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B Y T
HA PHN TCH
TP 1
(DNG CHO O TO DC S I HC)
M S : .20.Y.14
NH XUT BN GIO DC
H NI 2007
Ch o bin son :
V KHOA HC V O TO B Y T
Ch bin :
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Li gii thiu
Thc hin mt s iu ca Lut Gio dc, B Gio dc & o to v B Y t ban hnh chng
trnh khung o to Dc s i hc. B Y t t chc bin son ti liu dy - hc cc mn c s v
chuyn mn theo chng trnh trn nhm tng bc xy dng b sch t chun chuyn mn trong
cng tc o to nhn lc y t.
Sch HO PHN TCH c bin son da trn chng trnh gio dc ca Trng i hc Y
Dc Thnh ph H Ch Minh trn c s chng trnh khung c ph duyt. Sch c cc tc gi
PGS.TS. V Th Bch Hu, ThS. Phng Th ng, ThS. Trn Th Trc Thanh, ThS. Phan Thanh Dng,
ThS. Nguyn Hu Lc Thy bin son theo phng chm : Kin thc c bn, h thng ; ni dung chnh
xc, khoa hc ; cp nht cc tin b khoa hc, k thut hin i v thc tin Vit Nam.
Sch HO PHN TCH c Hi ng chuyn mn thm nh sch v ti liu dy - hc chuyn
ngnh Dc s i hc ca B Y t thm nh nm 2007. B Y t quyt nh ban hnh l ti liu dy -
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hc t chun chuyn mn ca ngnh trong giai on hin nay. Trong thi gian t 3 n 5 nm,
sch phi c chnh l, b sung v cp nht.
B Y t xin chn thnh cm n cc tc gi v Hi ng chuyn mn thm nh gip hon thnh
cun sch ; Cm n GS.TS. T Vng Nghi, PGS.TS. Trn T An c v phn bin cun sch sm
hon thnh kp thi phc v cho cng tc o to nhn lc y t.
Ln u xut bn, chng ti mong nhn c kin ng gp ca ng nghip, cc bn sinh vin
v cc c gi ln xut bn sau sch c hon thin hn.
V KHOA HC V O TO - B Y T
LI NI U
HO PHN TCH l mt mn hc dnh cho cc hc vin thuc ngnh Ho. khoa Dc ca
Trng i hc Y Dc Thnh ph H Ch Minh, mn ny c ging dy cho:
- sinh vin Dc nm th 3 (h chnh quy 5 nm)
- sinh vin Dc nm th 2 (h tp trung 4 nm)
nhm trang b cc kin thc c bn v ho hc phn tch t sinh vin Dc hiu r hn cc mn
Bo ch, Dc liu, Ho dc, Dc lc, Kim nghim thuc l cc mn nghip v s c hc tp
cc nm k tip.
Ho phn tch cng l mt trong nhng mn hc nhm cung cp cc kin thc nn tng rt quan
trng sau khi tt nghip, d lm vic bt k cc v tr no th Dc s cng xc nh c nhim v
ca mnh l trc tip hay gin tip gp phn lm cho thuc phi ng v cht lng v v s lng
khi ti tay ngi s dng.
Vi mc ch trn, b mn Ho Phn tch Kim nghim bin son sch Ho phn tch, tp 1,
cho sinh vin ngnh Dc theo ch o ca B Y t v B gio dc o to.
Ni dung sch Ho phn tch, tp 1, gm cc phn sau:
Phn I: l phn i cng gm cc chng tng qut cp n:
- i tng, chc nng v phn loi ca ho hc phn tch.
- Cc loi phn ng ho hc, khi nim v cc yu t nh hng n cn bng ho hc, hng s cn
bng v nh ngha v hot , nng .
- Cc khi nim v sai s v ng dng ton thng k x l cc kt qu thu c t thc nghim
nhm m bo chnh xc theo yu cu ca ngnh Dc.
Phn II: l phn nh lng gm cc chng vit v:
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- Cch biu th v tnh ton nng dung dch ca mt cht c s dng thng xuyn khi phn
tch.
- Nguyn tc v cch th hin cc bc tin hnh phn tch khi lng.
- Nguyn tc, phn loi, gii thch cc khi nim, c ch cng nh cc ng dng ca cc phng
php phn tch th tch: acid base; oxy ho kh; kt ta v to phc ch yu s dng trong ngnh
Dc.
Cc cn b ging ca b mn c gng cp nht ho kin thc bin son v vn lun mong gio
trnh s mang li cho hc vin kin thc b ch, chnh xc.
Chng ti knh mong qu thy c, qu ng nghip, qu c gi v cc sinh vin c k v nu
nhng kin ng gp, ch gip cc thiu st chng ti hon thin hn ti liu ging dy ny.
Chn thnh cm n v mong nhn c nhng kin ng gp qu bu ca qu v.
Ch bin
PGS.TS. V TH BCH HU
Phn I
I CNG
Chng 1
I CNG HO PHN TCH
MC TIU
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NI DUNG
1. M U
Th d: pht trin v hon thin nhng lun thuyt v cc phng php phn tch.
Th d: s thnh lp chuyn ngnh Ho phn tch v thuc phng chng dch bnh.
Cu trc su ca mn hc ny c th chia ra phn tch nh tnh v phn tch nh lng. Phn tch
nh tnh gii quyt vn l cc hp phn no c trong i tng phn tch, phn tch nh lng cho
bit v hm lng ca tt c hay ca tng hp phn.
3. PHN LOI
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3.2. Phn loi da theo th tch v khi lng cht phn tch
- Phn tch th: lng mu th cht rn 0,1 - 1 g, lng mu th dung dch t 1 - 100 ml.
- Phn tch bn vi lng: lng mu th t 0.01 - 0,1 g, dung dch t 0,1- 0,3 ml.
- Phn tch vi lng: lng mu th t 10-3 -10-2 g, dung dch t 10-2 - 10-1 ml.
- Phn tch siu vi lng: lng mu th t 10-6 - 10-12 g, dung dch t 10-3 - 10-6 ml.
- Phn tch ng v: chuyn ngnh trong phn tch t s dng, nhng phn tch ny thng dng
trong vt l, m, sinh hc. Th d nh: xc nh nc deuterium trong nc thng, cng nh ca oxy
"nng" (ng v oxy 18) trong hn hp vi s ng v ph bin oxy 16. Phn tch ng v cn thit khi
nghin cu cc nguyn t nhn to.
- Phn tch nguyn t (nguyn t - ion): phn tch nhng nguyn t no c trong i tng nghin
cu, hm lng l bao nhiu.
- Phn tch phn t: y l s pht hin v xc nh hp cht ho hc c c trng bng khi
lng phn t xc nh. Th d: phn tch hn hp kh, xc nh trong khng kh nhng thnh phn
chnh (N2, O2, CO2, O3, kh tr). Mt trong nhng phng php phn tch phn t ngi ta s dng
phng php
sc k.
- Phn tch nhm chc: i vi phn tch ho hu c cn c mt dng phn tch gia phn tch
nguyn t v phn t - l phn tch nhm chc. Phn tch ny trc ht xc nh nhm chc, ngha l
xc nh tng nhm hu c ring bit nh nhm carboxyl, hydroxyl, amin,...
- Phn tch cht: Trong phn tch cht ngi ta xc nh trong dng no c mt hp phn ta quan
tm trong i tng phn tch ny v hm lng ca nhng dng ny. Th d: trong mc no ca s
oxy ho c mt nguyn t As(III) hay As (V), trong trng thi ho hc no c mt nguyn t (th d
ng trong khong cht c th dng oxyd hay sulfit hay hn hp nhng hp cht ny). Phn tch cht
c nhiu ci chung vi phn tch phn t hay tng.
- Phn tch tng (pha): l phn tch i tng trong h d th. Th d: sunfit v oxyd km phn
b trong khong cht khng ng th m to nhng tng khc nhau. Ngi ta dng cc phng php
khc nhau tch v xc nh cc h d th tham gia trong thnh phn cu trc (cc tng) ring bit,
khc nhau v tnh cht, v cu trc vt l v phn tch nhau bi gii hn b mt.
Xc nh theo c tnh ca tnh cht o hay theo kh nng ghi nhn tn hiu tng ng.
C th chia ra:
- Phng php ho hc: l phng php da trn nhng phn ng ho hc. Th d: phn ng acid-
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Phn tch nh tnh l xc nh cc nguyn t, cc ion, cc phn t c trong thnh phn cht phn
tch.
tin hnh phng php nh tnh ngi ta dng nhiu phng php c bn cht khc nhau, cc
k thut, cc ng li khc nhau: phng php ho hc, vt l v ho l.
4.1.1. Phng php ho hc
Phng php ho hc l nhng phng php nh tnh da trn cc phn ng ho hc. Nhng
phng php trong phn tch c s dng rng ri trong thc t, phng php ny khng i hi trang
b phc tp nhng cn c mt s nhc im l: trong trng hp cn phi tch cht ra khi cc tp cht
v phi tch dng tinh khit thng rt kh khn, i khi khng thc hin c, khng pht hin c
nhng lng cht rt nh.
4.1.2. Phng php vt l v ho l
Phng php vt l v ho l l nhng phng php da trn cc tnh cht vt l ca cc cht cn
phn tch.
Th d: S nhum mu ngn la n kh khng mu thnh mu c trng do cc hp cht bay hi
ca mt s nguyn t ho hc Na+, K+,...
Phng php so mu ngn la: Ngn la Na+ c mu vng, K+ c mu tm, Ba2+ c mu xanh lc
nht.
Phng php phn tch quang ph hng ngoi, phng php o quang (quang ph hp th), phng
php cc ph, phng php sc k v.v...
Dng phng php vt l v ho l c th tch c cc nguyn t m chng kh b tch bi cc
phng php ho hc, phng php vt l v ho l c nhy v chnh xc cao nhng phi c trang
b phc tp, my mc t tin khng phi tt c cc c s u trang b c nn phng php ho hc
vn ng vai tr quan trng trong cng tc phn tch.
Phn tch nh lng cho php xc nh thnh phn v lng cc hp phn ca hp cht cho hoc
ca hn hp cc cht. Khc vi phn tch nh tnh, phn tch nh lng cho kh nng xc nh hm
lng ca cc hp phn ring r ca cht phn tch hoc hm lng chung ca cht cn xc nh trong
cht nghin cu.
Cc phng php dng trong phn tch nh lng:
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5.1. Mu th - xc nh i tng
u tin phi xc nh r mc tiu (cn nhng thng tin g) v yu cu phn tch (nh tnh hay nh
lng). Thu thp thng tin v mu th: bn cht, ngun gc, cch ly mu, tnh trng mu v bo qun
mu.
La chn phng php phn tch da trn nhng thng tin c trc nh: c mu phn tch, phng
tin phn tch, yu cu phn tch,.. t kt qu phn tch tt ph thuc nhiu vo s la chn phng
php.
5.3. Ly mu th
y l bc quan trng nht trong c quy trnh phn tch. Chn mu i din c thnh phn phn
nh ng thnh phn mu cn phn tch. T mu i din chn v chun b mu lm th nghim v phn
tch theo yu cu.
5.4. X l mu th
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Trong ngnh Dc, Ho hc phn tch gi vai tr quan trng. N c mt trong sut qu trnh sn
xut (kim nghim nguyn liu, bn thnh phm, v sn phm cui cng), bo qun, lu thng v s
dng thuc. Cc phng php phn tch s dng rt phong ph v a dng thuc cc lnh vc: vt l,
ho hc v sinh hc. Hin nay ngi ta cn quan tm nhiu ti cc phng php kim nghim dng
trong i tng sinh hc, (th d nh phn tch mu, nc bt, dch no ty, gp phn vo cc nghin
cu sinh dc hc v dc ng hc).
8.1. ng dng
Ho phn tch ng vai tr quan trng trong s pht trin khoa hc k thut v nhiu mn khoa hc
t nhin: ho hc, a cht, a l, khong vt hc, vt l, sinh hc, sinh ho, nng ho, y dc hc.
Trong nhng lnh vc ny thc hin cc cng trnh nghin cu khoa hc u i hi phi p dng cc
phng php phn tch. Da vo cc thng tin ca phn tch ho hc m cc nh a cht tm kim cc
khong cht. Da vo kt qu phn tch mu cc thy thuc chn on c tnh trng sc khe ca con
ngi. S nh lng cc ion K+, Ca2+, Na+ trong dch t bo ng vt cho php cc nh sinh l hc
nghin cu vai tr ca cc ion ny trong s dn truyn lung thn kinh cng nh trong c ch co v dui
ca cc c. Cc nh ho hc gii thch cc c ch phn ng ho hc nh vo vic nghin cu vn tc
phn ng, nh c cc phng php phn tch hin i m ngi ta tng hp c cc cht ho hc mi,
...
Ngy nay vi s pht trin ca khoa hc k thut tin tin i hi chuyn ngnh Ho phn tch ngy
mt hon thin, p ng nhu cu trn Ho phn tch tin ti phi gii quyt c 5 vn sau:
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T KHO
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CU HI LNG GI
1. Cho bit i tng ca ho hc phn tch. S lin quan ca ho hc phn tch vi ngnh Dc v
cc mn khoa hc khc.
2. Th no l phn tch nh tnh? Nu cc phng php phn tch trong phn tch nh tnh.
CU HI TRC NGHIM
2. Phn tch nh lng cho php xc nh..... ca cc hp phn trong cht nghin cu:
a. y dc hc c. khong vt hc e. ch cu a,b
b. a cht d. tt c cc cu trn
a. 3 c. 5 e. 7
b. 4 d. 6
Chng 2
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CN BNG HO HC
MC TIU
NI DUNG
1. PHN NG HO HC
1.1. nh ngha
Cc ti liu v phn ng ho hc hin nay phn loi nhiu kiu phn ng theo cc c ch nhng ch
yu tp trung cc loi sau:
Trong phn ng ny, 2 hay nhiu cht n gin s kt hp to nn cht phc tp hn.
Dng c bn: A + X AX
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Dng c bn: AX A + X
2H2O 2H2 + O2
Th d 1: carbonat kim loi, khi un nng to thnh cc oxid kim loi v kh CO2(k).
Th d 2: Hu ht cc hydroxid kim loi, khi un nng phn hy thnh oxid kim loi v nc.
Ca(OH)2(r) CaO(r) + H2O(k)
Th d 3: Cc clorat kim loi khi un nng phn hy thnh clorid kim loi v oxy.
2KClO3(r) 2KCl(r) + 3O2(k)
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Th d 3: Trao i nguyn t hydro c trong acid bng kim loi c hot tnh
Zn(r) + 2HCl(nc) ZnCl2(nc) + H2(k)
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Dng c bn: AX + BY AY + BX
Th d 1: Phn ng to ta
NaCl (nc) + AgNO3(nc) NaNO3(nc) + AgCl(r)
Th d 2: Phn ng to kh
HCl(nc) + FeS(r) FeCl2(nc) + H2S(k)
Th d 3: Phn ng to nc. (Nu phn ng gia acid v base th gi l phn ng trung ha)
HCl(nc) + NaOH(nc) NaCl(nc) + H2O(l)
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Hnh 2.2. Chuyn N2O4 (k) 2NO2 (k), h thng cn bng cc 10, 11 v 12
Tu theo nhit v khi lng ban u ca N2O4 (c th c ln NO2 hay khng) s dng m
nng ca NO2 v N2O4 trng thi cn bng ca h ny s khc h khc.
Ch :
- Mt h thng cn bng khng cn bt c nng lng no duy tr s cn bng.
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- Khng nn ln ln trng thi cn bng v trng thi tnh. Trng thi tnh l trng thi m cc nng
u khng i theo thi gian.
- Cn bng ho hc l trng thi ng trong cht tham gia phn ng v sn phm chuyn i lin
tc cho nhau. Tc mt i v xut hin ca chng bng nhau.
Bng 2.1 nu vi d liu thc nghim lin quan n phn ng ny 25 C. Nng ca kh c
din t bng nng mol v c tnh t s phn t ca kh c mt t lc phn ng bt u cho n lc
phn ng cn bng xy ra trong 1 th tch ca bnh cu (tnh bng lt).
Phn tch cc d liu t s cn bng s cho thy trong khi t s cho nhng gi tr thay
Cng cn ch l s m 2 ca [NO2] trong biu thc trn bng h s cn bng t lng ca NO2
trong phng trnh (2.1).
Khi nim ny thu c khi xt phng trnh ca phn ng thun nghch:
A+B C+D (2.3)
A, B: Cc cht tham gia phn ng
C, D: Sn phm to thnh.
Phng trnh (2.3) l biu thc ton hc tun theo nh lut tc dng khi lng.
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3. HOT V NNG
Hot aH+ ca ion hydro c trong mt dung dch cho c th c xc nh bng cch n gin
l o pH.
Mt cch tng qut, gia hot v nng c mi lin quan theo cng thc:
a = C hay a=fC
vi a: hot ; (hoc f): h s hot ; C: nng mol;
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Cc ion dng Mm+ v cc ion m Xx- phi cng c mt trong mt dung dch v khng c cch no
tch ring hot ca cc ion dng v m. Do vy, thng dng i lng hot ion trung bnh
(a)
a = C (MmXx)-(m+x)
i vi c 2 ion dng v m, C l nng t lng ca cht in ly (stoichiometric concentration).
Trng hp ny h s hot trung bnh c tnh theo biu thc:
nh lut tc dng khi lng l nh lut biu din mi lin quan gia nng (hot ) ca cc
cht phn ng v ca sn phm phn ng trng thi cn bng.
nh lut tc dng khi lng ch p dng c vi cc dung dch l tng l dung dch ca cc
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(2.5)
Ka c gi l HSCB, trong aA, aB, aC, aD l hot cn bng ca cc cht phn ng (A, B) v
cc sn phm phn ng (C, D); m, n, p, q l cc h s t lng tng ng.
Nu tnh theo nng
Thay cho hot , HSCB cng c th biu din qua nng Ci, p sut ring Pi hoc phn mol Xi
ca cc cu t i tng ng. Trong cc trng hp ny HSCB c k hiu Kc, Kp, Kx.
Kc - hng s cn bng:
(2.6)
(2.7)
K1: hng s tc ; [A] v [B] l nng tng ng ca cht phn ng A v B thi im kho st.
Nu coi (2.4) l phn ng c bn hai chiu, thun v nghch, V2 l tc phn ng xy ra theo chiu
ngc li. Phn ng c c trng bng hai hng s tc K1 v K2 vi
(2.8)
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(2.9)
Trn thc t, (2.4) thng biu din mt phn ng phc tp (bao gm nhiu giai on, qua nhiu va
chm) th biu thc (2.6) ni chung khng ng. Trong trng hp ny hm tc phn ng ph thuc
nng c dng phc tp. Ch trong mt s trng hp tc phn ng c th biu din bng hm m:
(2.10)
HA = H+ + A-
Ka c gi l HSPL nhit ng; a: hot ca ion hoc phn t; g: h s hot . Trong nhng
trng hp, khi c th chp nhn h s hot khng i:
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- Acid yu nh acid acetic khng th cho ht proton acid ca n cho dung mi. Thay vo hu ht
acid cn li khng phn ly, ch mt phn nh hin din di dng base lin hp
CH3COOH (nc) + H2O (l) H3O+ (nc) + CH3COO- (nc) (2.11)
Hng s cn bng ca phn ng ny c gi hng s phn ly acid Ka. Ka ca acid acetic l 1,75 x
10-5
NH3 + H+ NH4+
Vi hng s cn bng
Hng s cn bng Kb ny c gi l HSKB ca ion phc Ag(NH3)2+; v Kb cng ln, ion phc
phn li cng nhiu nn Kb cn c gi l hng s phn ly ca phc cht. (trnh by trong chng 10).
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Th d: i vi KCl (kali clorid) gia cc ion t do K+, Cl- v cp ion K+Cl- c cn bng:
HSKH ph thuc vo hng s in mi D ca dung mi v nng cht tan: Kkh ca KCl 0,1 M
trong acid acetic vi D = 6,2 l 106,9 v trong metanol vi D = 32,6 l 101,15. Trong dung mi c D
cng nh, Kkh cng cao; trong benzen, clorofom hu nh khng c ion t do, v D rt nh.
vi hng s cn bng
Hng s cn bng K cng c gi l HSB ca ion phc Ag(NH3)2+; v K cng ln, Ag(NH3)2+
c to nn cng nhiu nn K cn c gi l hng s to thnh phc cht. (trnh by trong chng 10)
b) Hng s bn iu kin (Phn ng to phc)
(trnh by trong chng 10)
4.2.3. Hng s cn bng ca cc phn ng trao i
Tch s tan (Phn ng to ta)
Phn ng to ta xy ra khi c 2 hay nhiu cht ha tan kt hp vi nhau to thnh cht khng
tan gi l ta. Phn ng kt ta chung nht l phn ng hon v m trong 2 hp cht ion ho tan trao
i cc phn.
Th d: Pb2+ (nc) + 2Cl (nc) PbCl2 (r)
Tuy nhin, trong vic x l s cn bng ca s kt ta, cng thng xuyn gp phn ng ngc
chiu m t s phn ly ca ta ny.
PbCl (r) Pb2+ (nc) + 2Cl (nc)
2
Trong phn ng ny c mt hng s c gi l tch s tan (solubility product, Ksp) l tch nng
cc ion ca hp cht t tan trong dung dch bo ho cht
TST ca PbCl2 = Ksp = [Pb2+] [Cl-]2 = 1.7 10-5
i vi cc cht tan kh, c nng bo ho ln, khng p dng tch s nng , m phi tnh theo
tch s hot a (trnh by trong chng 9)
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Hng s K cho bit v chiu mc hon ton ca phn ng. Nu K ln rt nhiu hn 1 (K>>1) th
phn ng s chim u th to ra C v D; K cng ln, phn ng theo chiu thun cng hon ton.
Nu K nh rt nhiu so vi 1 (K< 0,1) th phn ng khng hon ton, K qu nh th phn ng to C
v D hu nh khng xy ra.
V K l mt hng s do nu thay i mt tha s [A] hoc [B] hoc [C] hoc [D] th s ko theo
s thay i mt hay nhiu tha s khc. Nh vy, mun quyt nh chiu ca phn ng ta c th thay
i nng ca cc cht.
Khi bit hng s cn bng ho hc K, ta c th tnh ton:
- Nng cn bng ca cc ion cht in ly yu, nu bit nng ban u ca chng.
- Nng cn bng ca ca cc cht tham gia phn ng hoc sn phm to thnh ca cc phn ng
ho hc.
- Nng cn bng cc ion hydro, hydroxyd, in ly ca cht in ly trong cc dung dch nc
ca cc acid hoc baz yu, cc mui thu phn, dung dch m...
- Nng cn bng ca cc cation, anion v tan ca cht in ly t tan trong nc.
5. CC YU T NH HNG N CN BNG HO HC
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S tng hay gim p sut ring phn ca cht kh cng tng t nh s thay i nng . Xt phn
ng th kh:
H2 + Cl2 2HCl
S phn t kh hai v bng nhau do khi thay i v p sut s khng lm thay i trng thi cn
bng. Nhng i vi phn ng tng hp NH3 (phng trnh 2.12) trn th hn hp s gim th tch, do
khi tng p sut th h thng cn bng s dch chuyn theo chiu thun.
V nng ca cc cc cht kh tu thuc p sut ring phn ca chng v khng ph thuc vo
tng p sut ca h thng, do khi thm hay b mt lng kh tr s khng lm thay i cn bng
phn ng ca cht kh .
Hu ht phn ng c s tham gia ca cht phn ng v sn phm dng phn tn trong dung mi.
Nu lng dung mi thay i th nng ca tt c cc cht phn ng v sn phm s thay i.
Th d: phn ng to phc Bc-amoniac trong nc:
Ag+ + 2NH3 Ag(NH3)2+
(2.13)
Hoc c th vit l
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V Q ln hn 2, cn bng phi c ti lp bng cch dch chuyn sang tri v lm gim nng
ca Ag(NH3)2+. Hn na, v tr cn bng mi s hng v pha c s cht tan nhiu nht. Nu dung dch
Ag(NH3)2+ c c m c, bng cch lm bay hi th cn bng c ti lp theo hng ngc li.
Kt lun tng qut ny c th p dng vi bt k phn ng no, bt k pha rn, lng hay kh. Vic gia
tng th tch lun lm phn ng din ra u tin theo hng c s phn t nhiu nht v s gim th tch
th thc y phn ng theo hng c t phn t nht. Nu s phn t c hai v phng trnh l nh
nhau cn bng ca phn ng khng b nh hng bi s thay i th tch.
Nh vy, h thng cn bng ca phn ng s b ph v khi thay i nng ca cht tham gia phn
ng hay sn phm to thnh.
- H thng cng c th ph v mt cch gin tip
Th d s phn ly ca AgCl
AgCl Ag+ + Cl- (2.14)
nh hng trn tan ca AgCl bng cch thm AgNO3 th r rng, nu thm vo mt cht c th
to phc bn v tan c vi Ag+ nh amoniac th s xy ra phn ng sau:
Thm amoniac lm gim nng Ag+ di dng ion phc . V s gim nng Ag+
lm tng tan ca AgCl v phn ng (2.15) ti lp im cn bng. T cc phn ng (2.14) v (2.15) s
lm r tc ng ca amoniac trn tan ca AgCl v amoniac cng l mt cht tham gia phn ng.
Gii:
HNO3 l acid mnh, acid ny s phn ng vi NH3
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Khi thm t HNO3 vo s lm gim NH3. Vic gim nng NH3 s lm phn ng (2.16) xy ra
theo chiu to ra cht phn ng, gim tan AgCl.
6. BI TP V CN BNG HO HC
thun tin cho vic tnh ton cc hng s cn bng ngi ta c th x l cc hng s cn bng
theo cc cch sau y:
- T phn ng cho nu ta o ngc phn ng th hng s cn bng ca phn ng mi s l
nghch o ca phn ng u. Th d, hng s cn bng cho phn ng
L nghch o ca phn ng
l 1,05 250 C. Nu p sut ring phn trng thi cn bng ca PCl5 v PCl3 ln lt l 0, 875
atm v 0,463 atm th p sut ring phn trng thi cn bng ca Cl2 250 C l bao nhiu?
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Mt phn ng cho lc bt u c 0,249 mol kh N2; 3,21.10-2 mol kh H2 v 6,42.10-4 mol NH3
trong mt bnh cha 3,5 lt 375 C. Nu hng s cn bng KC i vi phn ng N2 (k) +3 H2 (k)
2NH3 (k) c gi tr l 1,2 nhit ny th:
- QC > KC: T s gia cc nng ban u ca sn phm v cht tham gia qu ln. t c cn
bng, mt lng no ca sn phm phi chuyn thnh cht tham gia. Phn ng di chuyn theo chiu
tri.
- QC > KC: Phn ng ang thi im cn bng .
- QC < KC: T s gia cc nng ban u ca sn phm v cht tham gia qu nh. t c
cn bng, mt lng no ca cht tham gia phi chuyn thnh sn phm. Phn ng di chuyn theo
chiu phi.
Nu trng hp hng s s dng l KP th tnh QP.
Gii
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Thay i (+) chng t s tng ln v thay i (-) chng t s gim nng . Tip n l vit biu
thc hng s cn bng theo nng cn bng:
x = 0,816 M
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Khi mt hp cht khng tan nh Pb(IO3)2 c cho vo dung dch, mt phn cht rn s tan ra. Cn
bng t c khi nng Pb2+ v tha mn tan sn phm i vi Pb(IO3)2. im cn
bng, dung dch b bo ha bi Pb(IO3)2. Lm th no xc nh c nng ca Pb2+ v v
tan ca Pb(IO3)2 trong dung dch bo ha khi cho Pb(IO3)2 vo nc ct.
V hng s cn bng ca n
(2.18)
Khi cn bng c thit lp, hai ion c to ra tng ng vi mi ion Pb2+. Nu chng ta gi
nh nng mol ca Pb2+ im cn bng l x th nng ca l 2x.
PbI2 Pb2+ + 2
Trng hp trn l tnh ton tan ca Pb(IO3)2 trc tip trong nc ct v cht rn l ngun duy
nht cung cp Pb2+ v cho dung dch. tan ca Pb(IO3)2 s b nh hng nh th no nu chng
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PbI2 Pb2+ + 2
7. KT LUN
Chng ny trnh by cc loi phn ng, khi nim v s cn bng ho hc, hng s cn bng,
hot , nng m rng hiu bit v cn bng ho hc. T chng ny hc vin s c th hiu mt
cch tng qut cn bng ho hc ca cc phng php s dng trong ho hc phn tch vn dng
trong tnh ton.
T KHO
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Phn ng ho hc Nng
Cn bng ho hc H s hot
Hng s cn bng Hng s phn ly
Hot Hng s bn
CU HI LNG GI
CU HI TRC NGHIM
a. c th xy ra th kh hoc lng d. ch a v c ng
b. c th xy ra th rn hoc lng e. c ba cu u ng
c. nhit , p sut nht nh th thnh phn hn hp trng thi cn bng l khng i
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c. Nhn hai phn ng vi nhau th hng s cn bng mi s l tng ca cc hng s cn bng ban
u.
d. a v b
5. Cn bng ho hc l trng thi.......... m trong cht tham gia phn ng v sn phm chuyn i
lin tc cho nhau. Tc mt i v xut hin ca chng bng nhau.
a. ng c. tnh e. lng
b. ng yn d. kh
BI TP
Chng 3
S DNG THNG K
TRONG PHN TCH S LIU
MC TIU
NI DUNG
1. M U
Khi tin hnh php phn tch vi mt mu bt k, qua bao gi chng ta cng c c cc kt qu
(s liu) t thc nghim. Cu hi c t ra l: s liu thu c c gn vi gi tr thc c ca mu
khng? Qu trnh phn tch c mc phi sai s khng? Gi tr thc nm khong no ca cc s liu
thc nghim? v.v
Sai s trong phn tch l khng th trnh khi, tuy nhin trong qu trnh phn tch cn khng ch sai
s mc thp nht c th, c ngha l kt qu thu c khi tin hnh mt php phn tch lun lun mc
phi sai s. Gi tr thc ca mu o l i lng khng th xc nh, nhng nu xc nh c cc sai s
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(3.1)
Trong : n: l tng s ln o; i : gi tr o c th i (i = 1, 2, 3, , n)
(3.2)
lch chun l i lng cho bit mc dao ng gia cc gi tr xi so vi gi tr trung bnh Xtb.
y l i lng c trng cho phn tn ca s liu (xi) v th hin mc ca sai s ngu nhin.
(3.3)
lch chun tng i l t s gia lch chun so vi gi tr trung bnh. RSD th hin gi tr
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(3.4)
RSD c th c tnh bng t l phn trm RSD% hay cn gi l h s bin thin CV (Coefficient of
Variation):
(3.5)
(3.6)
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(3.7)
Th d: vi th d 1, gi tr e c tnh:
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ton sai s.
Khi trnh by v kt qu bng s liu, cc ti liu c th cp n 2 loi l sai s tuyt i v sai s
tng i.
Sai s tuyt i l hiu gia gi tr trung bnh Xtb v gi tr thc M. Thng thng khng th xc
nh c gi tr thc m ch chp nhn gi tr ng tin cy nht trong dy s liu l Xtb hay mt
cch gn ng l hiu ca gi tr o c v Xtb.
Sai s tng i S l t s gia sai s tuyt i v gi tr thc M hoc gi tr trung bnh Xtb. Thng
thng sai s tng i c biu th di dng phn trm.
(3.9)
Th d: hm lng thc ca Paracetamol trong vin nn l 500,2 mg; Codein l 30 mg. Sau khi tin
hnh xc nh theo phng php sc k lng hiu nng cao cho thy hm lng Paracetamol l 500,9
mg v Codein l 30,7 mg.
Sai s tuyt i khi xc nh hai hot cht trn l nh nhau: + 0,7 mg.
Sai s tng i th khc nhau:
Sai s ngu nhin hay cn gi l sai s khng xc nh l sai s gy nn bi nhng nguyn nhn
khng xc nh c, khng bit trc, khng c nh, thay i khng theo quy lut nn khng th hiu
chnh hay loi tr m ch c th hn ch bng cch tng s ln phn tch v thao tc mt cch cn thn,
ng thi nh gi cc s liu thc nghim bng ton hc thng k.
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Sai s h thng hay cn gi l sai s xc nh l sai s bit r nguyn nhn v c th hiu chnh
c. Sai s ny thng do cc nguyn nhn sau:
- Sai s do mu o: gy ra khi mu phn tch khng i din. Vic ly mu l tp hp cc thao tc
nhm ly mt lng mu i din tin hnh phn tch, ng thi vic ly mu cn tun theo cc
th tc quy nh.
- Sai s do dng c: d t hay nhiu th tt c cc dng c o lng lun c sai s h thng. Sai s
ny l do qu trnh ch to v chun ho dng c v.v
Th d: - Cc dng c o lng thng thng nh pipet chnh xc, buret, bnh nh mc l cc dng
c dng ly th tch chnh xc nhng do trong qu trnh ch to hoc s dng khng ng quy nh
c th gy ra mt sai s: th tch ca mt buret 25 ml c sai s l 0,03 ml c ngha l th tch tht s
ca buret l nm trong khong [24,97 25,03] ml; bnh nh mc c th tch l 100ml nhng nu thc t
ch c 99,90 ml th sai s l 99,90 100,00 = - 0,10 ml.
Sai s dng c thng d pht hin v hiu chnh c bng cch nh k chun ho cc dng c
trong phng th nghim.
- Sai s do phng php o: phng php o lng cng gy ra sai s h thng. V vy, khi p
dng mt phng php mi phn tch lun lun phi xy dng v thm nh quy trnh chng minh
mt cch khoa hc rng sai s ca phng php l rt thp v c th chp nhn c. Sai s do phng
php thng kh pht hin v l nguyn nhn chnh gy ra sai s h thng. Thng thng pht hin
sai s phng php c th tin hnh theo cc cch sau:
- Thc hin song song mu trng loi cc p ng gy ra do cc cht khng cn phn tch.
- Phn tch mu chun kim tra ng ca phng php.
- Phn tch cng mt mu nhng bng phng php d kin v thc hin song song vi t nht mt
phng php khc v so snh hai kt qu.
- Sai s do ngi lm cng tc phn tch: ngi lm cng tc phn tch i hi phi c k nng
ngh nghip v kinh nghim phn tch. Sai s do tng c nhn l iu khng trnh khi, mi c nhn c
mt kh nng ring v quan st s thay i mu ca dung dch; quan st im tng ng trong chun
; c v tr mc nc gia hai vch; c tn hiu o c t my mc; hoc do cu th; do nh
kin u dn n sai s.
Sai s do c nhn c th khc phc c khi thao tc ng theo quy nh v nhiu kim nghim vin
thc hin trn cng mt mu th.
XC NH SAI S H THNG
Bng cch xc nh mu chun bit hm lng, gi tr M coi nh bit trc, Xtb thu c t thc
nghim. so snh s khc bit gia gi tr M v Xtb (trong trng hp thm nh phng php mi)
thng s dng thng k tnh gi tr ttn ri so snh vi tlt theo bng (3.1) cn c vo bc t do (n 1) v
xc xut P (95%).
Nu ttn < tlt, kt lun khng tm thy sai s h thng
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(3.10)
ttn = 0,3786 < tlt = 2,45 nn kt lun phng php khng c sai s h thng (P = 95%).
Th d: trc khi phn tch xc nh hm lng ca Na2CO3 c trong mu th, mt sinh vin c
tng kim tra li quy trnh phn tch xem c sai s h thng hay khng bng cch phn tch mt mu
bit hm lng M = 98,76%. Cc kt qu thu c sau 5 ln thc hin:
Nh vy tlt = 2,78 < ttn = 3,91, kt lun phng php c sai s h thng (P=95%).
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P
n
0,1 (90%) 0,05 (95%) 0,01 (99%)
3 0,941 0,970 0,994
4 0,765 0,829 0,926
5 0,642 0,710 0,821
6 0,560 0,625 0,740
7 0,507 0,568 0,680
8 0,468 0,526 0,634
9 0,437 0,498 0,598
10 0,412 0,466 0,568
Bc 2: tnh gi tr Qtn ;
(3.12)
(3.13)
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n Tlt n Tlt
3 1,412 11 2,343
4 1,689 12 2,387
5 1,869 13 2,426
6 1,996 14 2,462
7 2,093 15 2,493
8 2,172 16 2,523
9 2,237 17 2,551
10 2,294 18 2,623
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5. SO SNH CC DY S LIU
Kt qu thu c t o lng thc nghim thng mc phi cc sai s hoc ngu nhin hoc h
thng. Gi tr trung bnh X thng ch st gn vi gi tr thc M, gi tr ny li nm trong khong tin cy
no vi xc sut bt gp mong mun.
Vic so snh gia cc dy s liu c thc hin nh cc bng chun xem cc dy s liu ny l
ng nht hay khc nhau c ngha gip cho vic so snh gia cc phng php, gia cc ngi phn
tch v gia cc l sn xut.
Cc vn thng gp trong thc nghim l :
- C hai gi tr trung bnh XnA v XnB thu c t 2 dy o c lp nhau, mt dy c nA kt qu,
dy kia c nB kt qu. Hai gi tr trung bnh sai khc khng nhiu. Phi kt lun sai khc ny c ng k
khng?
- C mt gi tr phn tch X ca sn phm c bit trc qua nhiu ln lm thc nghim. Ngi
thc hin phn tch lp li phng php v cn so snh kt qu o c Xi vi gi tr bit trc X
xem khc nhau c ngha hay khng?
- C mt l thuc c thc hin nh lng vi 2 phng php khc nhau v cho 2 dy kt qu
khc nhau. Cc nh phn tch cn phi so snh kt qu o c trn cng mu bng 2 phng php khc
nhau xem c khc nhau hay khng?
- Trong trng hp so snh hai dy kt qu:
S dng th nghim F (F-test) kim tra chnh xc hay lp li ca hai dy kt qu xem c
ng nht hay khng.
S dng th nghim t ( t-test) so snh hai gi tr trung bnh xem s khc nhau gia hai gi tr ny
c ngha hay khng.
(3.14)
So snh Ftn vi Flt c tra t bng (3.4). Flt ph thuc vo bc t do ca hai th nghim A, B v
ph thuc vo mc xc sut cho trc thng thng l P = 95%.
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Bc t do ca A: nA -1; bc t do ca B: nB 1
Do Flt = 6,978 > Ftn = 1,88: chnh xc ca hai phng php l nh nhau (P = 95%).
Trong phn sai s h thng chng ta bit kt qu phn tch b nh hng chnh bi ba nguyn
nhn chnh: do mu, do phng php, do kim nghim vin. Thc hin nhng cp th nghim song song
tm ra nguyn nhn gy sai s trong ch mt yu t thay i. Th d nh cng thc hin song song
hai phng php khc nhau trn cng mt mu th, cng mt kim nghim vin ri so snh c hay
khng c s khc bit gia hai gi tr trung bnh ca hai phng php ny. Tng t nh vy so snh
hai gi tr trung bnh ca hai kim nghim vin hoc ca hai mu o
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(3.15)
(3.16)
(3.17)
tlt c tra t bng (3.1) vi P = 95% v t do c tnh theo cng thc sau:
(3.18)
Nu ttn < tlt kt lun hai phng php cho kt qu khng khc nhau.
Nu ttn > tlt kt lun hai phng php cho kt qu khc nhau.
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tlt c tra t bng (3.1), t do n = (7 + 5 - 2) = 10; ttn = 1,34 < tlt = 2,23 nn kt lun hai phng
php A v B cho kt qu khng khc nhau (P = 95%).
Th d: hm lng ca Na2CO3 (%kl/kl) c hai kim nghim vin C v D chun bng phng
php acid-base cho ln lt kt qu nh sau:
C D
86,82 81,01
87,04 86,15
86,93 81,73
97,01 83,19
86,20 80,27
87,00 83,94
SC = 0,32 SD = 2,16
Do Ftn = 45,6 > Flt = 7,15 nn hai phng sai C v D khc nhau.
t do :
Do ttn = 4,62 > tlt = 2,57, nn kt lun kt qu phn tch ca C v D khc nhau (P= 95%).
6. CH S C NGHA
S liu thu uc t thc nghim c th l s o trc tip khi c trn thang o ca cc dng c o
lng hoc s o gin tip l s o tnh c t mt hoc vi s o trc tip thng qua cng thc ton
hc.
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Mt s o trc tip c th c nhiu CSCN tin cy (ch s chc chn) nhng duy nht ch c mt
CSCN khng tin cy (ch s nghi ng) ng sau cng k t tri sang phi. CSCN phn nh mc
chnh xc ca dng c o lng.
Th d:
- Trn thang o ca buret c th tch l 25ml, vch chia nh nht l 0,1ml. Gi s th tch ti
im tng ng khi chun l V = 18,75 ml, nh vy c 4 ch s c ngha l 1; 8; 7 v 5. Trong
1; 8; 7 l cc ch s chc chn v ch s 5 l ch s nghi ng hay cn gi l ch s khng tin cy. Ch
s 5 cn ty thuc vo kh nng c lng ca ngi quan st: c th c l 2 hoc 4 hoc 7 v.v 9.
- Khi cn trn cn phn tch c nhy l 0,1 mg, kt qu c c l 1,2326 g, nh vy c 5 ch
s c ngha trong ch s 6 cui cng l ch s nghi ng.
- S lng CSCN ca mt s o c tnh t ch s u tin khc 0 k t tri sang phi. Mi ch
s 0 sau CSCN u tin bt k v tr no u l CSCN. Hay ni cch khc, ch s 0 ng trc
ch s khc 0 u tin ca mt s o khng phi l CSCN. Ch s 0 ng gia hai ch s khc 0
hoc ng sau cng u l CSCN.
Th d: V = 18,75 ml : c 4 CSCN, 5 l CSCN khng tin cy.
M = 0,0020 g : c 2 CSCN, 0 l CSCN khng tin cy.
M = 5,06 g : c 3 CSCN, 6 l CSCN khng tin cy.
M = 0,15 (M/l): c 2 CSCN, 5 l CSCN khng tin cy.
Khi mun chuyn i n v o lng thun li cho vic tnh ton kt qu o cui cng, s lng
CSCN ca s o phi c gi nguyn.
Th d: chuyn 0,28 g ra n v mg. Ta thy 0,28 g c 2 CSCN nn khng th chuyn thnh 280 mg
(3 CSCN) m phi l 0,28.103 mg hoc bng 2,8.102 mg.
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- i vi kt qu phi tnh ton qua nhiu bc: th ch c lm trn kt qu cui cng m khng
lm trn cc bc trung gian.
Th d: - pha dung dch chun HCl c nng xp x 0,1N dng chun dung dch NH4OH cn
c cc bc nh sau: pha dung dch chun HCl c nng xp x 0,1 N, sau dng dung dch gc
Na2B4O7 0,1N xc nh li nng HCl. Ly chnh xc 10ml dung dch Na2B4O7 em chun
bng dung dch chun HCl trn vi ch th Helianthin n khi mu chuyn t vng sang cam. Th
tch HCl cn dng l 9,75 ml, nng chnh xc ca dung dch acid c tnh nh sau:
Dng acid HCl ny nh lng dung dch NH4OH cha bit nng : ly chnh xc 10 ml
NH4OH v vi git ch th Tashri, nh HCl n khi mu chuyn t xanh l sang tm. Th tch HCl cn
dng l 9,8 ml, nng dung dch NH4OH c tnh nh sau:
Cch lm trn s phi tun theo quy tc ch s c ngha. Cch thc lm trn CSCN cui cng ca
php tnh ty thuc vo gi tr ca ch s nghi ng ng sau n.
- CSCN sau cng ca s o gin tip c tng mt n v nu ng sau n l ch s nghi ng
ln hn 5; nu nh hn 5 th vn gi nguyn.
Th d: 71,56 lm trn thnh 71,6
71,54 lm trn thnh 71,5
- Khi ch s nghi ng ny bng 5 th CSCN sau cng ca s o gin tip c tng mt n v
nu n l mt ch s l; nu n l mt ch s chn (k c s 0) th vn gi nguyn.
Th d: 71,55 lm trn thnh 71,6
71,05 lm trn thnh 71,0
71,25 lm trn thnh 71,2
T KHO
CU HI LNG GI
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1. Gii thch s khc nhau gia: sai s h thng v sai s ngu nhin; sai s tuyt i v sai s tng
i.
2. Trnh by cc khi nim v cng thc tnh cc i lng trong ton thng k: gi tr trung bnh,
lch chun, gii hn tin cy v khong tin cy v.v
3. Nu cc bc x l kt qu phn tch; ng dng vo bi tp sau:
Sau 6 ln xc nh hm lng (mg) ca mt hot cht trong ch phm thu c kt qu nh sau:
116,0 ; 97,9 ; 114,2 ; 100,6 ; 108,3 ; 104,5. Hm lng thc ca mu phn tch nm trong gii hn no?
Gi s hm lng thc ca mu M = 100,0; hy tm xem phng php c sai s h thng hay khng?
CU HI TRC NGHIM
a. Sai s h thng d. C a, b, c u ng
b. Sai s ngu nhin e. Ch b, c ng
c. Sai s th
3. Mt kim nghim vin c nhm th tch ti im tng ung khi nh lng, vy trong phn
tnh ton kt qu ngi ny mc phi:
4. Loi sai s no c th hiu chnh v loi tr khi tin hnh phn tch mu?
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a. 5 ch s c ngha d. 1 ch s c ngha
b. 4 ch s c ngha e. Khng cu no ng
c. 2 ch s c ngha
a. Ch s c ngha tin cy c. Cu a v b u ng
b. Ch s c ngha khng tin cy d. Khng cu no ng
Phn II
Chng 4
NNG DUNG DCH
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a. 5 ch s c ngha d. 1 ch s c ngha
b. 4 ch s c ngha e. Khng cu no ng
c. 2 ch s c ngha
a. Ch s c ngha tin cy c. Cu a v b u ng
b. Ch s c ngha khng tin cy d. Khng cu no ng
Phn II
Chng 4
NNG DUNG DCH
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MC TIU
NI DUNG
1. M U
Dung dch l mt h ng th gm hai hay nhiu cu t (phn t hay ion). Mt dung dch bt k u
gm cht tan v dung mi. Thnh phn ca cht tan trong dung dch c biu din bng nng .
Nng l mt c tnh nh lng c bn ca dung dch.
Ngi ta biu th nng ca dung dch bng lng cht tan c ho tan trong mt lng xc nh
dung dch hay dung mi.
(4.1)
(4.2)
Trng hp pha mt dung dch trong ho tan m gam cht tan vo b gam dung mi th nng
phn trm ca dung dch l:
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(4.3)
Th d 1: Tnh nng phn trm C% (kl/kl) ca dung dch natri carbonat nu cn 25 g Na2CO3 pha
trong 250 ml nc
Gii:
Trong bi ton ny,
m: khi lng cht tan = 25 g
b: khi lng dung mi = V.d = 250 1 = 250 (g)
m + b: khi lng dung dch = 25 g + 250 (g)
Nng phn trm ca natri cacbonat:
Th d 2: Alizarin c dng lm thuc th. Khi pha ngi ta ho tan 0,25 g trong 100 ml nc, nh
vy nng phn trm C%(kl/kl) ca alizarin s l:
Trong ho phn tch, nng phn trm c coi l gn ng, ho cht c cn trn cn k thut.
2.1.2. Nng phn trm khi lng theo th tch: C%(kl/ tt)
(4.4)
(4.5)
Th d 1: Khi pha mt dung dch glucose u trng, nu s dng 200 g glucose pha thnh 1000 ml,
nng dung dch glucose tnh theo nng phn trm:
Th d 2: pha 1 lt dung dch tim truyn NaCl 0,9%, lng NaCl c tnh theo cng thc:
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(4.6)
Th d: Ngi ta ly 960 ml ethanol tuyt i pha thnh 1000 ml dung dch. Nh vy nng ca
dung dch cn l:
Cng thc
(4.7)
(4.8)
(4.9)
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Th d 1: Tnh nng mol ca dung dch H2SO4, bit rng pha mt dung dch c th tch l 500
ml, lng H2SO4 m c cn dng l 49 gam. Khi lng mol ca H2SO4 (M = 98 g)
Gii
Th d 2: Nc bin tiu chun cha 2,7 g mui NaCl trong mi 100 ml dung dch. Xc nh nng
mol ca NaCl trong nc bin.
Gii:
Khi lng NaCl: m = 2,7 (g)
Khi lng mol ca NaCl M = 58,5 g
Th tch ca dung dch V = 100 ml
Mt dung dch cha mt phn t gam cht tan trong mt lt dung dch c gi l dung dch phn
t. T dung dch phn t c ly lm n v, ngi ta so snh dung dch m c hn: 2M, 3M... hay
dung dch long hn: 0,1M (decimol), 0,01M (centimol), 0,001M (milimol)...
Cch biu th nng ng lng do nh ho hc ngi c Karl Friedrich Mohr pht biu mc
ch n gin ho cc php tnh.
Cch biu th nng ny da trn khi nim khi lng ng lng (ng lng gam) ca mt
cht.
K hiu E gam
ng lng gam ca mt cht c tnh tu thuc vo bn cht ca phn ng ho hc.
i vi mt acid: ng lng gam l phn t mol ca acid chia cho s proton hot tnh (H+)
Th d 1: ng lng gam ca acid hydrochloric trong phn ng trung ho l:
HCl + NaOH NaCl + H2O
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i vi mt base, ng lng gam l phn t gam ca base chia cho s proton hot tnh (H+)
cn thit trung ho n.
Th d: ng lng gam ca natri hydroxyd c tnh khi phn ng vi HCl
ng lng gam ca mt cation c tnh bng cch ly khi lng gam ca cation chia cho
in tch ca cation
ng lng gam ca mt anion l khi lng gam ca anion chia cho s ng lng ca ion
kim loi tng ng to ta hoc phc cht.
Th d:
- Trng hp 1. Cation v anion c cng s in tch
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S ng lng gam ca cht A bng s gam cht A chia cho ng lng gam ca cht
(4.10)
Nng ng lng c biu din bng s ng lng gam ca cht tan c trong 1 lt (1000
ml) dung dch.
K hiu: CN
Cng thc:
(4.11)
(4.12)
(4.13)
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Th d: Xc nh nng ng lng ca dung dch nitrat bc khi ho tan 1,35 g AgNO3 thnh
250 ml dung dch.
Bit khi lng mol AgNO3 = 108, ng lng gam AgNO3 = 108 (s in tch Ag+ = 1).
Mt dung dch cha mt khi lng ng lng ca cht tan c go l dung dch c nng
nguyn chun N. Bn cnh nng nguyn chun, ngi ta cn s dng bi s ca N nh dung dch
2N, 4N..., c s ca N nh dung dch 0,1N, dung dch 0,01N...
tnh ton lng cht tan A cn thit pha dung dch ng lng cho bit trc, ngi ta suy
lng m t cng thc (4.13)
(4.14)
Cc tnh ton trong cch chun theo nng ng lng gn ging vi cch tnh ton trong
chun theo nng phn t. C mt s khc bit l ti im tng ng tch ca cc th tch (tnh
bng ml) ca cc dung dch cc cht phn ng vi nng ng lng th bng nhau
ml A. NA = ml B. NB
VA.NA = VB.NB
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(4.15)
4.1.2. chun
Biu th s gam hay miligam cht tan c trong 1 mililt dung dch
K hiu: T
(4.16)
(4.16a)
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T dung dch H2SO4 2M, p dng cng thc tnh CM suy ra khi lng
i vi nhng dung dch c nng rt long, ngi ta thng s dng nng phn triu (ppm).
Nng phn triu biu th s gam cht tan c trong 106 gam dung dch hay hn hp. Ngi ta cn
biu th s microgam ca cht tan c trong 1 ml dung dch hay s miligam cht tan c trong 1 lt dung
dch.
K hiu: ppm
Cng thc:
(4.17)
(4.18)
(4.19)
V khi lng ring ca nc l 1, khi mt dung dch c lng cht tan qu t so vi lng dung
mi, ngi ta quy c 1 ml dung dch = 1 g, v l , dung dch c nng 1 ppm tng ng vi 1g
cht tan c trong 1 ml dung dch hay 1,00 mg/1 lt dung dch
Th d: TCVN 5501 - 1991 quy nh gii hn nng nitrat c trong nc ung l 5ppm.
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Nng ppb hay nng phn t biu th s gam ca cht tan c trong 109 gam ca dung dch hay
hn hp.
K hiu: ppb
Cng thc:
(4.20)
(4.21)
Dung dch 1 ppb ca mt cht tng ng vi 1 mg cht trong 1 ml dung dch hay 1 g trong 1 lt
dung dch.
Trng hp biu th nng ca cht kh, ngi ta thng dng n v cht kh trong mt th tch
hn l trong khi lng.
Th d: 8ppb monoxyd carbon trong khng kh c ngha l 8l CO c trong 1 lt khng kh.
(4.22)
(4.23)
Th d 1: Tnh nng phn trm ca dung dch NH4OH 14,8M, bit rng khi lng ring l 0,899
g/ml, khi lng mol phn t l 17,03.
Gii
p dng cng thc (4.22)
Th d 2: Tnh nng mol ca dung dch H2SO4 98% (d = 1,84 g/ml), phn t gam = 98.
Gii
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(4.25)
6. MT S BI TON V NNG
Th d 1: Cn bao nhiu ml acid hydrocloric m c 12,1 N pha long thnh 1 lt dung dch HCl
c nng 0,1 N?
Gii
p dng cng thc VANA = VBNB
Ly 8,26 ml dung dch HCl 12,1 N pha trong nc c 1 lt dung dch HCl 0,1 N
Th d 2: Dung dch amoniac m c cha 28 % (kl/kl) NH3, khi lng ring 0,899. Tnh th tch
ca dung dch ny cn dng pha 500 ml dung dch c nng 0,25M. Phn t mol ca NH3 l 17,03.
Gii
- Tnh khi lng gam ca NH3 c trong mt lt dung dch:
- Tnh th tch ca dung dch 14,8 M pha long thnh 500 ml dung dch nng 0,25 M
p dng cng thc
Vm c . Nm c = Vpha long . Npha long
Trong Nm c = 14,8 M. Vm c =?
Nh vy:
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Ly 8,45 ml dung dch amoniac 14,8 M pha vi nc thnh 500 ml dung dch
Th d: Tnh nng mol ca acid nitric (M = 63) trong mt dung dch, bit rng khi lng ring
l 1,42 v cha 70% (kl/kl) HNO3.
Gii
T cng thc (4.23) suy ra nng mol ca acid nitric:
T KHA
CU HI LNG GI
1. Phn bit cc loi nng : nng phn trm, nng mol, nng nguyn chun v nng
ng lng.
2. Tnh nng mol ca cc dung dch sau:
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4. Tnh nng ng lng ca dung dch Na2CO3 khi s dng mt th tch HCl 0,1 N l 30,60ml
trung ho 150 mg mu th.
5. Ngi ta dng nng ppm trong trng hp no?
CU HI TRC NGHIM
a. s gam cht tan / 100 ml dung dch d. s mg cht tan / 100 g dung dch
b. s mg cht tan / 100 ml dung dch e. s gam cht tan / 1000 g dung dch
c. s gam cht tan / 100 g dung dch
a. s mg cht tan / 100 g dung dch d. s ml cht tan / 1000 g dung dch
b. s ml cht tan / 100 ml dung dch e. s ml cht tan / 100 g dung dch
c. s lt cht tan / 100 g dung dch
a. s ml cht tan / 100 ml dung dch d. s ml cht tan / 100 g dung dch
b. s ml cht tan / 1000 ml dung dch e. s ml cht tan / 10 g dung dch
c. s mg cht tan / 100 ml dung dch
a. s gam cht tan / 1000 ml dung dch d. s ml cht tan / 1000 ml dung dch
b. s mg cht tan / 1000 ml dung dch e. s ml cht tan 100 lt dung dch
c. s ml cht tan / 100 ml dung dch
5. S gam kali dicromat cn thit pha 250 ml dung dch kali dicromat 2M l
6. Tnh nng mol ca mt dung dch ethanol (C2H5OH = 46). Bit rng trong 85,0 ml dung dch
c cha 1,7 g ethanol.
7. Cho bit nng ng lng ca dung dch H2SO4 98% c d = 1,84 g/ml
a. 36,8 N c. 28,5 N e. 42 N
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b. 35,3 N d. 45 N
Chng 5
PHNG PHP PHN TCH KHI LNG
MC TIU
NI DUNG
1. LCH S
Thodore W. Richards (1868 1928), cng vi cc sinh vin Trng i hc Harvard pht trin
v ci tin nhiu k thut phn tch khi lng, xc nh c khi lng nguyn t ca 25 nguyn t.
V l nm 1914 ng l ngi M u tin nhn gii Nobel v ho hc.
2. NGUYN TC
C s ca phng php phn tch khi lng l nh lut thnh phn khng i v nh lut ng
lng.
Trong nh lut thnh phn khng i, t s khi lng cc nguyn t c trong thnh phn mt cht
lun lun nh nhau. Cn vi nh lut ng lng, khi lng cc nguyn t tham gia phn ng lun
lun khng i v t s gia chng khng thay i.
Phng php phn tch khi lng da trn vic o lng khi lng c thc hin nh cn phn
tch, mt dng c cung cp cc kt qu rt ng v chnh xc.
Trong phng php ny, cht cn xc nh c tch ra di dng nguyn cht hay di dng hp
cht c thnh phn xc nh. T hp cht thu c ny, sau khi cn trn cn phn tch, ngi ta tnh
c khi lng ca cu t cn xc nh v hm lng phn trm ca n.
Th d: xc nh hm lng bc trong bc nitrat, ngi ta ly chnh xc khong 0,2549 g
AgNO3, ho tan trong nc v kt ta ion bc bng acid hydrocloric
Sau khi x l thch hp kt ta thu c, v cn trn cn phn tch, khi lng ta AgCl thu c l
0, 2148 g. Tm khi lng bc trong kt ta.
Gii:
Da vo phng trnh ho hc trn ta c: c mt phn t AgCl (M =143,35 g) th lng bc tng
ng l 107,90 g. Nh vy khi thu c 0,2148 g s suy ra hm lng ca bc
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3. PHN LOI
Phng php phn tch khi lng bao gm phng php tch, phng php ct v phng php kt
ta.
Trong phng php ny, cht cn xc nh c tch ra t cht phn tch di dng t do v c
cn trn cn phn tch.
3.1.1. Phng php xc nh trng lng tro
Mu rn c t chy v nung n trng lng khng i. Tro thu c em cn. Da vo trng
lng ca tro ngi ta tnh hm lng phn trm ca n trong mu cho.
Th d: xc nh hm lng tro sulfat ca terpin hydrat, ngi ta cn 1 g ch phm (cn chnh
xc) em nung vi acid sulfuric. Tro thu c em cn trn cn phn tch. Dc in Vit Nam III quy
nh, lng tro sulfat khng c qu 0,1%.
3.1.2. Phng php tch
Dng tch n cht ra khi hn hp. Th d nh lng vng v ng trong hp kim. Trc ht
ngi ta ho tan mt lng cn xc nh ca hp kim trong nc cng thu (hn hp acid nitric v
acid sulfuric), sau thm dung dch hydro peroxyd mc ch kh ion vng n vng nguyn t. Lc
vng c tch ra, ra loi tp cht, sy v nung, ngui, em cn. Da vo khi lng vng
c tch ra, ngi ta suy ra hm lng vng c trong mu.
3.1.3. Phng php in trng lng (Electrogravimetry)
Cht cn xc nh c dng in tch ra v bm trn mt in cc bng platin (catod). Da vo
khi lng tng ln ca catod, ngi ta suy ra hm lng.
Th d: Khi cho dng in mt chiu i qua mt dung dch c cha ion ng, trong nhng iu kin
xc nh th ng s tch ra, bm ln catod. Cn catod trc v sau th nghim s suy ra hm lng ng
trong hn hp.
Ngi ta tch mt cch nh lng cht cn phn tch di dng mt hp cht bay hi. Trong
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phng php ny, cht phn tch hay cc hp cht b bin i c lm bay hi mt nhit thch
hp hay do tc dng vi mt thuc th thch hp. Cht bay hi c thu hi v cn. Khi lng ca
mu c xc nh mt cch gin tip t s mt trng lng.
Cc phng php lm bay hi thng l phng php trc tip v phng php gin tip.
3.2.1. Phng php trc tip
Cht sau khi lm bay hi c hp th bng mt cht thch hp c xc nh khi lng. S
chnh lch v khi lng ca cht hp th trc v sau phn ng l khi lng ca cht cn xc nh.
Th d: nh lng natri hydrocarbonat trong vin thuc khng acid. Ngi ta cn mt lng mu t
thuc vin nghin mn v x l bng acid sulfuric long bin i hydrocarbonat thnh dioxyt carbon:
NaHCO3 + H2SO4 CO2 + H2O + NaHSO4
Trong phng php ny, ngi ta xc nh khi lng cn cn li ca cht sau khi tch hon ton
cht cn xc nh. Hiu s khi lng trc v sau khi ct cht cn xc nh cho ta kh nng tnh c
hm lng ca cht.
Th d: BaCl2 ngm 2H2O. xc nh lng nc kt tinh, ngi ta cn mt lng mu, em sy
nhit 100 - 105oC. ngui, cn mu ln hai xc nh lng nc mt.
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Trong phng php khi lng da trn s to ta, cht phn tch c tc dng vi thuc th thch
hp to thnh hp cht t tan, sau c lc, ra, sy v nung. Cht ny c cn trn cn phn tch.
Qu trnh nung c th gy ra s bin i v mt ho hc ca ta, v vy trong phn tch ngi ta
phn bit dng kt ta v dng cn.
Dng kt ta: dng to thnh khi cho cht cn phn tch tc dng vi thuc th thch hp.
Th d: Khi xc nh ion trong dung dch Na2SO4, ngi ta dng ion Ba2+ kt ta. Ta to
thnh l BaSO4.
Dng cn: dng to thnh sau khi c x l bng nhit (sy v nung) c cn xc nh hm
lng.
Dng cn cng c th l dng kt ta th d nh trng hp ca BaSO4, ta to thnh sau phn ng,
khng b bin i sau khi sy v nung, sn phm em cn l BaSO4 ngi ta gi dng ta ging dng
cn.
Nhng dng cn li l calci oxyt v calci oxalat b phn hy sau khi nung, phn ng c th vit:
CaC2O4.2H2O CaC2O4 CaO + CO + CO2
4. C IM
Phng php phn tch khi lng l mt trong s t k thut o lng da trn nn tng ca n v
SI nh khi lng v mol, c hng s xc nh nh s Avogadro v khi lng ca 12C, cho php xc
nh hm lng ca cc cu t ring bit trong mt mu cho ca cht phn tch. Thng c dng
khi nh gi thnh phn ca mu. Xc nh cc kim loi (cc cation), cc phi kim loi (cc anion), thnh
phn ca hp kim, cc hp cht hu c...
Nhc im ca phng php ny l thi gian xc nh ko di, di hn so vi phng php phn
tch chun .
5. CCH TNH KT QU
Cc kt qu trong phn tch khi lng thng c tnh t hai s o thc nghim: khi lng mu
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th v khi lng ca sn phm c thnh phn xc nh. Hm lng phn trm ca sn phm c
tnh bng cng thc:
A: cht cn nh lng.
Th d: xc nh lng piperazin c trong sn phm thng mi, ngi ta c th to ta piperazin
diacetat bng acid acetic. Cn sn phm to thnh, tnh hm lng ca piperazin tinh khit.
thc hin ngi ta cn mt lng mu 0,3126 g ho trong 25 ml aceton, thm 1ml acid acetic.
yn 5 pht, sau lc ta, ra bng aceton, sy kh 110C, em cn thu c mt lng 0,7121 g.
Tnh hm lng phn trm ca piperazin?
Gii
Khi xc nh trc tip, cc sn phm d bay hi thng c tch ra di dng hp cht bay hi c
thnh phn xc nh. Cc tinh th hydrat b phn hy tch ra nc, cc carbonat b phn hy to thnh
CO2... V vy ngi ta tnh lng cht cn xc nh theo s tng khi lng ca b phn hp th. Hm
lng phn trm ca hp cht bay hi c tnh xut pht t t l tng ng.
p: khi lng dng cn cht cn xc nh theo s gia tng khi lng ca cht hp th.
a: lng cn ca mu.
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Mu ban u l cht rn. Vi a gam mu A, sau khi kt ta, khi lng dng cn thu c l p gam.
F: h s chuyn, dng chuyn t khi lng mol dng cn sang khi lng nguyn t cn phn
tch.
Th d:
Mt cht ty ra thng mi cha phosphat c khi lng 0,3516 g. Ngi ta ph hy cc hp cht
hu c bng cch un nng n . Cn thu c cho tc dng vi HCl chuyn P thnh H3PO4. Ion
y khi lng ca cht phn tch l P c tnh bng cch nhn khi lng ca dng cn vi mt
hng s. Hng s ny c cu to bi cht cn phn tch v dng cn. Hng s ny c gi l tha s
chuyn hay yu t khi lng, k hiu F
Nh vy F c tnh:
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6.1. Xc nh lng mu
Hm lng ca dng cn ph thuc vo lng cht nghin cu. Lng cht nghin cu c nh
hng n chnh xc ca s phn tch.
Lng cn cht phn tch cng ln th chnh xc cng cao, tuy nhin nu lng cn qu ln gy
bt li trong qu trnh lc, ra. Ngc li nu lng cn qu nh s dn n sai s ln.
Lng mu cn thit lm kt ta c tnh t phng trnh ca phn ng gia cht cn phn tch
v thuc th.
6.1.1. i vi kt ta dng tinh th
Lng mu cn thit c tnh theo cng thc:
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Th d: Tnh lng mu cn thit ca Fe(NO3)3.9H2O khi tin hnh phn tch khi lng. Bit rng
dng cn l Fe2O3.
Gii
Phng trnh phn ng c th vit nh sau:
Cc phn ng thng xy ra trong dung dch, do mu th phi c ho tan trong dung mi thch
hp trc khi cho tc dng vi thuc th to ta.
Cn ch n cc yu t nh hng nh cu to cht, nhit , mi trng. Th d trng hp cht
khng tan trong nc nhit thng, cn un nng bng cch cch thy hay cht tan c khi c s
hin din ca acid...
6.2. Thuc th
Thuc th gm thuc th to ta v c v hu c.
6.2.1. Thuc th v c
Cc thuc th ny to vi cht cn phn tch thnh cc mui hoc cc oxit rt kh tan. Thuc th v
c to ta chn lc nhng khng c hiu.
Mt s thuc th v c
To ta cc cation v c. Cc cation v c thng c kt ta di dng cromat, halogenid,
hydroxyd, oxalat.
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To ta cc anion v c
Mt s anion v c c th c kt ta bng cch s dng cc phn ng dng trong to kt ta cc
cation nh bng trn, ch i ngc cht phn tch thnh cht to kt ta (thuc th).
Th d nh ion cromat c th c xc nh bng cch cho tc dng vi dung dch BaCl2. Ngoi ra
cn c th s dng cc thuc th sau:
Cht phn tch Thuc th Dng ta Dng cn
6.2.2. Thuc th hu c
Thuc th hu c c tnh chn lc cao hn thuc th v c. Thuc th c hai loi, loi to vi cht
phn tch thnh cht khng ion ho, rt t tan gi l cc hp cht kt hp, loi th hai to thnh cc cht
trong c lin kt gia cht v c vi thuc th l lin kt ion.
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Mt s thuc th hu c
Cht cn
Thuc th Dng ta Dng cn
phn tch
Natri tetraphenylborat
Na[B(C6H5)]4 K+ K[B(C6H5)]4 K[B(C6H5)]4
Nhm chc hu c
Thuc th Dng cn
cn phn tch
6.3. S kt ta
Sn phm l tng ca mt phn tch khi lng l khng tan, d lc, d lm sch v c thnh phn
xc nh. Mc d c t cht t nhng yu cu ny, nu s dng nhng k thut thch hp cng c th
p ng c. Th d mt ta c tan gim khi trong dung dch lnh v tnh tan ca hu ht cc hp
cht u gim nhit thp.
Cc tiu phn ca cht kt ta phi ln c th tch d dng khi lc, khng c qu nh
lm tc lc hoc i qua giy lc. Kch thc ta ln hn ch c s bm cc cht l ln ta. Ngoi ra,
ta cn hin din dng hn tng keo, kch thc cc tiu phn trong khong 1 1000 nm qua c
hu ht cc lc.
Dng ta
- Ta phi c tan nh ta c hon ton.
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Gi s khi lng ca Cr2O3 v BaCrO4 thu c l nh nhau bng 1 mg. Sai s i vi Cr dng
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Lng thuc th. m bo kt ta c hon ton cht cn phn tch, lng thuc th s c
cho vi lng d t 10 15% so vi lng c tnh t phn ng. i vi nhng thuc th c tnh bay
hi, lng thuc th gp 2 3 ln so vi l thuyt.
Ch : Trong mt s trng hp, lng tha thuc th c tc dng lm tan ta to thnh.
Th d: nh lng ion Hg2+, ngi ta s dng KI to kt ta HgI2. Nhng vi lng KI d
HgI2 s to phc K2[HgI4] tan:
S cng kt c nhiu nguyn nhn khc nhau, ngi ta phn bit 3 dng cng kt: hp ph, hp lu
v ni hp. Ngoi ra s hu ta cng l nguyn nhn gy bn ta.
Hp ph (adsorption)
Hp ph l hin tng cc ion hoc cc phn t cht bn trong dung dch bm dnh ln b mt ta
mi to thnh. Tinh th cng nh hp ph bn cng nhiu. Nng cht bn trong dung dch cng ln,
s hp ph cng mnh v nhit cng thp bn cng d b hp ph ln b mt ta.
Hp ph l mt hin tng thun nghch v cng to ra s gii hp ph. S hin din ng thi ca 2
hin tng i nghch ny dn n mt trng thi cn bng ng, ngi ta gi l cn bng hp ph.
Trong trng hp ny, c th x l bng cch to tinh th ln nu l ta tinh th v thng c th
loi b bn bng cch ra.
Hp lu (Occlution) l s gi cc tp cht tan trong mi trng vo bn trong ta do ta to thnh
qu nhanh, cc tinh th mi to thnh c th bc ly cht bn pha trong. Hp lu ch xy ra i vi
ta tinh th.
Ni hp (Inclusion) l hin tng m cc ion tp kt ta vo cc tinh th li ca ta to thnh tinh
th hn hp. Hin tng ny xy ra khi cc ion ca tp c cng kch thc v cng in tch vi ta do
to thnh cc ion ng hnh. Ngoi ra hai mui ny cn phi c cng lp tinh th. Th d ta BaSO4
c hnh thnh khi thm dung dch BaCl2 vo dung dch cha ion sulfat, c s hin din ca ch.
Nhng ion ch thay th mt phn ion bari trong tinh th to thnh tinh th hn hp vi BaSO4. S to
thnh tinh th hn hp ny rt kh trnh khi mt s ion kt hp hin din trong mu. Trng hp ny
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cng xy ra i vi ta keo. Bin php tt nht l chn thuc th khc khng gy ra s to thnh
tinh th hn hp.
Hu ta (posprecipitation)
Hin tng ny xy ra nu ta tip xc lu vi dung dch, th d nh ta HgS nu tip xc lu
trong dung dch c cha Zn2+, mc d mi trng acid mnh vn c th xut hin ta ZnS trn b mt
ca HgS. Thng hay gp nht l ta CaC2O4 c hu ta l MgC2O4.
6.3.4. To kt ta
Vi ta tinh th. Nhiu ta tinh th nh BaCrO4, BaSO4, CaC2O4... thnh thong thu c di
dng nhng tinh th rt mn c th qua c l lc gy ra s mt khi lng ca dng ta trong qu
trnh x l. Hin tng bn ta l mt trong nhng yu t ngn cn s kt ta.
hn ch cc yu t nh hng n kt qu phn tch, vic to cc kt ta tinh th cn tun theo
cc iu kin sau:
- Tin hnh kt ta vi dung dch mu v thuc th long.
- Thm dung dch thuc th vo chm v khuy trong qu trnh to ta.
- Thc hin kt ta vi dung dch cht kt ta nhit cao.
Trong mt s trng hp, cn thm vo cht lm tng tan v trnh hin tng cng kt.
Th d to ta BaSO4 ngi ta thm HCl gim ta ph BaCO3 v gim cng kt Ba(OH)2.
6.4. Lc v ra ta
6.4.1. Lc ta
Lc l giai on tch kt ta ra khi dung dch to ta. Tu theo lng ta v cch chuyn t dng
ta sang dng cn, ngi ta c th s dng dng c lc thch hp nh giy lc hay phu lc.
Giy lc
lc ly ta ngi ta s dng giy lc khng tro. Giy lc ny sau khi t chy v nung, li
khi lng tro rt nh, c th b qua.
Giy lc khng tro c mn khc nhau. Tu theo kch thc ca cc ht kt ta, ngi ta s dng
cc loi giy lc mng hay dy, c phn bit bng mt di bng c mu bao chung quanh hp giy
lc. Giy lc bng c dng trong trng hp lc cc kt ta dng keo v nh hnh. lc phn
ln cc kt ta, c th s dng loi bng mu trng c mn trung bnh, cui cng lc cc kt ta tinh
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th nh nh BaSO4 hay CaC2O4, ngi ta dng giy lc mn nht (bng mu xanh bin).
Khi tin hnh lc, iu quan trng nht l phi ch n lng ta cn lc chn kch thc ca
giy lc ph hp. Ta khng c chim hn 1/3 chiu cao ca giy lc m bo ta s c ra
sch sau khi lc.
Phu lc
Phu lc xp hin nay c dng ph bin trong cc phng th nghim. Phu lc lm bng s, lc
di p sut gim. Loi lc ny chu c nhit cao nhng li c nhc im l ht m.
6.4.2. Ra ta
Cht to ta thm vo phi l cht bay hi lng tha ca cht ny c th b loi sau khi nung.
b) Ra ta bng dung dch cht in ly. C nhiu cht kt ta khi ra vi nc s to hin tng
pepti ho, tr thnh dng keo v i qua c lc nh trng hp ca ta AgCl (AgCl: Ag+.....NO3-),
ngi ta x l bng cch ra ta keo ny vi dung dch c cha cht in ly bay hi c th loi sau
khi nung nh HNO3 hay NH4NO3.
6.5. Sy v nung
Sau khi lc, ngi ta sy ta cho n khi lng khng i. S sy c tc dng loi dung mi v tt
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c cc cht c th bay hi. Nhit v phng php sy ph thuc vo phng php lc v dng ta
thch hp. Trong mt s trng hp ngi ta nung sn phm chuyn thnh dng cn c thnh phn
xc nh.
Nhit i hi thu c sn phm thch hp tu thuc vo cc cht kt ta. nhit 110C,
loi nc v cht cht bn d bay hi. sy sn phm ngi ta c th dng t sy, n Bunsen
hoc n Meker.
Hnh 5.2 cho thy s mt khi lng theo nhit ca
mt vi cht kt ta thng dng nh bc clorid, calci oxalat v
nhm oxit. S sy ca 3 ta ny n gin l loi nc v
cc cht bn d bay hi bm vo ta. Nhit s dng rt
khc nhau to ra mt ta khan c khi lng khng i.
i vi bc clorid, nhit cn loi nc ht m l trn
110C trong khi loi nc hon ton nh trng hp ca
nhm oxit, nhit phi trn 1000C.
ng biu din nhit khi lng ca calci oxalat kh
phc tp. Di 135C, mt phn t nc b loi to thnh
CaC2O4.H2O. Hp cht ny sau chuyn thnh oxalat khan
225C. S thay i t ngt v khi lng nhit 450C
cho thy l c s phn hy calci oxalat thnh calci carbonat v
monoxyt carbon. Nc cui cng ca ng biu din tng
ng vi s bin i calci carbonat thnh calci oxit v CO2.
Nh vy, khi nh lng Ca2+ bng phng php phn tch Hnh 5.2.Tc dng ca nhit ln
khi lng vi ta oxalat, bn cht ca dng cn ph thuc khi lng ta
nhiu vo nhit .
Khi nung kt ta giy lc chy thnh than, than to thnh c th kh mt s cht khi nung. Trong
trng hp ny cn phi dng phu lc s thay cho giy lc.
6.6. Cn
7. NG DNG
7.1. Xc nh nc kt tinh v ht m
Dc in Vit Nam III c tiu chun "Gim khi lng do sy kh" trong cc chuyn lun xc
nh nc ht m hoc c nc ht m v nc kt tinh vi nhit nh sau:
105oC 5oC: Nhit thch hp xc nh m.
120oC 200oC: Nhit thch hp loi nc kt tinh.
tnh kt qu, p dng cng thc:
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7.2.1. Nguyn tc
- Cn mu.
- Chuyn mu v dng ho tan.
Thm dung dch thuc th c nng thch hp un nng kt hp khuy.
un cch thu.
yn cho ta kt tinh lc.
Ra ta bng nc nng.
Nung - cn - tnh kt qu.
7.3.1. Nguyn tc
Cho dung dch AgNO3 vo mt dung dch cha ion Cl-, Br-, I- s thu c cc ta bc halogenid.
Ra ta, sy v cn kt qu.
Th d: nh lng NaCl c trong dung dch mu. NaCl phn ng vi AgNO3 theo phng trnh:
Thm nc vo mu, thm HNO3. Cho dung dch AgNO3 khuy mnh.
Sy ta v tnh kt qu.
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7.3.3. Nhn xt
Sy ta nhit 1300C.
Ta bc d b phn hy, trnh nh sng.
Ta AgCl d b hp th Ag+ to ra lp in kp trong trng hp trong dung dch c lng tha
AgNO3 thm HNO3 ion ph lp in kp.
T kha
CU HI LNG GI
CU HI TRC NGHIM
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a. 5 - 10 % c. 15 20% e. 25 30%
b. 10 15% d. 20 25 %
Chng 6
PHNG PHP PHN TCH TH TCH
MC TIU
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NI DUNG
1. M U
Ngi t c s cho phng php phn tch th tch l nh bc hc L.J. Gay - Lussac (Louis
Joseph GAY LUSSAC) 1778 - 1850.
Phng php chun th tch l phng php phn tch nh lng trong ch yu l s o chnh
xc th tch ca dung dch c nng xc nh cn thit phn ng hon ton vi cht phn tch.
S chun c thc hin bng cch thm t t mt dung dch chun vo dung dch ca cht cn
phn tch bng buret cho n khi ngi ta nhn thy phn ng gia cht chun v cht phn tch xy ra
hon ton. Th tch ca thuc th dng trong nh lng c xc nh bng s chnh lch th tch ca
cht chun gia hai giai on, u v cui phn ng.
Phng php th tch c s dng rng ri trong phn tch v nhanh chng v n gin.
2.1. nh ngha
2.1.1. im tng ng
1 mol 1 mol
im tng ng l mt im l thuyt, khng th xc nh bng thc nghim.
2.1.2. im kt thc
Et = Veq - Vfin
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Hp cht c tinh khit rt cao c dng lm cht gc trong cc phng php th tch v phng
php khi lng.
Tnh chnh xc ca phng php ph thuc vo cch nh gi cht lng ca hp cht ny. Mt
cht chun bc mt phi t cc tiu chun sau:
tinh khit cao 99,95%
Tnh n nh trong khng kh.
Khng c nc hydrat ho thnh phn cht rn khng thay i khi c s thay i m tng
i.
C tnh tan tt (thch hp) trong mi trng khi thc hin chun .
Khi lng phn t tng i cao hn ch sai s tng i khi cn mu (sai s <0,1%).
Trn thc t ch c rt t hp cht t c cc tiu chun trn.
Th d:
- Kali naphtalat (M = 204,22 g), mui lun lun dng khan, ch cha ti a 0,003% nc.
KHCO3 (M = 100,11 g)
Dung dch chun l mt thuc th c nng bit trc c dng chun trong cc phng
php phn tch th tch.
Cc dung dch chun gi mt vai tr ch yu trong tt c cc phng php chun , v vy cn thit
phi kim tra nhng tnh cht cn phi c trong dung dch, cch pha v biu th nng ca cc dung
dch ny.
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Phng php phn tch th tch chnh xc khi nng ca dung dch chun chnh xc. C hai
phng php c bn xc nh nng ca dung dch chun.
Phng php trc tip: Trong phng php ny, mt lng cn chnh xc cht chun ho hc bc 1
(s cp) c ho tan trong mt dung mi thch hp v pha long trong bnh nh mc n th tch
chnh xc.
Phng php so vi mu chun (etalonnage): dung dch dng lm chun c so bng cch chun
vi
- mt khi lng cht chun ho hc s cp.
- mt khi lng cht chun ho hc th cp.
- mt th tch ca mt dung dch chun khc.
Phn ln dung dch dng lm chun c xc nh nng bng phng php ny do cc thuc th
khng t c tiu chun ca cht chun ho hc s cp.
Nng ca dung dch chun thng c biu th l nng mol v nng ng lng.
Nng mol cho bit s mol ca thuc th cha trong mt lt dung dch.
Nng ng lng biu th s ng lng gam ca thuc th c trong mt lt dung dch.
2.3.1. Cht ch th ho hc
Ch th l cht c cho vo dung dch khi tin hnh nh lng. S thay i v pH, th oxy ho
kh... s lm thay i mu ca ch th.
Cc ch th thng dng trong phng php phn tch th tch:
a) Ch th ni: ch th cho vo dung dch khi tin hnh nh lng.
Ch th mu: metyl da cam, phenolphtalein.
Ch th to ta: kali cromat.
Ch th to hunh quang: fluorescein.
b) Ch th ngoi: ch th ngoi, dng dng c nh a thu tinh ly dung dch ri cho tc dng vi
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2.3.2. Ch th l ho
o s i mu ca dung dch bng phng php quang ph, phng php in ho nh o in th,
o cng dng in hay o d dn in.
Ngi ta thng da trn c s phn ng phn loi cc phng php phn tch th tch.
Phng php dng nh lng cc acid, base v mt s mui trong mi trng l nc hay mi
trng khan. Phng php ny da trn s trao i proton H+
Th d: nh lng acid hydrocloric bng natri hydroxyd
Da trn phn ng oxy ho kh tng ng vi s trao i electron gia hai cht: mt cht cho mt
hoc nhiu electron, cht th hai nhn electron.
Th d: nh lng st III clorid bng dung dch thic
Da vo phn ng to thnh phc cht. Phng php complexon c s dng ph bin dng nh
lng cc ion kim loi nh nh lng calci v magnesi trong nc vi thuc th l EDTA.
4. K THUT CHUN
K thut chun trong phng php th tch ni chung rt n gin. K thut thng ch cn o
th tch ca cc dung dch vi nhng dng c chnh xc nh pipet, buret, bnh nh mc. Cc dng c
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Phng php chun n gin nht l t buret hiu chnh chnh xc, ngi ta nh tng git
dung dch chun B vo mt th tch xc nh dung dch hay mt lng cn xc nh cht A ha tan
trong dung mi thch hp. Khi phn ng kt thc, bit lng dung dch chun B dng phn ng vi
cht cn nh lng A th c th tnh hm lng ca cht A.
Chun trc tip thng dng nh lng mt acid bng mt base hay ngc la. Th d: nh
lng HCl bng dung dch chun NaOH vi ch th l phenolphtalein. Dung dch acid hydrocloric c
cha trong bnh nn, dung dch natri hydroxyd chun c thm t t tng git bng buret cho n khi
phn ng kt thc c nhn bit nh vo s i mu ca ch th.
Chun ny p dng trong trng hp khng th thc hin chun trc tip. Ngi ta thm mt
th tch chnh xc, d dung dch chun B vo mt th tch xc nh dung dch hoc mt lng cn xc
nh A ha tan vo dung mi thch hp. Khi phn ng kt thc, lng d thuc th B khng tham gia
phn ng c chun bng dung dch thuc th h tr khc, bit nng chnh xc.
Th tch thuc th B trong chun ny khng c t hn 15 20 ml trong phng php a lng.
Th d: nh lng Mg2+ bng phng php complexon:
Phng php ny c li trong cc trng hp:
Khng chn c ch th kim loi thch hp cho ion cn xc nh. Chng hn khng th chun
trc tip Co2+, Al3+ vi ch th en eriocrom T c v ch th ny to vi Co2+, Al3+ phc bn vng
n ni khng b EDTA ph v.
Ion cn xc nh nm trong ta BaSO4, PbSO4... lm phn ng vi EDTA xy ra chm.
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Ngi ta dng phng php ny khi cht cn nh lng khng phn ng vi dung dch chun nn
cn c mt cht trung gian.
Th d: Dung dch natri thiosulphat l mt cht kh tt c dng chun cc cht oxy ho yu
nh iod nhng khng chun c cc cht oxy ho mnh nh KMnO4, K2Cr2O7. V vy trc ht
cho K2Cr2O7 tc dng vi thuc th trung gian KI (B1) trong mi trng acid gii phng iod, iod
tch ra tng ng nh lng theo t l vi K2Cr2O7. Nu chun iod c gii phng ra [thay cho
K2Cr2O7,(A1)] bng dung dch chun chnh Na2S2O3 (B) th c th tnh ra lng K2Cr2O7 (A).
ng ong.
Pipet khc .
Dng ly mt th tch dung dch gn ng.
Pipet chnh xc mt vch, pipet hai vch, phn phi mt th tch dung dch chnh xc c nh.
Buret dng ong mt th tch chnh xc thay i.
Bnh nh mc dng pha mt dung dch c th tch chnh xc, thng dng pha dung dch
chun, pha long dung dch. Th tch cht lng trong bnh c biu din bng mililt. Trn bnh c ghi
dung tch v nhit (thng l 20C). Cc bnh nh mc thng c dung tch khc nhau t 25 2000
ml.
Dng c chnh xc bng thu tinh c chia thnh 2 loi:
Loi A:
Loi B: Sai s trong o lng thng nh hn 2%. Nhng dng c ny ch dng trong pha ch m
thi.
Th d 1:
- Pipet chnh xc loi A 20 ml c dung sai 0,02ml c ngha l pipet c th phn phi mt th tch
l 19,980 ml < th tch phn phi theo l thuyt < 20,020ml. Nh vy dung sai s l
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Buret 50 0,05
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10 0,02 0,04
6. CCH TNH KT QU
tnh c kt qu trong phng php phn tch th tch cn phi bit th tch v nng ca cht
chun.
Th d:
Dung dch acid hydrocloric c chun ho bng dung dch natri hydroxyd chun. Nu trung ha
25 ml dung dch HCl ngi ta s dng 32,20 ml dung dch NaOH 0,0950N. Tnh nng ng lng
ca HCl.
T nng c xc nh, tnh c:
- Hm lng gam /lt
Pg/l = NA EA
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T KHA
CU HI LNG GI
CU HI TRC NGHIM
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c) cht chun bc 2
d) thuc th
e) cht ch th
4. c im ca mt dung dch chun:
a) bn, c cng thc xc nh.
b) khng b ht m, khi lng phn t kh ln.
c) c nng xc nh.
d) bn, phn ng nhanh, hon ton v phn ng chn lc i vi mu.
e) bn, phn ng nhanh, hon ton, phn ng chn lc v c nng xc nh, t tn thi gian, t tn
km, k thut n gin.
Chng 7
PHNG PHP ACID BASE
MC TIU
NI DUNG
1. MT S KHI NIM C BN
- Theo Lewis: acid l cht c kh nng nhn i electron cn base l cht c kh nng nhng i
electron t do.
- Theo Bronsted: acid l cht c kh nng cho H+ v base l cht c kh nng nhn H+.
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Theo (7.1), nu phn ng theo chiu t tri sang phi th HA l acid (cho H+) v nu theo chiu
ngc li th A- l base (nhn H+).
Tng t, theo (7.2) th B l cht nhn H+: base v HB+ l cht cho H+: acid.
Trong (7.1) HA / A- to thnh 1 cp acid base lin hp v trong (7.2) l cp BH+ / B.
Vit gp (7.1) v (7.2) li thnh:
HA + B HB+ + A
acid 1 base 2 acid 2 base1
a) Tng qut ho khi nim acid base: khng xem acid hay base l nhng cht hin din ring r
nhng l 1 cp acid base lin hp v nu c acid l c base.
Dung mi c proton hot ng l dung mi c tnh acid hay base v c th tc ng ln cc cht tan
acid hay base c trong dung dch.
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Nu nc l 1 acid H 2O OH + H+
Nu cn l acid ROH RO + H+
hay cn l base ROH + H+
Thc t [SH] hoc [H2O] c xem nh l mt hng s v c rt t phn t chu s phn ly.
Th d: Trong 1 lt nc c 107 phn t gam (hoc 1,8 g nc) b phn ly thnh 100 g H+ (dng
H3O+) v 1,7 g OH.
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Ch
- Thay v vit [H3O+] ngi ta vit [H+].
18oC 0,62 1014 0,79 107 25oC 1,2 1014 1,1 107
- Trng hp 1 acid
HA + SH A + [ ]
acid + dung mi base + proton c solvat ho
(7.6)
Kt qu: tnh acid ca cht tan cng mnh th cng d phng thch H+, [SH2+] cng ln, Ka cng
ln v pKa cng nh. Lc ca base lin hp A cng yu khi acid cng mnh.
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- Trng hp 1 base
B + SH BH+ + S-
Base 1 dung mi acid acid 1 base t dung mi
V (7.7)
Theo (7.5)
c
v theo (7.6) :
2.4. D on phn ng
Xt pK ca 2 cp acid - base
Th d:
Acid acetic tc ng trn amoniac trong dung mi l nc.
Cp acid acetic / acetat: pKa = 4,74 v cp ion amoni / amoniac: pKa = 9,2.
Trong nc, acid acetic b phn ly v amoniac cng b phn ly theo phn ng cn bng c hng s:
(7.9)
(7.10)
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Kt qu: phn ng (7.8) cng dch chuyn v pha phi th cng ln hay cng nh, ngha
l cng ln.
Trong thc t, thay v s dng [H+] ca dung mi (*), ngi ta s dng lg[H+] = pH gi l th
hydrogen ca dung mi hay l pH.
(7.11)
Hng s ion ho c tun theo trong dung mi tinh khit v trong cc dung dch:
- Nu nc tinh khit, mt phn t dung mi khi phn ly phng thch 1 H+ v 1 OH .
- [H+] = [OH-] = 10 7, do vy pH ca nc tinh khit l 7.
- Nu trong nc c acid th s c H+ chuyn t acid vo nc ngha l c xut hin nhng ion
H3O+ ph. Do vy [H3O+] hay [H+] > 10-7 v pH < 7, nng acid cng ln th pH cng nh.
- Ngc li, khi cho 1 base vo nc, base ny b phn ly to OH- v v Knc = [H+] [OH-] nn
[OH-] tng th [H+] phi gim. Do vy [H+] < 10-7 v pH > 7.
1.1.1. ng cong pH
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Hnh 7.1. pH theo s pha long dung dch HCl Hnh 7.2. pH bin thin theo s pha long
(3 < pH < 7) dung dch HCl (0 < pH < 7)
Cc ng cong ny minh ha s bin i pH theo [H+] ca mi trng tnh bng ion cho php hiu
rng :
- Khi pH thay i 1 n v th [H+] thay i 10 ln (hnh 7.1).
- vng pH nh (khong 0 - 2), [H+] thay i nhiu m pH thay i khng ng k. Ngc li khi
tin gn n s trung ho, [H+] chnh lch t cng lm pH thay i nhiu (hnh 7.2).
2.5.3. Thay i pH theo nhit
Nhit (oC) 0 15 23 30 37
Ch : bin i ny rt quan trng nht l trong lnh vc sinh hc. Gi tr pH bnh thng ca mu
o c 37oC: 7,35 < pH < 7,45. Do vy, khi o phi k n sai s khi thay i nhit .
Nh vy, dung mi c kh nng nhn H+ cng cao (c tnh base) th cn bng ca 2 phng trnh
trn cng dch sang phi : Ka cng ln pKa cng nh acid cng mnh.
Trong cc dung mi c tnh acid th lc ca cc cht ho tan l base yu s tng ln v nhiu base
yu li tr thnh base mnh (gii thch tng t cho dung mi c tnh base).
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Th d:
Acid formic l dung mi t c tnh base hn nc v l acid nn kh nng nhn H+ yu, kh pht
hin tnh acid HCl trong acid formic l 1 acid yu.
Ngc li formamid c tnh base nhiu hn nc - v l base nn pht hin tnh acid tt hn. V vy
acid acetic yu trong nc li c coi nh l 1 acid mnh trong formamid.
Hnh 7.3. Thang biu din kh nng cho v nhn H+ca mt s dung mi
- Th d 2: HCl lun lun l 1 acid trong dung mi acid formic (HCOOH) v kh nng cho H+ ln
hn ca dung mi nhng nc trong acid formic lun lun l 1 base v nc nhn H+ ca dung mi.
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Nh vy:
- Dung mi nhn H+ mnh nht (c tnh base mnh) th cc cht tan s l acid.
- Dung mi cho H+ tt nht (c tnh acid mnh) th cc cht kho st s l base.
y l cng thc c th dng trong mi tnh hung. Nhng trong nhiu trng hp ngi ta c th
dng cc cng thc gn ng, nht l tnh pH ca dung dch acid hay base bit c pKa.
Cc cng thc ny ch c gi tr i vi nhng cht phn ly H+ yu trong dung mi phn ly kho st.
t cc k hiu: HA: acid mnh; B: base mnh; Ha: acid yu; b: base yu.
pH ca 1 acid yu
Cho 1 acid yu Ha, nng ban u l c trong dung mi nc:
(7.12)
(7.14)
- Theo (7.13): trong nhng phn t Ha cho vo u tin c cc phn t khng phn ly: nng l
[Ha]; 1 s phn t khc b phn ly cho a: nng l [a-].
- Theo (7.14): H+ l ca:
Hoc nhng phn t nc b phn ly ( )
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C 2 c lng sau:
- Ha xem nh l acid yu (ngha l km phn ly) s phn t b phn ly c th b qua so vi s
phn t khng phn ly. Nh vy, c th b [a-] trong (7.13) v vit:
c = [Ha] + [a-] [Ha]
- S H+ do nc phn ly xem nh c th b qua so vi s H+ trong (7.14) do acid phn ly (gi s
acid khng qu yu). Do vy, c th b so vi [H+]Ha v vit:
HA + b bH+A (7.15)
Mui bH+A khi cho vo dung mi phn ly c th xem nh b phn ly hon ton.
bH+ A bH+ + A
Trong dung dch lc ny cn acid bH+ c lc tht s (nhng cng ch l mt acid yu do lin hp
vi 1 base yu) c nng c (tnh bng mol/l) ca mui v 1 base A (c lc = 0). Nh vy ch l dung
dch acid yu v c tnh theo cng thc tnh pH ca dung dch acid yu:
pH = 1/2pKa 1/2lg c
pH ca mt base yu
Khi p dng cho 1 dung dch nc ca base b (nng u = c) c th suy lun ging nh trng
hp pH ca 1 acid yu. Phng trnh din t s phn ly ca base v nc:
Ngi ta c :
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Biu thc Ka :
Ging nh mi trng hp khc, khi ho tan hon ton mui ny b phn ly thnh BH+ v a.
BH+ l acid lin hp vi 1 base mnh B nn coi nh acid c lc b qua.
a + H2O Ha + OH
b + Ha bHa bH+ + a
bH+ (lin hp vi base yu b ban u) l acid c lc tht s d ch l acid yu.
a- (lin hp vi Ha ban u) l base c lc tht s d ch l base yu.
Nh vy lc ny dung dch cha ng thi mt acid yu v mt base yu v cc cht ny phn ng
vi dung mi nh sau:
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Hai hng s Ka v khng c lp v nng [H+] tm thy trong c hai phng trnh. V do
vy c th lin kt thnh mt biu thc duy nht:
(7.16)
c = [a] + [Ha]
y cn minh ha mt c lng ph nh sau:
Gi s acid bH+ v base a- b phn ly theo t l rt gn, th [b] [Ha]
v iu kin ny: [bH+] = c [b] v [a-] = c [Ha]. Do vy [bH+] [a-].
Phng trnh (7.16) c n gin ho : KaKbH+ =[H+]2 hay
- S dch chuyn tng h gia acid v base: mt acid mnh ui mt acid yu t mui ca n v
mt base mnh ui mt base yu ra khi mui ca n.
Th d:
HCl + C6H5COONa C6H5COOH + NaCl
Hin tng ny c m t nh sau: mui b phn ly hon ton trong dung dch v cc ion c
phng thch phi tha mn c nhng cn bng lin quan n hoc acid hoc base yu tng ng.
Th d: Mui BH+a- b phn ly thnh B + Ha v Ha b phn ly thnh H+ + a- th gi tr ca hng s
ion ho Ka phi tun theo
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Khi thm 1 acid mnh HA, acid ny b phn ly hon ton s lm tng [H+] v gi nguyn Ka c
l do a- ca mui b phn ly s kt hp vi H+ ca acid mnh HA to nn phn t Ha. Nh vy iu
ny s a tr li s li ion ho (reculisation) acid Ha.
2.8.1. nh ngha
Cht lng tnh (ampholyte = amphotre) l cht cng lc c th coi nh va l 1 acid va l 1 base,
th d nh nc. Ngoi ra cng cn nhiu kiu cht lng tnh khc nh:
- Cc phn t hu c mang cng lc nhng nhm cho H+: COOH, SO3H, phenol v nhng
nhm nhn H+: amin.
Nhng cht c bit nhiu nht l cc amino acid NH2CHRCOOH m tm quan trng sinh
hc rt ln. Cht n gin nht l acid aminoacetic hay glycin. Ngoi ra cng cn nhiu phn t nh
acid paraaminobenzoic v nhng dn xut sulfonic nh taurin (NH2CH2CH2SO3H) s dng nhiu
trong ngnh Dc.
Mt cht lng tnh c th c xc nh bng 2 hng s Ka1 v Ka2 tng ng vi tnh cht acid v
tnh cht base. nh du s lin quan ca 2 tnh cht ny, cht lng tnh c tng trng bi HAB
(HAB vit hoa khng biu th g v lc acid hay lc base).
Tnh acid ca cht lng tnh
(7.17)
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HAB + SH S + HABH+
Vy, cp acid v base HABH+ / HAB c hng s Ka2 l:
(7.18)
(7.19)
(7.20)
a) pH ng in (pHi)
Khi nu pH < pHi, ion HABH+ chim u th v theo (3.7.a) nu pH gim th [H+] tng v lc
[BA-] phi gim v [HABH+] tng.
Ngc li, pH> pHi th ion BA- chim nhiu hn.
Ch : cng thc tnh pH dnh cho pH ng in ging vi cng thc tnh pH gn ng cho dung
dch mui ca mt acid yu v base yu v pHi th dung dch cha cng nng acid v base (ging
nh trng hp ca mt mui bH+a-).
b) Amphion
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L nhng cht lng tnh c hai nhm chc kiu acid amin. pH ng in, dung dch ch yu
khng nhng cha cc dng NH3+CH2COOH v NH2CH2COO- m cn cha nhng ion ng thi
mang in tch dng v in tch m: NH3+CH2COO-. Ion ny gi l amphion hay zwitterion.
Nng [SH2+] v [S-] khng qu quan trng v phi tun theo cn bng tng i ca dung mi v
hng s ion ho ca dung mi Ki : 2SH S- + SH2+
Mt cht lng tnh c tnh cht acid hoc base nhiu hay t hn do ph thuc vo pH ca dung dch
s tm thy mt gi tr gn vi .
Th d: trong nc pH ny thng l 7 3 tng ng vi gi tr:
khi pH = 4 th [H3O+] = 10-4 v [OH-] = 1010
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3.1. nh ngha
Hnh 7.6. Dng lacton khng mu trong mi trng trung tnh hay acid (a)
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Trong mi trng acid: dung dch azoic c mu v hai dng ng phn c c do proton ho
nit amin.
Trong mi trng kim: dung dch azoic c mu vng v cn c mt lot nhng ni i lin hp
nhng c nhiu kh nng hy ti ch nhng ni i ny.
- Dn cht anthraquinon (alizarin sulfonat Natri). Nitrophenol (hnh 7.11).
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Tn ch th mu Mu Mu pH ca vng chuyn mu
Khi pH= pKA th mu sc ca cht ch th c phn chia gia hai dng, lc mu sc ca n nhy
nht.
Nu pH = (pKA + 1) th = 1 v = 10
Nu pH = (pKA 1) th = 1 v = 0,1
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Ch th pH ca vng chuyn mu
- Helianthin 3,1 4,4
- Giy qu gn vng trung tnh
- Phenolphtalein t 8,3 10
Nu trung ho mt base yu bng mt acid mnh hay trung ho mt base mnh bi mt acid yu th
khong pH thay i t ngt s b gim i.
Ch :
- Khi nh lng, nu khong pH chuyn mu ca ch th cng nh th s chuyn mu cng r,
khong ny thng l hai n v pH.
- Ngc li trong trng hp o mu theo pH: nu s chuyn mu cng tri ra mt vng pH ln th
php o cng d thc hin. Th d: xanh bromothymol chuyn mu vng pH = 5.8; vng lc pH =
6.2; xanh l pH = 7; xanh dng pH = 8.
a) Ch th c th s dng trong nhng vng pH qu cao hay qu thp
Cc loi ch th ny cho php thc hin khi nng acid hay base ln. Ch yu lin quan n cc
php phn tch nh lng.
Th d: mi trng acid c nng hoc pH khc nhau tm tinh th s c mu khc nhau:
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Ch th Tashiri
- Dung dch A: -Xanh methylen 1% / EtOH 25ml (mu h tr)
- methylen 1% /EtOH 100ml
- iu ch ch th Tashiri: dung dch A: 100 ml; EtOH: 100 ml; nc: 200 ml. Thm NaOH long
n khi mt mu ;
pH t 5,45 5,50 mu hng xanh l. Ch th ny thch hp nh lng amoniac.
Ch th hn hp hai phtalein
- Phenolphtalein 1% / EtOH 50% 20 ml
- Naphtolphtalein 1% / EtOH 50% 10 ml
pH t 9,6 9,7, mu t hng tm. Ch th ny thch hp nh lng chc acid th hai ca
acid phosphoric.
1 pH xc nh, thnh phn ca hai dng mu ny khng i. Do vy khi cho 1 lng tha cht ch
th cng s khng lm bin i t l v li cng kh thy chuyn mu nn khng c li.
Trong thc hnh, thng thm 1 git dung dch 2% (khong 0,1 mg v l 100 ln t hn trng hp
thm phenolphtalein).
S trung ho dung dch HCl bng dung dch NaOH vi cng th tch, cng nng cho thy s bin
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i nh sau:
- Lc bt u : dung dch ch c acid HA. Gi c l nng ca dung dch acid HA b phn ly hon
ton th [H+] = c hoc pH = .
Trung ho 100 ml HCl 1N bng NaOH 1N. Kho st s bin i v tnh [H+], pH trong c hai
trng hp khng k s pha long v c k s pha long.
Hnh 7.12. Bc nhy pH Hnh 7.13. Trung ho acid mnh (0,1N) bng
base mnh (0,1N)
Bng 7.4. Bin i [H+ ] v pH khi trung ho 100ml HCl 1N bng NaOH 1N
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Khi trung ho dung dch HCl bng dung dch NaOH c nng long hn trng hp trn th s
thy khong bin i pH t ngt thu ngn li.
Th d c th: Trung ho 100 ml HCl 0,1N bng NaOH 0,1N. Kho st s bin i v tnh [H+], pH
trong c hai trng hp khng k s pha long v c k s pha long.
ng cong chun thu c ging trng hp trn vi s chnh lch mt n v pH. Kt qu l
s bin i pH cn im tng ng lun nhanh nhng bao ph mt vng pH nh hn : pH = 5,4.
(bng 7.5, hnh 7.14, 7.15)
Bng 7.5. Bin i [H+] v pH khi chun HCl 0,1N bng NaOH 0,1N
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Hnh 7.14. Trung ho acid mnh (0,1N) Hnh 7.15. Trung ho acid mnh (c)
bng base mnh (0,1N) hoc ngc li bng base mnh (c) vi cc nng khc nhau
cng nng , ng cong chun ca cc acid mnh khc nhau nh HCl, H2SO4 li ging
nhau v nhng acid ny phn ly hon ton.
3.5.1. Bin i pH
S trung ho dung dch CH3COOH (Ha) bng dung dch NaOH vi cng th tch, cng nng cho
thy s bin i nh sau:
- Lc bt u : dung dch ch c acid yu. Gi c l nng ban u ca dung dch Ha.
- Trong lc chun : hn hp gm mt dung dch acid Ha cha b trung ho v mui BHa do acid
b trung ho, ngha l mt dung dch acid Ha (nng gim dn) v base lin hp [a-] (nng tng
dn).
Nng [Ha] v [a-] lin quan bi cng thc :
(7.22)
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a + H2O OH + Ha
Ha H+ + a
H2O H+ + OH
V Ha l acid yu - phn ly t cho nn [H+ ] <<< [BH+] v [OH] <<< [a-] (mui phn ly hon ton)
nn nu b qua [H+] v [OH] trc [BH+] v [a-] th biu thc (7.23) tr thnh:
[a-] [BH+] = [B] (7.24)
Tnh [Ha]:
(7.25)
Khi [B] = c/2 (lc phn na [Ha] c trung ho) th: ; v pH = pKa. Gi tr c
bit ny ca pH (gi l pH bn trung ho) khng lin quan n nng acid.
Trung ho 100 ml CH3COOH 0,1N bng NaOH 1N. Kho st s bin i v tnh [H+], pH. (pKa
ca acid acetic = 4,74)
Gii:
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base acid cn li pH ca hn hp
thm (ml)
vo (ml)
0 100 2,87
50 50 4,74
90 10 5,69
99 1 6,73
99,9 0,1 7,73
100 0 8,73
100,1 tha 0,1 9,7
101 base 1 10,7 pH=1
Theo bng 7.6, so vi vic trung ho HCl 0,1N bng NaOH 0,1N, bin i pH nh sau:
Ch : khi tha base mnh B th pH thay i ging trng hp ca vic nh lng acid mnh bng
base mnh (bng 7.5) v hn hp lc ny l dung dch ca 1 base mnh B v base yu a-. C th coi nh
ch c base mnh B.
Nhn xt:
Khi trung ho mt acid yu bng mt base mnh th s thay i pH cn im tng ng s t hn
trong trng hp trung ho mt acid mnh bng mt base mnh.
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Thm 0,1 ml dung dch chun quanh gi tr l thuyt 100 ml, pH bin i l 2 (i vi trng
hp trung ho acid mnh bng mt base mnh pH bin i l 5,4).
ng cong chun ging nhng trng hp trc. Ch : im tng ng lun lun l im
un ca ng cong chun nhng gi tr pH 7. Mt khc, khi trung ho 50% acid th ng cong
ny c mt im un th hai tng ng v lc pH = pKa (hnh 7.18).
Hnh 7.18. Trung ho acid yu (c) c nng Hnh 7.19. Trung ho cc acid yu (1N) c K
a
khc nhau bng base mnh (c) khc nhau bng base mnh (c)
Cc gi tr pH ph thuc pKa ca acid. Acid cng yu pKa cng ln, ng cong trong thang pH
cng cao, pH im tng ng cng cao v bc nhy pH cn im tng ng tri ra trn mt
vng nh. (hnh 7.19)
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Hnh 7.20. Trung ho base yu (0,1N) bng acid mnh (c) v ngc li
- Trong lc chun , hn hp gm mt dung dch acid mnh HA v acid yu bH+ (do s phn ly
mui bHA v vi mt c lng chp nhn th dung dch c coi nh ch c acid mnh HA).
- Trc khi n im tng ng, ng cong tng ng khc rt t vi ng cong trung ho mt
acid mnh bi mt base mnh, nhng sau im tng ng th bin i pH t ngt km th hn.
- Nh vy, bc nhy pH cn im tng ng tri trn mt vng pH nh hn trng hp trung
ho acid mnh bi mt base mnh.(hnh 7.21)
3.8.1. Bin i pH
- Lc bt u: gi c l nng ban u ca dung dch acid HA, pH theo cng thc tng qut: pH
=1/2 pKa 1/2 log c.
- Trong lc chun : bin i pH hi khc vi trng hp trung ho acid yu bng base mnh.
- Ti im tng ng: hn hp gm dung dch ca mui bHa m pH theo cng thc tng qut:
pH = pK + pKbH+
a
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Hnh 7.21. ng cong chun khi trung Hnh 7.22. ng cong chun khi trung
ho 1 acid mnh bng 1 base yu ho 1 acid yu bng 1 base yu
ng cong trung ho 1 acid mnh (cho tt c acid a chc hay n chc c lc mnh) bng 1 base
mnh lun ging nhau. Kt qu l trong lc chun khng th phn bit nhiu chc acid khc nhau
ca mt acid a chc (polyprotic acid). Nh vy, trong mi trng nc th ng cong trung ho ca
HCl 1N bng NaOH 1N ging nh trng hp chun H2SO4 1N bng NaOH 1N v php nh lng
khng tch bit c hai chc acid ca H2SO4.
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- Lc bt u: (ch xt chc acid th nht, nhng chc acid sau c lc yu, c th b qua).
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im un tng ng vi mt cc i ca ng o hm ny.
a) Chn thuc th chun : chn nhng cht phn ly H+ mnh trong dung mi kho st.
b) Chn nng thuc th : khi pha long 1/10 dung dch cht kho st, bin i pH gim 2 n v.
Do d dng kt lun l khi thc hnh vi dung dch m c N hay N/10 thch hp hn l dung dch
qu long (v s km chnh xc).
c) Chn dung mi
- Ho tan nht. Th d : acid bo mch di ho tan trong ethanol d hn trong nc.
- Pht hin tt nht tnh acid (hay base): th d: trong acid acetic, nh lng alcaloid d hn trong
nc.
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b) Xc nh pKa
- o nhiu pH trong khi trung ho. Tht vy, pKa c tnh theo pH sau khi thm base chun [B]
4. DUNG DCH M
4.1. nh ngha
Dung dch m l dung dch khng li s thay i pH khi thm acid hay base mnh vo dung dch
hoc l dung dch m khi pha long th pH ca dung dch thay i t. S thay i ny thng trong
mt vng gii hn pH.
Dung dch m l dung dch cha trong mt dung mi phn ly (nh nc), hoc mt acid yu v
mui ca mt acid yu (= acid yu v base lin hp ca n). Dung dch m ny thng c pH acid.
Hoc mt base yu v mui ca mt base yu (= base yu v acid lin hp ca n). Dung dch m ny
thng c pH kim.
4.3. C ch ca hiu ng m
Xt mt dung dch hn hp ca acid (hay base) yu v mui ca base (hay acid) mnh nh dung
dch acid acetic (Ha) v mui acetat Na (BHa) trong nc.
Mui ho tan trong nc phn ly hon ton: BH+ a- BH+ + a- (7.26)
(7.28)
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- Kh nng m: khong pH m trong dung dch m cn nng lc m (phn ng cho hay nhn
proton m khng c bin i quan trng v pH).
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4.5. nh gi kh nng m
Kh nng m cng ln khi mt s lng ln dung dch m c cho vo dung dch kho st.
mt nng xc nh ca dung dch m th kh nng m l ln nht khi c mt acid v base lin hp
ca m vi nng tng ng (equimolar). chnh l v tr im un ca ng chun (hnh
7.24).
Khi thc hnh, dung dch m cn hiu qu, ngi ta nhn thy nng acid yu [Ha] hay [bH+]
bng t nht l 10% [base] (v ngc li).
pH ca m c tnh theo cng thc tng qut lin quan n pH v pKa:
Nh vy:
- nu [base] gp 10 ln [acid] th pH = pKa + 1
kh nng m: pH = pKa 1
Nh vy, khi c qu nhiu acid hay base thm vo th pH s vt ra ngoi vng m v pH s tng
hay gim nhanh. Kh nng m lin quan n lng cht c th thm vo dung dch m khng gy ra
mt s thay i hot ion c ngha no.
- Dung lng m (buffer capacity) acid base ca mt dung dch cn duy tr pH: l s lng
(mmol) ca acid mnh hay base mnh thm vo 1 lt dung dch ny (mmol/l hay mM) lm thay i 1
n v pH.
Khi trung ho mt dung dch acid mnh (HCl) trong nc bng mt dung dch chun base mnh
(NaOH hay KOH) s nhn thy ng cong gn nh bng phng gia pH = 0 v pH = 2 ngha l c
mt kh nng m (d khng c im un nh giai on bn trung ho).
Hin tng ny c m t khi xt mt acid mnh v mt base c lc gn nh bng 0 (Th d: cp
HCl/ Cl-).
Trong trng hp acid mnh mt cch l tng, tc ng m vn hin hu v n dng chnh cp
dung mi H3O+ / H2O.
Bng 7.7. m KCl HCl gia pH = 1,0 v pH = 2,2 (theo Clark v Clubs)
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Ma M + a-
Ly logarit v o v, ta c:
(7.29)
Ma M+ + a-
Hng s in ly ca base a- c biu din bng h thc:
Ly logarit o 2 v, ta c:
(7.30)
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H thc ny cho php tnh pH ca dung dch m cha base yu v mui ca n, trong COH-, Ca-
CHa l nng cc ion OH-, a- v ca Ha lc cn bng. pH ny ch ph thuc vo t s nng acid
hoc base yu v mui ca n ch khng ph thuc pha long hn hp.
- Thit lp v duy tr hot ion hydro chun ho my o pH: cc dung dch m hay c s
dng c pH: 4,01: 7,00: 9.00
- Lm n nh pH trong thnh phn pha ch ca cc quy trnh nh lng o quang ph UV- Vis.
- Lm n nh pH trong thnh phn ca mt s pha ng khi trin khai sc k lng hiu nng cao.
(th d: h m phosphat...)
- iu ch cc dng nh lng gn vi im ng in (approach isotonicity).
- Thc hnh trong cc quy trnh phn tch, nht l khi phn tch cc dch sinh hc. Cc dung dch
m c dng trong cc h thng sinh l c chn cn thn khng can thip vo hot tnh dc
lc ca thuc hay chc nng bnh thng ca c th.
Nhiu th nghim v quy trnh nh lng trong Dc in i hi phi iu chnh n pH mong
mun hay duy tr pH chuyn bit bng cch thm dung dch m. Khi o pH, cn phi c dung dch
m chun.
Cc dung dch m ch yu c dng trong phn tch ho hc phi tng thch vi cc cht xc
nh v thuc th s dng.
Dd a. acetic N (ml) 18,5 17,6 16,4 14,7 12,6 10,2 8,0 5,9 4,2 2,9 1,9
Dd acetat Na M (ml) 1,5 2,4 3,6 5,3 7,4 9,8 12 14,1 15,8 17,1 18,1
Nc ct v. (ml) 100 100 100 100 100 100 100 100 100 100 100
pH 3,6 3,8 4,0 4,2 4,4 4,6 4,8 5,0 5,2 5,4 5,6
Bng 7.9. Cng thc pha m acid citric phosphat dinatri c pH = 2,2 - 8,0
Acid citric 0,1M 98 93,8 89,1 84,15 79,45 75,3 71,5 67,8 64,5
Phosphat dinatri
100 100 100 100 100 100 100 100 100
0,1M v. (ml)
pH 21oC 2,2 2,4 2,6 2,8 3,0 3,2 3,4 3,6 3,8
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Acid citric 0,1M 61,45 58,60 55,90 53,25 50,70 48,50 46,40 44,25 42 39,55
Phosphat dinatri 0,1M
100 100 100 100 100 100 100 100 100 100
v. (ml)
pH 21oC 4,0 4,2 4,4 4,6 4,8 5,0 5,2 5,4 5,6 5,8
Acid citric 0,1M 36,85 33,90 30,75 27,25 22,75 18,15 13,05 9,15 6,35 4,30 2,75
Phosphat dinatri
100 100 100 100 100 100 100 100 100 100 100
0,1M v. (ml)
pH 21oC 6,0 6,2 6,4 6,6 6,8 7,0 7,2 7,4 7,6 7,8 8,0
pH 230C 7,2 7,4 7,6 7,6 8,0 8,2 8,4 8,6 8,8 9,0
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Hnh 7.25. Lin kt ca boric Hnh 7.26. Chun ch acid boric (1) v chun
vi nc acid boric khi c mt mannitol (2)
- To phc c th lm tng tnh acid: Th d: acid boric (pK = 9,2) nu c mt polyol (glycerol
hay mannitol) s to phc. Phc polyol-boric c pKa = 4 d nh lng bng NaOH.
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ca cn c th chim u th vi iu kin:
- Base kh mnh.
- Pha long nhiu im tng ng nng cao kh lc in ly.
- nh lng trong mt dung mi sinh proton hn
Th d: dung mi l acid acetic s lm tng tnh base ca cafein (alcaloid) v do d chun
cafein bng acid percloric. Ngoi ra khi nh lng alcaloid cng c th dng acid formic t phn ly hay
hn hp hai dung mi ny acid acetic v acid formic.
Hai phng trnh sau s dng cng mt lng acid, nh vy c th phn bit base v carbonat.
5.2.5. nh lng mui ca acid mnh v base mnh; mui ca acid yu v base yu v cht
lng tnh
- Mui ca acid mnh v base mnh khng c tnh acid hoc base v cc anion v cation c lc coi
nh b b qua.
- Mui ca acid yu v base yu to nn cng lc cc acid v base c lc. Khng th nh lng trc
tip bng php o acid base. Trong thc t khng th nh lng acetat alcaloid trong mi trng
nc. Nhng c th s dng cc tc ng sau:
a) Tc ng ca dung mi; c th gim lc ca 1 trong nhng cu t hay tng lc ca cc cht ho
tan bng tc ng a proton ca dung mi.
b) Tc ng ho hc:
) nh lng mui amoniac: thm formol vo dung dch to thnh hexamethylen tetramin
khng c tnh base trong nc:
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5.3. Xc nh mt s nguyn t
Vi nguyn t nh C, N, S, Cl, Br, F .... c nh lng bng phng php trung ho. Ty tng
trng hp, nhng nguyn t ny c chuyn thnh acid hay base v c c chun .
5.3.1. Nitrogen
Ion dihydrogen borat c sinh ra l 1 base mnh c th c chun bng dung dch chun HCl
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Dng hp kim Devarda (50% Cu, 45% Al, 5% Zn) kh nhng ion ny thnh ion ammonium ri
chng ct hon ton ly amoniac v nh lng. Ngoi ra, hp kim Arnd (60% Cu, Mg 40%) cng
c s dng.
Trong phng php chun trung ho th vic nh tnh, nh lng cc dung dch cha Na2CO3,
NaHCO3, NaOH dng ring hay dng hn hp cho nhng th d rt ng quan tm: do phn ng loi
i cht th ba nn trong 1 lng thch hp ca bt k dung dch no cng ch cha 2 trong 3 thnh phn:
NaOH + NaHCO3 Na2CO3 (n khi mt hay c hai cht phn ng ban u c dng ht).
Thnh phn trong mu Lin quan gia V v Vbcg khi chun th tch mu bng nhau
NaOH V = Vbcg
Na2CO3 V = 1/2Vbcg
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Kt qu s c sai s 1% .
- Amin dy thng thng c hng s phn ly 10-5. Do c chun thng bng acid mnh.
- Amin thm - (anilin v dn cht) thng rt yu trong mi trng nc (Kb 10-10) c th chun
bng phng php tha tr hoc nh lng trong mi trng khan.
- Amin vng thm pyridin cng ging amin thm.
- Amin vng bo ho piperidin c khuynh hng kt hp vi amin thng v c chun trong
mi trng nc.
C nhiu amin qu yu / nc phi c chun trong mi trng khan nh acid acetic tng
tnh kim.
Ester thng c xc nh bng cch x phng ho vi mt lng base chnh xc bit chun.
R1COOR2 + OH R1COO + HOR2
Lng base tha c chun bng acid chun. Cc ester thay i nhiu theo tc x phng ho.
C ester cn vi gi un nng hon tt qu trnh. Mt t ester tc ng nhanh cho php chun trc
tip bng base. Thng thng, tin hnh bng cch un ester v KOH 0,5M hi lu trong 1-2 gi. Sau
khi lm lnh, lng base tha c chun bng acid.
Trong dc in cc nc c trnh by "Ch s ester hay ch s x phng ho": S miligram KOH
cn thit trung ho acid t do v x phng ho cc ester c trong 1 gam cht kho st.
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S acetyl ho thng c thc hin bng cch trn cn thn mu th vi mt th tch bit
anhydrid acetic bit trong pyridin. Sau khi un nng, thm nc vo thy phn nhng anhydrid
khng phn ng:
(CH3COO)2O + H2O 2CH3COOH
Sau chun acid acetic bng dung dch KOH hay NaOH / cn. Song song thc hin mu trng.
Nu c amin th chuyn sang amid bng anhydrid acetic.
Trong cc dc in c trnh by Ch s acetyl hay ch s acetyl ho pyridin l s miligam acid
acetic cn ester ho nhng sn phm c nhm chc hydroxyl OH trong mt gam cht kho st.
R2 c th l nguyn t H. Sau phn ng, HCl phng thch c chun bng base. y, cc iu
kin phn ng cng thay i ty cht. Th d, i vi aldehyd ch cn 30 pht l . Nhiu ceton khc
phi un hi lu vi thuc th trong 1 gi
- Ch s hydroxylamin: Ch s ny c din t bng s miligam KOH cn trung ho cc acid
sinh ra do phn ng ca mt lng tha chlorhydrat hydroxylamin vi 1 gam cht kho st.
Lng mui ton phn trong mt dung dch c th c xc nh chnh xc bng dung dch chun
acid base. Khi cho qua ct trao i nha ion, mui ny chuyn thnh mt ng lng acid hay base
v c th nh lng bng phng php trung ho.
Acid chun hay base chun cng c iu ch bng nha trao i ion. Ngi ta dng mt dung
dch cha mt lng mui tinh khit bit nh l NaCl c ra qua ct nha v pha long n mt
th tch bit c. Mui ny phng thch mt lng ng lng acid hay base t nha trao i s cho
php tnh s mol thuc th bng phng php trung ho.
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tnh acid hay base ca n bng cch thay i dung mi th li d thy im kt thc.
Bt li khi chun trong mi trng khan: Dung mi t tin, bay hi v c.
- a s dung mi u c h s dn n ln hn nc nn phi c cha trong bnh c kim tra nhit
ca thuc th trnh sai s khi o th tch.
6.1. C ch
Trong dung mi khan (l dung mi khng ion ho), acid cng cho H+ v c solvat ho nhng v
hng s in ly ca dung mi ny thp nn H+ solvat ho ch yu hin din dng cp ion vi anion
acid:
HA + S SH+ A
Sau base B s tc ng vi cp ion ny to thnh:
SH+A + B BH+A + S
Phn ng ny xy ra l v B l base mnh hn dung mi S
Thng dng nhng dung mi lng tnh (amphiprotic) v qua giai on t phn ly nh ba dung
mi lng tnh hay dng acid acetic khan, ethanol, ethylendiamin.
Ph thuc vo:
- lc ca cht phn tch (acid hay base).
- tnh acid hay base vn c ca dung mi.
- hng s in ly ca dung mi.
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H3O+ + b bH+ + H2O - Khi chun base b yu bng HClO4 trong mi trng
khan vi dung mi l CH3COOH
Nu k y l phi tnh lc ca nc
CH3COOH2+ClO4 + b bH+ClO4 + CH3COOH
(7.32)
Nh vy cc phng trnh (7.31) v (7.32) cho thy tnh y ca phn ng acid, base t l thun
vi hng s t phn ca acid yu v t l nghch vi hng s t phn ca dung mi.
Phng trnh ny c ngha: Phn ng trung ho l cnh tranh H+ gia dung mi v acid (hoc base).
Acid formic, acid acetic, acid sulfuric cho H+ tt hn l nhn H+. Trong loi dung mi ny tnh base
ca cht tan c nng ln.
Th d: Anilin C6H5NH2 trong nc c hng s phn ly K=106,9 nn rt kh chun nhng li
c th l base mnh hn trong acid acetic khan v dung mi ny cho H+ d hn nc.
Ethylendiamin, amoniac lng c i lc nhiu i vi H+ (kh nng nhn H+ nhiu hn) do vy l
dung mi base. Trong loi dung mi ny, tnh acid ca cht tan s nng ln.
Th d: Phenol c hng s phn ly K =10-10 yu trong nc li mnh trong ethylendiamin v
c chun bng base chun.
Acid acetic c hng s in ly thp ( = 6,2) nn cn phi c nhiu nng lng mi thc hin
c qu trnh in ly.
MeOH, EtOH (DMeOH = 33, DEtOH = 24) l dung mi c hng s in ly trung bnh.
Dung mi c hng s in ly thp phi chu mt bt li khi dng lm mi trng chun acid-
base v s phn ly l to ra 2 ion c in tch i khng nhng do dung mi in ly yu nn kh nng
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Dung dch chun acid percloric 0,1N trong acid acetic khan
y l mt monoacid (E = M = 100,45) rt mnh, nht l trong mi trng acetic khan.
Acid percloric khan - km bn v d n - c bn trn th trng di dng dung dch nc khong
72%. Nh vy n khng phi l cht chun.
Cch iu ch dung dch ny thnh acid chun :
- Ho long 14,5 gam acid percloric 70% - 72% (8,5ml) trong khong 900 cm3 acid acetic bng
dng phn tch.
- Kh nc c trong dung dch ny bng cch thm 29 -30 gam anhydrid acetic. Cht ny phn ng
vi nc cho hai phn t acid acetic.
- Sau khi ngui, thm acid acetic khan n vch 1000 cm3 v lc. Chuyn vo l c nt mi v
cho nc t phn hy trong 48 gi. Chun dung dch ny bng mt dung dch mui chun pha trong
acid acetic khan. Bo qun trnh m.
Ch : khng c cho tha nhiu anhydrid acetic v gy nguy c to nn sai s dn n t nhng
phn ng amid ho vi nhng amin s cp v th cp.
Dung dch ny dng nh lng nhng acid yu trong mi trng tuyt i khan nc.
iu ch theo cch sau:
Dehydrat ho trc MeOH bng cch un si hi lu vi s hin din ca Mg v chng ct hay tip
xc trong 2 - 3 ngy vi m phn t tamis moleculaire.
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Thm mt lng natri kim loi (2,5g / 150 ml MeOH). Ho long vi benzen khan (qsp 1000 cm3).
Trc khi s dng, dung dch pha ch s c chun bng acid benzoic trong pyridin hay
butylamin.
c) Dung dch tetrabutyl ammonium hydroxyd (C4 H9)4 N+OH
Dung dch ny l 1 base mnh tan c nhiu trong mi trng benzen: MeOH 5% hoc benzen
95%. Hai dung dch rt kim ny rt ho anhydrid carbonic ca khng kh nn kh bo qun.
- Dng ch th (theo kinh nghim): tm tinh th, tm methyl, soudan III, tropeolin 00.
- o th in cc.
- Ch th trong mi trng khan.
Acid acetic hoc acid formic l nhng dung mi c kh nng nhn proton yu hn nc nn nhng
base rt yu trong nc cho vo dung mi ny li tr nn mnh hn.
Nhng cht ch th chuyn mu trong nc mi trng rt acid li chuyn mu cc pH trung
bnh ca mi trng khan v do vy hay c s dng.
Trong nhng dung mi cho proton (acid). Ch th hay dng nht l tm tinh th, a - naphtol benzen,
orange IV, paradimethylaminobenzen (PDAB = vng methyl), xanh oracet B.
Cn trong nhng dung mi nhn proton (base), ngi ta hay dng ch th xanh thymol,
paranitrophenylazo - 4 resorcinol, orthonitranilin.
Cc ch th mu ny cng hay c s dng trong dung mi c proton hot ng (mi trng nc).
Tht vy, cc ch th ny l nhng acid (hay base) yu hn nhng cht nh lng. C ch chuyn mu
ging nh c s phn ly ca dung mi hay khng.
Phi kt hp dung mi, cht chun , im kt thc, xt tan, gi c thuc th, c, trang thit
b,
nh lng acid: acid benzoic (C6H5 COOH); acid succinic; acid sulfanilic; phtalat
Cc cht gc
acid kali.
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AH + C5H5N A C H NH+
5 5
nh lng base
C ch
RNH + CH COOH RNH CH COO
2 3 3 3
Trng hp c bit:
Kh tan: un nng cn thn v c th acetyl ho nhng nhm amin. Thm lng t acid formic
lm tng hng s in ly ca dung mi nhm d ho tan cht cn nh lng nhng lng acid formic
a vo cng t cng tt v pKa ca acid formic (3,75) < pKa ca acid acetic (4,75) nhng i khi acid
formic c th trung ho cc base yu.
T KHA
CU HI LNG GI
1. Trnh by thuyt Bronsted v Lewis v acid - base. Trong bi, acid - base c vit theo quan
im no.
3. Trnh by cc giai on khi tin hnh chun trung ho. pH thay i nh th no khi chun
100 ml HCl 0,1N bng NaOH 0,1N (khng tnh n s pha long)?
4. nh ngha dung dch m. Kh nng m? Dung lng m? Trnh by vic ng dng dung dch
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CU HI TRC NGHIM
2. Theo thuyt acid base nu trong bi, acid l nhng cht c kh nng proton.
4. .................l dung dch khng li s thay i pH khi thm acid hay base mnh vo dung dch hoc
l dung dch m khi pha long th pH ca dung dch thay i t.
5. pH ca dung dch natri hydroxyd (.19.10-3 mol.dm-3) l: Xem NaOH nh phn ly hon ton
7. Mt mu cha 15,0 cm3 HCl c chun bng dung dch NaOH 0,0830 mol.dm-3 . im kt
thc t c sau khi thm 19,2 cm3 NaOH. Nng ca HCl l bao nhiu?
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25oC th Knc =
a. 14 c. 7 e. 0
b. 14 d. 7
10. Dung dch chun hay c s dng nh lng base yu trong mi trng khan nc l
dung dch
a. acid percloric 0,1N / acid hydrocloric
b. acid percloric 0,1N / acid acetic
c. KOH/MeOH
d KOH /EtOH.
e. acid percloric 0,1N / acid acetic khan
Chng 8
PHNG PHP OXY HO KH
MC TIU
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NI DUNG
1. S OXY HO KH
Phn ng oxy ho - kh l phn ng trao i electron gia hai hp cht: mt hp cht nhng
electron (cht kh) v mt kia nhn (cht oxy ho).
Th d: Thm dung dch st(III) clorid vo thic(II) clorid th phn ng cn bng nh sau:
2FeCl3 + SnCl2 2FeCl2 + SnCl4 (8.1)
mi nguyn t gam st (III) (55,85 gam) b kh thnh st (II) phi s dng 96,493 ( 96500)
Coulomb (1 Faraday) v cn s dng (2 96.500) Coulomb mi nguyn t gam thic (II) (118,70
gam) b oxy ho thnh thic (IV).
Trong phn ng trn, in tch clorid khng thay i do khng tham d vo phn ng oxy ho - kh.
Phn ng (8.1) c xem nh th d chung ca 2 phn ng cng mt lc:
s kh: s nhn e
Khi xut hin th, ngha l dung dch thic (II) c khuynh hng cung cp nhng e cho dung dch
st (III). Dng in i qua cho n khi to s cn bng. Nh vy, cp oxy ho - kh kt hp dng oxy
ho v dng kh s tng ng vi s trao i e.
Ni chung, 1 phn ng oxy ho - kh c th trnh by nh sau:
1.2. Nhn xt
Phn ng oxy ho - kh tc l qu trnh cho nhn electron c th thc hin trong cc dung dch ring
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r (hnh 8.1). Cn trong phn ng acid base th qu trnh chuyn H+ t acid sang base ch c thc
hin trc tip trong mt dung dch (hnh 8. 2), H+ khng th chuyn t cht cho sang cht nhn thng
qua mt dy dn in t nh trong phn ng oxy ho - kh.
V tc phn ng: c nhiu phn ng oxy ho xy ra chm nn cc phng php chun da
vo phn ng ny thng i hi tng nhit , thm xc tc. L do l phn ng xy ra qua nhiu giai
on. Qu trnh chuyn electron l mt trong chui cc giai on (ph v lin kt, proton ho, sp
xp li phn t...)
V s c mt ca dung mi nc: trong phn ng oxy ho - kh nu phn t nc tham gia vo
phn ng:
2H2O O2 + 4H+ + 4e
1.3. Th oxy ho kh
Khi 1 kim loi nhng vo dung dch mui ca kim loi ny s to mt bn pin.
Th d:
- Km nhng trong dung dch km sulfat to bn pin (bn pin oxy ho)
- ng nhng trong dung dch ng sulfat cng to bn pin (bn pin kh).
Pin in ho Galvanic c to thnh bi 2 bn pin, mi bn pin gm mt thanh kim loi nhng
trong dung dch in ly (hnh 8. 3). Hai bn pin ni nhau bng mt cu mui v c hai bn pin cng
c ni nhau bn ngoi bi mt dy dn (hnh 8. 4). Cu mui l mt hng ro c l xp ngn s trn
ln ca dung dch nc trong cc bn pin nhng cho php cc ion di chuyn c hai chiu duy tr
trung tnh in tch. Theo s sp xp ny th cc electron cung cp bi phn ng oxy ho s i ngang
qua dng in bn ngoi n ni xy ra phn ng kh. Khi cc bn pin c ni nhau th phn ng t
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T: nhit tuyt i
F: s Faraday (96500 Coulomb)
n: lng e s dng
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- Nu dung dch c pha long y th hot aMn+ c th s dng ln vi nng kim loi
[Mn+].
- Khi thay R = 8,314 J/ K. mol v F bng gi tr ca n ( 25oC th T = 273o + 25o = 298oK) v
tip tc chuyn ln thnh lg (ln aMn+ = 2,303 lg amn+) th phng trnh Nernst tr thnh
E0: th chun ca h thng oxy ho - kh to thnh bi kim loi v ion tng ng ca n Mn+ / M0.
Cl2 + 2e 2Cl
Khi nim tng qut ny cng p dng cho H+ (ch l dng oxy ho t nguyn t hydro).
2H+ + 2e H2
Theo quy c, th chun Eo ca hydro bng 0,00 volt v th oxy ho - kh ca nhng h thng khc
c xc nh bng cch so snh vi th ca in cc ny.
Nh vy, c th phn loi nhng h thng oxy ho - kh khc nhau c to thnh bi kim loi v
ion tng ng theo th chun ca n (bng 8.1).
Th cng thp, kim loi cng c khuynh hng cung cp ion i vo dung dch.
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Mt kim loi khi ho tan vo dung dch c th cho nhng ion tng ng vi nhiu ho tr khc nhau.
K+ + e K0 2,92 I2 + 2e 2I +0,5345
Th d: Nguyn t thic c nhng ion thic (II) v thic (IV). Sn4+ + 2e Sn2+.
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Cng cch ny, c th phn loi h thng oxy ho kh c thnh lp bi halogen v cc ion ca
n:
F2 + 2e 2F + 2,65
I2 + 2e 2I + 0,534
Nh vy clor oxy ho bromid v iodid phng thch ln lt brom v iod cn brom th oxy ho
nhng iodid phng thch iod.
Trong thc t, cht oxy ho v cht kh ca mt cp lin hp thng tham gia vo nhng phn ng
khc nh phn ng acid base, phn ng to phc, phn ng kt ta. Do th oxy ho - kh nhn
c gi l th oxy ho - kh biu kin cng b nh hng bi nhiu yu t khc do cc phn ng ny.
1.5.1. nh hng ca pH
(8.2)
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As3+ As5+ + 2e
Arsenic (V) tng ng vi acid arsenic H3AsO4.
l nhng a acid (nhiu proton trong mt acid) m s ion ho thay i theo pH ca mi trng
(lin quan n pKa ca nhng nc acid khc nhau).
Vi nhng pKa tng ng: pK1 = 2,2; pK2 = 7,0; pK3 = 11,5.
Vi nhng pKa tng ng: pK1 = 8,1; pK2 = 12,1; pK3 = 13,4
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- pH = 2,2 tr i, tnh acid th nht b ion ho v H2AsO4 chnh l dng chim u th:
Theo nh ngha, th chun c xc nh khi nng ca dng oxy ho bng nng ca dng
kh: th chun biu kin ca 3 h thng tng ng vi 3 s cn bng c cho theo biu thc:
E0 = E0 0,059pH, E0= E0 0,0885pH, E0= E0 0,118pH
Th oxy ho - kh chun biu kin gim khi pH tng v nh vy nh hng ca pH trn h thng (
/ H3AsO3) quan trng hn trn h thng ( / H3AsO3) v hn h thng
(H3AsO4 /H3AsO3). dc ca tng on thng tng ng vi 3 phn cng ln khi s ion ho cng
ln.
Xt mt phn ng c in kh iod bng anhydrid arsen
I2 + 2e 2I
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Xt mt kim loi c kh nng cho hai ion c in tch khc nhau, ion M2+ tng ng vi dng oxy
ho v ion M+ dng kh.
E0 l th chun ca h thng: M2+ + e M+
Nhng ion kim loi ny c kh nng to phc vi thuc th X v nhng hng s phn ly ca mi
phc cht nh sau:
(8.3)
(8.4)
(8.5)
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(8.6)
Thm ion cyanid (CN) vo dung dch cha Co3+ / Co2+ s lm mt i cc ion t do ny do to nn
phc cyanid: Co(CN)63 v Co(CN)64
(8.7)
(8.8)
Kox v KKh ln lt l nhng hng s phc ca Co3+ v ca Co2+. T cc phng trnh (8.7) v
(8.8) ngi ta thu c:
E'0 = E0 + 0,059 lg
1.5.3. nh hng ca s to kt ta
Tng t nh trng hp to phc, dng oxy ho Mox hoc dng kh Mkh to thnh hp cht t tan
vi mt cht Y no . Kt qu l nng gim lm thay i th in cc ca cp. Gi s dng kh
Mkh to kt ta vi Y:
Mkh + mY Mkh Ym
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(8.9)
Nh vy, nu dng kh ca cp to hp cht t tan th khi kt ta c TST cng nh, nng thuc
th Y cng ln th th oxy ho - kh cng tng. Nu kt ta xy ra vi dng oxy ho Mox th d dng
suy ra th oxy ho ca cp s gim i.
Th d:
Tnh th chun biu kin ca cp Cu2+/Cu+ khi thm ion I- to kt ta CuI vi TST = 10-12. Bit
v nng [I]=[1M]
Hai bn phn ng: Cu2+ + e Cu+
Cu+ + I CuI
Cu2+ + e + I CuI
v E = E0 0,0591.lg(10 12/1) = 0,8792(V)
Kh2 pe + Ox2
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(8.10)
(8.11)
Trong trng hp phn ng ch s dng 1 electron [th d nh s oxy ho ca Fe(II) bng cesium
(IV)], biu thc tr thnh:
1.7. Th im tng ng
(8.12)
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Th d 1: Tnh K
Oxy ho Sn (II) bi Fe(III)
Fe3+ + e Fe2+ ; = + 0,77 (volt)
2.1. nh ngha
Php chun oxy ho - kh l phng php phn tch th tch dng dung dch chun ca cht oxy
ho chun cht kh nh st (II), mangan (II), iodid.... hoc dung dch chun ca cht kh chun
cht oxy ho nh st (III), Mn (VII)...
Ngoi ra, c nhng hp cht khng c tnh oxy ho - kh nhng phn ng hon ton vi cht oxy
ho hay cht kh (to kt ta hoc phc cht) cng c th nh lng theo phng php ny.
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bng trnh by E0 ti thiu cho phn ng xy ra hon ton. Tuy nhin hiu E0 ch cho ta
bit kh nng xy ra phn ng, cn thc t phn ng c xy ra khng, tc nhanh hay chm ph thuc
c vo bn cht ho hc ca chng. Nh nu trn phn ng oxy ho - kh thng l qu trnh phc
tp, xy ra qua nhiu giai on trung gian. Do vy tc phn ng thng l chm, nhiu khi khng p
ng yu cu nh lng.
a) Tng nhit : Khi nhit tng thng th tc phn ng tng theo. i vi h ng th khi
nhit tng 10oC, tc phn ng tng ln khong 2-3 ln. Th d phn ng gia dung dch KMnO4
vi acid oxalic H2C2O4 xy ra chm nhit thng, khi un nng phn ng ny xy ra kh nhanh.
Nhng c trng hp khng th dng nhit lm tng tc phn ng, v tng nhit s lm bay
hi cht phn ng (nh iod), to phn ng oxy ho do oxy ca khng kh.
b) Tng nng : Trong mt s trng hp ngi ta tng nng ca thuc th lm tng tc
phn ng v hay s dng k thut chun ngc xc nh nng .
c) Dng cht xc tc: Cc phn ng oxy ho - kh xy ra qua nhiu giai on trung gian. Cht xc
tc thng lm tng tc ca cc giai on trung gian ny. V d: iodid (I) c dng xc tc cho
phn ng oxy ho S2O32 bng H2O2.
Tng t nh trng hp chun acid-base. Trong qu trnh chun oxy ho - kh, nng
thuc th v cht cn chun lun thay i. iu dn n s thay i th. C th biu din s bin
i ca th theo th tch cht chun trn mt th nh biu din s bin i pH theo th tch cht
chun (bi chun acid base).
Bi ton: V ng cong chun khi nh lng 50,0ml dung dch Fe2+ 0,2M bng dung dch
0,1M mi trng l H2SO4 (duy tr nng 1M trong sut qu trnh chun v [H+] lun lun
l 1M).
Gii:
Phng trnh phn ng xy ra nh sau:
5 mol st (II) + 1mol permanganat /mi trng acid cho 5 mol st (III) v 1 mol mangan
Bn phn ng 1: 5Fe2+ + 5e 5Fe3+ ; E0 = 0,68 volt / H2SO4 1M
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- Tnh th ti im tng ng
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5 0,65 20 1,37
10 0,68 25 1,50
15 0,71 30 1,51
Nhn xt
ng biu din nh lng trong phng php oxy ho - kh c dng tng t nh trong phng
php trung ha. gn im tng ng c bc nhy th t ngt. C th dng ch th pht hin
im ny.
ng biu din khng ph thuc vo pha long dung dch v trong phng trnh tnh th E
cho thy t s nng cht oxy ho v cht kh khng thay i khi pha long.
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2.5.1. nh ngha
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chn cht ch th cho mt php chun ngi ta thng dng phng php v ng biu din
s bin thin ca th theo th tch, ch th s chn thng c th chun gn vi th chun ti im tng
ng ca phn ng oxy ho kh.
Phn ng i mu khng lun lun nhanh ca ch th mang mu s dn n sai s h thng trong khi
nh lng.
Mt khc, vi mi trng phn ng c mu khng s dng c cht ch th. loi i cc bt li
ny, ngi ta s dng php chun th.
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3.1.1. Nguyn tc
3.1.2. Vai tr ca pH
Mn7+ + 3e Mn4+
(Mn4+ di dng MnO2 ta nn kh s dng)
Mn7+ + e Mn6+
- Trong mi trng trung tnh hay kim, phn ng km lp li hn trong mi trng acid, s oxy
ho ngng nhng giai on khc nhau v sn phm c mu do cn s dng k thut chun tha
tr khi mun thc hin trong mi trng ny. Thc t hay s dng mi trng acid chun bng
phng php permanganat.
Trong thc t, s oxy ho nhng ion Cl ch xut hin khi nng mui cao v khi nhit mi
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trng cao hn nhit ca phng th nghim. Do c th phng thch Cl2, phi trnh nh lng
FeCl2 bi phng php permanganat trong mi trng HCl v ion Fe2+ li cng xc tc phn ng ny.
Trong nhng trng hp c bit HCl cng c dng khi oxy ho trc tip anhydrid arsen
(phng php Bright).
b) HNO3: ion nitrat khng nh hng bt li nhng v HNO3 trong thng mi lun lun
cha nhng ion nitr v anion ny kh permanganat nn acid HNO3 thng khng uc dng.
- Dung dch chun KMnO4 0,1N: mui ny t kh d dng khi c mt nhng tp hu c, do khi
cn trc tip ha tan th nng thng di mc mong mun.
- iu ch: Ho tan khong 3,25 g KMnO4 ny trong 1 lt nc un si trc. Bo qun dung
dch trong l sch v vi ngy trc khi thc hin chun li. Trong khong thi gian ny nhng
cht hu c s b oxy ho v nng gim nh. Khi tt c nhng cht hu c b oxy ho th nng
ca dung dch hu nh bn vng. Lc qua bng thu tinh hay phu thu tinh xp. Dch lc c cha
trong nhng chai thu tinh mu v nh sng xc tc s phn hu permanganat. Khi s dng, xc nh li
nng bng dung dch acid oxalic.
- Bo qun: trnh nh sng hon ton v nh sng xc tc s phn hy permanganat.
a) nh lng mui st II: (Fe2+ c tnh kh) trong thc t hay s dng mui Mohr
Fe2+ Fe3+ (mi trng H2SO4)
Nu mui st II dng clorid th s dng cromat acid kali hay cerium (IV) lm tc nhn oxy ho v
Cl s lm ri nh lng do to Cl2.
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c) nh lng peroxyd
Hydroperoxyd (nc oxy gi) (peroxyd hydro) va c tnh oxy ho, va c tnh kh.
Khi tc dng vi cht kh mnh hn th th hin tnh oxy ho:
(O2)2 + 2e + 4H+ 2H2O
Trng hp hydroperoxyd l cht kh: s dng dung dch kali permanganat 0,1N nh lng
nc oxy gi trong mi trng acid.
C ch phn ng: KMnO4 phn hy hydroperoxyd phng thch oxy theo phng trnh:
tnh c cc loi nng ca dung dch hydroperoxyd phi tnh c ng lng gam, ng
lng th tch ca hydroperoxyd:
ng lng gam:
= 5,6 N
l th tch oxy gii phng ra do 1 lt dung dch hydroperoxyd b phn hy hon ton.
N l nng ng lng ca dung dch hydroperoxyd.
Ch : php nh lng ch cho kt qu chnh xc khi nng dung dch hydroperoxyd em chun
xp x 1 th tch.
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Ch : nhng cht bo qun (acid benzoic...) trong nc oxy gi c th dn n nhng sai s tha v
nhng hp cht ny b dung dch permanganat oxy ho.
d) nh lng nitrit
Cc nitrit trong mi trng acid c oxy ho bng KMnO4.
nitrit b phn hy d dng cho nn nitrit vo buret v cho t t vo dung dch chun
c acid ho trc bng H2SO4 n khi mt mu dung dch.
Vic s dng trc tip KMnO4 phn tch cc hp cht hu c hin nay t c s dng.
3.2.1. Nguyn tc
Phng php iod bao gm vic nh lng s dng tnh cht oxy ho kh ca h thng iod/iodid
(I2/2I)
Iod (I2) l mt halogen c tnh oxy ho mnh thu 1 electron khi tc dng vi cht kh.
I2 + 2e 2I
Ngc li iodid (I) c tnh kh d nhng 1 electron khi tc dng vi cht oxy ho:
2I - 2e I2
Do vy dung dch I2 nh lng cht kh v dung dch iodid nh lng cht oxy ho:
I2 + 2e 2I
Cc k thut chun c gii thiu trong bi phng php phn tch th tch, phn ny s nhc
s b cch tin hnh trong php o iod.
Tin hnh: chun cc dung dch c tnh kh bng dung dch chun iod.
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Th oxy - kh chun E0= + 0,535 V cho thy iod l mt tc nhn oxy ho yu ( v tr gia ca bng
th oxy ho - kh chun).
I2 + 2e 2I ; E0 = + 0,535 (V)
Tuy vy, c vi cht c chun trc tip bng dung dch iod thch hp hn v tc ng oxy ho
nh ca iod li c li trong khi s dng cht chun mnh hn c th gy ra s oxy ho khng t
lng.
Tin hnh: thm mt lng tha dung dch KI vo mu cha cht oxy ho. Cht oxy ho ny b
iodid kh, kt qu to thnh mt lng iod tng ng v c chun bng natri thiosulfat chun.
Iod to thnh trong phn ng u tin tng ng vi lng tc nhn oxy ho Aox c trong mu.
K iod to thnh c chun bng natri thiosulfat, cc ion iodid v tetrathionat l cc sn phm.
3.2.2.3. Chun th
Tin hnh: cho mt th tch chnh xc dung dch cn nh lng tc dng vi mt lng d thuc
th no , phn ng sinh ra mt lng cht mi tng ng ho hc vi lng cht cn xc nh.
Dng dung dch chun nh lng cht mi sinh ra.
Th d: nh lng K2Cr2O7 bng cch cho tc dng vi KI tha (mi trng acid) gii phng
iod (lng tng ng).
K2Cr2O7 + 6KI + 7H2SO4 3I2 + Cr2(SO4)3 + 4K2SO4 + 7H2O
3.2.3.1 Vai tr ca pH
V h I2/2I trong thang th oxy ho kh v tr gia (th chun oxy ho kh = 0,54 volt pH =
9) nn tnh oxy ho hay tnh kh ca h ny thay i theo bn cht ca cp oxy ho - kh hin din v
theo pH ca mi trng phn ng.
- Trong mi trng acid: kh nng oxy ho ca iod th hin i vi cc h thng c th oxy ho
kh thp hn h thng (I2/2I). Th d: iod c th oxy ho thic clorid (SnCl2), hydro sulfua (H2S), acid
sulfur (SO2), natri thiosulfat (Na2S2O3).
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Tuy nhin, trong dung dch acid mnh th phn ng s chy theo chiu ngc li, arsenic (V) thnh
arsenic (III):
H3AsO4 + 2I + 2H+ H3AsO3 + I2 + H2O
- Trong mi trng kim pH 9 thng mc phi sai s do iod oxy ho thnh hypoiodid (IO-)
khng bn v phn hu thnh iodat ( ), IO- c tnh oxy ho mnh hn iod, n chuyn c ion
thnh S4O6 dn n sai s do khng nn tin hnh php o iod trong mi trng kim.
I2 + 2OH IO + I + H2O
3.2.3.2. Nhit
Tin hnh nhit thng (trong phng) v tin hnh nhit cao th iod s b thng hoa v
nhy ca ch th gim, dn n sai s kt qu nh lng.
Khi nh lng bng k thut chun th, phn ng gia kali iodid v cht oxy ho cn tin hnh
trong 10 n 15 pht phn ng xy ra hon ton, ng thi kali iodid khng b phn hy thnh iod,
cn trnh nh sng do phn ng:
3.2.3.4. Ch th
Ch th thng s dng h tinh bt. Trong chun trc tip, nu h tinh bt c thm vo sm
qu th iod s hp th trn h tinh bt d dn n sai s khi pht hin im kt thc.
Khi nh lng dung dch iod c nng thp th nn thm h tinh bt hay thioden v khi c mt
iodid, cc cht ny s cho phc mu xanh dng.
Khi c mt ca cc dung mi hu c khng c oxy (cloroform, carbon tetraclorid) th mt git tha
s lm cho pha hu c ny c mu hng.
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Sai s oxy l vn khi chun tha tr bng iod. Trong dung dch acid, oxy t khng kh oxy
ho iodid thnh iod.
O2 + 4I + 4H+ 2I2 + 2H2O
Phn ng ny gy ra sai s tha khi chun gin tip bng iod. Sai s gia tng theo tnh acid.
Sai s oxy trnh c khi thc hin trong kh quyn tr hoc thm carbon dioxid rn hay natri
bicarbonat vo dung dch acid to ra s bo v ca carbon dioxid hoc trnh tha acid.
a) Dung dch iod: iod l mt cht rn tan c trong mt s dung mi hu c nhng li t tan trong
nc v d bay hi. Nhng khi c mt ca iodid (nh NaI hay KI) th iod phn ng vi iodid to
thnh phc anion triiodid c mu nu m c th tan c trong nc.
I2 + I I3
Do vy, khc phc khuyt im khng tan trong nc ca iod, dung dch chun iod c th
iu ch bng cch ho tan cn thn mt lng iod trong dung dch nc c iodid. Trong cch vit v
cn bng phng trnh ho hc, ngi ta vit n gin dung dch iod ho tan trong iodid l I2.
Cc dung dch iod c pha ch nh th phi c bo qun trnh nh sng trong nhng l mu, c
nt kn trnh s oxy ho cc iodid do oxy ca khng kh v trnh mt iod do bay hi. Phi trnh mi
vt ng v kim loi ny d dng oxy ho cc iodid do oxy ca khng kh.
b) Dung dch kali iodat: KIO3 (M = 214,02):
Khi c mt 1 lng tha iodid v H+, 1 ion iodat phng thch 3 phn t iod s dng 6e-
Pha dung dch kali iodat 0,1N theo Dc in Vit nam III (trang PL 28). C th thm vo dung
dch ny mt lng tha KI trong lc iu ch (15 g/lt) hay trong trng hp ngc li, cho I vo mu
th nghim ca dung dch ny lc s dng. Hn hp c acid ho bng 1 th tch tha dung dch HCl
hay H2SO4 long. Iod phng thch s c chun bng natri thiosulfat.
Khi pha, thm dung dch I vo lc nh lng (ging trng hp ca kali iodat).
- pha dung dch kali bromat 0,1N theo Dc in Vit nam III (PL 27).
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d) Dung dch kali dicromat: (K2Cr2O7; M = 294,21) ging trng hp trn, khi c mt lng tha
KI trong mi trng acid th kali dicromat c th phng thch iod theo phn ng:
Phn ng thc hin vi s c mt ca 1 lng tha acid. Dung dch natri thiosulfat c cho vo
buret. im tng ng c xc nh nh h tinh bt c thm vo cn im tng ng. Ion Cr3+
c mu xanh lc. S chuyn mu t xanh dng m n xanh lc.
- Pha ch: thng thng, dung dch natri thiosulfat c pha ch nng 0,1N. Nc dng
pha phi ui kh carbonic trc v acid i vo dung dch ny s lm c t t thiosulfat do to ta lu
hunh:
Phi bo qun trnh nh sng. Cn thm vo mt t cht bo qun nh natri borat (3%) hay cn
amylic (0,8%) trnh nhim vi sinh vt.
2 + I2 + 2I
- Chun trc tip: Php o iod trong phn tch hp cht v c nh lng natri thiosulfat, cc
sulfit, cc cyanid, cc mui kim loi.
- Chun tha tr: (php o iodid)
+ Phn tch hp cht v c: nh lng halogen, cc hypohalogenid, cc iodat, cc arseniat, cc
peroxyd: nc oxy gi, cc mui kim loi: mui ceric, mui ng, cc ferricyanid.
+ Phn tch hp cht hu c: Vi hp cht hu c c kh nng gn vo iod mt cch nh lng
nhng mi trng thch hp v vi mt lng tha iod nn nh lng lun lun theo k thut chun
tha tr. Song song thc hin mt
mu trng.
p dng k thut ny nh lng cc dn cht ca lu hunh hu c c cha nhm thiol, cc
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hydrazin v dn cht ca chng, nh lng gin tip cc formaldehyd, nh lng gin tip cc
aldehyd
+ Xc nh ch s iod
nh ngha: ch s iod l s gam iod c kh nng c nh trn ni i ca 100 g cht kho st.
chnh l phn trm iod c gn bi mt cht.
Trong nhng iu kin c bit, iod c th c kh nng c nh trn ni i (trong mi trng khan).
Tht vy, mt mnh iod khng th t gn trc tip v phi dng 1 halogenid (iodid, clorid hay bromid)
tc ng bng cch t phn cc ho thnh I+ X theo phn ng:
R C = C R + R CX Cl R
Thuc th phi c cho vo vi lng tha v sau mt thi gian tip xc xc nh s c nh
lng. Mt lng tha dung dch nc KI c thm vo v nh vy s phng thch nh lng iod
bng tc ng ca halogenid iod trn KI:
XI + I I2 + X
Iod c phng thch s c nh lng bng natri thiosulfat. Trong nhng iu kin ny, mt
nguyn t halogen X tc ng nh mt nguyn t iod v t tnh ton kt qu. Thc hin song song
mt mu trng.
Vic xc nh hm lng nc trong nhng cht v c cng nh cht hu c thng rt quan trng.
Cho n nay, c nhiu phng php vt l v ho hc nh lng nc, nhng k thut Karl
Fischer m t nm 1935 c s dng nhiu do tnh chnh xc v chuyn bit cng nh do tnh ton kt
qu tng i n gin.
Nguyn tc nh lng nc theo Karl Fischer: khi c mt nc th iod tc ng trn anhydrid
sulfur cho acid sulfuric (H2SO4) v acid iodhydric (HI).
Phn ng ny li c Bunsen thc hin vi s c mt ca pyridin lm cho phn ng hon ton dch
chuyn v pha phi bng cch kt hp base ny vi nhng acid to thnh theo phn ng l thuyt tng
qut:
2H2O + SO2 + I2 + 4C6H5 N (C6H5NH+)2 SO4 + 2C6H5NH+I
Trong nhng iu kin cho, lng iod c tiu th thay i theo lng nc c mt trong phn
ng, 1 phn t iod tng ng vi 2 phn t nc.
nhy ca phng php tng c th gp i nu phn ng xy ra vi s c mt ca MeOH, 1 phn
t ca dung mi ny s thay th 1 phn t nc. Phn ng c th b phn hy thnh 2 giai on lin
tip:
- Iod v anhydrid sulfur kt hp trc vi pyridin.
SO2 + I2 + 3C6H5 N C6H5 N + C6H5 NI2 + C6H5 NSO2
Sau phn ng ton phn ny, mt phn t nc tiu th 1 phn t iod, mt phn t anhydrid sulfur,
3 phn t pyridin v mt phn t methanol.
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H2O + C6H5 N + C6H5 NI2 + C6H5 NSO2 2C6H5 NH+I + C6H5 N+SO3
3.3.1. Nguyn tc
Trong mi trng acid, natri nitrit tc dng vi amin thm bc nht to mui diazo khng mu
(phn ng diazo ho).
NaNO2 + HCl HNO2 + NaCl
T th tch dung dch natri nitrit 0,1M phn ng, tnh nng hoc hm lng cht cn xc nh.
Cc nitrit (NaNO2) bn hn l HNO2. Chng ho tan tt trong nc. Cht ha tan km nht l
AgNO2 (bc nitrit) nhng tan tt nhit nng. Vi mui phc cha ion NO2 km tan, Th d: K3[CO
(NO2)6], (NH4)3[CO(NO2)6],....
l anion ca HNO2. Acid ny ch hin hu trng thi t do trong dung dch acid long
nhit lnh v s b phn hy mt cch d dng thnh anhydrid nitr v nc:
2HNO2 N2O3 + H2O
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Ti im tng ng, 1 git tha dung dch natri nitrit s phn ng vi ch th tropeolin 00 lm cho
dung dch nh lng c mu vng.
Cch dng ch th mu tropeolin 00: cho 4 git ch th mu vo bnh nh lng, nh dung dch natri
nitrit 0,1M vi tc 2ml trong 1 pht. Khi mu chuyn sang mu nht ri mt mu th tc nh
natri nitrit chm li (1 git trong 1 pht), n khi xut hin mu vng nht bn vng trong 2 - 3 pht th
kt thc nh lng.
C th dng hn hp tropeolin 00 (4 git) v xanh methylen (2 git) thay cho tropeolin 00, chuyn
t mu tm thnh xanh da tri.
- Xc nh cc ch phm c cha nhm amin thm bc nht nh procain, cc sulfamid hoc nhng ch
phm khc m qua bin i ho hc chuyn c thnh hp cht c nhm amin thm bc nht.
3.4.1. Nguyn tc
Bicromat l mt cht chun v c th pha ch dung dch c chun chnh xc bng cch cn n
gin. Phn ng cng c th c thc hin trong mi trng HCl c pH 1-2 v cc ion Cl khng gy
ri phn ng v cc cht hu c c trong nc khng kh bicromat.
Dung dch chun c bo qun tt ngay c di nh sng. Ngc li, c mt khuyt im l
kh ghi nhn c im tng ng do s thay i mu ca mui crom: c mu vng hi m
3+
trong dung dch long thnh Cr mu xanh lc. Ch th cn thit s dng l diphnylamin p-sulfonat
(khng mu dng b kh v tm nht dng b oxy ho) hoc dimethyl furoine.
Kali bicromat (K2Cr2O7) phi c sy kh trc 120oC 130oC v nghin nh ri ho tan trong
nc (c th dng nc m). Dung dch 0,1N ca cht ny rt bn v c th bo qun v hn.
a) nh lng mui st (II) hay mui st (III) bng my chun th hay bng ch th mu sau khi
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nh lng cn EtOH: cn ethanol tinh khit c oxy ho bi bicromat trong mi trng acid
thch hp n khi to thnh acid acetic:
CH3 CH2OH + O2 CH3COOH
3.5.1. Nguyn tc
Th chun biu kin ca h thng Ce4+/Ce3+ thay i theo bn cht ca acid c s dng acid
ho mi trng v nng ca n.
Th thp nht c quan st trong mi trng acid hydroclohydric v cao nht trong mi trng
acid percloric.
Trong mi trng nitric, gi tr ca th gim nh khi chun ca acid i t 1N n 8N.
Ngc li, trong mi trng percloric th ny tng theo nng ca acid.
Cc thay i ny c c do s to thnh phc trong mi trng kho st.
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- Tht vy, trong mi trng sulfuric th Ce4+ hon ton dng phc tetrasulfatoacetic [Ce(SO4)4]
H4. Kt qu l khi tng nng acid sulfuric t nh hng n th oxy ho - kh v khng to phc khc
vi phc trc.
- Ngc li, trong mi trng percloric th to thnh phc [Ce(OH)2]2+,[Ce(OH)]3+, [OHCeO
CeOH]4+, [CeOCeOH]5+ m nng tng ng lin quan vi nng ca acid percloric. Kt qu
l th oxy ho - kh gia tng theo nng acid tng.
- Trong mi trng acid yu hay trung tnh: Ce4+ ta khi to Ce(OH)4 v cc tnh cht oxy ho ca
chng bin mt.
Bng 8.4. Th chun biu kin ca h thng Ce4+/Ce3+o c trong cc acid khc nhau
Thng thng, cc dung dch chun 0,1N c iu ch trong mi trng sulfuric (1-3M) hoc
trong mi trng percloric. Dung dch sulfuric ca mui ceri c th c bo qun trong 1 nm. Cc
dung dch percloric ca mui ceri ch c th gi trong mt gi.
Cc dung dch dng chun li dung dch ceri hay c s dng: dung dch permanganat hay
bicromat, mui st II, anhydric arsen.
3.5.3.1. nh lng cc hp cht v c: mui st (II), peroxyd, nitrit (nh php o permanganat).
3.5.3.2. nh lng cc hp cht hu c: cc acid nhit nng hoc lnh (acid lactic, acid
pyruvic), alcol, aldehyd, polyalcol. V s oxy ho xy ra thng chm nn phi s dng phng thc
chun ngc nh sau: cho mt lng tha ion ceric vo dung dch cn nh lng, sau mt thi gian
phn ng thch hp th nh lng ion ceric tha bng mui st (II).
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T KHA
CU HI LNG GI
CU HI TRC NGHIM
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3. Phn ng oxy ho - kh l phn ng trao i ....... t cht tham gia ny sang cht tham gia kia.
a. H+ c. cation e. electron
b. OH- d. ion
7. Mt kim loi c th cho nhng ion tng ng vi nhiu ho tr. Ion c in tch dng ln nht
tng ng vi dng... (A)... Ion c in tch dng nh nht tng ng vi dng... (B)
a. pH c. s to thnh kt ta e. ch a v c ng
b. s to phc d. c ba cu tr li trn
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b. SO2 d. iod
Chng 9
PHNG PHP KT TA
MC TIU
- Gii thch c biu thc tch s tan, tan v ngha ca n trong phn tch.
- Trnh by c cc yu t nh hng n tan cht in ly t tan v tnh c tan ca cht
trong cc iu kin c th.
- Trnh by c hin tng hp ph khi chun theo phng php bc.
- Trnh by c nguyn tc, iu kin tin hnh v ng dng ca 3 phng php: Mohr, Fajans,
Volhard.
- Nu c ng dng ca phn ng kt ta- ho tan trong phn tch.
NI DUNG
1. L THUYT V S KT TA
Phn ng kt ta l phn ng to thnh cht rn t cc cht tan trong dung dch. Trong qu trnh
phn tch nh tnh, nh lng ta thng phi s dng n phn ng kt ta tch ring cc ion phn
tch khi cc ion khc.
Khi ha tan mt cht no trong nc, th hai qu trnh ngc chiu nhau s xy ra cng mt lc.
Khi dung dch ca cht no cha bo ha, th qu trnh ha tan nhng lng mi ca cht s
ln hn qu trnh kt ta n t dung dch.
Th d:
Khi dung dch qu bo ha, c hin tng ngc li qu trnh tch cht tan khi dung dch ln hn
qu trnh ha tan n.
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Khi dung dch bo ha c kt ta cht tan lng xung di, trng thi cn bng ng c thit lp.
Trong trng hp ny tc ha tan bng tc kt ta.
Khi cn bng c thit lp, trong 1 n v thi gian c bao nhiu ion Ag+ v Cl chuyn thnh kt
ta, cng c by nhiu ion chuyn t b mt kt ta vo dung dch.
Theo nh lut tc dng khi lng khi cn bng c thit lp, trong dung dch nc bo ha ta c:
Tch s nng cc ion ca cht in ly t tan trong dung dch nc bo ho gi l tch s tan v
c k hiu bng ch T cng vi cng thc ho hc ca cht in ly .
Th d: [Ag+ ] [Cl ] = TAgCl
- Nu tch s [A]m [B ]n < TAmBn kt ta khng tch ra m b ha tan (mun kt ta tan c).
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c trng cho tnh tan ca kt ta, ngoi T, ngi ta cn dng tan S. tan S v T lin quan
mt thit vi nhau, bit T c th tnh c tan v ngc li. tan tnh theo mol/l, g/l.
- i vi cht in ly t tan dng AB (cng ho tr), th d AgCl, BaSO4
AB A+ + B
i vi cht in ly dng AB
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2H2O H3O+ + OH
H thng ny c th vit:
(9.2)
Ph hp vi iu kin ca cn bng trung ha in tch:
2[ M2+] + [ H3O+] = [ OH] (9.3)
2[ M2+] [ OH]
Thay vo phng trnh (9.1) v sau khi bin i s l:
[M2+] = (T/4)1/3 = S (9.4)
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Bc 2: Xc nh cc nng cn bng l n s
S = [ Fe3+]
Bc 3: Vit cc hng s cn bng cho phn ng bc 1
[ Fe3+] [ OH] 3 = T = 2. 10-39
[ H3O+] [ OH] = 1,00. 10-14
Bc 4 v 5: Vit phng trnh bo ton khi lng v phng trnh cn bng in tch
[ OH] = 3[ Fe3+] + [ H3O+]
Bc 6: Xc nh n s v s phng trnh c lp c
Bc 7: Tm cch gim n s a h v mt phng trnh n gin
3[ Fe3+] [ OH]
Bc 8: Gii phng trnh bc 7 tm ra nng cn bng ca mt n s
[ Fe3+] (3[ Fe3+] )3 = 2.10-39
[ Fe3+] = [ (2.10-39)/ 27] 1/4 = 9,27.10-11
S = [ Fe3+] = 9,27.10-11 (mol/l)
Bc 9: Kim tra li p s tm, kim tra cc gi thuyt bc 7.
Gi thit rng: [ OH] 3[ Fe3+] = 3 (9,27.10-11) = 3.10-10
Khng nn tnh rng [ H3O+] nh hn 3[ Fe3+] nhiu m trong trng hp ny ta theo di hin
tng nguc li: 3[ Fe3+] << [ H3O+] [ H3O+] = [ OH]
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S = 2. 10-18 (mol/l)
Gi thuyt 3[ Fe3+] << [ H3O+] l ng. iu ny khng nh thm rng trong cch tnh u khi gi
thit khng ng c sai s ln.
Cc th d trn chng minh rng tan ca cc hydroxyd kim loi c tnh tng t nh tan
ca cc hp cht mang tnh kim yu; cc tnh ton ny c th khng nh chn 1 trong 2 kt qu gn
ng. Nh vy tn ti khong gi tr tch s tan nn khng ly mt kt qu ngay t cc gi tr gn ng
m tip tc gii theo cc phng trnh (9.1), (9.2), (9.3) tng ng vi c ba trng hp thay i.
Khi thm d thuc th kt ta, tan ca kt ta gim xung v ph thuc vo lng d ca ion
thm vo ng dng vi mt trong cc ion to thnh kt ta.
Th d:
- Tnh tan ca AgCl trong dung dch NaCl 0,1M. Bit TAgCl = 1,7.10-10
tan AgCl trong dung dch NaCl 0,1M so vi tan trong nc gim i 7647 ln.
1.3.2. nh hng ca ion l (ion khng cng tn) ln tan ca cht in ly t tan (hiu ng
mui)
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t tan. tan ca mt s mui t tan tng ln khi c cc mui tan khc khng c ion chung vi
chng. Nng mui khng c ion chung vi cht in ly t tan c thm vo cng ln th tan ca
n tng ln cng nhiu, v sc ion ca dung dch tng ln, do a cc ion khc vo, hin tng ny c
gi l hiu ng mui. S thm cc cht in ly khc nhau gy nh hng khc nhau n tan ca cht
in ly t tan v lc ion ca dung dch khng nhng ph thuc vo nng m cn vo ln in tch
ca cc ion.
Th d: tan ca PbSO4 tng ln khi c NaNO3, tan ca BaSO4, SrSO4, CaSO4 tng ln khi
thm KCl, NaNO3, KNO3 v.v... vo dung dch.
Tnh tan ca CaSO4 trong nc v trong dung dch NaCl 0,1M, bit = 6,26.10-5
Do tan ca CaSO4 trong dung dch NaCl 0,1M tng ln so vi tan trong nc gn 3 ln
tan ca kt ta c ngha quan trng trong phn tch nh lng, n ph thuc vo nng ion
hydro trong dung dch. C hai trng hp ch yu l anion ca kt ta l anion ca mt acid yu v cc
hydroxyd ca cation kim loi.
Ion hydro c nh hng ln n tan ca cc cht khc nhau. Trong mi trng acid, tan ca
cht t tan cng ln nu T ca n cng ln v [H+] cng ln.
= 5,6 10-8
= 3,8 10-9
> > do trong mi trng acid, BaC2O4 tan tt hn, SrC2O4 tan km
hn, CaC2O4 tan km hn c. tan ca cc mui ny trong acid HCl ln hn trong CH3COOH (phn
ng tm Ca2+: CaC2O4/ CH3COOH trng khng tan).
tan ca cht in ly cho trong nc cng ln v acid to thnh mui cng yu th tan
ca cht in ly trong acid cng ln (hng s phn ly ca acid c tham gia vo thnh phn mui
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Nu thm acid mnh vo dung dch ny th anion B- s lin kt vi H+ to thnh acid yu HB. Khi
cn bng s b ph hy v kt ta s b tan v [A+] [B] = TAB. Mi mt anion B c trong dung
dch v lin kt thnh phn t HB tng ng vi cation A+, do :
[A+] = [HB] + [B]
Thay gi tr [A+] t phng trnh biu din TAB ta c:
y [H+] = CHB [HB] ngha l nng ion H+ bng hiu s gia nng chung ca acid v
phn khng phn ly ca n.
Trong trng hp ring, khi [H+] = KHB
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tan ca mui acid yu t tan (trong k c hydroxit v mui base) trong dung dch nc ca
acid mnh to v p sut cho trc tng ln so vi tan ca n trong nc tinh khit. Hn na tan
ny cng tng khi T ca cht in ly t tan, nng ion hydro cng cao v hng s phn ly ca acid yu
to thnh mui ny cng nh.
- Khi tnh tan ca mui t tan trong acid k ti h s hot ngi ta dng cng thc:
Ta tnh: trc
y pH = 4 [H+] = 10-4
Thay vo phng trnh ta c:
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tan ca ta c th thay i khi c mt cc cht to thnh phc vi anion hay cation ca ta. Nh
vy s to phc nh hng n tan ca ta. Nu nh bit hng s bn ca phc c th tnh c
tan ca ta khi c tc nhn to phc.
Ag+ + NH3
+ NH3
NH3 + H2O + OH
Bc 2: Xc nh cc nng cn bng l n s
(9.7)
(9.8)
(9.9)
(9.11)
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Bc 6: Cn bng in tch
[ ] + [ Ag +] + [ ]+[ ] = [ Br ] + [ OH ] (9.13)
Bc 7: Loi bt n s; gi thit:
-[ ] nh hn nhiu cc s hng khc trong phng trnh (9.11). iu ny thy r t phng
trnh phn ly Kb.
[ Br ] [ ] (9.14)
Bc 8: Tm cc gi tr gn ng ca n s
[ NH3 ] = 0,10 - 2[ Br ] (9.16)
(9.17)
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AgCl + Cl
+ Cl
+ Cl
Khi nng cc ion cng tn tng trong nhng phn ng ny lm tng tan ca ta. Trn hnh 9.1
kho st s ph thuc tan tm thy qua thc nghim ca AgCl theo logarit nng KCl trong dung
dch. Khi nng Cl nh hn 10-3M gi tr tan tm thy qua thc nghim hu nh khng khc so
vi tnh ton theo tch s tan ca AgCl.
Khi nng Cl tng cao, tan tnh c tin ti gn bng 0, trong lc ny cc i lng o c
tng ln t ngt.
Khi nng KCl gn bng 0,3M, tan ca AgCl ging nh trong nc nguyn cht, nu trong
dung dch 1M, tan AgCl gn nh gp 8 ln ln hn i lng ny.
Khng t trng hp s tng tan khi cho lng tha ion cng tn, c bit l trng hp cc
hydroxyd lng tnh nh Al(OH)3 v Zn(OH)2. Cc cht ny c to thnh dng ta t tan khi cho
kim tc dng vi cc ion tan trong dung dch. Cc hydroxyd ny tan trong lng tha ion OH to
thnh phc hydroxo nhm - km. i vi nhm phng trnh c th vit nh sau:
Al3+ + 3OH Al(OH)3 rn
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Al(OH)3 rn + OH Al(OH)4
Ging nh trng hp ca AgCl, tan ca Al(OH)3 v Zn(OH)2 sau khi t ti thiu, s tng t
ngt khi nng ca ion cng tn tng. Nng ion OH- tng quan vi tan ti thiu, c th tnh
ton khi bit hng s cn bng ca phn ng.
Th d: Vi nng no ca OH th tan ca Zn(OH)2 t ti thiu? Hy tnh tan ti thiu?
Zn(OH)2 rn + 2OH
S = [Zn2+] + [ ] (9.18)
Hng s cn bng:
T = [Zn2+] [OH]2 = 1,2. 10-17 (9.19)
(9.20)
(9.21)
c tan ti thiu, ta ly vi phn phng trnh (9.21) v cn bng o hm theo [OH] tin ti 0
Nu
Th
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Tch s tan ch l hng s mt nhit nht nh. Nhit thay i th tan cng thay i. S
thay i ca tan theo nhit c lin quan ti hiu ng nhit khi ha tan.
i vi cht thu nhit, khi ha tan, tc l nhit gim khi tan, th tan s tng cng vi nhit .
V d: PbI2 tan rt nhiu khi un nng, khi lm ngui dung dch mi un nng th PbI2 kt tinh li,
vy nh vng sng rt c trng.
tan AgCl 100oC ln gp 25 ln tan ca n 10oC.
i vi cht ta nhit khi ha tan th tan s gim khi nhit tng.
V d: CaSO4.2H2O c tan thay i rt t khi nhit bin thin 0oC 60oC. 60oC phn t
CaSO4.2H2O mt bt nc kt tinh thnh CaSO4.0,5H2O, CaSO4 c tan gim r rt khi tng nhit
. tan ca n 60oC ln gp 3 ln tan 100oC.
1.4.1. Ha tan kt ta
ha tan kt ta ny cn gim nng ca A hoc B hoc c hai ion cn bng chuyn dch
sang phi. C nhiu cch lm gim nng A hoc B:
- Dng phn ng ho hc to cht t phn ly hoc cht bay hi.
- Nu kt ta c tch s tan qu nh c th dng phn ng oxy ho - kh lm gim nhiu nng
ion A hoc B.
- C th ha tan bng cch chuyn ta kh tan thnh ta d tan. V d chuyn ta CaSO4 thnh
CaCO3.
Mun kt ta hon ton mt cht t dung dch cc kt ta tch ra phi c tan nh. V vy, cn
phi to mi iu kin gim tan ca kt ta nh:
- Cho thuc th d lm gim tan nhng lu khng cho d qu nhiu v xem c s to phc
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1.4.3. Kt ta phn on
Trong dung dch nu c nhiu cht (nng gn bng nhau) cng to kt ta khi ta thm dn mt
thuc th vo. Cht no c T nh s kt ta trc, cht c T ln hn s kt ta sau. l hin tng kt
ta phn on.
Th d: Trong dung dch c ion Cl v I vi nng 10-2 mol/l. Thm dn dung dch AgNO3
vo. V TAgI = 10-16 nh hn TAgCl = 1,8 10-10, nn tch s ion Ag+ v I- vt TAgI nn ta c ta AgI
trc. Khi kt ta AgI tip tc to thnh
th [I] s gim dn, cn [Ag+] tng dn v ta AgCl bt u xut hin lc [Ag+][Cl] > TAgCl.
Nh vy, cho AgNO3 vo dung dch ny kt ta c hon ton I di dng AgI, ion Cl vn cn
ha tan. tch c ion I khi hn hp.
Nguyn tc kt ta phn on l dng mt lng thuc th thch hp va kt ta ion c T nh
hn nhng cha kt ta ion c T ln hn. Trong thc hnh phn tch, mt s trng hp tch
cc ion di dng kt ta, ngoi yu t khc nhau v tan ln, ngi ta cn vn dng thm cc yu
t khc nh pH, s to phc... qu trnh tch c hon ton.
L phng php nh lng da trn vic dng phn ng kt ta (to thnh hp cht t tan) gia
thuc th v cht cn nh lng.
Phng php kt ta cho php ta nh lng cc anion nh Cl, Br, CN, SCN, , ,
v.v... v ngc li nh lng cc cation to thnh ta vi cc anion trn.
Th d: Ag+ + Cl AgCl .
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- Phng php thu ngn I: da trn vic dng dung dch chun mui thu ngn (I), to thnh hp
cht thu ngn I khng tan nh Hg2Cl2, Hg2Br2, Hg2I2 .
- Phng php thu ngn II: da trn vic dng dung dch chun mui thu ngn (II) to thnh hp
cht thu ngn II km phn ly: HgCl2, Hg(CN)2, Hg(SCN)2...
Tuy nhin cc phng php thu ngn (I), (II) c nhc im l mui thu ngn rt c nn t s
dng.
Phn tch chun da trn vic dng cht kt ta l dung dch chun Ag+ (AgNO3).
Ag+ + An AgAn
Phng php bc dng ch yu xc nh ion halogenid v Ag+.
Trc khi thm AgNO3 vo dung dch NaCl 0,1N phn ly hon ton thnh ion, nng ca Cl-
trong dung dch bng nng chung ca NaCl.
[Cl] = C (nng NaCl) 0,1N = 10-1
pCl = -lg[Cl] = -lg10-1 = 1
pKa = -lgK
pH = -lg[H+]
pCl: ch s nng ging nh ch s phn ly acid.
- Khi thm 90% AgNO3 0,1N th cn 10% Cl khng kt ta
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Bng 9.1. Chun 100 ml dung dch NaCl 0,1N bng dung dch AgNO3 0,1
(khng k s pha long)
Dung dch
AgNO3 thm NaCl cn li (%) [Cl] pCl [Ag+] pAg
vo (%)
0 100 10-1 1 - -
0,1
100,1 1,7. 10-6 5,77 10-4 4
AgNO3(d)
1
101 1,7. 10-7 6,77 10-3 3
AgNO3(d)
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10
110 1,7. 10-8 7,77 10-2 2
AgNO3(d)
* im tng ng
Khi thm 100% AgNO3 0,1N, im tng ng ta c dung dch bo ha AgCl, [Cl] = [Ag+ ],
do :
[Cl-] = [Ag+ ] =
[Ag+ ]= 10-4
pAg = 4, [Cl]= 1,7. 10-6 (mol/l), pCl = 5,77
Hnh 9.2. ng cong chun dung dch NaCl 0,1N bng dung dch AgCl 0,1N
Nhn xt
ng biu din c dng chung ging cc ng biu din nh lng khc, gn im tng ng
c bc nhy pCl = 4-5,77, pAg = 5,77-4.
Tr s bc nhy ph thuc vo nng dung dch cn chun v dung dch chun. Nng cng
ln th bc nhy cng di (Nu nng 1N bc nhy bt u pCl = 3 v kt thc pCl =6,77 di hn
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Bng 9.2. nh hng ca nng dung dch cn chun v dung dch chun n
s thay i ca pCl khi chun 100 ml dung dch NaCl bng dung dch AgNO3
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Phn tch ng cong chun v cc s liu bng 9.2 c th kt lun rng nng dung dch cn
chun v dung dch chun cng ln th bc nhy chun cng ln. nng 1N, bc nhy t 3
6,77, vi nng 0,1N bc nhy ngn hn t 4 5,77 trong khi vi nng long 0,01N, bc nhy
khng c s cch bit 4,73 5,04.
Tuy nhin cn ch rng, khi chun dung dch 0,1N bc nhy ln, v vy khng nn chun
cc dung dch vi nng ln hn 0,1N. Sai s chun do vic o khng chnh xc khi dng cc dung
dch c nng ln c bit tng ln rt nhiu so vi khi chun cc dung dch c nng nh.
- nh hng ca tan cht kt ta
Cc hp cht to thnh trong qu trnh chun theo phng php kt ta l cc cht t tan. Tuy
nhin sai s gy ra do tan ca chng c th lm sai lch kt qu phn tch, v vy khng th b qua
tan c. nh hng ca tan cht kt ta tch ra n bc nhy chun c a ra bng 9.3.
Trn c s cc s liu ca bng 9.3 ngi ta xy dng ng cong chun .
pHal
Dung dch Nng NaHal khi chun
AgNO3thm hay AgNO3 (%)
vo (ml) NaCl NaBr NaI
(TAgCl = 1,7. 10-10) (TAgBr= 3,3. 10-13) (TAgI = 8,5. 10-17)
Trc im tng ng
0 100 1 1 1
50 50 1,3 1,3 1,3
90 10 2 2 2
99 1 3 3 3
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99,9 0,1 4 4 4
Ti im tng ng
100 0 4,885 6,211 8,035
Sau im tng ng
0,1
100,1 AgNO3 (d) 5,77 8,42 12,07
1
101 AgNO3 (d) 6,77 9,42 13,07
10
110 AgNO3 (d) 7,77 10,42 14,07
Phn tch ng cong chun v cc s liu bng 9.3, c th kt lun rng tan ca hp cht
kt ta cng nh th bc nhy chun cng ln. Khi chun dung dch NaHal 0,1N bc nhy
chun l: NaCl bc nhy (45,77 ), NaBr (48,42); NaI (412,07 ). Bc nhy chun trong tt c
cc trng hp ny l ln.
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- N l mt h khng ng nht (khc vi dung dch tht l mt h ng nht). Dung dch keo c
tnh cht in ly do s xut hin in tch trn b mt phn chia - s to thnh lp in kp ca ion v
gn lin vi chng l tnh cht hp ph.
- Cc ht ca dung dch keo mang in tch dng hoc m. S tch in ca cc ht keo do hp ph
cc anion (tch in m) hay cation (tch in dng) trn b mt ca n. Th d: cc halogenid bc hp
ph Ag+ hay ion Hal nh khi cho AgNO3 vo dung dch NaCl, kt ta AgCl to thnh trong mi
trng d NaCl nn ta ny s hp ph u tin ion Cl trong dung dch. Kt ta to ra cc ht mang in
tch m. Nh vy in tch ca ht keo c xc nh bng in tch ca cc ion b hp ph trn b mt
ca n v ph thuc vo iu kin to thnh keo. Cc ht keo bao gm cc phn t v ion lin kt vi
chng v cc ion tri du trong dung dch to thnh mixen. Mixen to thnh t cc nhn khng tan trong
mi trng v bao bc bng lp in kp cc ion. Mt lp ion c gi l lp hp ph nm trn b
mt ca nhn lm cho n tch in. Trong thnh phn lp hp ph c mt phn ion tri du m phn
chnh ca n to thnh lp th hai. Mixen trung ha in (tng in tch bng khng).
- S ng t keo
Cc ht keo tch in c th bin thnh cc ht ln bng cch c bit. Qu trnh kt hp cc ht keo
thnh cc ht ln hn gi l s ng t keo. S ng t keo c th xy ra bng s tng nhit , tc dng
ca nh sng, dng in cao tn, siu m, lc, trn, khuy dung dch...
- S pepti ho
Pepti ho l qu trnh chuyn dung dch keo ng t tr v trng thi phn tn ban u, ngc vi
s ng t, ngha l lc kt ta chuyn thnh keo. Hin tng ny thng xy ra khi ngi ta ra ta
keo ng t bng nc. Do gim nng cht lm ng t, ra kt ta khng ch loi cht bn m cn
loi c cht in ly to nn s ng t keo. Cc ht keo tr li tch in, y nhau phn tn trong dung
dch, chuyn n thnh h keo. Nh vy ra ta lm gim tp cht, nhng ng thi c th mt mt
phn kt ta.
ngn nga hin tng ny ngi ta khng ra kt ta bng nc m thng ra ta bng dung
dch cc cht in ly bay hi, cc cht ny c th c loi khi kt ta bng sy kh. Th d ra ta
AgCl bng dung dch HNO3 long, khi sy kh 110oC acid ny bay hi ht.
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nhn (mixen) lp s cp lp th cp
- Khi c d ion Ag+
Cht ch th c dng trong phng php bc cn khng i mu cho n khi ton b ion cn xc
nh chuyn thnh kt ta (chuyn thnh kt ta ca dung dch cn xc nh vi dung dch chun trc),
cht ch th to vi ion ca dung dch cn chun kt ta mang mu, c tan ln hn tan cht kt
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Ngi ta dng cht ch th cng nh khng dng cht ch th (so snh c v.v...) Ta ch nghin
cu cc phng php dng ch th. C 3 phng php:
- Nguyn tc
Phng php ny da trn phn ng gia Ag+ v Cl vi ch th K2CrO4, im tng ng
K2CrO4 tc dng vi lng Ag + d to ta gch.
Khi cha ti im tng ng Ag2CrO4 cha to thnh khi cha c lng d ion halogenid nn
iu kin cn thit ca php nh lng ny l Ag+ phi kt ta hon ton vi Cl di dng AgCl trc
khi ta Ag2CrO4 c to thnh. Do nng ca ch th phi bng bao nhiu sai s ch th
khng qu 0,1% (im kt thc nm trong phm vi bc nhy). Trong khong sai s chun 0,1%
nng c th thay i t 0,35 M 1,1.10-4M.(Khi = 0,1 M).
[ ]= /[Ag+]2 = 0,35 M
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Th d: Ag+(d) + Br AgBr
Ag+ + SCN AgSCN
3SCN + Fe3+ Fe(SCN)3 ( thm)
Theo l thuyt ngi ta cho rng mu ca Fe(SCN)2+ to thnh nng 6,4.10-6 M. Hy tnh
nng Fe 3+ l bao nhiu phc mu to thnh.
sai s chun bng khng, mu ca Fe(SCN)2+ cn xut hin khi nng Ag+ cn li trong
dung dch bng tng nng SCN
[Ag+ ] = [SCN] + [Fe(SCN)2+]= [SCN] + 6,4. 10-6
hay TAgSCN / [SCN] = 1,1. 10-12 / [SCN] = [SCN] + 6,4. 10-6
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Thay vo biu thc i vi hng s bn nng [SCN- ] to lng Fe(SCN)2+ m bng mt thng
c th pht hin c.
[Fe3+] = 0,27 M
Chun theo phng php Volhar nng ny khng bt buc. Nng Fe3+ c th dao ng
trong khong 0,002 1,6 M, sai s l thuyt khng hn 0,1 %. Trong thc t nng [Fe3+] trn 0,2M
th mu vng ca n lm ta kh nhn s i mu ca dung dch chun .
V vy ngi ta dng nng Fe3+ khong 0,01 M.
- iu kin ca phng php
+ Mi trng phi acid mnh (dng HNO3 m c) trnh s thu phn ca Fe3+, trnh ta Ag2O
v lm gim hin tng hp ph.
+ C th nh lng cc halogenid trong mi trng acid mnh v khng th chun cc halogenid
trong mi trng trn bng phng php Mohr hay phng php dng ch th hp ph.
+ Ngi ta dng phng php ny nh lng Cl, I, Br, SCN v Ag+. Nhng nu nh lng
Cl theo Volhard, mt kh khn thng xy ra khi nh lng bc cn li.
Theo phng trnh phn ng
Ag+(d) + Cl AgCl
Ag+ + SCN AgSCN
thi im khi lng d Ag+ c chun li bng SCN-, cc ion SCN d s phn ng vi AgCl
AgCl + SCN AgSCN + Cl (9.24)
V AgSCN (TAgSCN = 10-12) t tan hn AgCl (TAgCl = 1,7 x 10-10) nn cn bng chuyn dch t tri
sang phi.
Phn ng t ti cn bng khi t s
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Mui dinatri mu
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HE H+ + E
Khi cha t n im tng ng cc tiu phn keo ca ta AgI to thnh trong phn ng s hp
ph cc ion I c tha trong dung dch, cc tiu phn u mang in tch m nn khng hp ph cc ion
Eosinat (E).
Vng nht
mAgI + nI [AgI]m nI
tm
mAgI + nAg+ [AgI]mnAg+
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2.5. Sai s ch th
Nh bt k chun no, c th c sai s ngu nhin v sai s h thng. Sai s ngu nhin c lin
quan n dc ca ng cong chun . lch chun ca gi tr th tch im tng ng cng
nh, dc cng ln. Nh vy lch chun ca gi tr th tch cng nh bao nhiu, nng ca ion
chun cng ln v tan ca ta to thnh cng nh.
Sai s h thng lin quan ti s khng trng nhau ca im tng ng v im kt thc. Nu nh
to thnh hn hp t tan loi AB th ti thi im cha t ti im tng ng f<1 gy sai s m, khi
qua im tng ng f>1 gy ra sai s dng.
im kt thc, nng ca ion (nh halogenid) [Hal]KT bng tng nng ion cha chun
(hoc chun ) ngha l Co (1 f) hay Co (f 1) v nng ca cc ion tham gia vo s tnh tan
ca ta AgHal m bng [Ag+]KT hay [Hal]KT.
[Hal]KT = Co (1 f) + [Ag+]KT
[Ag+]KT = Co (f 1) + [Hal]KT
M Co = CoHal- = CoAg+
Suy ra
D dng thy rng sai s h thng cng nh bao nhiu, nng ca cht cn chun v cht chun
cng ln v im kt thc cng gn im tng ng.
tnh sai s chun , ngi ta lm th nghim kim tra cho dung dch AgNO3 vo dch nh tng
CaCO3 vi ch th cromat cho n khi xut hin mu . Th tch tm c dng tnh kt qu.
Trong phng php bc ch yu dng dung dch chun l AgNO3, dung dch chun NH4SCN c
chun li bng dung dch AgNO3.
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- C th pha dung dch AgNO3 0,1N bng cch ha tan mt lng tnh trc tinh th AgNO3 tinh
khit ho hc trong mt th tch nc xc nh.
- Hoc pha AgNO3 t ho cht khng c tinh khit lm, c nng xp x ri c xc nh theo
NaCl tinh khit ho hc.
Dung dch AgNO3 b thay i khi lu. Di nh hng ca nh sng, s phn hy c tng ln,
v vy ngi ta dung dch trong chai thu tinh mu nu.
Khng th pha dung dch NH4SCN c nng chnh xc theo lng cn ca cht, v NH4SCN ht
m. V vy ngi ta pha dung dch c nng gn ng vi yu cu, sau xc nh nng ca dung
dch NH4SCN xp x 0,1N bng dung dch chun AgNO30,1n.
Ngui ta xc nh ion clorid trong cc clorid tan da trn s chun trc tip lng cht cn phn
tch hay dung dch ca n bng dung dch chun AgNO3, vi ch th kali cromat. Nu xut pht t sn
phm tinh th th tnh hm lng phn trm ca NaCl hay Cl trong mu. Nu phn tch dung dch NaCl
th tnh hm lng ion Cl hay NaCl trong dung dch thnh gam.
nh lng trc tip ion clorid bng dung dch chun AgNO3 vi ch th fluoressein c tin hnh
trong mi trng trung tnh, mu trn b mt ca ta chuyn t vng sang hng.
nh lng trc tip KI bng dung dch chun AgNO3, vi ch th eosin c tin hnh trong mi
trng acid, mu trn b mt ca ta chuyn t hng sang tm.
nh lng clorid theo phng php Volhard bng cch chun ngc. Cho mt lng d chnh
xc vo dung dch NaCl cn nh lng, to ta trng ca AgCl, lc b ta AgCl (hoc cho dung mi
hu c nh benzen vo dung dch phn tch). nh lng Ag+ d bng dung dch chun NH4SCN vi
ch th phn st amoni.
T KHA
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CU HI LNG GI
1. Vit biu thc tch s tan, tan; Cc cng thc tnh tan trong nc nguyn cht, khi k ti h
s hot .
2. Nu cc yu t nh hng n tan v cch tnh tan trong tng iu kin c th.
3. Nu tnh cht ca dung dch keo, gii thch hin tng ng t v pepti ho.
4. Nu ngha ca phn ng kt ta ha tan trong phn tch.
5. Kho st ng biu din nh lng v nu cc yu t nh hng n ng cong chun kt
ta.
6. Nu s hnh thnh dung dch keo ca bc halogenid.
7. Nu nguyn tc, iu kin tin hnh v ng dng ca phng php Mohr, Fajans, Volhard.
8. Nu ng dng ca phng php o bc trong phn tch.
9. Cho bit tch s tan ca cc mui iodid nh sau:
iodid T
AgI 8,50. 10-17
PbI2 7,10. 10-9
BiI3 8,10. 10-19
11. Hy tnh tan AgCl trong dung dch NaCl c nhng nng sau:
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CU HI TRC NGHIM
1. Mun c kt ta:
2. Mun c kt ta tan c:
3. Cng thc tnh tan trong nc nguyn cht ca cht in ly t tan dng AB (cng ho tr):
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b. K2CrO4 d. eosin
Chng 10
PHNG PHP TO PHC
MC TIU
Trnh by c nh ngha phc cht v phn bit c phc cht cng, phc cht ni, mui
kp.
Gii thch c ngha ca hng s to phc, hng s bn iu kin.
Trnh by c nguyn tc v cch chn ch th trong phng php chun bng complexon
III.
Trnh by c cc k thut chun bng complexon III.
NI DUNG
Phc cht l nhng hp cht phn t c to thnh do mt kim loi (nguyn t trung tm) nh Ag,
Cu, Ni, Co, Fe, Hg... ni vi cc phi t c th l ion m hay phn t (NH3, H2O, Cl, F, CN,...).
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Phn t NH3 lng cc, cc m quay v pha ion kim loi v to thnh lin kt phi tr bng 2
electron t do lp ngoi cng ca nit.
Ngi ta thy rng s ti a nhng tiu phn c th gn vi nguyn t trung tm gi l s phi tr
cc i, s phi tr cc i thng l 2, 4, 6 hoc 8. in tch ca ion phc bng tng i s cc in
tch (dng v m) ca ion trung tm v phi t.
- Nhng phc cht ch c mt ion trung tm nh: [Ag(NH3)]+, [FeF6 ]3 c gi phc n nhn.
Phc c nhiu ion trung tm cng loi nh [Fe2(OH)2]4+, [Cu3(OH)4]2+ gi l phc a nhn.
1.2.2. Ni phc
Trong ni phc, kim loi to thnh vi phi t (thng l phn t hu c) va bng lin kt phi tr
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Ho tr 1: a Ho tr 5: an
Ho tr 2: o Ho tr 6: on
Ho tr 3: I Ho tr 7: in
Ho tr 4: e Ho tr 8: en
(Ghi ch: cng c th gi theo cch thm ui at vo tn nguyn t trung tm trc khi thm ch s
La m ch ho tr).
Phc cht trong dung dch cng phn ly nh cc mui n gin, c phc cht phn ly hon ton, c
phc cht phn ly khng hon ton, ngha l c phc cht bn v phc cht khng bn. biu th
bn ca phc cht, ngi ta dng hng s bn .
Xt th d cn bng gia kim loi (M) vi s phi tr bng 4 ca phi t (ligand) (L):
M+L ML
Hng s cn bng ca phn ng:
K l hng s bn.
Tng t cn bng gia M v phi t c s phi tr l 2
M + 2L ML2
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2. Zn (NH3) 2+ + NH3
3. + NH3
4. + NH3
Zn2+ + 2NH3
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K1K2 = 2
biu th bn ca phc cht ngi ta dng hng s khng bn, nghch o ca hng s bn 1/
c gi l hng s khng bn K hoc hng s phn ly ca phc cht, hng s ny cng nh phc cht
cng bn. Ngi ta cn thng dng i lng lgK c k hiu pK. Da vo hng s bn ca phc cht
c th bit c mc bn hoc khng bn ca chng. Hng s bn cng ln phc cng bn. Th d:
Phc FeY c = 1025,1 (tc K = 10-25,1) bn hn phc NiY 2 c = 1018,62 (K = 1018,62).
Nu bit hng s khng bn ca phc cht ngi ta c th kho st s cnh tranh to phc.
1.5. ngha
[ ] Ag+ + 2NH3
c th vit:
Thay cc gi tr nng ca cht to phc [Ag+] v ca phi t [NH3] vo biu thc hng s khng
bn:
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b) i vi
Do
Ta bit rng K khng bn cng nh phc cht cng bn vng, = 10-16,3, = 10-8,7,
vy phc km complexonat bn hn Mg complexonat, nn trong dung dch tn ti phc Zn
complexonat.
- C nhiu mui phc kh tan trong nc c to thnh bi cc cation kim loi nng v cc anion
ca nhng acid phc. Th d: Ni2+ to mui t tan vi hexacyanocobaltat (III) Ni3[Co(CN)6]2 mu xanh
l cy.
- C nhiu ion phc c bn cao, c mu c trng dng trong phn tch nh tnh v nh lng.
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Th d: Ngi ta pht hin K+ bng cch cho tc dng vi Na3[Co(NO3)6] to ra phc dng ta
mu vng K3[Co(NO3)6].
nh lng Fe3+, ngi ta cho Fe3+ tc dng vi thuc th NH4SCN, phc to thnh c mu
mu, o ph hp th trong vng kh kin.
C nhiu trng hp ngi ta dng phn ng to phc che cc ion ngn cn qu trnh phn tch.
Th d: Trong qu trnh phn tch, Fe3+ c th ngn cn s pht hin cc ion khc, ngi ta che Fe3+
bng cch thm H3PO4, NaF, Na2C2O4 hoc Na2C4H4O6 vo dung dch phn tch, ion Fe3+ s to vi
cc cht thnh ion phc bn vng khng mu: [Fe(PO4)2]3, [FeF6]3, [Fe(C2O4)3]3, [Fe(C4H4O6)
3 3+
3] . Khi cc anion phc c to thnh bn vng ngay c khi cho thuc th nhy i vi Fe nh
NH4SCN cng khng tc dng r rt vi Fe3+.
Ngi ta dng cc phn ng to phc ha tan nhng kt ta khng tan trong nc, trong acid v
trong kim. Nh trng hp Ag+ tc dng vi nhm halogenid (Cl, Br, I) to thnh cc mui bc
halogenid khng tan. tch AgCl ra khi cc cht khc, ngi ta cho vo ta mt lng tha NH3,
AgCl to thnh phc [Ag(NH3)2]Cl tan.
- Ngi ta dng phn ng ny khi mun lm thay i (tng hay gim) tnh acid, tnh base ca mt
hp cht.
Th d:
tng tnh acid ca acid boric, ngi ta thm vo dung dch mt lng glycerin. Lc ny c s
lin kt anion ca acid boric thnh phc glyceroborat km theo lm yu lin kt ca n vi hydro. Do
acid yu tr thnh acid mnh.
tng tnh base ca Al(OH)3, ngi ta thm fluorid vo dung dch Al(OH)3, Al3+ to phc bn
[AlF6]3 v OH c gii phng ra, do vy lm tng tnh kim ca dung dch.
Al(OH)3 + 6 F [AlF6]3 + 3 OH
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Chiu phn ng t tri sang phi. Khi thm F- vo dung dch th Fe3+ mt kh nng oxy ho I do
to thnh phc [FeF6]3 , do vy cn bng phn ng chuyn dch t phi sang tri.
2.1. S lc v cc complexon
- Complexon II (Trilon BS) l acid etylen diamin tetra acetic (EDTA), vit tt l H4Y. y l acid 4
nc. Trong dung dch ca EDTA c th tn ti cc dng: H4Y, H3Y, H2Y2, HY3, Y4 v tu thuc
vo pH ca mi trng dng no s l ch yu. pK1 = 2,0, pK2 = 2,73, pK3 = 6,24, pK4 = 10,34.
EDTA l tinh th mu trng, tan t trong nc, nhit 20oC tan ca n ch l 28,3 mg trong
100 ml nc. tan H4Y ti thiu pH 1,6 1,8. Khi tng hay gim nng ion hydro tan thay i
(hnh 10.1).
tan cao ca H4Y trong acid v c c gii thch bng s to thnh cc dng trao i proton
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H5Y+ v H6Y2+. S trao i proton ca anion Y4 v s phn b cc dng trao i proton khc nhau
ph thuc vo pH c biu th trong s (hnh 10.2) v biu phn b (hnh 10.3).
Hng s phn ly acid ca ion H6Y2+ bng: pKa,1 = 0,9; pKa,2 = 1,6;
Hnh 10.3. Biu vng to thnh nhng dng khc nhau ca EDTA
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Dihydrat Na2H2Y.2H2O tan tng i tt trong nc: 108 g/l 22oC. Trong nc, Na2H2Y phn ly
thnh Na+ v H2Y2, thnh phn ca dung dch complexon III ph thuc vo pH cng ging nh thnh
phn ca dung dch EDTA. V vy, ngoi phn t lng ra tt c cc tnh cht i vi complexon II u
ng vi complexon III v ngc li. Nhng v complexon III d iu ch c di dng tinh khit
nn hay dng hn c.
Theo cc phng trnh trn mt ion kim loi bt k ho tr u phn ng vi mt phn t EDTA, t
l (1:1) nn trong phng php complexon nng ng lng bng nng mol, E = M.
1 mol cation phn ng vi EDTA khng ph thuc vo ho tr ca n lin kt vi 1 mol Na-EDTA.
T hnh 3 thy rng phn ng xy ra mi trng kim yu v trung tnh c th vit di dng:
Mn+ + HY3 MY(n4)+ + H+
2.3.1. C ch phn ng
Trong cc nhm complexon tng tc vi ion kim loi to phc do ho tr chnh l nhm cacboxyl
(COOH), cn ion lin kt ph l nhm amino bc ba ( N). Mui ni phc vi EDTA to thnh, mt
mt, do s th cc nguyn t hydro hot ng ca nhm cacboxyl bng ion kim loi to phc, y
EDTA kt hp vi ion kim loi to phc bng ho tr chnh, mt khc do s tng tc vi nguyn t
nit c kh nng to lin kt ph (phi tr) vi ion kim loi to phc.
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Phn ng to phc gia EDTA vi ion kim loi c th biu din bng phng trnh chung:
Mn+ + H2Y2 MY(n4)+ + 2H+ pH = 4 6
Trong trng hp khng b nh hng bi cc qu trnh khc, phn ng to phc c vit gn li:
Mn+ + Y4 MY(n4)+
lgKMY Ba2+ = 7,76, lgKMY Pb2+ = 18,04, lgKMY Ca2+ = 10,70, lgKMY Mg2+ = 8,70
Ta c nhn xt sau:
Cc complexonat ca mt s kim loi bn vng n mc c th dng complexon ha tan cc ta
kh tan nh: BaSO4, PbSO4, CaC2O4,...
Hng s to phc cng ln phc cng bn vng, do c th xy ra phn ng cnh tranh to phc.
V d thm Mg- complexonat vo dung dch Ca2+ th:
Ca2+ + MgY2 CaY2 + Mg2+
V lgKMY Ca2+ = 10,7 > lgKMY Mg2+ = 8,7
Hoc nu thm complexon vo dung dch cha Ca2+ v Mg2+ th Ca2+ s to phc trc.
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Hng s bn ca cc complexonat ca cc ion kim loi khc nhau, nhiu khi s khc nhau rt ln.
iu ny cho php c th chun mt s ion kim loi trong cng mt dung dch bng phng php
complexon. Trn hnh 10.8 cho thy rng gi tr pH ti thiu c th c nh c im kt thc chun
ca cc cation khc nhau, cc kim loi nng ho tr 2 c th chun mi trng acid yu cn ion
Fe3+ mi trng acid mnh.
Ngi ta kho st cn bng to phc ca ion kim loi (Mn+) vi EDTA thy rng mc to phc
ph thuc vo pH ca dung dch. Khi chun cation to phc km bn (th d Ca2+ v Mg2+), yu cu
mi trng kim. Ngc li, chun cation to phc bn hn (km hay niken) c th tin hnh trong
mi trng acid. Ngi ta thy rng s ph thuc vo pH khi chun bng dung dch EDTA thng
tin hnh trong dung dch m c pH c nh. S c nh pH cho php tnh c cc s c ngha.
xy dng ng cong chun ca ion kim loi vi EDTA trong dung dch m, ngi ta dng
k hiu 4
(10.3)
C: nng chung khng to phc ca EDTA, bng tng nng cn bng ca tt c cc dng
EDTA.
C = [Y4] + [HY3] + [H2Y2] + [H3Y] + [H4Y]
4: k hiu phn ca cc tc nhn khng to phc tn ti dng Y4(tr MYn4). Ngi ta cn thy
rng 4 ch ph thuc vo pH v hng s phn ly ca EDTA K1, K2, K3, K4.
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(10.4)
biu thc mi s l:
pH 4 pH 4
Hng s bn iu kin cho php tnh ton d dng nng cn bng ca ion kim loi v phc trong
bt k im no ca ng cong chun , ngi ta thy rng biu thc cho hng s bn iu kin khc
biu thc cho hng s bn c s dng sm ch khi no nng cn bng phn ly hon ton ca anion
[Y4] thay th vo gi tr C (nng chung ca EDTA). y l iu rt quan trng v C xc nh t
php t lng ca phn ng d dng hn l [Y4].
Trn hnh (10.5) biu th s ph thuc logarit ca hng s bn iu kin ca phc i vi mt s
kim loi vo pH ca dung dch, nh hng ca pH ln i lng 4 (nhnh bn tri ca ng cong), s
to thnh hydroxocomplexonat v phc complexon vi NH3 ngha l do s tng 4 (nhnh bn phi ca
ng cong).
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Xy dng ng cong chun 50,0ml dung dch Ca2+ 0,0100M bng dung dch EDTA 0,0100M
trong dung dch m pH 10,00.
1. Tnh hng s bn iu kin: cc gi tr 4.
2. Tnh pCa trc im tng ng: Trc im tng ng nng chung ca Ca2+ bng tng
nng tha cha chun ca ion Ca2+ v ion Ca2+ to ra bi s phn ly ca phc. Nng phc s
bng nng chung ca EDTA c ngha l C. C th cho rng gi tr C nh hn so vi nng ion
Ca2+ khng to phc. V vy, th d sau khi cho 25,00ml (50%) dung dch chun .
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3.Tnh pCa im tng ng: thi im ny nng CaY2 trong dung dch bng 0,0050M v
s phn ly ca phc ny l ngun duy nht sinh ra ion Ca2+. Nng ion Ca2+ s bng nng chung
khng to phc EDTA:
[Ca2+] = CEDTA
4. Tnh pCa sau im tng ng: Sau im tng ng, nng chung CaY2- v EDTA d dng
tnh. Th d:
- Sau khi cho d 1% dung dch chun (51 ml):
Ly gi tr gn ng, c th vit:
[CaY2] = 4,95. 10-3 [Ca2+] 4,95. 10-3 M
CEDTA = 9,90. 10-5 + [Ca2+] 9,90. 10-5 M
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Ly gi tr gn ng, c th vit:
[CaY2] = 4,55. 10-3 [Ca2+] 4,55. 10-3 M
CEDTA = 9,10. 10-4 + [Ca2+] 9,10. 10-4 M
Trn hnh (10.6) m t ng cong chun ca ion Ca2+ trong dung dch m vi cc gi tr khc
nhau ca pH. T y nhn xt rng pCa c s thay i r rng ch pH 8.
Bng 10.3. Chun 50 ml Ca2+ 0,0100 M bng dung dch EDTA 0,0100 M
50 2,48
90 3,28
99 4,30
100 6,27 T
101 8,54
110 9,54
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V ml EDTA
Hnh 10.7. ng cong chun 50,0 ml 0,0100 M cc dung dch cation pH 6,0
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Trn hnh 10.7 cho thy rng khi chun cc cation to phc bn (c hng s to phc ln) im
kt thc chun thy r ngay c dung dch acid.
ng cong trn hnh 10.8 cho thy rng gi tr pH ti thiu no c th c nh im kt thc
chun ca cc cation khc nhau khi khng c cht cnh tranh to phc.
Trong chun to phc, im kt thc chun c th pht hin nh s nhn thy bng mt cng
nh s dng cc phng php phn tch dng c. S la chn phng php ph thuc vo cc yu t,
th d nh yu cu xc nh chnh xc v chn lc, chun dung dch c v c mu, chun trong
mi trng hn hp phc tp.
Trong phng php nhn bng mt, xc nh im kt thc bng cch s dng ch th kim loi. Ch
th kim loi l ch th lm thay i mu ph thuc vo nng ion kim loi. Ch th kim loi thng l
hp cht hu c, tc dng vi ion kim loi chun to mu ca phc. Ch th kim loi chia thnh hai
nhm:
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Nhm 1: Ch th t n khng c mu, nhng tc dng vi ion kim loi to mu ca phc c mu.
Th d khi chun phc st III, ch th dng thng l acid salicylic hay sunfosalicylic. Phc ca st
III vi acis salicylic (t l phn t 1:1) c mu . Cng mu ca phc thng khng cao, v vy
nhn thy r mu ca phc, nng ch th cn ln hn gp 10 ln nng ion kim loi chun .
Nhm 2: Trong loi ny, ch th kim loi l cc hp cht hu c, trong phn t c nhm mang mu
(chromophor), tc dng vi ion kim loi to hp cht ni phc, c mu khc vi mu ca ch th lc ban
u. Ch th ny gi l ch th kim loi chrom. Ngi ta chia ch th ny lm 3 nhm
Ch th c nhm chc azo N = N. in hnh l en eriocrom T.
Ch th xp trong nhm triphenylmetanic. Th d kxilen da cam
Ch th bn vng. Trong nhm ny c murexit, dithizon, alizarin....
2.6.1. Yu cu i vi ch th
Ch th kim loi cn phi c khong pH la chn, tc dng vi ion kim loi to ra phc bn vi t l
M: Ind = 1: 1. Hng s bn iu kin ca cht ch th phi nh hn hng s bn iu kin ca phc kim
loi vi EDTA, ngha l 10 < KMY /KMInd 104.
Trong trng hp mun t gi tr ln, hng s bn ca phc MInd cho php s dng t l khng
ln ca nng ch th v kim loi
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Hnh 10.9. Gin phn b i vi dung dch murexid khi c ion calci
1- H 4Ind-, - tm; 4- CaH 4Ind +, vng cam;
2- H 3Ind 2, tm; 5- CaH 3Ind, cam;
3- H 2Ind 3, xanh tm; 6- CaH2Ind , .
2.6.2.1. C ch
( tm) ()
Khi nh complexon xung:
Ca2+ + HY3 CaY2 + H+
Gn im tng ng c s cnh tranh to phc
CaH2I + HY3 CaY2 + H3I2
Tm
Cc iu kin i vi cht ch th kim loi
Phn ng to phc vi ion kim loi l phn ng thun nghch v mu ca dng t do phi khc vi
mu ca dng phc
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Khng mu tm Hng
Phc ca ch th vi kim loi phi km bn hn phc ca complexon vi kim loi.
Mind (n-m) + Y4 MY(n4) +Indm
2CaH2I + 2H2Y2 2CaY2 + 2H3I2 + 2H+
Hng Tm, pH = 9 11
Thng cc ch th kim loi ng thi cng l acid a chc, nn mu ca ch th thay i theo pH
ca dung dch, khi s dng ta phi c nh pH ca dung dch bng cc h m thch hp phn ng
xy ra nhanh, hon ton v mu ca ch th t do khc vi mu ca phc.
Hng s to phc ca cc ch th nh en eriocrom T, murexid vi mt s ion kim loi c trnh
by bng 10.4; 10.5.
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tm Tm Xanh
pH = 9 11. Murexid c mu tm (H3I2) v to phc vi Ca2+ c mu (CaH2I).
Murexid v en eriocrom T u km bn trong dung dch nn thng khng pha dung dch sn m
dng dng rn (nghin trn vi NaCl).
Kxilen da cam. Kxilen da cam l cht mu hu c dy triphenylmetanic. Cht ch th c mu vng.
Trong mi trng acid pH nh hn 7, n to vi cc ion kim loi (Zn2+, Th(IV), Zr(IV) v.v.. phc
cht mu . Cc cation c xc nh bng chun EDTA vi ch th kxilen da cam l Fe3+(pH = 1-
1,5), Zr4+(pH = 1-2), Bi3+(pH = 2-3,5), Zn2+(pH =5-6)...
Kxilen da cam l 3,3- bi [ di(cacboximetyl) aminometyl]- o-krenzolsunfophtalein:
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Cht ch th c mu xanh. Trong mi trng kim n to vi cc cation kim loi phc cht mu
nho. Ngi ta dng n khi chun bng cc dung dch complexcon cc cation km, cadmi (pH = 9-
10), mangan (pH= 10), magnesi (pH = 10-11), calci (pH > 12), ...
PAN
PAN l tn tt ca 1-(2-piridinazo) naphtol-2 c cng thc cu to l:
PAN c dng lm cht ch th chun trc tip nhiu ion. N to phc mu hng hoc
tm, tm vi nhiu ion kim loi. Trong khong pH kh rng cht ch th t do c mu vng.
-Vi Bi3+: dung dch HNO3 c pH =1-3 cht ch th i mu t hng sang vng lc.
Cht ch th ny to phc mu hoc nho vi nhiu ion kim loi trong khong pH rt rng t 1-
11,5. Cht ch th t do c mu vng nn khi chun trc tip cc ion kim loi mu ca dung dch s
chuyn t nho sang mu vng. Th d:
Vi Bi3+: pH =1-3, dung dch HNO3.
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Trong cc trng hp chung, sai s chun c th d dng tm nu bit nng chung ca ion kim
loi hay EDTA im kt thc chun , lng ion chun f v hng s bn iu kin ca phc MY
(n4)+. Nu im kt thc chun t sm hn im tng ng th nng chung ca ion kim loi
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Da trn nguyn tc cho mt lng d EDTA v sau xc nh lng d, thc hin trong nhng
trng hp khi phn ng to phc vi EDTA xy ra chm hay khng c ch th thch hp xc nh
im kt thc. Th d phc ca Cr3+ ng hc tr, do phc vi EDTA c to thnh rt chm. Sau
khi cho lng tha EDTA v un nng crom kt hp hon ton thnh complexonat. Tin hnh chun
d EDTA gi tr ti thiu pH (pH: 1,5 2) bng dung dch chun Fe (III) m khng cn ch rng
phc FeY bn hn phc CrY mt bc. Phn ng trao i CrY + Fe3+ FeY + Cr3+ xy ra sau thi
gian, cn thit i vi chun , thc t khng xy ra.
Phng php chun ngc tin li hn khi xc nh cc ion kim loi c mt cc anion m n to
vi ion kim loi cn xc ng l hp cht t tan. Th d nh c th xc nh Pb2+ khi c s hin din ca
; xc nh Mg2+ khi c ion ... EDTA ngn cn s to ta. La chn ion kim loi i vi
chun tha EDTA trong phng php chun ngc ch hai iu kin: hai ion ny cn to phc
cht c mu vi ch th kim loi; hng s bn iu kin ca phc vi EDTA cn phi thp hn ca phc
EDTA vi ion cn xc nh, nhng khng c thp hn K = 108
Th d: nh lng , kt ta anion bng mt thuc th cha cation thch hp: cho d BaCl2
Ba2+ + BaSO4
2.8.4. Chun th
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Da trn phn ng m trong ion cn xc nh ca kim loi M1 n+thay th ion ca kim loi M2n+
m n km bn hn phc vi EDTA
M1n+ + M2Y(4m) M1Y(+n) + M2m+
Ion thay th ca kim loi M2m+ v lng tng ng (ng lng) vi M1 chun bng dung
dch EDTA vi s c mt ca ch th kim loi thch hp.
Th d: Da trn c s Mg2+ to phc vi complexon phc cht km bn (pK = 8,7) so vi a s
cc cation khc (Ca2+, pK = 10,7). nh lng Ca2+, ta thm MgY2 vo dung dch ri chun
Mg2+ b y ra bng dung dch chun EDTA.
Ca2+ + MgY2 CaY2 + Mg2+
Mg2+ + HY3 MgY2 + H+
Tha
T Vcomplexon suy ra Ca2+ c trong mu.
- Trng hp c complexon tinh khit ho hc: cn mt lng chnh xc complexon, pha trong nc
vi th tch xc nh.
- Trng hp khng c complexon tinh khit, pha dung dch c nng xp x, sau xc nh li
nng .
xc nh nng complexon ngi ta dng calci cacbonat tinh khit ho hc, ZnO tinh khit ho
hc hay MgO tinh khit ho hc. Ho tan mt lng cn chnh xc tnh trc ca cc cht trong
mt t acid (nu l CaCO3, MgO ha trong HCl tinh khit, nu l ZnO ha trong H2SO4 tinh khit), sau
cho nc n th tch xc nh. Chun dung dch complexon bng cc dung dch va pha nh
CaCl2, MgCl2, ZnSO4 vi cc ch th thch hp.
Phng php complexon xc nh calci da trn phng php chun trc tip cc ion ca n
bng dung dch chn EDTA vi cht ch th murexit hay crom xanh en acid. Cht ch th to vi ion
calci phc cht mu . Khi chun bng EDTA, im tng ng mu chuyn sang mu c
trng ca cht ch th t do.
Khi chun mui calci bng EDTA, xy ra s to phc CaY2 v acid:
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2.10.2. Xc nh cng ca nc
cng ca nc c biu th bng s mili ng lng gam canxi v magne trong 1 lt nc.
cng ton phn ca nc l tng mui calci v magnesi tan trong nc. C th xc nh cng
ton phn bng complexon III vi ch th en eriocrom T.
Ly mu nc cn nh lng, cho thm ch th en eriocrom T pH = 10, ch th s to phc mu
vang vi mt phn Mg2+ trong mu. Khi nh EDTA vo, EDTA s phn ng vi Ca2+ t do, sau
vi Mg2+ t do (v phc CaY2 bn hn phc MgY2), n im tng ng EDTA s ph phc ca
ch th vi Mg2+, gii phng ra ch th t do c mu xanh.
Trong mi trng acid (pH: 2 3), EDTA tc dng vi Fe3+ to phc c mu vng nht FeY. Nu
dng ch th l acid salicylic hay acid sulfosalicylic pH n tc dng vi Fe3+ to thnh phc c mu
tm . Trong iu kin ny Al3+, Ca2+, v Mg2+ khng cn tr vic xc nh Fe3+. Ti im tng
ng mt mu tm v dung dch c mu vng nht.
Cho Ba2+ cn nh lng tc dng vi mt lng d chnh xc EDTA. nh lng EDTA d bng
dung dch Mg2+.
Ba2+ + BaSO4
nh lng Ba2+ cn li bng complexon III. quan st d dng s chuyn mu ca ch th, thm
vo dung dch mt lng Mg2+ nht nh v qu trnh nh lng c tin hnh hon ton tng t
nh nh lng cng ton phn ca nc.
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T KHA
CU HI LNG GI
1. Nu nh ngha phc cht, phc cht cng, ni phc, cho th d minh ha.
2. Phn tch ngha ca hng s to phc, hng s khng bn ca phc, hng s bn iu kin.
3. Trnh by phn loi ca ch th dng trong phng php to phc.
4. Nu cc yu cu ca ch th kim loi.
5. Trnh by ngha ca hng s bn iu kin.
6. Hy phn tch nh hng ca pH n cn bng to phc.
7. Lm th no tng tnh chn lc ca chun to phc?
8. Trnh by ng dng ca phn ng to phc trong phn tch.
9. Nu nguyn tc ca phng php complexon, gii thch ng lng ca ion kim loi trong
phng php complexon?
10. nh ngha complexon. Nu tnh to phc ca complexon III.
11. Trnh by cc phng php pht hin im kt thc chun .
12. Nu c ch chuyn mu ca ch th kim loi; Tn cc ch th thng dng trong phng php
complexon.
13. Trnh by cc k thut chun bng complexon.
CU HI TRC NGHIM
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a. H5Y+ c. H2Y2 e. Y4
b. H3Y d. HY3
a. pH > 12 c. pH = 9-11 e. pH = 7
b. pH = 7-8 d. pH < 3
9. Ch th dng dng rn
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10. nh lng Ba2+ bng phng php complexon dng k thut chun
P N CU HI TRC NGHIM
Cu
Chng
1 2 3 4 5 6 7 8 9 10
1 b c e d d
2 d a e d a
3 d c c c d b e c c b
4 c e a a c a a
5 d e b a e b e
6 b d a e
7 c b e c e c e d a e
8 a c e c d a b c d e
9 c a b b a e a a c b
10 c d d c e e c a d c
Ting Vit
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4. Hong Minh Chu, T Vn Mc, T Vng Nghi, C s ho hc phn tch, Nh xut bn Khoa
hc v K thut, 2002.
5. Kiu Dinh, Ho i cng, Nh xut bn i hc v Trung hc chuyn nghip, H Ni, 1969.
6. Phm Gia Hu, Trn T An, Trn Tch Ha phn tch I B mn Ha Phn tch, Trng i
hc Dc H Ni, H Ni, 1998.
Ting nc ngoi
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Bin tp v sa bn in:
VNG MINH CHU
Trnh by ba:
BI QUANG TUN
Ch bn:
THI SN
HO PHN TCH TP 1
M s: 7K725M7 DAI
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