng phc cht khng bn nn khng c gi tr trong phn tch . Sr 2+,
Ba2+, Mg2+ cng tc dng yu vi murexit do c th xc nh c Ca 2+ trong dung
dch hn hp Ca2+, Sr2+, Ba2+, Mg2+.
* Cc cch chun .
+ Chun trc tip.
Cho hn hp m thch hp vo dung dch phn tch, sau cho rt t cht ch

189

th tng ng (ch th thng c dng di dng dung dch hay tinh th trn ln vi
NaCl hay KCl, nhng di dng dung dch khng bn nn dng di dng kh c
trn ln vi t l ch th: NaCl hay KCl = 1:200 hay 1: 500. Khi chun ly khong 20
- 30 mg hn hp ny). Dung dch lc s c mu ca phc cht to thnh bi ion kim
loi vi cht ch th. Sau nh phn bng dung dch chun com-plexon ti gn ti
im tng ng cht ch th c gii phng ra dng t do.
V d: Chun dung dch Mg2+ bng dung dch chun trilon B trong dung dch
m NH3 + NH4Cl c pH 9 - 10 vi ch th ET OO.
Mg + + ET.OO
[Mg - ET.OO] o
2

mn ( nho)

Mg + + H 2Y ^ MgY + 2H +
2

(t do)

2-

2-

2 2-

[Mg - ET.OO] + HY =^ MgY + 2H + + ET.OO

xanh bic

+ Chun ngc.
Cho mt lng d complexon bit nng chnh xc vo dung dch phn tch
iu kin pH thch hp ri chun lng complexon tha theo cch chun trc tip.
Da vo lng complexon ban u v lng tha ta d dng tnh c lng ion
kim loi cn xc nh. V d theo s :
Men+ + Trilon B (cho d) -- MeYn-4 + Trilon B (tha)
Trilon B tha c chun trc tip bng dung dch chun MgSO 4 hay ZnSO4
vi ch th ET.OO trong mi trng m amoni. Cch chun ngc c dng
khi:
* Phc cht c to ra bi ion kim loi cn xc nh v cht ch th qu bn, bn
hn complexont tng ng.
* Khng c ch th thch hp.
* Phn ng to complexonat qu chm.
* Men+ cn xc nh dng kt ta.
V d: Khng chun trc tip Co2+, Ni2+, Al3+. Khng chun trc tip c
3+
Tl d rng TlY- rt bn nhng Tl3+ khng phn ng vi cc cht ch th thng dng.
Khng chun trc tip c Pb2+ dng PbSO4 hay Mg2+ dng
NH4MgPO4 hay Ca2+ dng CaC2O4.
+ Chun thay th.
Phng php c da vo tnh cht km bn ca complexonat Mg: Na 2MgY.
Ngi ta cho complexonat Mg (thng l d) tc dng vi ion kim loi cn xc nh,
m ion kim loi ny tc dng c vi complexonat thnh MeYn -4 bn hn MgY2-kt
qu ion Mg2+ b y ra ra khi Na2MgY mt lng tng ng theo phn ng:
2-4
2
9 Men+ + MgY ^ MeYn + Mg + ^ sau ta ch vic chun
trc tip lng Mg2+ c gii phng ra bng complexon vi ch th ET.OO trong mi
trng m pH = 9 -- 10. Phng php ny c ng dng khi khng dng c
phng php chun trc tip (tng t nh chun ngc).
V d: HgY2- + Hg2+ ^ HgY2- + Mg2+.

190

BI TP

156. Vit cc cn bng xy ra trong dung dch khi ha tan K4[Fe(CN)6] trong nc.
157. Vit biu thc cc hng s khng bn tng nc v tng cng ca phc gia Bi 3+
v I-, bit rng Bi3+ to phc vi I- c s phi tr cc i l 4.
158. lon Fe3+ to phc vi ion CN- c s phi tr cc i l 6. Hy vit cc cn bng
to phc khi thm dn dung dch KCN vo dung dch Fe3+. Vit cc biu thc biu din
hng s bn tng nc v tng cng ca cc phc .
159. Nng ca dung dch chun trilon B (Na2H2Y) c xc nh theo dung dch
c cha trong 1 lt 24g Fe(NH4)(SO4)2.12H2O. C 10ml dung dch trn th chun ht
10,3ml dung dch trilon B. Hy tnh
N Na H Y . T Na H Y/Fe O v NaHY/CaO
160. Hy tnh nng Ca2+ v Mg2+ (mlg/l) trong dung dch theo cc s liu sau.
xc nh tng lng Ca2+ v Mg2+ ngi ta chun 20ml c cha Ca2+ v Mg2+ vi
ch th ET-OO bng Na2H2Y ht 18,15ml. xc nh ring Ca2+ ngi ta thm vo
20ml dung dch trn 19ml dung dch Na 2H2Y 0,112N lng d Na2H2Y nh phn bng
dung dch CaCl2 0,102N th ht 12ml.
161. Ha tan 0,114g CaCO3 nguyn cht trong HCl v pha long thnh 250ml. Chun
25ml dung dch thu c ht 40,25ml dung dch EDTA. Tnh:
a. Nng mol/l ca dung dch EDTA. b.
chun ca EDTA theo CaO.
c. Tnh cng ca mt mu nc theo s ppm Ca2+ bit rng khi chun 100ml
nc th phi dng ht 6,25ml dung dch EDTA ni trn.
162. Ha tan 0,65g mt mu hp kim ca nhm. Tch b cc nguyn t gy cn tr,
thm nc n 250ml. Ly 20ml dung dch, thm complexonat magi d ri chun
dung dch thu c pH = 9 dng ET-OO lm ch th ht 7,6ml dung dch ETDA
0,1M.
Tnh hm lng % ca Al trong hp kim.
2

TI LIU THAM KHO

163.
Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch,
NXB KH & KT, 2002.
164.
Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc,
2000.
165.
Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002.
166.
Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch,
NXB H&TH Chuyn nghip, 1984.
167.
H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v
Nguyn Huyn dch. NXB KH & KT, 1976.
168.
B.H.AneKceeB, KaniHecTBeHHbi aHani3, MocKBa, H3gaTej[bcTBo
"XiMira",
1972

191

169.
B.H.AneKceeB, KonecTBeHHMH aHani3, MocKBa, H3gaTej[bCTBo
"XiMira",
1972

192

CHNG 6
CN BNG TRONG DUNG DCH CHA HP CHT T TAN. PHNG
PHP CHUN KT TA
6.1. Cn bng trong dung dch cha hp cht t tan. 6.1.1.
iu kin to kt ta - Tch s tan.
Khi cho dung dch NaCl tc dng vi AgNO3, ion Ag+ v Cl" kt hp vi nhau to
thnh AgCl t tan tch ra khi dung dch. Cc ion NO3" v Na+ khng tham gia vo
phn ng kt ta nn cn li tt c trong dung dch. AgCl s ngng kt ta khi t n
cn bng.
Ag+ + Cl" ^ AgCl ngha
l khi tc kt ta bng tc ha tan.
Tc kt ta t l vi din tch b mt S ca kt ta tip xc vi dung dch v
vi hot ca cc ion kt ta. Tc ha tan ch t l vi b mt S ca kt ta tip xc
vi dung dch.
VKT = Ki Ag . Cl" . VHT = K2.S
VKT v VHT l tc kt ta v tc ha tan. a + v
aQ- l hot ca Ag+ v Cl"
a

Khi t n cn bng VKT = VHT ngha l: K1aA + . aCl" . S = K2.S

T suy ra: a + .a

K
=

TACl: gi l tch s tan ca AgCl.

1
i vi cc cht t tan c cng thc BmAn, tch s tan ca chng l:
B A = B A y hot ca B phi ly tha ln m v hot ca A phi ly tha
ln n v BmAn tan trong dung dch theo phng trnh:
(6.1)
BmAn ^ mB
r
r
n
+ + nAm"
Nu ngoi ion do cht rn tan ra khng c ion no khc th lc ion ca dung dch
s nh, h s hot xp x bng 1 nn c th coi hot bng nng , v tch s tan
bng: TB A = [B]m .[A]n (6.2)
K

.a

H thc ny l ni dung ca quy lut tch s tan. Theo quy lut ny th:
* Khi TB > [B]m.[A]n, tc l tc phn ng ha tan ln hn tc phn
ng to thnh kt ta, A v B khng kt hp c vi nhau thnh kt ta. Dung dch
iu kin ny gi l dung dch cha bo ha i vi BmAn v nu thm BmAn vo
dung dch ny th n c th tan thm n khi t cn bng, tc l khi:
B A *
Khi TB A = [B] [B] .[A] .
m
n
.[A] , tc l tc ha tan bng tc kt ta, kt ta khng
tan thm v cng khng to thm. Dung dch iu kin ny c gi l dung dch bo
ha, v thm BmAn vo dung dch ny th n s khng tan thm.
A

193

* KhiTB < [B]m.[A]n, tc l tc kt ta ln hn tc ha tan, A v B s kt

hp vi nhau thnh BmAn lm gim nng ca A v B n khi T BmAn = [B]m.[A]n th
phn ng li t cn bng. Dung dch ny gi l dung dch qu bo ha.
Mt kt ta c th c dng trong ha phn tch khi n t tan v tinh khit. V vy
cn xt n cc yu t nh hng n tan v lm kt ta ko theo tp cht. 6.1.2.
Quan h gia tan v tch s tan. Cc yu t nh hng n tan. 6.1.2.1. tan v
tch s tan.
tan (S) ca mt cht l nng mol/l ca cht trong dung dch bo ha
nhit nht nh. Tch s tan ca cht l tch s hot ion ca n trong dung dch
bo ha. Ngoi ra, tan c th c tnh bng g/lit hoc mg/lit. tan ph thuc vo
nhit . Tch s tan v tan u l cc i lng c trng cho dung dch bo ha nn
c th tnh tch s tan t tan hay ngc li.
V d 1: Tnh tch s tan ca Mg(OH)2 200C, bit rng 100ml dung dch bo ha
nhit ny cha 0,84mg Mg(OH)2.
Mg(OH)2 phn ly theo phn ng: Mg(OH)2 ^ Mg2+ + 2OH (6.3) Vy: TM ) = a
+ .a2 = [Mg + ].f + .[OH-] .f
J
Mg + OH
Mg +
OH tan ca Mg(OH)2 bng: S =
0,84.1000
-4
= 1,44.10 mol/lit
1000.58,32.100
Theo phng trnh (6.3) mi phn t Mg(OH)2 phn ly cho ta mt ion Mg 2+ v hai
ion OH".
A

OH

Mg(OH)

&

Vy: [Mg2+] = 1,44.10"4 M v [OH"] =

2.1,44.10"4 M = 2,88.10"4 M Lc ion
ca dung dch bng: -2(4.1,44.10- +
4

2,88.10- ) = 4,32.10Vy 1g f =4

2+

0,5.^4,32.10=-0,0416 f + = 0,91; f = 0,98

4

Mg2+

t2+ =

'

'

OH- '

1,44.10-4.0,91 = 1,31.10Mga

- =

2,88.10-

2+

-4

.0,98 = 2,84.10OH
Tch s tan ca Mg(OH)2 l: TM = 1,31.10"4
.(2,84.10"4)2 = 1,1.10"i vi cht t tan, nng ion trong dung dch bo ha rt
nh nn c th coi h s hot f = 1, tc l coi hot bng nng .
Theo gi thit ny thTMg(OH) = 1,19.10 11
ch khc khi c k n hot l 9%.
Ni chung, khi tan khng ln hn 10"4 M hoc l khi tch s tan khng ln hn
10"8 th c th coi f = 1 tnh tch s tan.
V d 2: Tnh tan ca Ca3(PO4)2 trong nc 200C. Bit rng
nhit th tch s tan TCa ( ) = 10Ta c phng trnh phn ly sau:
Ca3(PO4)2 ^ 3Ca(OH)2

11

PO

32,5

194

+ + 2PO43" Nu gi S l tan ca Ca3(PO4)2 th: [Ca2+] = 3S; [PO43"] =

2S. Vy: TCa (PO = (3S)3.(2S)2 = 33.22.SS = ^p^- => S = 1,3.10"5
3

4)2

7(mol/lit)
V S < 10"4 M nn gi thuyt trn coi hot bng nng l ng. Trong trng hp
tng qut, cht t tan c cng thc BmAn, ta c phng trnh phn ly: BmAn 5=*
mBn+ + nAm"
">n+-imr A m"-in _______

____ rT

c\m / o\n _________

m nci(m+n)

195

= [B ] TBmAn (6.4)
[A ] = mm.
(mS) .
(nS) =
mnS;
S = (m+|

196

nn
Cch tnh tan t tch s tan trn y ch c th p dng khi tnh tan trong
nc nguyn cht ca cht rn c ion khng tc dng vi ion ca nc.
Trng hp ny rt him trong thc t v thng phn ng kt ta xy ra trong
dung dch cha nhiu ion khc ngoi ion ca kt ta. Nh vy s c trng hp ion ca
kt ta tc dng vi cc ion khc trong dung dch v s nh hng n tan ca kt
ta.
Ta ln lt xt nhng yu t nh hng n tan ca mt cht t tan. 6.1.2.2. Cc
yu t nh hng n tan ca mt cht t tan.
*nh hng ca lon chung (lon cng tn)
lon chung l ion c trong thnh phn ca kt ta.
Theo quy lut tch s tan th tch s hot ca cc ion ca kt ta trong dung dch
bo ha lun lun l mt hng s nhit nht nh. Nu hot ca mt trong cc
ion tng th hot ca cc ion kia phi gim.
V d: Tnh tan ca BaSO4 trong 0,01M dung dch Na2SO4 v so snh vi
tan ca n trong nc. Bit TB SO = 1,1.10 10.
tan ca BaSO4 trong nc nguyn cht l: S = yj 1,1.10 10 = 1,05.10-5 mol/lt
Trong dung dch Na2SO4 0,01M, tan S ca BaSO4 bng nng [Ba2+]. Vy nng
ca ion SO4 bng tng nng ca SO4 do BaSO4 v Na2SO4 phn ly ra. [SO4 "] = S +
0,01
V tan ca BaSO4 rt b, khi c Na2SO4 li cng b hn nn SO 4 do BaSO4
phn ly ra khng ng k, vy c th coi [SO4 ] = 0,01.
Vy: TBaSO = S(S + 0,01) = 0,01S = 1,1.10 10 ; S = 1,1.10"8mol/lit.
Nh vy tan ca BaSO4 trong Na2SO4 0,01M nh hn trong nc nguyn
2"

2"

2"

2"

cht:

1,05.10

8 = 950 ln
1,1.10 T ta thy tan ca cht t tan b gim i khi thm vo dung dch ca
n cht in ly no c ion cng tn (ion chung) vi cht t tan. V vy kt ta hon
ton ion no th khi tin hnh kt ta, ngi ta thng dng d thuc th (ion chung)
v khi ra kt ta ngi ta cn thm vo nc ra mt t dung dch c cha ion chung,
nh vy gim sai s ca php nh lng
*nh hng ca nhng lon khc lon ca kt ta (lon l)
Cc ion l lm tng tan cu kt ta v s lm tng lc ion ca dung dch, ngha
l lm gim h s hot f trong biu thc tch s tan, do nng ion ca kt ta s
tng lm tng tan ca kt ta, nh hng ny cn gi l hiu ng mui.

197

V d: Tnh tan ca AgCl trong KNO3 0,1M. Bit 258

0
C TAgCl = 1,8.10"10 Trong nc nguyn cht, lc ion qu nh, coi nh f = 1. Do ,
tan ca AgCl l: S =
lgf

1,8.10 10 = 1,34.10 -5M

Trong dung dch KNO3 0,1 M lc ion ln, c th l:

0,5.V
-0,88 ; f = 0,76
S2f 1 + VJ
Nu tnh n h s hot th TAgCl = [Ag + ]f + [Cl- ]f

198

v S
=

AgCl

1,8.10 0""
0,76= 2
1,76.1 5M

(0,1 + 0,1)
= 0,1

199
Vy tan ca AgCl trong nc nguyn cht l: 1,34.10"5 M v tan ca
-5
AgCl trong KNO3 0,1M ln hn trong nc nguyn cht:
- = 1,33 ln.
3
1,34.10* nh hng ca nng li
" Nu anion A"
ca kt ta MAn l gc ca mt dung dch axt yu th trong dung dch s c cn bng:
MAn ==== Mn+ +
nA" nA" + nH+ ====
nHA
tan S ca kt ta bng [Mn+]:
S = [Mn+] (6.5)
v tch s tan ca MAn bng:
T = [Mn+][A"]n (6.6)
nKS
K + [H + ]
tnh S t T ta thay trong (6.6) gi tr [Mn+] = S v [A"] = ' '
1,76.10

v [A- ] = Ca.K m CA = [HA] + [A"] = nS

K [H ] K l hng s phn ly ca HA; K = __A
[HA]

[H+][A-]

200

T = Si n.K.S
K + [H
+]

)K
:
S( K + [H
nS + ]

201

Vy: Sr

(n

+T
n

an

(n
+T
1+
=> S
1)
n
=
Y

[HU
K
(6.7)

V d 1: Tnh tan ca CaF2 trong HCl 0,01M. Bit KHF = 6.10"1)

4
, T = 4.10"11 Thay n = 2, [H+] = 10"2, K = 6.10"4 v T = 4.10"11; ta tnh c: S
= 1,4.10"3 mol/lit
" Nu anion l gc ca a axit th thay gi tr:

202
[Am-]
nK1K2K3...KmS
[H + ] + K1[H + ] - + K1K2K3...Km
,'
_
,
r . 2-, nK,K2S
1 2
Nu m = 2, ta c: [A2- ] =---------2
-------------2
[H + ] + K1[H+ ] + K1K2
m

m 1

203

T=S

nK1K2S Y
^[H + ] + KJH + ] +
K1K2 )
2

204

(n+1)

Vy:
S

T
n

1 +

HH

[H +

(6.8)

]Y
2

K K

1 2)

V d 2: Tnh tan ca CaC2O4 trong dung dch c pH = 4, T = 2.10" 9.

Bit H2C2O4 c K1 = 6.10"2, K2 = 6.10"5. \
(6.9)
(6.10)
Thay cc gi tr tng ng vo biu thc (6.8) ta tnh c: S = 7,4.10"5
mol/lit. * nh hng ca cht to phc
M + X =i== MX1 ; p MX
1

+ X ^ MX2 ;

MXn"1 +

X ==== MXn ; p
Nu M ca kt ta MA to phc vi X ln lt theo cc phng trnh sau
y:
MA ^= M + A
; [M][A] = TMA
(6.11)
[M][X]
[MX2 ] :
[MX][X]
[MX ]

JM]
[X]
[MX]
2P

[MX

(6.12)

n-1M, A c th mang 1, 2, ... in tch, cn X c th dng phn t hay

ion; p , p , p , p l hng s to phc (hng s bn ca phc) ca cc nc. Gi S l
tan ca MA th c th vit:
S = [M] + [MX] + ... + [MXn]
[MX

S
=
[
M
]

205

(
1
+
p1

[
X
]
+
P1
P2
P]

+
...
+

n
p1

[
X
]
(
6.
1
3
)
i=1

n
i=n

K hiu

pi

thay cho tch p1p2p3 ... pn

i=1

Ta li bit vi mt phc c dng MXn ta c cc hng s bn tng nc p ,

v hng s chung p = p .p . ... p , vy nu ta thay cch tnh cc hng s tng
nc bng hng s chung p (i ch phc ca mt ligan " phi t), ngha l c i nc
phn ly
s c: S = [M](1 + p1[X] + p2[X]
1

p2, pn

][X]

n
2

+ ... + pn[X]n) = [M]p i[X]i vi p0 = 1.

206

i=0

S Vy:

[M]

[X]
Pi

i=0

S
.S = T hoc S:
i[X]Thay gi tr ca [M] trn v [A] = S vo (6.9) Ta c:
i=0

(6.14)

i=0

V d: Tnh tan ca AgCl trong dung dch m NH 4Cl 0,01M, bit

TAgCl 1,8.10"i
I
10

, p1 = 103,2, p2 = 103,8.
AgCl Ag+ + Cl"

207
s =3 [Ag+]
+ [Ag(M3) ] + [Ag(NH3)2+l = [Ag+](1 +
10 '2.10-3 + 107.10-6) = 12,7[Ag+] Vy: [Ag+] = 127;
[CH = s10+ 0,01; T = [Ag+][Cr] = 1^(s + 0,01) = 1,8.10
1 8 10
+

10

12 7
Nu coi s << 0,01 th: s = '

'- = 2,3.10-7 mol/lit

0,01

*nh hng ca nhit

Tch s tan T ch l 1 hng s mt nhit nht nh. V vy nu nhit thay
i th tan cng thay i. i vi cc cht khi ha tan thu nhit th tan s tng khi
nhit tng, nhng i vi cc cht khi ha tan ta nhit th tan s gim khi tng
nhit .
V d: Pbl2 tan nhiu khi un nng, tan ca AgCl 100 0C ln gp 25 ln tan
ca n 100C; CasO4.2H2O c tan tng theo nhit n 600C. Trn 600C th
cht ny s mt bt nc thnh CasO4. j1H2O nn tan li gim khi tng nhit .
Nh vy canxisunfat c tan ln nht 600C.
*nh hng ca kch thc ht kt ta
i vi cng 1 lng cht, kt ta ht nh tan nhiu hn kt ta ht ln, ngha l
tch s tan ca kt ta ht nh ln hn tch s tan ca kt ta ht ln v trn b mt ca
cc tinh th nh c nhiu gc v cnh, cc ion cc v tr gc v cnh d tan hn
nhng v tr khc, v cc v tr bn trong cc ion b gi cht hn. Do trong thc t
mun c kt ta tch c hon ton ra khi dung dch ngi ta tm mi cch thu
c tinh th ht ln.
Trong phn tch ngi ta thng phi lm kt ta hon ton mt ion no nhm
tch n ra khi cc ion khc c trong dung dch hoc nh lng ion . V khng c
kt ta no tuyt i khng tan nn "s kt ta hon ton" ch c ngha tng i. Khi
tin hnh tch th mt ion no c coi l c kt ta hon ton nu lng ca n
cn li trong dung dch sau khi lm kt ta khng cn gy cn tr n phn ng i vi
ion khc c trong dung dch v khi tin hnh nh lng th mt ion c coi l kt ta
hon ton nu lng cn li ca n trong dung dch ch nm trong gii hn chnh xc
ca php cn (0,1 -- 0,2 mg). i vi cc mc ch phn tch thng thng th php lm
kt ta c coi l hon ton khi nng ion cn tch cn li trong dung dch dao ng
trong khong (10-5 - 10-6) M.
*nh hng ca dung mi
Thng phn ln cc cht v c t tan trong dung mi hu c hn trong nc do
phn cc ca dung mi hu c nh hn phn cc ca nc.
V d: CasO4 tan kh trong nc (s = 7,8.10 -3 mol/lt) nhng hu nh khng tan
trong ru etylic.
V vy trong trng hp nu kt ta c to ra t dung dch nc c tan kh
ln th cn thit tin hnh kt ta trong dung mi hu c thch hp. 6.1.3. Kt ta phn
on 6.1.3.1. Bn cht ca kt ta phn on
Gi s c 2 ion A v B trong dung dch c nng CA v CB cng kt ta c vi
ion X ca thuc th tng ng cho kt ta AX v BX. Nu cho dn thuc th

208

X ta xt xem:
* AX hay BX kt ta trc?
* Khi no th c hai cht AX v BX cng kt ta?
* Khi AX v BX cng kt ta, iu kin no dn n hp cht kt ta trc s
hon ton?
Ta ln lt nghin cu nhng vn . gii
quyt c vn th nht, ta thy:
Theo quy tc tch s tan, hp cht no s kt ta trc khi tch s nng cc ion
to ra kt ta vt qu tch s tan ca hp cht . Ngha l thm dn thuc th, nu
[A][X] > TAX th AX kt ta trc hay [B][X] > TBX th BX kt ta trc.
Gi s AX kt ta trc, ta nghin cu xem lng thuc th cn thit cho vo bao
nhiu t c kt qu .
[A][X] > TAX

--

[X] > TfX[A]

Trong khi BX
cha kt ta th:
[B][X] < TBX

[X] < [B]

Vy r rng lng thuc th cho dn dn vo dung dch AX kt ta trc cn
BX cha kt ta phi tha mn bt ng thc:
< [X] < Tbx
Tbx
(6.16)
[A]
[B] .
Theo bt ng thc ny th khi nh dn dn thuc th mun bit xem hp cht
TT
r

no kt ta trc ta ch vic so snh hai t s:

v^-.
CC
AB

H qu:
Trong trng hp n gin nu AX v BX c cng thc tng t v CA = CB th hp
cht no c tch s tan nh hn hay tan nh hn s kt ta trc. V d 1:
Trong dung dch hn hp I- v Cl- c nng ban u [I-] = [Cl-] = 10-1M. Khi cho
dn dung dch AgNO3 th AgI hay AgCl kt ta trc? Bit TAgI = 10-16, TAgCl = ,10-10.
V nng ban u [I-] = [Cl-] v TAgCl > TAgI nn khi cho dn dung dch AgNO3
vo th Agl kt ta trc. Kt lun trn hon ton ng, v rng nu so snh:
-1

AgI-10 = 10 15 v T AgC- = 10 = 10 [ V ]
[CH 10"
R rng Agl kt ta trc.
Khi no th AX v BX cng kt ta?
A + X ^ Ax
T
^
r

109

209

[A] gim dn, do

tng dn, mun AX tip tc kt ta cn phi thm X
[A]
vn tha mn bt ng thc (4.16) v qu trnh ny vn tip din n mt lc:

210

T T [X] >-^ - = -^
[A] [B]
AX

Khi c AX v BX cng kt ta. Do ta rt c: 1 = (6.17)

[B] T

BX

Khi AX v BX cng kt ta, khi no th AX kt ta hon ton, BX mi kt ta

Nu AX kt ta trc hon ton trong dung dch [A] cn li < 10-6M, t
(6.17) ta rt ra c iu kin: [A] = T^B] < 10-6M

Vy hin tng to thnh ln lt cc kt ta trong dung dch nh kho st trn

tch hon ton cht A ra khi cht B c gi l kt ta phn on. V d 2: Theo v d 1,
khi Agl v AgCl cng kt ta,
[I ]cn li = TAgL[Cl- ] = 10-1^10 = 10-7 M
-

R rng AgI c kt ta trc hon ton ri khi AgCl mi kt ta, ngha l c

th dng AgNO3 tch I- hon ton khi Cl- trong dung dch I-, Cl- c cng nng
0,1M.
6.1.3.2. ng dng ca kt ta phn on.
* Pht hin Ba2+ trong dung dch gm Ba2+, Sr2+ bng dung dch SrSO4 bo ha.
V TBaSO4 = 1,1.10-10 < TsrSO4 = 2,2.10-7.
* Pht hin Sr2+ trong dung dch gm Sr2+, Ca2+ bng dung dch CaSO4 bo ha
v TSrSO4 = 2,2.10-7 < TCaSO4 = 2,4.10-5.
* Trong phn tch nh lng c th dng dung dch AgNO3 chun lin tc
dung dch hn hp I-, Cl- da vo s kt ta phn on ca I- v Cl-.
* Trong phng php chun kt ta dng phng php Mo, da vo s kt ta
phn on ca Cl- v CrO4 c th chun dung dch Cl- bng dung dch AgNO3 khi
dng K2CrO4 lm ch th.
6.1.4. Chuyn mt hp cht kh tan ny sang mt hp cht kh tan khc 6.1.4.1. Bn
cht ca vn
Gi s khi cho mt dung dch thuc th B vo mt cht kh tan AX lm cho kt ta ny
chuyn thnh mt cht kh tan khc. Ax > BX Khi trong dung dch s tn ti cc
cn bng:
2-

ddB

AX Y A + X 1 + B
2l
BX
V nguyn tc nu cho lng B ln, cn bng 2 chuyn dch t trn xung ko
theo cn bng 1 chuyn dch t tri sang phi, v r rng s chuyn kt ta c hon
ton hay khng s ph thuc vo:
-

AX

BX

211

- Lng thuc th thm vo.

Trong iu kin no AX chuyn hon ton sang BX?
Gi thit cn bng (1) v (2) ang chuyn dch t tri sang phi v t trn xung,
ngha l AX ang tan v BX ang c to thnh, ta c th vit c:
[B][X] > T

BX

AX

> [B] > ^ (6.18) v [A][X] = T

> [X] = yA-

(6.19)
Thay gi tr ca [X] vo (6.18) ta c: > ^ (6.20)
Vy mun kt ta AX chuyn c hon ton sang kt ta BX phi cho thuc th B mt
lng nh th no lun lun tha mn bt ng thc (6.20) Vic chuyn kt ta ny
c th xy ra trong 3 trng hp sau:
* Trng hp 1: Nu TBX < TAX tc l chuyn t hp cht d tan sang mt hp
,T
cht kh tan hn. Trng hp ny thc hin c d dng, v khi t s
< 1.
V d: Chuyn SrSO4 sang SrCO3 bng dung dch Na2CO3 bo ha v TSSO = 2,8.10> TSCO = 1,6.10 nn ch cn mt lng nh Na2CO3 s m bo
[COI ]
SrCO3 = 1,6.10
=
-3

c: i: > _ =r = 5,7.10 .
[SO4 ] TSrSO4 2,8.10- ' ^
* Trng hp 2: Nu TBX = TAX cng c thc hin kh d dng v khi
[B]
cng ch cn tha mn iu kin: ------> 1.
[A]
V d: Chuyn CaC2O4 thnh CaCO3 c TCaC = 2,3.10 TCaCO = 7,1.10- .
7

5 7 1 0

* Trng hp 3: Nu TBX > TAX, chuyn mt cht kh tan thnh mt cht d

tan hn, thc hin kh khn hn v khi ^ > 1 v trng hp nu t s ln
hn 1 rt nhiu th khng th thc hin c.
V d: Khi chuyn BaSO4 c T = 1,1.10-10 thnh BaCO3 c T 8.10-9 bng dung dch bo
ha Na2CO3. Trng hp ny thc hin c nhng kh khn hn v phi cho mt lng
thuc th Na2CO3 kh ln lun lun tha mn: [CO2-] > BCO = 8.10- 73 [SO2-] TBaSO4~
1,1.10-10 " Trong thc hnh ngi ta thc hin nh sau:
Cho mt lng dung dch Na2CO3 bo ha ln vo kt ta BaSO 4, khuy u,
un nng, lng, lc kt ta qua ly tm, b dung dch i ( loi SO 42-) v cho mt
lng mi dung dch bo ha Na2CO3 ( tng CO32-) v c lp li qu trnh ny vi ln.
T

212

6.1.4.2. ng dng ca s chuyn kt ta.

*Ha tan kt ta:
C nhng trng hp khng th ha tan kt ta mt cch d dng nh axit chng
hn, gii quyt vic ny ngi ta chuyn kt ta sang mt kt ta khc d tan hn.
V d khng th ha tan BaSO4 bng ngay c axit mnh nh HCl hay HNO 3, nhng nu
chuyn kt ta thnh BaCO3 th c th dng axit yu CH3COOH cng c th ha tan
hon ton BaCO3 c.
*Tch ion:
V d: Tch S2- ra khi hn hp S2-, SO32- bng cch cho mt lng thch hp
bt CdCO3 vo.
Do tan ca SCdS < SCdCO < SCdSO nn kt ta CdCO3 d dng chuyn sang
kt ta CdS. Kt qu trong dung dch ta c mt hn hp kt ta CdS + CdCO3 (cn
tha) lc kt ta. Mun tch CdS ta ch nh vo hn hp kt ta mt t axit axtic th
CdCO3 tan ht, lc, ra kt ta CdS, sau dng HCl c ha tan CdS th ta s thu c
dung dch c cha S2- ( dng H2S). 6.1.5. Ha tan kt ta.
Qu trnh ha tan l qu trnh lm ngc vi qu trnh to kt ta. i vi mui
(hp cht) loi MmAn.
MmAn ^ mMn+ + nAm-iu kin ha tan kt ta l phi
thit lp iu kin tch s hot ca cc ion trong dung dch b hn tch s tan: aM
.aA < TM
Mun vy, cn phi lm gim nng ca cc ion trong dung dch bo ha. Do
nguyn tc chung v ha tan kt ta: Mun ha tan kt ta th phi gim nng ca t
nht mt trong cc ion do kt ta phn ly ra trong dung dch.
Trong thc t c th dng cc bin php sau: 6.1.5.1. Ha tan kt ta bng cch to
vi ion ca kt ta thnh mt hp cht t phn ly.
Trong trng hp ny cc hp cht t phn ly c to thnh c th l axit yu,
baz yu, nc v phc cht.
hiu r bn cht ca vn v rt ra c nhng kt lun cn thit, ta nghin
cu mt cch tng qut trng hp n gin sau:
Gi s dng thuc th cht in ly mnh XY ha tan kt ta MeA to ra mui tan
MeY v cht t phn ly XA theo phn ng sau: MeA + XY ^ MeY + XA
V c th vit: MeA 5=* Me+ + A+
XY = Y
+ X+ 11
XA
MeA + X+ ^ Me+ + XA
^ r Qua cc cn bng trn ta thy rng: ha tan
kt ta MeA phi lun lun chuyn dch cn bng t tri sang phi v t trn xung.
Vy r rng ha tan kt ta cng hon ton nu:
+

m-

213
* Tng nng [X+]: lng thuc th ln.
* KXA cng nh, tc l cht XA c to ra cng t phn ly th s kt hp gia A -v
X+ cng mnh.
- TMeA khng nh qu hay kh ln, tc l MeA kh tan. Trn y l nghin cu mt
cch nh tnh, by gi ta nghin cu mt cch nh
lng: Tnh tan ca kt ta MeA: SMeA mol/lit
C 1 mol MeA tan ra s cho 1 iong Me+ v 1 mol XA. Vy: SMeA
= [Me+] = [XA]
|Me||XA|
V:
= K ht
Kht: hng s ha tan ca cn bng
T trn ta rt ra c: SM A
ht[X+ ]
+
[X ] = Ctt: nng ca thuc th lc cn bng.
By gi ta tnh Kht Ta c th vit: [Me+][A-] =
TMeA

214
V ta c: -Jk_J. = K
[XA]

XA

T trn rt ra c: Kht

= MeA

215
MeA

Vy :

S-. . =

216

R rng tan S tng khi:

* TMeA cng ln so vi KXA cng nh.
* Ctt cng ln cng tt (gii hn n nng ca dung dch bo ha).
Ch : Nu TMeA nh hn th SMeA s gim, nhng nu XA c tch ra khi
mi trng phn ng (bay hi hay tan nhiu trong dung mi hu c) th SMeA s tng.
H2WO4 + 2OH- ^ WO42- + H2O
(NaOH)
Mg(OH)2 + 2NH4+ ^ Mg2+ + 2NH4OH
(NH4C)
CaC2O4 + 2H+ ^ Ca2+ + H2C2O4
(HCl)
* AgCl + 2NH3 ^ [Ag(NH3)2]Cl 6.1.5.2.
Ha tan kt ta bng phn ng oxy ha-kh
Nu mt trong cc ion ca kt ta c tnh oxy ha hay tnh kh th ngi ta thng
dng cc dung mi c tnh oxy ha hay tnh kh ha tan kt ta .
V d: CuS khng ha tan bng axit HCl v: T CuS = 10-45 v axit H2S c to ra c
KH S = 6,9.10-23 nn ngi ta thng dng HNO3 c un nng theo phn ng:
V d:

3CuS + 8HNO3 ^ 3Cu(NO3)2 + 3S + 4H2O + NO do tc dng oxy ha

ca HNO3 nn S2- ^ S0 lm cho S2- gim i rt nhiu.

217

6.1.5.3. Ha tan kt ta bng phng php phi hp c hai phng php trn
Nu kt ta rt t tan, ngha l T MeA cc k qu nh, nu ta ch dng bin php i
ha tr ion khng thi th cha gim nng ion n mc cn thit kt ta tan
ra hon ton.
V d: Kt ta HgS c T = 10-53, bi vy mun ha tan kt ta trong trng hp
ny cn phi kt hp c 2 bin php trn.
V d c th ha tan HgS bng nc cng toan:
3HgS + 4HCl + 2HNO3 ^ 3[HgCl4]2- + 3S + 2NO + 4H2O
Theo phn ng ny Hg2+ kt hp vi Cl- to thnh cht t phn ly [HgCl4]2- v S2b oxy ha thnh S0 do nng ca c Hg2+ v S2- u b gim, nn kt ta tan c.
6.1.6. L thuyt v cu to kt ta
170.
Kt ta tinh th v kt ta v nh hnh
Kt ta tinh th l loi kt ta m cc ion to ra kt ta sp xp theo mng li tinh th
theo mt chiu hng xc nh, lm cho kt ta c hnh dng nht nh. V d: PbCl2
trng, hnh kim; PbI2 vng, hnh vy ...
Kt ta v nh hnh l loi kt ta khng c cu to tinh th, kt ta khng c
hnh th nht nh.
V d: Kt ta Al(OH)3 trng; NiS en ...
Kt ta v nh hnh d bin thnh dung dch keo, b mt tng cng ln, kh lng,
kh lc, kh ra v d nhim bn.
171.
Hai giai on ca qu trnh kt ta
Qu trnh to thnh kt ta l qu trnh kh phc tp. Sau y ta th xt qu trnh
to kt ta BaSO4.
Ba2+ + SO42- ^ BaSO4 R rng l nu ch c 2 ion "n c"
Ba2+ v SO42- th khi gp nhau chng ch to thnh phn t BaSO4 v cha th c cu
trc tinh th. to nn cu trc tinh th cn phi c nhiu ion Ba 2+ v SO42- tp hp li
thnh nhng tp hp nh nhng vn cha phi l kt ta. Cc tp hp ny gi l mm
tinh th hay l trung tm kt tinh. Giai on ny ca qu trnh kt ta ng vi s to nn
trng thi keo ca vt cht.
T cc trung tm kt tinh ny cc phn t tip tc tp hp thm v ln dn ln n
mc c th thnh ht kt ta trng lng xung. Vy qu trnh kt ta gm 2 giai on:
*To mm tinh th
*Mm tinh th ln ln
Giai on sau ty thuc bn cht v iu kin kt ta m c th gy ra mt trong hai
hng khc nhau to thnh kt ta tinh th hay kt ta v nh hnh. * To kt ta tinh
th:
Nhng trung tm kt tinh mi c to thnh s ln dn ln thnh nhng ht tinh
th ln ri sau to thnh kt ta tinh th. Qu trnh ny xy ra khi qu bo ha ca
dung dch nh. T dung dch ny sinh ra chm v t cc trung tm kt tinh, tc l tc
kt ta nh hn tc nh hng, do to iu kin cho cc phn t c thi gian
phn b ln cc trung tm kt tinh theo v tr khng gian xc nh

218

hnh thnh nn nhng tinh th ln. Do to ra kt ta tinh th c ht ln phi c

gng tin hnh kt ta trong dung dch qu bo ha cng nh cng tt. * To kt ta v
nh hnh:
Nhng trung tm kt tinh s lin kt yu vi nhau thnh nhng tp hp nh, v cc
tp hp ny li kt hp vi nhau thnh nhng tp hp ln hn v cui cng to thnh
kt ta v nh hnh.
Qu trnh ny c th xy ra trong 2 trng hp:
*Do bn cht ca kt ta v v nh hnh:
Loi kt ta ny thng thy cc cht c tan kh nh, nh cc sunfua,
hydroxyt kim loi ... V tnh kh tan ca chng nn khi thm thuc th vo dung dch th
dung dch tc thi t trng thi qu bo ha v qu trnh tip din nh ni trn.
*Do iu kin kt ta:
Nu khi tin hnh kt ta t dung dch qu bo ha ln th s sinh ng thi nhanh
v nhiu trung tm kt tinh, do khng to iu kin nhng trung tm ln ln nn
s to ra kt ta v nh hnh.
V d: BaSO4 iu kin thng s kt ta dng tinh th nhng nu tin hnh
kt ta trong hn hp nc-ru 30-60% (trong dung mi ny BaSO 4 rt t tan) hay
dng dung dch c v cng mt lc th s to ra dung dch keo hay kt ta v nh
hnh.
Qua s kho st trn ta thy rng: Nu kt ta c to ra l v nh hnh hay tinh
th th phi tm nhng iu kin thun li nht tin hnh. C th i vi kt ta tinh
th cn tun theo nhng iu kin sau:
* Kt ta t dung dch long v thuc th long.
* Thm thuc th rt chm, tng git, nht l thi gian u.
* Kt ta t dung dch nng (c trng hp cn phi un nng dung dch thuc
th).
* Thm cc cht c tc dng lm tng tan ca kt ta. V d: khi kt ta BaSO4
th cho thm HCl, v n lm tng tan ca BaSO4 do to thnh HSO4-.
- Lc kt ta sau khi lm lnh dung dch.
i vi kt ta v nh hnh:
* Kt ta t dung dch nng.
* Thm cht in ly lm ng t keo c tt. V d: Cc loi mui amoni, cc
axt.
* Kt ta t dung dch c, thuc th c.
* Sau khi kt ta xong phi thm mt lng ln nc un nng (khong 100ml) v
khuy u lm gim qu trnh hp ph.
* Khng ngm kt ta lu trong dung dch m cn phi lc ngay sau khi kt ta, c
bit l khng un nng trnh hin tng kt ta chuyn sang dng khc v tng hin
tng cng kt.
6.1.7. Cng kt v kt ta sau - nguyn nhn lm cho kt ta khng tinh khit.
Thng kt ta khng th tch ra dng tinh khit m c km theo tp cht. Khi
tp cht kt ta ng thi vi kt ta chnh th gi l cng kt, v khi tp cht kt ta sau
khi kt ta chnh kt ta ht th gi l kt ta sau. Ta ln lt im qua cc

219

loi kt ta cng kt v kt ta sau.

6.1.7.1.Cng kt b mt.
Cng kt loi ny l s hp ph cc tp cht trn b mt ca kt ta. Nguyn nhn
ca s hp ph l nhng ion hay phn t b mt kt ta cn c kh nng ht thm
nhng ion hay nhng phn t trong dung dch. V khc vi nhng ion v phn t
trong kt ta, nhng ion v phn t b mt kt ta c nhng lc ha tr t do nn c
th lin kt tip c vi cc tiu phn khc trong dung dch.
Hp ph l mt hin tng thun nghch v nhng ion hay phn t b hp ph c
th tan tr li trong dung dch hay ni mt cch khc c th b "gii hp".
Khi tc hp ph bng tc gii hp cn bng hp ph c thnh lp, lng
tp cht b hp ph khng thay i na. C nhiu yu t nh hng n cn bng ny:
* nh hng ca din tch b mt.
Lng cht hp ph t l vi din tch b mt ca kt ta nn tinh th ca kt ta
cng ln th lng cht b hp ph cng nh.
* nh hng ca nng .
Qu trnh hp ph l mt qu trnh thun nghch nn s t n mt cn bng
ng.
V d: Kt ta AgCl trong dung dch KCl th s hp ph ion Cl-:
nAgCl + m Cl- ^ nAgCl.mCl-Theo cn bng ny nu tng [Cl-] th s hp
ph s tng. C ngha l nng cng ln th lng cht b hp ph cng
nhiu, nhng sau tng chm hn nng (hnh 6.1). Ngi ta chng
.<p K
minh
43 3
.
/
-----------c
s
rng:
a = KC
3-

------------------------------------------------7-^*~

tn
r
a: lng ion v hp ph: iong i vi 1g kt ta.
C: nng ca ion b hp ph trong dung dch. K, n: h s i vi mt h cho.
T h thc trn ta thy rng: Qu trnh phn hp ph (hay gii hp) gim chm khi
gim nng C. y l c s cho vic ra kt ta lm sch, nhng khng tuyt i
lm sch c.
*nh hng ca nhit .
Qu trnh hp ph l mt qu trnh ta nhit: nAgCl + mCl- ^ nAgCl.mCl- + Q nn nhit
cng thp hp ph cng mnh v nhit cng cao th gii hp ph cng mnh.
*nh hng ca bn cht kt ta v ion b hp ph.
Cng trong mt iu kin vi cng mt kt ta, cc ion ty theo bn cht ca
chng b hp ph nhiu t khc nhau. Thng ion b hp ph theo quy lut sau: ion to
vi ion ca kt ta hp cht cng t tan b hp ph cng nhiu, do ion ca kt ta b
hp ph nhiu hn c.
V d:
- AgI s b hp ph mnh I- hn Br-, hn Cl-, cn i vi NO3- th hp ph rt

220

yu v: SAgl < SAgBr < SAgCl, cn AgNO3 tan hon ton trong dung dch.
- BaSO4 hp ph trc ht ion Ba hoc SO 4 khi d Ba hay SO4 trong dung dch.
BaSO4 hp ph mnh SO42- hn CO32- v SB SO < SBCO , nu trong dung dch c
-

NO3- hay Cl- th BaSO4 hp ph NO3- nhiu hn Cl- v SB (NO ) < SBCl .
* nh hng ca iu kin kt ta.
V d vi kt ta v nh hnh nh Fe(OH)3, Al(OH)3 khi kt ta t dung dch c
t hp ph hn khi kt ta t dung dch long, do lng tp cht b hp ph cng t
hn.
Nhng i vi kt ta tinh th th khi kt ta t dung dch long tinh th s ln hn
khi kt ta t dung dch c, do cng t b hp ph tp cht hn.
Khi lu kt ta trong dung dch, kt ta s ln hn v c dng tinh th hon
chnh hn gi l hin tng lm mui tinh th, lng tp cht b hp ph cng gim
bt.
172.
Cng kt trong
Thng xy ra i vi kt ta tinh th, da vo c im ca cng kt trong, c
th chia ra lm hai loi:
* Cng kt do phn ng gia kt ta v thuc th d.
Khi cho Zn2+ phn ng vi K4[Fe(CN6)] th khng sinh ra kt ta Zn2[Fe(CN6)] m
sinh ra kt ta K2Zn3[Fe(CN6)]2. Kh nng ion kim loi kim i vo trong phc cht ph
thuc vo th tch v mc hydrat ha ca ion . lon cng nh cng d vo mng li
ca kt ta v cng t tan. lon hydrat ha cng yu vo mng li cng d. Mc
hydrat ha ca cc ion kim loi kim tng theo chiu: Cs+ < K+ < Na + < Li+. Nh vy
Cs+ d b cng kt hn c.
* Cng kt ng hnh
Nguyn nhn ca loi cng kt ny l kt ta v tp cht l nhng cht ng hnh,
tc l nhng cht c kh nng kt tinh trong cng mt mng li tinh th. V d: phn
nhm KAl(SO4)2.12H2O khng mu, ng hnh vi phn crm KCr(SO 4)2.12H2O mu
tm, v khi chng cng kt tinh vi nhau th s c tinh th mu tm m nht ty theo
nng tng i ca chng.
Thng th nhng ion kim loi c s phi tr v bn knh bng nhau th d thay th
nhau trong mng li m khng lm gim bn ca mng li. V d: Ra2+
0

2+

2+ 2+

(1,52A ) c bn knh gn bng Ba (1,43A ), nu trong dung dch Ba c rt t Ra nhng

khi cho SO42- vo th RaSO4 s kt ta ng thi cng BaSO4 trong cng mt
2+

2+

0 2+

mng li. Cn Ca2+ c bn knh nh hn bn knh ca Ba 2+ (1,05A0) nn Ba2+ v Ca2+

khng th cng kt tinh trong cng mt mng li.
173.
Cng kt c hc
Nhng tinh th thng c mng li khng hon ton nn c khe h hoc ch
trng ng y nc ci cha tp cht. Nhng tinh th nh khi kt hp vi nhau cng c
th gi tp cht gia.
174.
Ni hp 9
Trong qu trnh ln ln, tinh th c th mang theo tp cht trc b hp ph, th
t cho cc thuc th v dung dch tc dng vi nhau rt nh hng n cht b hp ph.
V d: Nu thm dn H2SO4 vo BaCl2 th tinh th BaSO4 ln dn trong mt dung dch c
d Ba2+ nn hp ph nhiu Ba2+ ko theo ion Cl-. lon SO42- s y dn

221

ion Cl- ra mt phn nhng vn cn mt t trn kt ta. Ngc li nu thm dn BaCl 2 vo

H2SO4 th tinh th BaSO4 ln dn trong dung dch c d ion SO4 nn hp ph ion SO42ko theo cation khc trong dung dch. Tc thm thuc th cng nh hng n lng
tp cht b hp ph. Nu thm ngay mt lc thuc th n d th kt ta s hp ph tp
cht nhiu. Nu thm t t th kt ta s tinh khit hn v kt ta ln hn nn hp ph
tp cht t hn v tp cht cng d b thay th bi ion ca kt ta hn. 6.1.7.5. Kt ta
sau
Cc loi cng kt k trn ch xy ra trong khi to thnh kt ta, nhng cng c
loi cng kt ch xy ra sau khi hon thnh kt ta mt thi gian, l kt ta sau.
V d: Nu lc ngay kt ta CuS khi kt ta bng H2S trong mi trng axt c ion
Zn2+ th khng c ZnS trong kt ta. Nhng nu lu kt ta trong dung dch trc khi
lc, trong kt ta s c c ZnS. C th gii thch hin tng ny nh sau:
Kt ta CuS tip xc lu vi dung dch bo ha H2S s hp ph H2S ln b mt kt
ta lm cho nng H2S tng ln r rt ZnS kt ta mc d nng axt trong
dung dch kh ln. 6.1.8. Vai tr ca cng kt trong phn tch
Hin tng cng kt c tc hi trc tip lm bn kt ta, do lm cn tr vic
tch cc ion cn xc nh ra khi dung dch phn tch. V vy cn phi tm bin php
chng cng kt nhng mt khc ngi ta cng s dng hin tng cng kt trong phn
tch vi lng. 6.1.8.1. ng dng.
* Tch:
V d mun tch Pb2+ (vi lng) trong nc c th dng bt CaCO 3, v Pb2+ b
CaCO3 cng kt.
* Lm giu dung dch:
Gi s t dung dch Ra2+ v cng long, ta c th lm giu dung dch nh sau: C
th cho bt BaSO4 vo dung dch trn, do tnh ng hnh nn BaSO4 s ko theo RaSO4.
Sau tch hn hp kt ta ny, ra sch, ri chuyn sang kt ta cacbonat, cui cng
dng axit ha tan thnh dung dch c th thch ty .
* Pht hin ion:
C th tm Mg2+ da vo hin tng Mg(OH)2 cng kt I2 to ra kt ta
Mg(OH)2.I2 (trong mi trng kim) mu ta sm (nng tm c gii hn 70
mg/lit).
6.1.8.1. Cch lm gim cng kt
Trng hp cng kt ngoi: Tm cch lm gim din tch b mt ca kt ta, tc
l to iu kin c c th tch ln hn, hay ni cch khc phi tun theo cc quy
tc thu nhn kt ta tinh th v v nh hnh trnh by trn.
cho tinh th ln ln, ngi ta lm mui tinh th bng cch ngm lu tinh th
trong dung dch nc ci.
V d: kt ta qua mt m ri mi lc cho tinh th nh tan ra v tng s
tinh th ln ln.
C th thay i dng ion c kh nng cng kt lm thay i bn cht ca chng
2-

222

v gim cng kt. V d: Kh Fe3+ xung Fe2+ t cng kt vi BaSO4 hn, hoc c
th dng cht to phc che.
Ra nhiu ln cng lm gim cng kt v y c qu trnh thun nghch.
Trng hp cng kt trong: Khng th loi tp cht bng phng php ra. Ta c
th gim bt cng kt bng cch kt tinh li nhiu ln v mi ln kt tinh li th lng
tp cht s gim dn.
V d: loi bt ion Mg2+ trong kt ta CaC2O4 th em ha tan CaC2O4 bng
HCl, sau trung ha axit ri kt ta li CaC 2O4. Ln ny nng Mg2+ nh hn ln
trc nn Mg2+ s b hp ph t hn. Kt tinh li nhiu ln, Mg 2+ cn li khng ng k.
Tt hn ht l nn p dng mt trong cc bin php sau:
* Tch ion b cng kt trc khi tin hnh kt ta bng nhiu cch nh chit chng
hn. V d tch FeCl3 bng cch chit mui bng CCl 4hay CHCl3 trong mi trng
HCl.
* Che du: C th dng thuc th thch hp tc dng vi ion b cng kt to thnh
phc cht bn t hay khng b cng kt.
* i ha tr: V d BaSO4 cng kt vi Fe3+ hay MnO4-, mun tch ra ch vic i
ha tr Fe3+ thnh Fe2+ hay MnO4 thnh Mn2+.
6.1.9. Dung dch keo trong ha phn tch
175.
Khi nim v dung dch keo.
C nhiu trng hp mc d tch s nng ca cc ion to thnh kt ta trong
dung dch vt qu gi tr tch s tan ca kt ta nhng kt ta to thnh vn khng
tch ra c m ch hnh thnh nhng ht rt nh l lng trong dung mi, dung dch
gi l dung dch keo. Cc phn t khuch tn trong dung dch keo gi tt l cc ht keo.
Dung dch keo khc vi dung dch thc ch n b c di nh sng phn
chiu. Cc ht keo c kch thc ln hn cc phn t dung mi rt nhiu nn chng c
kh nng khuych tn nh sng, tuy vy kch thc ca ht keo cng cn kh nh nn
khng th nhn thy bng mt thng, cng nh bng knh hin vi, d lt qua giy lc.
176.
Nguyn nhn bn vng ca dung dch keo
Bnh thng cc phn t keo l tp hp nhiu phn t v trung ha v in, khi va
chm nhau c th kt hp v vn li thnh kt ta lng xung.
Tuy nhin mt tnh cht c trng ca dung dch keo l c th khng tch ra thnh
kt ta trong mt thi gian rt lu do nguyn nhn sau:
* Hp ph cc ion c trong dung dch nht l cc ion to ra phn t keo, do cc
phn t keo tch in cng du nn y nhau v khng th kt hp vi nhau thnh kt
ta c.
* C th hp ph cc ion ca dung mi (i vi keo a dung mi), tc l b sol-vat
ha to thnh mt lp v solvat ngn cch cc phn t keo khng th kt hp vi nhau
c thnh kt ta, v d silic oxt.
177. S ng t v s pepti ha * S
ng t.
S chuyn mt dung dch keo (cn gi l sol) thnh kt ta (gel) gi l s ng
t.

223

Mun ng t mt dung dch keo thnh kt ta, c th dng 2 bin php sau:
- Trung ha in ca dung dch keo tch in bng cch thm cc cht in ly
tng ng.
- ung nng lm gim qu trnh hp ph v ph v v solvat. Bng 2 bin php
ny s to iu kin cho cc phn t keo lin kt vi nhau
thnh kt ta.
* S pepti ha.
Hin tng kt ta c ng t c th bin thnh dung dch keo gi l s pepti
ha (tc l gel thnh sol). S pepti ha thng xy ra 2 trng hp sau:
* C mt s cht keo ng t tip xc vi nc s to thnh keo, loi keo ny
gi l keo thun nghch.
* Kt ta c ng t tip xc vi nc c cha ion d b hp ph cng c th
chuyn thnh keo. V d nh kt ta Fe(OH)3 tip xc vi nc cha FeCl3 th s thnh
dung dch keo Fe(OH)3. 6.1.9.4. Trng thi keo trong ha phn tch
* Cch chng trng thi keo:
Trong qu trnh phn tch thng gp trng thi keo 2 khu:
* Trong qu trnh to kt ta khi cho d thuc th hay d ion cn kt ta, hay trong
dung dch ngui c cc ion b kt ta hp ph, kt ta s dng keo.
* C th trnh trng thi keo trong trng hp ny nh sau: Ta tin hnh kt ta
trong dung dch nng khng d nhiu thuc th, c thm cht in ly mnh thch hp
nh axt, NH4Cl, NH4NO3, ...
* Trong qu trnh ra kt ta: do lm tri mt ion trung ha in ht keo hay keo
a dung mi hp ph cc phn t ca dung mi.
Cch trnh: ra kt ta bng nc nng c thm mt t thuc kt ta (nu cn),
mt t cht in ly thch hp.
* ng dng trng thi keo trong ha phn tch:
* C mt s trng hp cn thit to ra dung dch keo nhn ra ion khi c t
dng kt ta c mu.
V d: Nhn ra Fe3+ (lng nh) dung dch keo mu mc Fe4[Fe(CN)6]3 ( iu
kin thng l kt ta).
Hay c th nhn ra lng nh Cd 2+ dung dch keo CdS (c th kt ta ngay
trong mi trng axt).
* Kt ta khng mu hay mu nht hp ph nhng cht mu v khi cht mu b
hp ph s i sang mu khc. Ngi ta dng cht mu lm ch th trong phn tch
nh lng m kt ta dng keo th s hp ph mnh. V d: kt ta AgCl khi b keo
ha dng mAgCl.nAg+ s hp ph mnh fluortxin lm cho n i mu, t mu vng
thnh hng. Trong trng hp ny cn duy tr trng thi keo, ta c th thm mt cht gi
l cht "bo v keo" nh extrin, tinh bt, gelatin, gm aralie, ...
6.2. Phng php chun kt ta 6.2.1.
c im ca phng php
Phng php chun kt ta l mt phng php phn tch th tch da vo phn
ng to thnh cc hp cht t tan. Cc phn ng mun dng c trong phng php
ny phi tha mn cc iu kin sau:

224

* Cc kt ta to thnh phi thc t khng tan, tc l phn ng phi hon ton.

* S to thnh kt ta phi kh nhanh tc l khng c hin tng qu bo ha.
* Phn ng phi chn lc, ngha l nh hng ca hin tng hp ph, ca cc
qu trnh cng kt kt ta khng lm sai kt qu phn tch.
- Phi c kh nng xc nh c im tng ng khi dng nh phn. y
l cc iu kin quan trng nht. Do ch c mt s t phn ng kt ta
dng c trong phng php kt ta.
*Phng php bc: Ag+ + X- AgX X- c
th l cc anion: Cl-, Br-, I-, CNS-.
Da vo phn ng ngi ta xy dng nn phng php bc (trong phng php
ny gm nhiu phng php, chi tit nghin cu sau).
*Phng php thy ngn: Hg22+ + 2X- 5= Hg2X2
Dng nh phn dung dch CNS- bng Hg2(NO3)2 dng Fe3+ lm ch th.
*Chun ion Ba2+ bng sunfat: Ba2+ + SO42- ^ BaSO4
Dng rdizoonat natri lm ch th. Khi c mt Ba 2+ th dung dch nhum mu ,
gn im tng ng mu s bin mt.
*Chun ch bng Cromat: Pb2+ + CrO42- ^ PbCrO4
Dng Ag+ lm ch th, gn im tng ng s xut hin mu gch do:
CrO42" + ^ 2Ag+ 'U Ag2CrO4^ gch
*Chun Zn2+ bng feroxyanua:
Da vo phn ng: 3Zn2+ + 2[Fe(CN)6] + 2K+ ^ K2Zn3[Fe(CN)6]2 ch th l
diphenylamin.
Trong tt c cc phng php trn th quan trng v c nhiu ng dng thc tin
nht l phn ng kt ta bng AgNO3. Do trong chng ny s xt c s l thuyt ca
phng php chun kt ta bc. 6.2.2. ng nh phn trong phng php bc.
Trong qu trnh chun dung dch cc cht to kt ta, nng ca ion to kt
ta s thay i. Nu ta biu din s bin thin ch s nng ion to kt ta pIon =
-lg[ion] (ion c th l cation c th l anion) trn trc tung theo lng thuc th thm
vo (trn trc honh) th ta s c ng cong nh phn pIon.
Ta kho st qu trnh chun dung dch NaCl bng dung dch chun AgNO3.
AgNO3 + NaCl ^ AgCl + Na+ + NO3 ; TAgCl = [Ag+][Cl-].
Trong qu trnh chun , nng [Cl -] s gim. Nu ta nghin cu s bin thin
ca pCl = -lg[Cl-] v pAg = -lg[Ag+] theo lng dung dch chun AgNO3 thm vo th s
c ng nh phn. Gi s chun 100ml dung dch NaCl bng dung
dch AgNO3 cng nng 0,1M bit TAgCl = 10-10, pAg + pCl = pTAgCl = 10.
6.2.2.1. Tnh pCl v pAg trong qu trnh chun .
* Trc im tng ng:
Khi cha thm AgNO3, trong dung dch ch c Cl- nn: [Cl-] = 10-1MpCl = 1.
- Thm 50ml dung dch AgNO3, tc l 50% Cl- i vo kt ta. Vy:
4-

[Cl-] =

= 0.033 -- pCl = 1,5 v pAg = 10 - 1,5 = 8,5.

* Thm 90ml AgNO3 0,1M tc l kt ta ht 90% lng Cl- v cn 10%

225

Cl" cha kt ta (tnh gn ng) do [Cl-] =

0,1.1
0 190

5,3.10-3M.

226
Vy pCl = 2,3. pAg = 7,7. Tng t nh vy ta tnh cho nhng th tch dung dch
chun thm vo khc nhau.
* im tng ng
Khi cho 100ml AgNO3 th ton b Cl" c kt ta ht thnh AgCl v [Ag+] =
[CH = 10"5. Vy r rang pAg = pCl = 5.
* Sau im tng ng
Khi cho tha AgNO3 so vi im tng ng. Gi s cho 100,1ml AgNO 3 th
tha ra 0,1ml AgNO3 tc tha ra 0,1% Ag+ so vi lng cn thit. Khi :
0,1.0,
= 10 M, do pAg = 4 v pCl = 6. Tng t nh vy ta tnh
1
100
4

[Ag+] =
cho cc th tch dung dch chun AgNO3 thm vo khc nhau: 101, 110. Cc s liu thu
c trnh by bng sau:
Bng 6.1. Gi tr plon khi chun dung dch NaCl bng dung dch AgNO3 0,1N
AgNO3

VAgNO thm vo (ml)

0
50 90 99 99,9
100 100,1 101
110
VNaCl cn li (ml)
100
50 10 1
0,1
0

CH
10-3,3.101
-2
5,3.10-3 5.10-4
5.10102.10-5
-5

-7

2.1010p
Cl
1,0 1,5
2,3 3,3
4,3 5,0
6,7 7,7
8,0

227
[Ag ]

-8

8,5
7,7
6,7
5,7
5,0
3,3
2,3
2,0

-8

-9

pA

3,3.10

2.10-7 2.1010-6
5.105,3.101

- -5

2.10

06.2.2.2. V ng nh phn v nhn xt

Biu din cc kt qu tnh ton trn ln th, ta c ng nh phn hnh
(ml)
ng
tng
ng
pA
T

g8

<

6,7
4,3

6.2.

9
0

10
0

VAgNO

Hnh 6.2. ng nh phn khi chun dung dch

NaCl 0,1M bng AgNOs 0,1M

Nhn xt:
* Dng ng nh phn ging nh ng nh phn trong phng php axt
-baz v phng php oxy ha - kh gn im tng ng c bc nhy.
* Bc nhy plon trn ng nh phn ph thuc vo nng ca dung dch.
Nu nng ca NaCl l 0,01M th bc nhy: 4,75 - 5,04; nu 1N th bc nhy: 3 7.
Vy nng cng ln , bc nhy plon cng di v ngc li.
* Bc nhy plon ph thuc vo tch s tan ca kt ta, tch s tan ca kt ta cng
nh th bc nhy cng di v ngc li. V d: ng nh phn khi chun dung
dch Nai 0,1M bng dung dch AgNO3 0,1M c TAgI = 10-4
--

-3
-2
-16

th c bc nhy l pl = 4,3 12,7. Ngi ta thy rng ng nh phn ch c bc

nhy khi T 10-10 i vi kt ta dng AB.
* Khi nhit ca dung dch tng th tan ca halogenua bc tng nn chun
km chnh xc, v vy trong 1 s trng hp ngi ta lm lnh dung dch trc khi
chun .
6.2.3. Cch xc nh im cui.
6.2.3.1. Phng php Mohr (Mo).
Dng chun dung dch Cl- bng dung dch AgNO3 vi ch th l K2CrO4 da
trn hin tng kt ta phn on: Ag+ + Cl- AgCl
* gn hay ti im tng ng nh mt git AgNO 3 cui cng kt ta gch
Ag2CrO4 xut hin ta s kt thc nh phn.
Do c phn ng: 2Ag+ + CrO42- ^ Ag2CrO4 gch. Mt vn
t ra l lng K2CrO4 cho vo bao nhiu cho hp l.
* Mun kt thc nh phn ti im tng ng ngha l khi xut hin kt
ta gch Ag2CrO4, ta c:
[Ag+]2[CrO4 ] TAg CrO 1,1.10 => [CrO2-] 1,1.10-12/[Ag + ] ti thi
-

<

2-

>

4 =

12

im tng ng [Ag+] = [Cl-] = 10-5, vy [CrO4 ]

2-

>

>

_10

1,1.10_2(M). Ta c

th tnh c nng [CrO4 ] gii hn:

2-

+ Gi s kt thc nh phn u bc nhy pCl = 4 khi Ag2CrO4 bt u

xut hin [Ag+]2[CrO42-] 1,1.10_12 v ta c
>

70^ K CrO = + Gi s kt thc nh phn cui bc nhy pCl = 6, l lun

nh trn ta c:
1,1.10[CrO4 ] _! 1,1M . Vy r rng mun kt thc rt gn im tng ng
[CrO

4_

>

>

th phi c thm mt lng K 2CrO4 th no thi im kt thc nh phn phi c

10
1 , 1 . 1 0 - 4 m .

_12
-4

M CK CO 1M
* Thc t, v cn chu nh hng ca nhiu yu t khc trong qu trnh nh phn
v nu nng ca ion CrO _ ln qu th mu vng qu m lm cho kh quan st s
xut hin mu gch ca kt ta Ag2CrO4 im cui. Do vy, ngi ta thng dng
<

4 <

2
4

10 git dung dch K2CrO4 5% trong th tch 50ml (tng ng vi

nng 0,001M). Nh vy, Ag2CrO4 bt u kt ta khi [Ag+] = 1,05.10-4,5 ; hay pAg =

4,5. Vic chun qu im tng ng mt t v sai s vo khong < 0,1% hon ton
tha mn i vi phng php phn tch th tch. iu kin chun trong phng
php Mo.
* Mi trng phn ng phi trung tnh, hay kim yu: pH = 6,5 - 10 nhng m
bo chnh xc cn thit nn thc hin pH = 8 - 10. V rng:
Nu trong mi trng axt mnh th kt ta Ag 2CrO4 tan mt do K2CrO4 mt vai
tr ch th. Do vy nu mi trng axt th phi trung ha bng NaHCO 3 hay bo-rac. Nu
trong dung dch c ion NH4+ th phi chun pH = 6,5 7,2 v pH cao qu 7,2 c
s hnh thnh r rt NH3 lm tan mt phn kt ta Ag2CrO4 v gy sai s.
* Nu mi trng kim mnh th thuc th AgNO 3 s tiu tn hn lng cn thit
do to Ag2O.
* Cn phi loi cc ion cn tr nh:
* Ba2+, Pb2+, Bi3+ v chng to kt ta vi CrO42-.
* S2-, SO42-, PO43-, C2O42- kt hp vi Ag+ to ra kt ta.
* Dung dch chun AgNO3 bao gi cng ng buret ch khng ng bnh tam
gic.
* nhy ca cht ch th gim khi tng nhit do tan ca Ag 2CrO4 tng, do
phi chun nhit thp.
Phng php Mo c th cho php chun dung dch NaCl n nng 0,001M
vi chnh xc 1% nu tin hnh hiu chnh cn thn lng Ag+ d. 6.2.3.2. Phng
php Volhard(Vonha).
Dng chun dung dch AgNO3 bng dung dch NH4CNS chun vi ch th
Fe3+ dng phn FeM4(SO4)2.12H2O nng 1M. Khi chun thng dng 1 -2 ml
dung dch phn st trn 100ml hn hp chun .
* Qu trnh chun nh sau:
* Nh dn dn dung dch chun NH4CNS vo dung dch AgNO3 c cha ch th
3
Fe +, phn ng s l: Ag+ + ' CNS ^ AgCNS
* gn im tng ng hay ti im tng ng khi ta nh git cui cng
thy dung dch nhum mu hng ta s kt thc chun v lc :
Fe3+ + 3CNS- w Fe(CNS)3 hay dng n gin: Fe3+ + CNS- ^ FeCNS2+.
Bc nhy pCNS = 8 - 4 v im tng ng pCNS = pAg = 6. Qua tnh ton
ngi ta thy rng nu kt thc chun trong khong bc nhy trn th phi thm
FeNH4(SO4)2 mt lng nh th no vo dung dch AgNO 3 nng Fe3+ ban u C0
tha mn iu kin: 3,16.10-4 < C0 < 3,16.
- ng dng quan trng ca phng php ny l c th chun ngc cc
halogenua X- (I-, Br-, Cl-). Nguyn tc ca php chun ngc nh sau: cho ion
halogen X- tc dng vi mt lng d dung dch chun AgNO3 ( bit chnh xc):
X- + Ag+(d) ^ AgX + Ag+(cn li) sau chun lng Ag+ cn
li bng dung dch chun NH4CNS theo phng php Vonha trc tip. T lng Ag+
ban u v lng Ag+ cn li ta bit c lng Ag+ tc dng vi lng X-, do tnh
c lng halogenua X-. Ch :
Trong s cc halogenua th chun ngc Br- v I- thun li v chnh xc hn

cn chun ngc Cl- kh khn hn, v tan ca kt ta AgCl (T AgCl = 10-10) ln hn

tan ca AgCNS (TAgCNS = 10-12) nn khi chun lng tha Ag+ cn li ng l
gn hay ti im tng ng, mt git dung dch cui cng NH 4CNS nh xung th lp
tc dung dch phi nhum hng ngay nhng li thy xut hin kt ta AgCNS do CNS kt hp Ag+ ca kt ta AgCl tan phn ly ra. V vy kt qu phn tch s b sai i.
AgCl ^ Ag+ + ClAg+ + CNS- ^ AgCNS
r
r 9
Mun chun ngc Cl theo phng php trn t kt qu tt c th dng mt
trong hai bin php sau:
+ Lc kt ta AgCl tch ra khi dung dch trc khi chun lng Ag+ tha cn
li.
+ Hoc cho thm mt t dung mi hu c thch hp nh: nitro benzen lm chm
qu trnh phn ly ca AgCl, ngn cn AgCl tip xc vi SCN-.
* u im ca phng php
* C th chun trong mi trng axt v AgCNS khng tan trong axit do c
th dng phng php ny xc nh lng Ag trong hp kim khi ph mu bng axit
mnh.
* Ba2+, Pb2+ khng lm cn tr trong phng php ny.
* Cc ion cn tr: mui ca thy ngn (I) tao kt ta vi CNS-, cc cht oxy ha
s oxy ha CNS-, cht c kh nng to phc bn vi Fe3+ nh F-, PO43-. 6.2.3.3. Phng
php dng ch th hp ph - phng php Fajans (Pha Gian)
* Hin tng hp ph trong qu trnh chun :
Trong qu trnh chun cc kt ta c xu hng ha keo, nht l cc halo-genua
bc. Kt ta keo hp ph chn lc, c bit hp ph mnh ion to ra kt ta c trong
dung dch nn s to ra nhng ht keo tch in cng du y nhau. V d: chun
dung dch KI bng dung dch AgNO3 ta thy rng:
+ Trc im tng ng trong dung dch c tha I - khi kt ta AgI s hp
ph mnh I- to thnh ht keo tch in m: nAgl + mi- 5=* nAgl.ml+ Sau im tng
ng: dung dch c tha Ag+, khi ta c ht keo tch in dng: pAgI + qAg+ 5=i
pAgI.qAg+
+ Trng thi kt ta AgI t tch in m (-) sang tch in dng (+) s c lc
khng tch in, lc gi l im trung ha in (hay cn gi l im ng in).
im ng in c th trng hay khng trng vi im tng ng ty theo bn cht
ca kt ta.
* Cht ch th hp ph
Cht ch th hp ph l nhng cht mu hu c in ly yu, do trong dung dch
chng phn ly yu thnh ion. Theo Fajans, cc anion ca ch th hp th khi b hp th
ln b mt kt ta tch in dng s b bin dng v thay i mu. Cc cht ch th
thng dng l fluoretxein v cc dn xut ca n nh eozin. Li dng tnh cht ny
xc nh im tng ng. V d nh cht ch th eozin l mt axit hu c yu k hiu
HE, trong dung dch tn ti theo cn bng: HE 5= H+ + E. E- trng thi t do c mu hng. Khi b kt ta hp ph s c mu tm hoa c. Nu
dng eozin xc nh im tng ng khi chun dung dch KI bng dung dch
AgNO3 ta

s thy:
+ Trc im tng ng: nAgI.mI- khng hp ph E- v cng du (-) nn dung
dch c mu hng.
+ Sau im tng ng: pAgI.qAg+ s hp ph E- do kt ta s nhum mu
tm hoa c.
chnh xc ca php chun vi cht ch th hp ph ph thuc vo cc yu t
sau:
* Tnh hp ph chn lc ca cht ch th
Trng hp l tng nht l cht ch th phi i mu ngay sau im tng ng
khi in tch kt ta va i du. Nhng iu ny cn ty thuc vo quan h gia lc
hp ph ca ion cht mu v ion li. S hp ph khng ch ph thuc vo tng tc
tnh in m cn ph thuc vo tnh cht phn cc ca cc cht, v vy an-ion cht mu
rt c th hp ph chy ua vi anion li. Chng hn, eozin c th y ion Cl - v chim
v tr ion to th.
AgCl, Cl- Na+ + flBr- ^ AgCl, ABr Na+ + ClDo s i mu li xy ra trc
im tng ng.
* Anh hng ca pH:
Cht mu b hp ph ch yu dng anion m nng ca n ph thuc pH, v
vy khi chun phi duy tr pH thch hp sao cho nng anion mu ln bo
m cn bng hp ph v s i mu r.
Fluoretxein l axt rt yu (Ka = 10-7
) do khng th chun pH < 7 v khi y cht ch th tn ti ch yu dng khng
phn ly v kh nng hp ph b hn ch. Mt khc, cng cn lu l dng axt ca
fluoretxein t tan trong nc. Diclofluo-retxein l axt mnh hn (Ka = 10-4), mt khc
kh nng hp ph ca anion ny mnh hn nn c th chun pH thp.
Trong bng 6.2 c ghi phm vi ng dng ca mt s cht ch th thuc dy fluoretxein.
Bng 6.2. Tnh cht v phm vi ng dng ca mt s cht ch th
thuc dy fluoretxein.
Cht ch th
Fluoretxein
Diclofluoretxein
Eozin

lon cn chun Cht

chun
Cl- (Br-, I-) Ag++
Cl- (Br-, I-) Br-, Ag+
I-, SCNAg+

Nng thp
pH Bin i mu
nht c th
chun (mol/l)
7-10 vng lc hng
5.10-3 5.10-4
4-10 vng lc hng
5.10-4
2-10 thm

* Tnh cht b mt ca kt ta:

S hp ph ph thuc nhiu vo b mt pha rn. Nu kt ta b ng t khi chun
th cht ch th hp ph s km tc dng. Cn trnh s ca cc ion kim loi a ha tr
(nh Al3+, Fe3+) c tc dng lm ng t mnh kt ta. trnh ng t c th cho vo
hn hp chun mt cht keo bo v, v d khi chun Cl - c th cho dextrin, gelatin.
Khng c chun cc dung dch c qu v s ng t s xy ra

d dng hn (nng chun khng c qu 0,025M). Ngoi cc cht ch th an-ion,

ngi ta cng dng c cc cht ch th cation nh metyl tm, rozamin 6G, metyl vng...
6.2.3.4. Chun Zn2+ bng K4[Fe(CN)6]
Trong phng php chun kt ta, ngoi vic chun cc halogenua bng
AgNO3, ngi ta cn chun Zn2+ bng dung dch K4[Fe(CN)6]. Trong mi trng
trung tnh hay axt yu ion Zn2+ tc dng vi K4[Fe(CN)6] cho mt kt ta kh tan
3ZnSO4 + 2 K4[Fe(CN)6] = KZn3 [Fe(CN)6]2 + 3K2SO4
xc nh im cui ca phng php ny, ngi ta dng ch th oxy ha -kh l
iphenylamin v trong dung dch chun c pha thm mt t K3[Fe(CN)6]. Khi Zn2+
kt ta ht vi K4[Fe(CN)6] th 1 git dung dch chun d s to nn mt cp oxy ha kh lin hp Fe(CN)6 /Fe(CN)6 trong dung dch nn xut hin mt th oxy ha v s oxy
ha iphenylamin lm cho n i mu, phi ngng chun ngay.
-

BI TP

178. Phn bit dung dch bo ha, cha bo ha, qu bo ha. Cho v d.
179. a) Th no l tch s tan ca cht kh tan trong
nc? b) Trnh by quy lut tch s tan.
c) Vit biu thc tch s tan v tan ca cc cht sau: AgCl, Ag2CO3, Ca3(PO4)2,
Fe(OH)3, K2Zn3[Fe(CN)6]2, MgNH4PO4.
180. Tnh tan ca CaC2O4 trong dung dch (NH4)2C2O4 5.10- M v so snh vi
tan ca n trong nc. Cho TCaC O = 2,57.10-9 250C.
181. Trong dung dch bo ha ca cht kt ta AB2X3 c cn bng:
AB2X3
A+ + 2B+ + 3X-Nng ca XHrong dung dch bo ha l 4.10-3M a)
Tnh
.
AB X b) Tnh tan ca AB2X3 trong dung dch BCl 5.10
-6
M.
182. Xt s kt ta phn on trong hai trng hp sau:
a. Cho dn dn dung dch Na2SO4 long vo dung dch hn hp Ba2+ v Ca2+ c
[Ba2+] = 10-2M, [Ca2+] = 10-1M. Bit TBaSO = 1,1.10- ,
= 6.10-5 250C.
b. Cho dn dn dung dch AgNO3 long vo dung dch hn hp (Cl- + CrO4 ) c [Cl-] =
[CrO4 ] = 10-2M Bit TAgCl = 1,8.10 , TAg CrO = 1,1.10 250C.
183. Hi tan ca MgF2 v BaCO3 c bng nhau khng, bit rng tch s ha tan ca
chng gn bng nhau.
184. Kt ta no s thot ra trc khi thm dn dung dch AgNO 3 vo dung dch cha
cc ion clorua, brmua cng nng . Bit TAgCl = 1,8.10-10 v TAgBr = 7,7.10-13
250C.
185. Tnh gi tr pH ca mi trng lc bt u kt ta v kt ta hon ton Mg2+
-2

10

2-

2-

2+

10

12

dng Mg(OH)2 nu ban u [Mg2+] = 10-2M. Bit TM (OH)2 = 1,8.10 11.

9. Chng minh:
Khi kt ta Cd2+ v Zn2+ c cng nng ban u [Cd2+] = [Zn2+] = 0,1M bng
H2S bo ha (nng 0,1M) pH = 5 th CdS kt ta hon ton m Zn2+ khng kt ta.
Bit H2S c K1 = 5,7.10-8; K2 = 1,2.10-15; TCds = 3,6.10-29; TZns = 1,2.10-23
0
25 C.
186. Thm vo dung dch cha 0,1M Pb(NO 3)2 v 0,01M Hg2(NO3)2 mt dung dch
KCl, hi cation no trong 2 cation Pb 2+ v Hg + s bt u kt ta trc v hi bao
nhiu phn trm ca cation cn li khi bt u kt ta cation th hai.
Bit THg2Cl2 = 1,1.10 YTpbcl2 = 2,4.10-4 25C
187. Tnh pAg v pCl khi chun 25ml dung dch AgNO 3 0,1M bng dung dch
NaCl 0,1M ti cc im khi thm 24ml, 25ml v 26ml dung dch NaCl.
Cho^ bit: TAgCl = 1,8.10-10 250C.
188. Tnh nng ion Br- v Ag+ trong dung dch khi chun 100ml dung dch KBr
0,1M bng dung dch AgNO3 0,1M sau khi thm 50,0; 90,0; 98,0; 99,0; 99,8; 100,0;
100,1; 100,2; 110,0ml dung dch chun. TAgBr = 4.10-13 250C.
189. Tnh pAg v pCl sau khi thm 21,0; 25,0 v 26,0ml dung dch NaCl vo 25,0ml
dung dch AgNO3 0,1M. TAgCl = 1,8.10-10 250C.
190. Cc phng php xc nh im cui trong qu trnh chun cc halogenua
bng bc nitrat.
191. Tnh bc nhy ca cc ng nh phn khi chun cc dung dch NaCl:
NaBr: Nai c nng 0,1M bng dung dch AgNO3 0,1M (bc nhy c coi l chun
tha hay thiu 0,1% AgNO3).
Cho bit: TAgCl = 1 , 8 . 1 0 ; TAgBr = 7,7.10-13; TAgi = 1,5.10-16 250C.
192. Tnh bc nhy pAg khi nh phn dung dch K 2CrO4 0,01M bng dung dch
AgNO3 0,1M. Cho TA c O = 1,1.10-12.
193. Chun 30ml dung dch ZnSO4 0,100M th phi dng ht bao nhiu ml dung
dch K4[Fe(CN)6] 0,05M.
194. Tnh hm lng ZnO c trong mu phn tch nu ly 0,380g mu ha tan thnh
dung dch, thm vo 24,30ml dung dch K4[Fe(CN)6] 0,051M ri chun lng
K4[Fe(CN)6] d th tn mt 8,40ml dung dch ZnsO4 0,104M.
195. Cn bao nhiu ml dung dch K4[Fe(CN)6] 0,0510M chun 25ml dung dch
ZnSO4 0,100M theo phng trnh phn ng:
2 K4[Fe(CN)6] + 3Zn2+ = K2Zn [Fe(CN)6]2 + 6 K+
196. Tnh nng ng lng v chun theo clo ca dung dch AgNO 3, bit rng
thm 0,1173g NaCl vo 30ml dung dch AgNO3 sau chun lng bc d th tn mt
3,20ml dung dch NH4SCN. Chun 10ml dung dch AgNO3 th tn mt 9,7ml dung dch
NH4SCN.
2

18

g2 r

TI LIU THAM KHO

197.
Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch,
NXB KH & KT, 2002.
198.

L c, Ha hc phn tch. NXB H Quc Gia H Ni, 2002.

199.

Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc,

2000.
200.

Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002.

201.
Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch,
NXB H&TH Chuyn nghip, 1984.
202.
H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v
Nguyn Huyn dch. NXB KH & KT, 1976.
203.
B.H.AneKceeB, KaniHecTBeHHbi aHani3, MocKBa, H3gaTej[bcTBo
"XiMira",
1972
204.
B.H.AneKceeB, KonecTBeHHMH aHani3, MocKBa, H3gaTej[bCTBo
"XiMira",
1972

CHNG 7
SAI S TRONG PHN TCH NH LNG HA HC

Gi tr ca mt php phn tch c nh gi ng v lp ca kt qu thu

c.
7.1. Mt s khi nim.
205. ng v lp.
ng phn nh s ph hp gia kt qu thc nghim thu c vi gi tr thc
ca i lng o.
lp phn nh s ph hp gia cc kt qu thu c trong cc th nghim lp li
trong cng iu kin thc nghim quy nh ca php phn tch. Kt qu phn tch c th
c c lp cao (chnh xc) nhng khng ng.
V d: Khi kim tra dung dch HCl c nng chnh xc 0,1000M, hai sinh vin A
v B thu c kt qu nh sau:
A: 0,1002 ; 0,0999 ; 0,1004 ; 0,0996 ; 0,1003
B: 0,1014 ; 0,1017 ; 0,1016 ; 0 1015 ; 0 1014
R rng, kt qu ca sinh vin A ng hn nhng km chnh xc hn so vi kt
qu ca sinh vin B.
ng v lp c lin quan cht ch vi sai s phn tch. Ngi ta phn bit
sai s h thng vi sai s ngu nhin.
206. Sai s h thng.
Sai s h thng lm cho kt qu phn tch khng ng. Nguyn nhn ca sai s h
thng l xc nh, v v nguyn tc c th bit c. Mi loi sai s h thng lm cho
kt qu phn tch dch chuyn theo mt chiu nht nh (tng hoc gim). Sai s h
thng c th khng i, cng c th thay i theo iu kin. V d, khi cn CaCl 2 trong
mt chn cn khng y np th kt qu cn s tng dn theo thi gian v CaCl2 l cht
ht m mnh. Sai s ny tng theo thi gian cn v b mt tip xc vi kh quyn ...
Tuy vy sai s h thng do vic pha ha cht trong bnh nh mc c chun ha sai l
i lng khng i, khng ph thuc cc iu kin phn tch khc. Trong phn tch ha
hc c th phn chia cc loi sai s h thng sau y:
* Sai s do s dng my, ha cht v thuc th, v d s dng cn v qu cn
khng ng, s dng cc dng c o th tch khng chnh xc. Sai s c th xy do cc
cht l t bnh thy tinh, s v. v ... xm nhp vo dung dch hoc thuc th c ln tp
cht.
* Sai s thao tc do ch quan ngi phn tch gy ra, khng ph thuc my, dng
c v khng lin quan vi phng php phn tch. Sai s ny c th rt nghim trng
i vi nhng ngi phn tch thiu kinh nghim hoc lm vic thiu suy ngh, cn thn.
Ngi mi lm phn tch th thng phm sai lm nghim trng do khng bit lm
vic. Tuy vy, khi quen cng vic v nu lm vic cn thn, nghim tc th sai s thao
tc thng l khng ng k.

* Sai s c nhn do kh nng ca ngi phn tch khng th thc hin chnh xc
mt s thao tc phn tch. V d khng th nhn bit chnh xc s chuyn mu ca cht
ch th ti im cui chun .
Thuc loi ny cng phi k n sai s tm l, tc l khuynh hng ca ngi
phn tch khi lp li th nghim mun chn gi tr ph hp vi gi tr o trc, hoc
gn vi gi tr ca bn. Sai s ny kh ph bin.
* Sai s phng php c lin quan vi tnh cht ha hc hoc tnh cht ha l ca
h o, t lin quan vi thao tc phn tch. V d, phn ng phn tch khng xy ra hon
ton hoc phn ng ph xy ra lm sai lch tnh hp thc ca phn ng chnh v.v ...
Tht ra sai s phng php c lin quan cht ch vi sai s thao tc. Trong nhiu
trng hp nu thao tc tt th c th lm gim sai s phng php v ngc li. Chng
hn, nu ra kt ta kho sao cho th tch nc ra khng ln th s mt mt kt ta do
tan s khng ng k, ngc li nu dng qu nhiu nc ra th lng cht mt i
khi ra s nhiu. Hoc nu iu chnh kho nhit khi nung th c th trnh c s
phn hy cht khi nung ... 7.1.3. Sai s ngu nhin.
Sai s ngu nhin nh hng n lp li ca kt qu o v lm gim chnh
xc phn tch.
Sai s ngu nhin do nhng nguyn nhn ngu nhin, khng nhn th y trc c
v lm cho kt qu phn tch dao ng theo cc chiu khc nhau (lc tng, lc gim).
Sai s ngu nhin lun lun xut hin d php phn tch c thc hin ht sc cn thn
v iu kin thc hin c gi c nh nghim ngt. Do c tnh ca n nh vy m
vic x l v nh gi sai s ngu nhin ca mi php phn tch l rt quan trng. N
cho php xc nh gi tr ca phng php phn tch, nh gi cht lng lm vic ca
ngi phn tch, nh gi so snh cng vic phn tch ca cc phng th nghim khc
nhau, v.v ... Do bn cht ca n m sai s ngu nhin phi c x l bng ton hc
thng k.
7.2. nh gi sai s ca cc php o trc tip.
Trong thc hnh phn tch ha hc phi tin hnh nhiu thao tc, trong bt buc
phi c php o trc tip, tc l so snh vt o vi vt chun nh cn, o th tch. Mi
php o trc tip u mc sai s ngu nhin v sai s ny cng vi cc sai s mc phi
trong cc giai on phn tch khc nhau s quyt nh chnh xc ca php phn tch.
Khi tin hnh th nghim chng ta thc hin mt s th nghim c lp trong cng
iu kin ging nhau v t cc kt qu ring l thu c ta tin hnh x l thng k
nh gi chnh xc ca php o. Cc i lng c trng thng k quan trng nht l
gi tr trung bnh cng v phng sai. 7.2.1. Gi tr trung bnh cng.
Gi s ta tin hnh n php o c lp i lng X vi cc kt qu X1, X2, . .
Xn.

_ X, ..............................................

Gi tr trung bnh cng: X = -----n

l gi tr gn vi gi tr thc ca i lng

cn o vi xc sut cao nht trong s cc gi tr o c.

7.2.2. Phng sai.
Phng sai ca php o phn nh phn tn ca kt qu o, c nh gi
bng:

239

(Xi - X)
s2 = ^
k

240

k = s bc t do. Nu ch c mt i lng cn o X th k = n - 1.
Gi tr s
thng c gi l lch chun ca php o.
lch chun ca i lng trung bnh cng s- c tnh theo:

241

(X

2
i-

X)

242

n(n -1)
Trong thc t tin tnh ton cc i lng X,s2,sX, ngi ta thng chn
trong dy n gi tr o c X1s . . Xn mt gi tr C sao cho C X. Sau tnh X v s 2
theo cc cng thc sau:
2

= ^

nn

yi

xX = C +

v s2

243

n-1

244

y, x 2 = y 2 -(y) v yi = Xi - C. V d 1:
Hy tnh gi tr trung bnh cng, lch chun, phng sai ca php xc nh
niken trong thp da vo cc s liu phn tch sau y:
Hm lng % ca Ni trong thp cc th nghim phn tch c lp: 0,69; 0,68;
0,70 ; 0,67 ; 0,68 ; 0,67 v 0.69.
yi.102
1
0
2
-1
0
-1
1
Eyiyi = 2.10-2

Xi %
0,69
0,68
0,70
0,67
0,68
0,67
0,69

yi .10
1
0
4
1
0
1
1
2
Eyiyi = 8.10-4

Chn C = 0,68
yi = Xi - C
tin khi tnh ton (khng phi x l cc s l) ta nhn yi vi 102 v tt
nhin yi vi 104.
2

Ta c:

X = 0,68 +

= 0,683
7

-4 2

s = 7,43.10

y x2 =4 8.10 4 -4^ = 7,43.10 7

43 10
= 1,238.10-4 6

s=

v1,238.10 4 =

1,11.10
SX = 1,238.10 =1,76.10
7
-2-4

--3

sX = 4,21.10

246

gi tr thc ca i lng phi o: s

247

Trong thc t s c nh gi ng vi mt tin cy a cho, v d a = 0,95 (95%) hoc

a = 0,99 (99%) . . . s c tnh theo: s = s-t k
t = h s Student ng vi s bc t do k ca php o v tin cy cho trong
,k

bng.
Khong tin cy ca gi tr o l khong ti c kh nng tn ti gi tr thc ca
php o vi xc sut a cho.
X
X
hay X
- S a< n <
+ Sa

Xt a,k <

<

+ sXt a,k

Bng 7.1. Cc gi tr h s Student tak ng vi a = 0,95 v 0,99

k
1
2
3
4
5
6
7
8
9
10
11
12
13
^^^^ a k
14
15
16
17
18
19
20
25
30
40
60
120

0,95
12,706
4,303
3,182
2,776
2,571
2,447
2,365
2,306
2,262
2,228
2,201
2,179
2,160
0,95
2,145
2,131
2,120
2,110
2,103
2,093
2,086
2,060
2,042
2,021
2,000
1,980

0,99
63,657
9,925
5,841
4,604
4,032
3,707
3,499
3,355
3,250
3,169
3,106
3,055
3,012
0,99
2,977
2,947
2,921
2,898
2,878
2,861
2,845
2,707
2,750
2,704
2,660
2,671

V d 2: nh gi chnh xc ca kt qu xc nh hm lng niken trong thp

theo cc s liu cho trong v d 1 vi tin cy = 0,95.

Kt qu tnh trong v d 1 cho ta: X =

0,683 sX = 4,21.10k = n - 1 = 6 vi a = 0,95; k = 6
ta c t = 2,447 (bng 7.1)
sa=0,95 = sX.t a,k = 4,21.10
-3
.2,447 = 1,03.10- chnh xc: S = 0,01
3

0,95

Kt qu o: X S
,

0 95

0,68 0,01 hay 0,67 < < 0,69

,S

Sai s tng i ca php xc nh: -=a- .100%

X
Trong v d trn th sai s tng i % 0,01.100 = 1,5%
0,68
7.2.4. S c ngha v cch ghi kt qu phn tch. 7.2.4.1. S
c ngha.
Kt qu ca mt php o trc tip cng nh ca mt thao tc phn tch phi c
ghi chp sao cho ngi s dng s liu hiu c mc chnh xc ca php o. V
nguyn tc, s liu phi c ghi sao cho ch c s cui cng l bt nh. Chng hn,
nu cn trn cn phn tch vi nhy 0,1mg th kt qu cn phi c ghi n s ch
phn mi mg, v d 1,2516 gam m khng vit 1,251 gam hoc 1,25160 gam. Cc s
1, 2, 5, 1 l cc s hon ton tin cy v chng ta c c t cc qu cn, cn s 6 l bt
nh v c ghi c tnh trn thang chia da theo kim ch hoc theo v tr dao ng ca
vch sng. Cc s tin cy cng vi s bt nh u tin c gi l s c ngha. Trong
kt qu cn trn ta c 5 s c ngha: 4 s tin cy (1, 2, 5, 1) v 1 s bt nh (6).
Phng php ti u xc nh s bt nh trong kt qu o l phng php tnh
cn tin cy nh thc hin trn. Trong v d 2, ta xc nh c cn tin cy l S =
0,01. Nh vy s th hai sau du phy l bt nh v khi ghi kt qu phn
0 95

tch phi lm trn n con s th hai sau du phy: X = 0,68 0,01, y c 2 s c

ngha, s 6 l tin cy, s 8 l bt nh. Trong thc t khng phi bao gi cng c y
thng tin ( lch chun, s php o) tnh c cn tin cy.
Do nu khng c mt thng tin b sung ngi ta thng ngm hiu rng s
cui cng c bt nh 1. Chng hn, nu vit s c th tch trn buret l 23,40 ml
th iu c ngha l buret c chnh xc 0,01ml, tc l vch chia trn buret n
0,1 ml, cn s c phn trm ml l bt nh (c lng).
S 0 c dng thit lp im thp phn khng c tnh vo s c ngha. V
d, trong s 0,0034 ch c hai s c ngha (3 v 4), nhng trong s 3,040 li c 4 s c
ngha.
i vi cc s dng phc tp ngi ta thng chuyn sang dng s ly tha thp
phn v cc s phn nguyn c tnh vo s c ngha. V d 1064 = 1,064.10 3 c 4 s
c ngha; 0,000520 = 5,20.10-4 c 3 s c ngha, hoc vit 5,2.10-4 c 2 s c ngha. S
liu 2,4 gam c 2 s c ngha. V nu quy ra mg th phi vit

2,4.103 mg (2 s c ngha) m khng vit 2400 mg (4 s c ngha).

i vi cc s logarit th cc s bn tri im thp phn (phn c tnh) khng
c coi l s c ngha v y l cc ch s ly tha. V d lnx = 3,135 c 3 s c ngha
(1, 3, 5); lgx = 2,68 c 2 s c ngha (6 v 8). 7.2.4.2. Quy tc tnh v lm trn s.
Trong cc php tnh ch c php lm trn kt qu cui cng (nhm trnh vic
gim chnh xc ca kt qu do vic lm trn cc giai on tnh trung gian).
* Cng v tr
Khi cng v tr ch gi li kt qu cui cng mt s s thp phn bng ng s thp
phn ca s hng c s thp phn t nht. V d 3: Thc hin php tnh: a. Y = 6,145 +
13,24 + 34,7 " Y = 54,085
Kt qu lm trn: Y = 54,1 (gi li 1 s thp phn)
b. X = 1374,252 - 309,48
X = 1064,772 Kt qu lm trn: X = 1064,77 (gi li
2 s thp phn)
* Nhn v chia
Khi nhn v chia cn gi li kt qu cui cng mt s s c ngha bng ng s c
ngha ca tha s c s c ngha t nht. V d 4: Thc hin php tnh:
3,084.0,275
a. Y =--------_--41,256
Y = 0,020557 lm trn Y =
0,0206 (3 s c ngha) -5
.3,7.10-8
b X = 6,125.10
b. X =------------
-------------------5,37.10X = 4,220.103
-6
lm trn X = 4,2.10-16 (hai s c ngha)
* Logarit
V d 5: Tnh logarit ca Y = 3,34.10lgY = -5 + 0,5237 = -4,476 (c 3 s c ngha
4, 7, 6 tng t trong Y cng c 3 s c ngha)
V d 6: pH = -lg[H+] = 6,47. Tnh [H+]. [H+] = 0-5
-6 47
' = 3,39.10-7 lm trn: [H+] = 3,4.10-7 (hai s c ngha tng t gi tr pH c hai s
c ngha).
* Trong mt s trng hp khi gi li cc s c ngha cn cn nhc sao cho bt
nh tng i kt qu cui cng ph hp vi bt nh tng i ca cc s liu
c dng tnh ton.
V d 7:
1:01
= 1,03 m khng vit 1,0 v bt nh tng i ca c hai s 1,01 v 0,98

V d
V 1,01
0,98 , 0,99 m
in
i nm A
0,01n 0,01
0,98 u bng 1%
1
8:
khng vit 0,990 bi v bt nh tng i
% ca c hai s 1,02
1.02
1,03
v 1,03 cng u bng 1%. Nu vit 0,990 th bt nh s l -0,001.100 = 1% .
0,990
V d 9:
lgx = lg2,114 bng 0,3251 phi vit 0,325 m khng vit 0,3251 bi v bt nh
ca x l 0,001 nn nu ly lg(2,114 0,001) s c 0,3249 v 0,3253. Nh vy s bt
nh l s th ba sau du phy.
V d 10:
lgx = -3,124 x = 10-3'124 = 7,5.10-4 m khng vit 7,52.10-4, bi v nu coi lgx = (3,124 0,001) th x bng 7,498.10-4 v 7,533.10-4 nh vy s th hai sau du phy l
bt nh!
Ch : Khi lm trn s nu s l b hn 5 th c th b i, nu s ln hn 5 th c
th thm 1 n v vo s trc. Nu nghi ng hoc s mt mt chnh xc th gi li
mt s sau s c ngha cui nhng phi vit tt xung thnh ch s di. V d: 6,832
lm trn thnh 6,83; 7,988 lm trn thnh 7,99 ; 6,455 lm trn thnh 6,45 5 nu khng
mun vit 6,45.

TI LIU THAM KHO

207.
Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn
tch, NXB KH & KT, 2002.
208.
2000.

Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc,

209.

Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002.

210.
Doerffl, Thng k trong ha hc phn tch. Trn Bnh v Nguyn Vn
Ngc dch, NXB H&TH chuyn nghip, H Ni, 1983.

PH LC

S2O8Ag

2-

2
2
2

1
10
5
6
6
2
6
2
4
10
2
3
2
1
2
1
2
1
1
2
2
1
2
2
1
2
2
1
2
2
3
2
2
2
2
1
2
2
1
2
3

+(trong 4M HClO4)
Ag2+(trong 4M HClo3)
NaBiO3 + 4H+ H2O2 +
2H+ pbo2 + 4H+
Ce(sO4)32-2BrO3- +
12H+
MnO4- + 8HClO3 +
6H+ BrO3Cr2O7+
2-

+ 14H+ MnO2i + 4H+

O2 + 4H+ 2IO3- +
12HBr2 (lng)
NO3+
+ 4H+ NO32- ++
3H-+ Cu2+ +
IHg2 +
+
2+
Ag
H
+
2 +
-g2 +
NO3- + 2HFe+
3
+
H3AsO4 +
2H[Fe(CN)6]CuHg2Cl2
Cusi + 2H+
TiO+
3-

2+
2+
2+

+ 2H+ S4O622HFe+
3+
2+
pb SnCd2CO2t + 2H+
V2+
2+
3

+
Ni2+ CdCr2+

+
Fe2+ +

S electron trao
i
_________2_________
2
2

2+
4-

+ H2O
2S2O3Fe
Pbi Sni Cd
H2C2O4 2+
Nii Cdi
CrAsH
V

2F- 2SO4Ag
+
+
+ Ag+BiO
+
+ Na+ + 2H2O 2H2O
+

SnH2S
Ti2+
4+

Dng kh
3
2-

pb2+ + 2H2O Ce3+

+ 3SO4 Br2 +
6H2O Mn2+ +
4H2O Cl- + 3H2O
Br- + 3H2O
2Cl2Cr3
+ + 7H2O
Mn2+ + 2H2O
2H2O I2 +6H2O
2BrNOt + 2H2O
HNO3 + H2O
CuI
Hg Hg
NO2t + H2O
FeHAsO2 + 2H2O
2I[Fe(CN)6]C
ui
2Hg +
2ClCu-

Bng 1. Gi tr
in th tiu chun
EDng oxy ha
1

2-

Eo (V)
4
+2,870
+2,000
+1,970
+1,927
+1,800
+1,770
+1,455
+1,440
+1,52
+1,51
+1,45
+1,45
+1,359
+1,33
+1,29
+1,23
+1,19
+1,087
+0,96
+0,94
+0,86
+0,85
+0,7994
+0,792
+0,8
+0,771
+0,56
+0,536
+0,356
+0,337
+0,268
+0,153
+0,15
+0,14
+0,1
0,09
= 0,00
-0,036
-0,126
-0,14
-0,402
-0,49
-0,255
-0,23
-0,402
-0,41
-0,44
-0,60

252
2

1
2+

Zn
FeS CdS
MnA
l
2-

2+
2+
3+

Mg2+NaL
i+

22223
211

3
Zni
Fe + S+
+
2-

Cd
+
SMni Ali
Mgi
Nai
Lii 4
-0,762
-0,95
-1,17
-1,19
-1,66
-2,37
-2,713
-3,03

253

Bng 2. Hng s phn li ca mt s axit, baz thng gp

Tn hp cht
AXIT
Axit nitro
Axit xyanhydric
Axit benzlic
Axit lactic
Axit fomic
Axit axtic
Axit sunfur
Axit sunfuhydric

Cng thc
HNO3
HCN

C6H5COOH
CH3CHOHCOOH
HCOOH
CH3COOH
H2SO3
H2S

Axit cacbonic

H2CO3

Axit crmic

H2CrO4

Axit tactric

H2C4HO6

Axit xalic

H2C2O4

Axit phtphoric

H3PO4

Axit limnic
BAZ
Amniac
Anilin
Mtylamin
Hyrxit ch
Quinin

NH4OH
C6H5NH2
CH3NH2
Pb(OH)2
C20H24C2N2.3H2O

Hng s phn ly K
4.10-4
7,2.10-10
6,3.10-5
1,37.10-4
1,77.10-4
1,80.10-5
K1 = 1,3.10-2 K2 = 5.10-5
K1 = 5,7.10-8 K2 =
1,2.10-15
K1 = 4,31.10-7 K2 =
5,61.10-11
K1 = 1,8.10-1 K2 =
3,2.10-7
K1 = 1,04.10-3 K2 =
4,55.10-5
K1 = 5,9.10-2 K2 =
6,4.10-5
K1 = 7,51.10-3 K2 =
6,23.10-8 K3 = 2,2.10-13
K1 = 8,4.10-4 K2 =
1,8.10-5 K3 = 4.10-6
1,79.10-5
4.10-10
1,38.10-4
K1 = 9,6.10-4 K2 = 3.10-8
K1 = 2,2.10-7 K2 =
3,3.10-10

pK=-lgK
3,4
9,14
4,2
3,86
3,75
4,75
1,89 5,3
7,24 14,92
6,37 10,25
0,75 6,5
2,89 4,34
1,23 4,19
2,127,2112,67
3,084,745,4

4,75
9,17
3,36
3,02 7,52
6,66 9,48

254

Bng 3. Tch s tan v tan ca mt s cht in li kh tan 18 -- 250

c
Loai cht
Cng thc
Tch s tan
tan (Mol/l)
tan (g/100ml)
-19
-5
Asenat
Ag3AsO4
4,5.10
1,84.10
8.5,10-4
7,4.10-5
2,6.10-2
9,54.10-1
Brmua
PbBr2 CuBr AgBr
-9
-5
5,3.10
7,3.10
1,05.10-3
Hg2Br2
7,7.10-13
8,8.10-7
1,65.10-5
-23
-8
5,2.10
2,8.10
1,57.10-6
Ca(OH)2 Mg(OH)2
3,1.10-55.102.10-21,1.10-4
1,48.10-3
Hyrxit
12
-14
-5
Cd(OH)2
1,2.10
1,4.10
6,42.10-4
Mn(OH)2Ni(OH)2
4.10-144,8.102,1.10-5
2,04.10-4
16
-16
-5
Fe(oH)2 Co(OH)2
6,3.10
5,4.10
1,87.10-4
Zn(OH)22Cu(OH)2
2.10-16 1.104,9.10-6
5,01.10-5
17
-6
Sn(OH)2Cr(OH)3
5,6.10
3,7.10
4,50.10-5
20
Al(OH)3
5.101,4.10-6
3,44.10-5
26
-31
-7
Fe(OH)3Sb(oH)3
5,4.10
2,4.10
1,40.10-5
-33
-9
1,9.10
2,3.10
2,34.10-6
3,8.10-18 4.101,2.10-8
3,51.10-8
12
-9
2,9.10
1,24.10-7
1,9.10-9
2,26.10-8
-11
1,9.10
2,03.10-8
3,28.10-10
-9
-3
8,7.10
1,3.10
5,99.10-2
Iua
PbI2Cui AgI 2 2
5,06.10-12
2,35.10-6
4,38.10-5
-16
-8
1,5.10
1,2.10 5,2.10
2,82.10-7
8
1,2.10-23
3,41.10-6
MgCO3
1,0.10-5 2,7.103,2.10-8 1,6.102,70.10-2,01.10Cacbonat
8
-9
5
-5
ZnCO3
8,1.10
9,0.10
1,78.10-6,94.101
BaCO3
4,8.10-9 1,6.106,93.10-5
5,91.10-4
9
-11
-5
CaCO3Sr
8,8.10
4,0.10 9,4.10
1,08.10-4
-11
6
-4
CO3
2,5.10
5.10 1,15.10
5,79.10-5
7
MnCO3Fe
6,15.10-12
3,9.10-7
3,17.10-3
-13
-6
CO3Ag2C
1,5.10
1,6.10 2,8.10
1,04.10-5
3
O3 PbCO3
2,5.10-14 9.10-17
2,76.10-6
CdCO3
1,29.10-4
HgCO3
8,57.10-5
9,2.10-3
1,03.10-4
xalat
MgC2O4BaC2O4.2
-7
-4
1,2.10
3,5.10
8,55.10-3
H2O
-8
-4
5,61.10
2,4.10
4,26.10-3
SrC24.H2OCaC2
1,53.10-8
1,2.10-4
3,05.10-3
o4.
-9
-5
2,57.10
5,1.10
7,45.10-4
H2OZnC2O4.2H2
1,35.10-9
3,7.10-5
7,01.10-4
O
-11
-6
3,2.10
5,7.10
1,68.10-4
PbC2O4Ag2C2O4
1,1.10-11
1,4.10-4
4,25.10-8
Hg I

255

Sunphat

Sunfua

Ag2SO4
CaSO4.2H2O
Hg2sO4
SrSO4
PbSO4
BaSO4
MnS
FeS
NiSa
NiSp
CoSa
CoSp
ZnS
SnS
CdS
PbS
CuS
Cu2S
Ag2S
HgS

7,7.10-5 6,1.105
6,3.10-7
2,8.10-7 2,2.109
1,08.10-10
1,4.10-15
3,8.10-19
3.10-21 2.10-28
7.10-23 2.10-27
1,2.10-23 1.1028
3,6.10-29
1,1.10-29
8,5.10-45
2.10-47
1,6.10-19
4.10-53
1,6.10-72

2,7.10-3
7,8.10-3
7,9.10-4
5,3.10-4
1,5.10-4
1,0.10-5
3,7.10-8 6,1.1019
5,5.10-11
1,4.10-14
8,4.10-12
4,5.10-14
3,5.10-12 1.1014
6,0.10-15
3,3.10-15
9,2.10-23
1,7.10-16
3,4.10-17
6,3.10-17
2,7.10-15

8,12.10-1
1,34.10-1
3,93.10-2
9,47.10-3
4,55.10-5
2,33.10-4
3,22.10-7
5,36.10-9
4,99.10-10
1,27.10-13
7,64.10-11
1,27.10-13
3,41.10-11
1,51.10-13
8,67.10-14
7,9.10-14 8,8.1022
2,71.10-15
8,43.10-16
1,47.10-25
1,39.10-13

6,3.10-5
1,6.10-5
1,7.10-7
3,9.10-2
1,35.10-5
1,6.10-5
5,9.10-3
1,5.10-5
1,3.10-4
1,3.10-7

8,65.10-4
4,19.10-4
1,38.10-5
1,08 1,86.104
7,55.10-4

Bi S

23

Pht pht

Clorua
Crmt

MgNH4PO4
Ag3PO4
Pb2(PO4)3
PbCl2
AgCl
Hg2Cl2
SrCrO4
BaCrO4
Ag2CrO4
PbCrO4

2,5.10-13
1,8.10-18
4,5.10-32
2,4.10-4
1,8.10-10
1,1.10-18
3,5.10-5
2,41.10-10
1,1.10-12
1,8.10-14

1,20.10-1
3,80.10-4
4,31.10-3
4,20.10-6

256

TI LI U THAM KHO

211.
Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch,
NXB KH & KT, 2002.
212.

L c, Ha hc phn tch. NXB H Quc Gia H Ni, 2002.

213.

Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc,

2000.
214.

Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002.

215.
Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch,
NXB H&TH Chuyn nghip, 1984.
216.
Doerffl, Thng k trong ha hc phn tch. Trn Bnh v Nguyn Vn
Ngc dch, NXB H&TH Chuyn nghip, H Ni, 1983.
217.
H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v
Nguyn Huyn dch. NXB KH & KT, 1976.
218.
B.H.AneKceeB, KaniHecTBeHHbi aHani3, MocKBa, H3gaTej[bcTBo
"XiMira",
1972
219.
B.H.AneKceeB, KonecTBeHHMH aHani3, MocKBa, H3gaTej[bCTBo
"XiMira",
1972

257

MC LC
Trang
3
5
Cht in ly mnh v yu.

Li m u
Chng 1. Dung dch cht in ly- Cn bng ha hc
220.
5
221.
Cn bng ha hc v hot .
5
222. Nhc li mt s kin thc cn dng
5
223. Cn bng v hng s cn bng.
6
Ti liu tham kho
9
Chng 2. i cng v phn tch khi lng v phn
tch th tch 10
224.Nguyn tc chung ca phng php phn tch khi lng
10
225.Cc phng php phn tch khi lng
10
226. Phng php y
10
227. Phng php kt ta
10
228. Phng php in phn
11
229. Phng php chng ct
11
2.3. Phng php kt ta.
11
230. Ni dung v yu cu ca kt ta trong phng php kt ta
11
231. iu kin tin hnh phn tch theo phng php kt ta.
12
232. Lc, ra, lm kh v nung kt ta.
14
2.4. Phng php in phn.
15
233. Ni dung
15
234. Cc thit b
15
235.ng dng ca phng php khi lng.
16
236.Phng php phn tch th tch
16
237. i cng
16
238. Mt s nh ngha v khi nim
16
239. Cc phn ng dng trong phn tch th tch
18
240. Phn loi cc phng php phn tch th tch
19
241. Cc phng php chun
19
242. Cch biu din nng trong phn tch
19
2.6.7. Cch tnh kt qu trong phn tch th tch
23
Bi tp 25
Ti liu tham kho
26
Chng 3. Cn bng axt - baz. Chun axt baz
27
3.1. ngha thc t cc quan nim v axit - baz.
27
243. Thuyt axit - baz ca Arnit
27
244. Thuyt axit - baz ca Bronsted - Lauri
27
3.2. Cn bng axit - baz trong mi trng nc.
31
245. Tch s ion ca nc, ch s hydrogen
31
246. Quan h gia KA ca mt axit v KB ca mt baz lin hp vi n 32

258

247. Tnh gi tr pH ca mt axit, baz hoc mui trong nc

32

259

3.3. Dung dch m

248. Khi nim v dung dch m
249. m dung
250. ng dng ca dung dch m.
3.4. Tnh nng cc thnh phn ca dung dch khi bit Ph
251. Trng hp n axit HA.
252. Trng hp a axit H2A.
253. Trng hp tng qut HnA
3.5. Chun axit - baz.
254. Bn cht ca phng php
255. Cht ch th trong phng php trung ha
3.6. Cch xc nh im tng ng trong phng php trung ha
256. Khi nim ng nh phn - ng cong Logarit
257. Nguyn tc xy dng ng nh phn axit - baz
3.7. Cc trng hp chun
258. Chun axit mnh bng baz mnh
259. Chun axt yu bng baz mnh hoc baz yu bng axit mnh
260. Chun axit yu bng baz yu hay ngc li
261. Chun a axit (hay a baz), hn hp axit (hn hp baz)
3.7.5. Mt s th d v phng php chun axit - baz
Bi tp 69
Ti liu tham kho
Chng 4. Cn bng oxy ha - kh. Chun oxy ha - kh
4.1. Cn bng oxy ho - kh.
262. nh ngha phn ng oxy ho - kh
263. Cch thnh lp cc phng trnh oxy ha - kh theo phng php
ion - electron
264. Cng cht oxy ho - kh. Th in cc
265. Chiu ca phn ng oxy ha - kh v cc yu t nh hng
266. Hng s cn bng v vn tc ca phn ng oxy ho - kh
4.2. Chun oxy ha-kh.
267. Ch th trong phng php oxy ha - kh
268. ng nh phn trong phng php oxy ha-kh
269. Mt s phng php oxi ha kh thng dng
Bi tp
Ti liu tham kho
Chng 5. Phc cht v thuc th hu c trong ha phn tch. Chun 100
Complexon
5.1. Phc cht.
270. nh ngha
271. Phn loi cc phc cht
272. bn ca phc cht
5.2. Thuc th hu c.
5.2.1. Cc phn ng ca thuc th hu c

41
41
41
43

43
43
44
44
45
45
45
52
52
53
53
53
58
62
64
66
70
71
71
71
72

74
77
80
86
86
88
92
98
99
100
100
100
102
106
106
107

260

273. c tnh ca thuc th hu c

274. C ch tng tc ca thuc th hu c
275. Mt vi loi thuc th hu c thng gp trong ha phn tch
5.3. ng dng ca phc cht v thuc th hu c trong ha phn tch.
276. Pht hin v xc nh ion
277. Che du
278. Thay i cng cc cht
279. Ha tan v tch
5.4. Chun to phc
280. Phng php thy ngn
281. Phng php xyanua
282. Phng php complexon
Bi tp
Ti liu tham kho
Chng 6. Cn bng trong dung dch cha hp cht t tan. Phng php
chun kt ta
6.1. Cn bng trong dung dch cha hp cht t tan.
283. iu kin to kt ta - Tch s tan.
284. Quan h gia tan v tch s tan. Cc yu t nh hng n
tan.
285. Kt ta phn on.
286. Chuyn mt hp cht kh tan ny sang mt hp cht kh tan khc. 126
287. Ha tan kt ta.
288. L thuyt v cu to kt ta.
289. Cng kt v kt ta sau-nguyn nhn lm cho kt ta khng tinh
khit
290. Vai tr ca cng kt trong phn tch.
291. Dung dch keo trong ha phn tch.
6.2. Phng php chun kt ta.
292. c im ca phng php.
293. ng nh phn trong phng php bc.
294. Cch xc nh im cui.
Bi tp
Ti liu tham kho
Chng 7. Sai s trong phn tch nh lng ha hc
7.1. Mt s khi nim.
295. ng v lp
296. Sai s h thng
297. Sai s ngu nhin
7.2. nh gi sai s ca cc php o trc tip.
298. Gi tr trung bnh cng
299. Phng sai
300. chnh xc ca php o trc tip
301. S c ngha v cch ghi kt qu phn tch

107
109
111
111
111
112
112

112
113
113
113
118
118
119
119
119
120
124
128
130
131
134
135
136
136
137
139
143
145
146
146
146
146
147
147
147
148
149
150

261

Ti liu tham kho

Ph lc
Ti liu tham kho
Mc lc

152
153
158
159