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Hóa Phân Tích PDF
Hóa Phân Tích PDF
PHN TCH
1
C s ha hc phn tch
Lm Ngc Th
T kho: C s ha phn tch, Phn tch nh lng, Chn mu, o mu, Phng php
phn tch.
Mc lc
Chng 1 M u ........................................................................................................ 8
1.1 Lnh vc ng dng phn tch nh lng....................................................... 8
1.2 Thc hnh phn tch nh lng.................................................................... 9
1.2.1 Chn mu.................................................................................................. 9
1.2.2 Chun b mu phn tch.......................................................................10
1.2.3 o mu ....................................................................................................10
1.2.4 Ha tan mu .............................................................................................10
1.2.5 Tch hn hp cn tr ...............................................................................10
1.2.6 Giai on kt thc php phn tch ............................................................10
1.2.7 Chn phng php phn tch ...................................................................11
Chng 2 nh gi tin cy ca nhng s liu phn tch ................................. 12
2.1 Mt s nh ngha.........................................................................................12
2.1.1 Trung bnh v trung v .............................................................................12
2
2.1.2 lp li .................................................................................................13
2.1.3 ng ...................................................................................................14
2.1.4 lp li v ng ca nhng d kin thc nghim ............................15
2.2 Phn loi sai s.............................................................................................16
2.2.1 Sai s h thng v sai s ngu nhin ........................................................16
2.2.2 Cc loi sai s h thng ...........................................................................16
2.2.3 nh hng ca sai s h thng n kt qu phn tch..............................17
2.3 Biu hin ca sai s h thng .......................................................................18
2.3.1 Pht hin sai s dng c v sai s c bit .................................................18
2.3.2 Pht hin sai s phng php...................................................................18
2.4 nh hng ca sai s ngu nhin .................................................................20
2.4.1 Xem xt nh hng ca sai s ngu nhin ln ng tc chun ho pipet .21
2.4.2 S phn b s liu ca nhng php o song song ....................................22
2.4.3 Nhng khi nim c bn ca thng k c in.........................................25
2.4.4 ng dng nhng phng php thng k ..................................................27
2.4.5 S dng nhng phng php thng k.....................................................29
2.4.6 Khong tin cy .........................................................................................30
2.4.7 Nhng phng php thng k kim tra gi thuyt ...................................36
2.4.8 Loi tr s liu mang sai s th bo.........................................................40
2.1 S lan truyn sai s trn cc php tnh .........................................................42
2.7.2 Php cng sai s h thng ........................................................................42
2.7.2 Cng sai s ngu nhin ............................................................................45
2.7.2 S lan truyn sai s php tnh lu tha .................................................47
2.7.2 S lan truyn sai s php LOGARIT v ANTI LOGARIT ...................49
2.2 iu kin c ngha ca ch s......................................................................50
2.3 Bo him cht lng (QA) v biu kim tra ............................................52
2.7.2 S cn thit ca bo him cht lng.......................................................53
2.7.2 ng dng biu kim tra.......................................................................54
Chng 3 Cc phn ng ha hc trong ha hc phn tch................................. 57
3.1 hon ton ca phn ng ..........................................................................57
3.2 Nhng yu cu c th v hon ton ca mt phn ng phn tch nh
lng ............................................................................................................60
3.3 Tc phn ng ...........................................................................................61
3.4 ngha ca tc phn ng i vi ha hc ...............................................63
Chng 4 Phng php tnh nng cc cht trong nhng dung dch cn bng
n gin...................................................................................................... 65
4.1 Mt s lun im c s ................................................................................65
4.1.1 Thnh phn ho hc ca dung dch ..........................................................65
4.1.2 Tnh cht axit - baz trong cc dung mi khc nhau ................................67
4.2 Phng php tnh nng cc cht trong nhng dung dch cn bng n
3
gin..............................................................................................................69
4.2.1 Trng thi cn bng..................................................................................69
4.2.2 Biu thc hng s cn bng .....................................................................70
4.2.3 Nhng phng php biu th hng s cn bng........................................70
4.2.4 Biu thc hng s cn bng ca nhng phn ng thng gp nht ..........72
Chng 5 tan ca kt ta ................................................................................... 90
5.1 nh hng ca cn bng cnh tranh n tan ca kt ta .........................90
5.1.1 M t cn bng phc tp ..........................................................................91
5.1.2 S gii bi tp bao gm mt s cn bng ............................................92
5.2 nh hng ca pH n tan ......................................................................93
5.2.1 Tnh tan nng ion hiro bit ...................................................94
5.2.2 Tnh tan nhng nng ion hiro khc nhau...................................96
5.2.3 tan ca hiroxit kim loi trong nc ................................................103
5.3 nh hng ca s to phc n tan.......................................................105
5.4 nh hng ca nng cht in li n tan..........................................110
5.5 Nhng yu t ph nh hng n tan ca kt ta ..................................118
5.6 Phn chia cc ion theo nng cht kt ta (kt ta phn on)................119
Chng 6 Qu trnh to thnh kt ta ................................................................. 123
6.1 Nghin cu thc nghim qu trnh to kt ta............................................123
6.2 L thuyt c in v s to thnh cc trung tm kt tinh............................126
6.3 L thuyt v s to thnh cc trung tm kt tinh Becker - Doring..............127
6.4 L thuyt to thnh cc trung tm kt tinh Christiansen - Nielsen .............129
Chng 7 Phn tch trng lng .......................................................................... 131
7.1 M u .......................................................................................................131
7.2 Tnh kt qu theo d kin phn tch trng lng ........................................131
7.3 Tnh cht ca kt ta v cht to kt ta.....................................................136
7.5.1 Tnh d lc v tinh khit ca kt ta .................................................136
7.5.2 Kt ta v nh hnh...............................................................................139
7.5.3 Nhng kt ta tinh th............................................................................142
7.5.4 Sai s do cng kt ..................................................................................143
7.5.5 Kt ta t dung dch ng th ................................................................144
7.5.6 Sy v nung kt ta ................................................................................144
7.4 V thiu st ca phng php phn tch trng lng .................................146
7.5.1 Thi gian thc hin phn tch trng lng .............................................146
7.5.2 Lnh vc ng dng ca phn tch trng lng .......................................147
7.5 ng dng phng php phn tch trng lng ...........................................147
7.5.1 Cc cht to kt ta v c ......................................................................147
7.5.2 Nhng thuc th c tnh cht kh ..........................................................147
7.5.3 Nhng cht to kt ta hu c ...............................................................147
7.5.4 Xc nh trng lng cc nhm chc hu c.........................................151
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7.5.5 Nhng phng php trng lng xc nh cc hp cht hu c
ring l ..................................................................................................152
7.5.6 Phng php chng ct..........................................................................152
Chng 8 M u v phn tch th tch ............................................................... 154
8.1 Nhng khi nim c bn ............................................................................154
8.2 Phn ng v thuc th dng trong phn tch chun ...............................155
8.2.1 Nhng cht chun gc............................................................................155
8.2.2 Dung dch chun ....................................................................................156
8.3 im cui trong cc phng php chun ..............................................156
Chng 9 Chun kt ta................................................................................... 161
9.1 ng chun kt ta .............................................................................161
9.2 ngha ca ch s khi tnh ng chun ..............................................163
9.3 Nhng yu t nh hng n tnh r rng ca im cui ...........................163
9.4 ng chun hn hp ...........................................................................166
9.5 Nhng cht ch th ha hc ca phng php chun kt ta..................169
Chng 10 L thuyt chun Axit Baz i vi nhng h n gin .......... 177
10.1 Thuc th chun chun axit - baz................................................177
10.2 Cht ch th chun axit - baz ........................................................177
10.2.1 L thuyt v tnh cht ca cht ch th ..................................................178
10.2.2 Nhng loi ch th axit - baz ...............................................................179
10.2.3 Sai s chun vi cc ch th axit - baz............................................183
10.2.4 Nhng yu t nh hng ti tnh cht ca ch th .................................183
10.3 ng chun axit mnh hoc baz mnh...........................................183
10.4.1 Chun axit mnh bng baz mnh...................................................183
10.4.2 Chun baz mnh bng axit mnh ...................................................187
10.4 ng chun axit yu hoc baz yu.................................................187
10.4.1 Tnh pH ca dung dch cha mt cp axit - baz lin hp....................187
10.4.2 nh hng ca lc ion n cn bng axit - baz..................................191
10.4.3 Dung dch m .....................................................................................193
10.4.4 ng chun axit yu......................................................................200
10.4.5 ng chun baz yu ....................................................................206
Chng 11 ng chun nhng h Axit Baz phc tp............................ 208
11.1 ng chun hn hp axit mnh v axit yu hoc hn hp baz mnh
v baz yu.............................................................................................208
11.2 Tnh ton nng cn bng ca cc h a axit - a baz........................211
11.2.1 Dung dch mui loi NaHA..................................................................212
11.2.2 Dung dch a axit .................................................................................215
11.2.3 Dung dch a baz................................................................................218
11.2.4 Dung dch m ca cc h axit yu v baz lin hp vi n ................219
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11.3 ng chun a axit ..........................................................................221
11.4 ng chun a baz.........................................................................227
11.5 ng chun cht in li lng tnh ..................................................229
11.6 Thnh phn ca dung dch a axit l hm s ca pH...............................231
Chng 12 Chun Axit Baz trong mi trng khng nc..................... 234
12.1 Dung mi chun khng nc.........................................................234
12.1.1 Phn ng axit - baz trong dung mi lng tnh ..................................235
12.1.2 Phn ng axit - baz trong dung mi aproton v dung mi hn hp ....241
12.1.3 Pht hin im cui khi chun trong dung mi hn hp..................241
12.2 ng dng phng php chun trong dung mi khng nc..................242
12.2.1 Chun trong axit axetic bng ...........................................................242
12.2.2 Chun trong dung mi baz.............................................................244
12.2.3 Chun trong dung mi aproton hoc trung tnh ...............................245
Chng 13 Chun to phc ............................................................................. 246
13.1 Chun bng cc thuc th v c ........................................................248
13.2 Chun bng cc axit aminopolicacboxilic ..........................................249
13.2.1 Thuc th .............................................................................................249
13.2.2 Phc ca EDTA vi cc cation kim loi...............................................251
13.2.3 Xy dng ng chun ....................................................................253
Chng 14 Chun Oxi ha kh ....................................................................... 265
14.1 Nhng khi nim c bn .........................................................................265
14.1.1 nh ngha............................................................................................265
14.1.2 Phng trnh Nerst ...............................................................................267
14.2 Nhng yu t nh hng n th oxi ha kh.........................................267
14.2.1 nh hng ca axit .........................................................................267
14.2.2 nh hng ca phn ng to phc .......................................................268
14.2.3 nh hng ca phn ng kt ta ..........................................................269
14.5 Hng s cn bng ca phn ng oxi ha kh ..........................................270
14.5 ng chun oxi ha kh ..................................................................272
14.5 Cc yu t nh hng ln ng chun oxi ha kh..........................274
14.2.1 Nng cht phn ng.........................................................................275
14.2.2 hon ton ca phn ng ..................................................................275
14.2.3 Tc phn ng v th in cc ..........................................................276
14.7 Chun hn hp ...................................................................................277
14.7 Cht ch th oxi ha kh..........................................................................279
14.7.1 Nhng ch th oxi ha kh thng thng..............................................279
14.7.2 Ch th c bit .....................................................................................283
Chng 15 Phn hy v ha tan mu................................................................... 284
15.1 Ngun sai s trong phn hy v ha tan mu..........................................284
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15.1.1 S ha tan khng hon ton cc cht cn phn tch..............................285
15.1.2 S mt i mt phn cht cn phn tch do bay hi ...............................285
15.1.3 a cht bn dung mi vo cht cn phn tch.....................................285
15.1.4 a cht bn t phn ng ca dung mi vi thnh bnh vo mu ........285
15.2 Phn hy mu bng axit v c trong bnh m .........................................285
15.2.1 Axit clohiric .......................................................................................286
15.2.2 Axit nitric .............................................................................................286
15.2.3 Axit sunfuric ........................................................................................286
15.2.4 Axit pecloric.........................................................................................286
15.2.5 Cc hn hp oxi ha.............................................................................287
15.2.6 Axit fluoric...........................................................................................287
15.3 Phn hy bng vi sng ............................................................................287
15.4.3 Bnh phn hy mu c iu chnh p sut ............................................289
15.4.3 Bnh vi sng p sut cao.......................................................................289
15.4.3 L vi sng.............................................................................................290
15.4.3 L thiu vi sng....................................................................................290
15.4.3 S dng phn hy vi sng trong bnh ng kn ....................................291
15.4 Phng php t chy phn hy cc mu hu c...............................291
15.4.1 t chy trn ngn la m (tro ha kh)..............................................291
15.4.2 Phng php t trong ng ..................................................................291
15.4.3 Thiu nhit vi oxi trong bnh cha ng kn.......................................292
15.5 Phn hy cc vt liu v c bng cht nung chy ...................................293
15.5.1 Thc hnh nung chy ...........................................................................294
15.5.2 Cc loi cht nung chy........................................................................294
Chng 16 Loi b cc tc dng cn tr.............................................................. 296
16.1 Bn cht ca qu trnh tch.......................................................................296
16.2 Tch bng kt ta......................................................................................297
16.2.1 Tch da trn s kim tra axit .........................................................297
16.2.2 Tch bng sunfua .................................................................................298
16.2.3 Tch bng cc cht kt ta v c khc .................................................299
16.2.4 Tch bng cc cht kt ta hu c........................................................299
16.2.5 Tch cc cht tn ti dng lng vt bng kt ta .............................299
16.3 Tch bng chit.........................................................................................300
16.3.1 L thuyt .............................................................................................300
16.3.2 Cc loi quy trnh chit .......................................................................304
16.4 ng dng cc quy trnh chit ..................................................................306
16.4.1 Chit tch cc ion kim loi dng chelat .............................................306
16.4.2 Chit cc phc clorua kim loi .............................................................310
16.4.3 Chit cc mui nitrat ............................................................................311
16.5 Tch bng trao i ion ............................................................................311
16.5.1 Tch nhng ion cn tr c in tch tri du vi ion cn phn tch .........311
16.5.2 Lm giu vt ca cht in li ..................................................................311
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16.5.3 Chuyn ha mui thnh axit hoc baz...................................................312
16.6 Tch cc hp cht v c bng chng ct.................................................312
Ph lc.................................................................................................................313
Ti liu tham kho.............................................................................................337
8
Chng 1
M u
Ngoi ngha ng dng, nhng kt qu phn tch nh lng cn rt quan trng trong cc
lnh vc nghin cu ha hc, sinh ha, sinh vt, a cht v cc khoa hc khc. Chng ta xem
xt mt s v d lm dn chng: Khi nim v c ch ca phn ln cc phn ng ha hc c
c t nhng d kin ng hc l nh cc php xc nh nh lng cc cu t trong phn
ng. Ngi ta bit rng, c ch chuyn cc xung ng thn kinh ng vt v s co li hoc
lm yu i cc c do s chuyn ion natri v kali qua mng quyt nh. Hin tng ny c
pht hin nh cc php o nng cc ion ny c hai pha ca mng. S nghin cu tnh
cht ca cc cht bn dn i hi phi pht trin nhng phng php nh lng cc tp cht
trong silic v gecmani tinh khit trong khong 106 1010 %. Trong mt s trng hp, php
phn tch nh lng cc lp b mt ca t cho php cc nh a cht pht hin nhng va
qung tng i su. Phn tch nh lng nhng lng rt nh ca cc mu ly t cc tc
9
phm ngh thut gip cc nh s hc bit c nguyn liu v k thut ca nhng cng trnh
ca nhng ha s thi trc v cng l phng php quan trng pht hin s gi mo.
Thng nhng kt qu phn tch nh lng bao gm nhng d liu ca hai php o hoc
i khi ca hai dy php o: lng ban u ca mu v lng hp phn cn xc nh trong
mu. V d, c th o khi lng, th tch, cng sng, hp th nh sng, cng
pht hunh quang, in lng. Nhng cng cn phi ni rng, nhng php o ch l mt
phn ca php nh lng thng thng. Hon ton khng km phn quan trng l nhng giai
on chun b trc, nhng giai on ny nng nhc lu di hn so vi php o.
1.2.1 Chn mu
1.2.3 o mu
1.2.4 Ha tan mu
Thng php phn tch c tin hnh trong dung dch mu. Trong trng hp l tng,
dung mi cn phi ho tan hon ton mu ban u (ch khng phi ch hp phn cn xc
nh) nhanh v m du khng xy ra s mt mt cht cn xc nh. ng tic l i vi
nhiu hoc chnh xc hn l i vi phn ln cc nguyn liu khng c nhng dung mi nh
vy. Thng nhng nh ha phn tch phi lm vic vi nhng cht kh ch ha nh qung,
cc cht cao phn t, cc t bo sng. Chuyn hp phn cn xc nh ca nhng nguyn liu
nh vy vo trng thi ha tan thng l cng vic phc tp i hi nhiu thi gian.
1.2.5 Tch hn hp cn tr
Chng 2
Trong chng ny s cp n nhng loi sai s ny sinh khi thc hnh phn tch,
phng php pht hin, phng php nh gi v cch biu din gi tr .
2.1 Mt s nh ngha
Thng thng, nh phn tch phi lp li php phn tch mu t hai n nm ln. Nhng
kt qu ring bit trong dy o song song t khi ph hp vi nhau nn cn phi chn gi tr
trung tm tt nht ca dy. S cn thit ca nhng php o song song l do hai nguyn
nhn. Mt l, gi tr trung tm c la chn ng tin cy hn so vi mi kt qu ring bit
khc. Hai l, s khc nhau v gi tr ca nhng kt qu ring bit khc m bo cho s
nh gi nh tnh v tin cy ca gi tr tt nht c la chn.
C th dng mt trong hai im xut pht t hai i lng, trung bnh v trung v lm
im trung tm ca dy.
Trung bnh, trung bnh cng v trung bnh mu, x , l nhng t ng ngha v l thng
s ca php chia tng kt qu ca nhng php o ring bit cho s ln o mu.
13
Trung v ca dy l kt qu gia, c s kt qu c gi tr ln hn v s kt qu c gi tr
nh thua bng nhau. Nu mu c s php o khng chn, c th ly im trung tm l trung v
cn i vi mu c s php o chn, c th ly trung bnh ca cp php o trung tm lm
trung v.
10,08 + 10,10
Trung v = x = = 10,09
2
Trong trng hp l tng, trung v v trung bnh phi trng nhau nhng thng iu
khng xy ra, c bit l nu s ln o khng ln.
2.1.2 lp li
Cng c th din t lp li bng lch khi trung v, 24,36% (xem bng trn). S o
lp li cng chnh l bin bin i hoc bin dy s liu, , ngha l hiu s gia kt
qu ln v nh nht (0,20%).
lch tiu chun v phn tn c dng lm hai tiu chun cho lp li. Cch xc
nh cc i lng ny s c cp n trong cc mc tip theo ca chng ny.
lp li tng i
0,08 100
lch tng i khi gi tr trung bnh = = 0,32 0,3%
24,31
0,067 100
lch trung bnh tng i khi trung v = = 0,3%
24,36
2.1.3 ng
Thng i lng c li hn, khng phi l sai s tuyt i m l sai s tng i, biu
din lch khi gi tr tht bng phn trm. i vi php phn tch xt trn:
15
0,05 100
Sai s tng i = = 0,21 0,2%
24,36
Hnh 2.1
Cc kt qu phn tch v phn b nh trn hnh 2.1 l do nh phn tch mc phi hai
loi sai s c bn.
16
2.2 Phn loi sai s
C th phn chia nhng sai s sinh ra trong qu trnh phn tch ho hc thnh hai nhm
ln khng ph thuc vo ngun gc ca chng.
Sai s ngu nhin l sai s xut hin trong kt qu ca nhng php o lp li nhiu ln.
Ngun gc ca sai s ny khng r, cn gi tr th dao ng ty v khng th o c. S
tn mn ca nhng kt qu gn gi tr trung bnh (hnh 2.1) l h qu trc tip ca sai s ngu
nhin. Ngc li, hiu s gia gi tr tht v gi tr trung bnh thu c ca cc nh phn tch
th 3 v th 4 ( xi xt) l do mt hoc mt s sai s h thng gy nn.
Sai s c bit: Sai s ny xut hin do khng hiu bit, do cu th, do nh kin hoc do
khuyt tt v sc kho ca ngi thc nghim. V d, chng c th xut hin do vn chuyn
mu khng ng cch, do b qua b chnh nhit i vi thit b o, do ra kt ta hoc do
ghi khng chnh xc ch s ca thit b
S nh kin c nhn cng l ngun sai s quan trng phi lun lun phng. Ngi
thc nghim v tnh c gng c c nhng ch s ca thit b nhm nng cao lp li ca
dy kt qu hoc l c gng t kt qu cao cho cng gn cng tt vi mt gi tr nh kin
trc c coi l gi tr tht ca php o. trnh sai s h thng loi cn lun nh nhng
khuyt tt ca c th con ngi v c gng khch quan hn khi quan st.
Sai s thit b: Sai s thit b do s khng hon thin ca thit b m nh phn tch s
dng gy nn hoc l do nh hng ca nhng yu t bn ngoi ln thit b. V d, th tch
ca nhng dng c nh mc (buret, pipet, bnh nh mc) thng khc mt cht so vi th
tch c xc nh khi chun ho chng, c bit l nhit ca cc dng c ny khi s dng
khc nhiu vi nhit khi chun ho. C th loi tr sai s h thng loi ny bng cch
chun ha dng c nh mc nhit tng ng
Sai s phng php: Sai s h thng thng xut hin do s sai lch ca tnh cht thuc
th hoc phn ng dng lm c s cho php xc nh khi tiu chun l tng. Nguyn nhn
17
ca nhng sai lch ny c th l: tc phn ng nh, phn ng xy ra khng hon ton, s
khng bn ca cc cht no , s khng c trng ca thuc th v s khng xy ra cc phn
ng ph cn tr qu trnh xc nh. V d, trong phn tch trng lng, nhim v t ra i
vi nh phn tch l tch nguyn t cn xc nh vo dng kt ta cng tinh khit cng tt.
Trong phn tch chun thng gp sai s phng php gn lin vi vic thm d thuc
th so vi lng l thuyt cn thit lm chuyn mu ca ch th l du hiu nh gi im
cui ca phn ng. Kt cc, ng ca ton b php phn tch c xc nh bng chnh
hin tng c trng .
Cn mt loi sai s phng php na c minh ho trn hnh 2.1, php xc nh nit
trong hp cht hu c, theo Ken-an, da trn c s oxi ho mu bng axit sunfuric c, nit
thng chuyn thnh amoni sunfat. Nhng hp cht cha vng piriin, v d, axit nicotinic,
c th khng b oxi ho hon ton trong nhng iu kin phn tch. Sai s m trong nhng kt
qu ca cc nh phn tch th 3 v th 4 chc l gn lin vi s oxi ho khng hon ton.
Sai s phng php l nhm sai s h thng nghim trng nht bi v thng thng
chng khng b pht hin.
Sai s h thng thng c chia thnh hai loi: loi hng nh v loi bin i. Gi tr
sai s hng nh khng ph thuc vo lng c o. Ngc li, sai s bin i tuyn tnh
gim hoc tng theo gi tr tuyt i, t l vi lng mu ly phn tch.
Sai s hng nh: Trong mt php phn tch c th bt k, sai s hng nh cng ln nu
lng cht c o cng nh, c th dng hin tng mt khi ra kt ta do tan ca n
lm v d.
Sai s h thng thng kh ln. Hn na, vic pht hin chng cng kh khn bi v
khng c mt phng php n gin v tin cy no cho php pht hin, c hay khng c loi
sai s ny.
Ngi ta thng pht hin sai s dng c v b chnh khi chun ho thit b. Tt nht l
chun ho nh k thit b bi v vi thi gian, ch s ca phn ln thit b sai lch do b hao
mn, n mn hoc do s s dng cu th.
Pht hin sai s phng php c bit kh khn. Ngoi ra vic b chnh nh hng ca
chng thng cng rt kh. C th pht hin sai s loi ny nh cc bin php di y:
Phn tch cc mu tiu chun. pht hin sai s h thng ca phng php ngi ta
phn tch nhng mu nhn to, c thnh phn bit trc v gn vi thnh phn vt liu cn
phn tch. Mu tiu chun cn phi c chun b rt cn thn nng ca hp phn cn
xc nh c bit trc vi tin cy cao. ng tic l, vic chun b mu c thnh phn
ng ht nh mt cht t nhin phc tp, thng kh khn hoc ni chung khng th lm
c.
Phn tch bng nhng phng php c lp. Hon thnh vic phn tch bng mt phng
php c lp vi chnh xc bit trc song song vi phng php c s dng trong
19
nghin cu l c bit quan trng nu khng c mu vi sch bit trc. Phng php c
lp khng cn gn vi phng php s dng nhm lm gim xc sut nh hng ng nht
ca mt yu t no ln c hai phng php.
Bng 2.2
Lng bc tm c
Lng cn, g
g %
Bin i lng mu. C th pht hin sai s c nh bng cch phn tch nhng lng
cht khc nhau. Nhng kt qu phn tch vi gi thit, nhng lng mu hp kim khc nhau
cha chnh xc 20% bc c dn ra bng 2.2. Mi php xc nh c km theo sai s c
nh bng 2 mg v dn ti s h thp kt qu. nh hng ca sai s gim dn khi tng
lng mu.
Bng 2.3
Lng cn, g Tm c
20
g %
Ngc li, s bin i s khng cho php pht hin sai s bin i tuyn tnh. Hnh 2.2
cng minh ho nhng kt qu phn tch nhng mu khc nhau ca cng mt hp kim bng
mt phng php vi sai s bin i tuyn tnh bng 0,5%. Nhng kt qu cng c dn ra
bng 2.2. th l ng thng. R rng l, khng bit c hm lng tht ca bc trong
hp kim c tn ti loi sai s nh vy hay khng? C th l khng nhn bit c.
H m l n g A g %
S a i s b i n i
2 0 ,3
2 0 ,1 G i tr th t
1 9 ,9
S a i s c n h
1 2 3 4 5 L n g c n (g )
Hnh 2.2
nh hng ca sai s c nh v sai s bin i tuyn tnh n kt qu xc nh bc (xem bng 2.2 v 2.3)
R rng l xut pht t ci tn ca n, sai s ngu nhin xut hin l do nhng sai s
khng bit c v khng kim tra c ca php o, nhng sai s l nguyn nhn ca s
tn mn kt qu khi o lp li, nh c ch r trn hnh 2.1 v d dy th nghim th 4.
21
2.4.1 Xem xt nh hng ca sai s ngu nhin ln ng tc chun ho pipet
nh hng ca sai s ngu nhin ln ng tc chun ho pipet tng i n gin, bao
gm vic xc nh trng lng nc (vi chnh xc n miligam) chy ra t pipet c
minh ha bng 2.4.
Tuy vy, lch trung bnh khi trung bnh s hc ca 24 ln o l 0,0054 ml v bin
dao ng l 0,023 ml. S tn mn kt qu l h qu trc tip ca sai s ngu nhin.
22
C th gii thch c s khng trng lp kt qu ca nhng php o lp li
(bng 2.4) khi gi thit rng mi php o c km theo nhiu sai s khng bit c, gy ra do
s khng trng lp nhng iu kin khng c kim tra thc nghim. Hiu ng tng cng
ca nhng sai s cng l mt i lng ngu nhin. Thng sai s b tr nhau nn tc
dng ca chng l cc tiu. Nhng i khi cng cng hp vi nhau cho sai s dng hoc m
cao hn. Ngun sai s khi chun ho pipet c th l nhng sai s gn lin vi sai s kim tra
bng mt mc cht lng vch, mc thy ngn trong nhit k v ch s ca cn: nhng ngun
sai s khc bao gm s dao ng trong thi gian dc ht nc t pipet, s bin i ca gc
nghing khi nc chy, s dao ng ca nhit ph thuc vo cch cm pipet. Chc chn
rng, ngoi nhng sai s k trn cn tn ti nhiu sai s khc. R rng l, ngay c mt ng
tc gin n nh chun ho pipet cng km theo nhiu bin i khng ln khng kim tra
c. Mc d chng ta khng vch r nh hng ca mi sai s trong s nhng sai s
nhng cng c th din t hiu ng tng cng ca chng di dng sai s ngu nhin phn
nh qua s phn tn s liu quanh gi tr trung bnh.
Khc vi sai s h thng, khng th loi tr sai s ngu nhin khi php o. Ngoi ra,
nh nghin cu khng c quyn b qua chng, coi chng l nh. Chc chn l c th cng
nhn rng, gi tr trung bnh ca 24 ln o th tch c dn ra bng 2.4 gn vi th tch tht
hn so vi bt k gi tr ring bit no. Nhng chng ti gi thit rng, ngi ta tin hnh
chun ho ch hai ln v mt cch ngu nhin hai ln o ph hp vi kt qu ca th nghim 1
v 7. Gi tr trung bnh t hai gi tr bng 9,992, khc vi gi tr trung bnh ca 24 php o
l 0,010 ml. Chng ta cng nhn thy rng lch trung bnh ca hai php o khi gi tr
trung bnh ring ca chng ch l 0,0010 ml. Trn c s gi tr lch khi gi tr trung bnh
nh nh vy c th xut hin s lc quan qu ng v sai s ngu nhin. Kt cc nu xut
hin s cn thit gi kim tra gi tr th tch chy ra t pipet vi chnh xc 0,002 ml c
th ngi ta s b qua s thiu chnh xc nghim trng. Trong trng hp ny, s khng bit
gi tr tht ca sai s ngu nhin to ra cm gic gi v tin cy vo cht lng tt ca
pipet. Thc t c th ch ra rng nu s dng pipet 1000 ln th chc chn trong 2 3 trng
hp th tch cht lng chy ra s khc gi tr trung bnh bng 9,982 ml, l 0,002 ml, v hn
100 trng hp l 0,01 ml v ln hn, bt chp tt c mi bin php phng nga ca nh phn
tch.
Bng 2.5 Nhng phng php t hp c th c 4 loi sai s khc nhau U1; U2; U3 v U4
+ U1 + U2 + U3 + U4 + 4U 1
23
U1 + U2 + U3 + U4
+ U1 U2 + U3 + U4
4
+ U1 + U2 U3 + U4 + 2U
+ U1 + U2 + U3 U4
U1 U2 + U3 + U4
+ U1 + U2 U3 U4
+ U1 U2 + U3 U4
U1 + U2 U3 + U4
U1 + U2 + U3 U4 0 6
+ U1 U2 U3 + U4
+ U1 U2 U3 U4
U1 + U2 U3 U4
U1 U2 + U3 U4 4
2U
U1 U2 U3 +U4
U1 U2 U3 U4 4U 1
Nu chng ta pht trin tip theo nhng bn lun trn y cho s rt ln sai s quy m
ngy cng nh, s ng cong phn b nhn c c dn ra trn hnh 2.3c. ng cong
hnh qu chung c gi l s phn b Gauss hay phn b chun ca sai s (khi xy dng
ng cong Gauss khng cn thit phi gi thit s ng nht ca nhng sai s ring bit.
ng cong c nhng c trng:
3. Xc sut xut hin gim dn gi tr sai s ngu nhin ca php phn tch ho hc tin
ti rt gn vi ng cong phn b Gauss. V d, nu xy dng th biu din s ph thuc
tn s xut hin mi lch khi gi tr trung bnh ca hng trm php o pH ca mt mu
vo gi tr lch th thu c ng cong tin gn ti ng cong c din t trn hnh
2.3d.
(b)
Tn s y
Tn s y S ln o pH
8
20
(d)
(c)
10
Hnh 2.3
Nhng quan st thc nghim khng nh gi thit cho rng, c th hnh dung sai s ngu
nhin ca php o phn tch di dng tch ly s ln nhng sai s nh c lp v khng
kim tra c. iu quan trng l s phn b phn ln nhng d kin phn tch theo ng
cong Gauss cho php ng dng phng php thng k nh gi gii hn sai s ngu nhin
theo lp li.
25
ng c l ng cong phn b chun hoc phn b Gauss. ng d l ng phn b
thc nghim c th thu c khi t lch khi gi tr trung bnh ca khong 250 php o
pH song song trn trc honh v s php o pH tng ng vi mi lch quan st c trn
trc tung.
Thng k cho php m t ton hc nhng qu trnh ngu nhin, V d, nh hng ca sai
s ngu nhin n kt qu phn tch ho hc. Nhng iu quan trng l nhn thc rng, ch c
th m t chnh xc bng cc phng php thng k c in khi s quan st ln v hn.
Hnh 2.4
Nhng ng chun phn b sai s c xy dng i vi mt v ch mt i lng c o bng hai phng php.
Phng php 1 tin cy hn do i lng nh hn.
Phng php cho 2 5 php phn tch song song c mt nh phn tch hon thnh
th nhng kt lun v sai s ngu nhin c th c, c th mc sai lm nghim trng v qu lc
quan. Trong nhng trng hp ny cn thit phi bin dng cc phng php c in. Trc
ht phi xem xt cc loi thc t v v vy xut hin ngh dng li mt cht mt s quy
lut quan trng ca thng k c in.
Tnh cht ca ng cong phn b chun: Hai ng cong trn ca hnh 2.4 l nhng
ng cong phn b sai s chun ca hai phng php phn tch khc nhau. ng cong trn
cng phn nh nhng d kin ca phng php chnh xc hn bi v nhng kt qu c tp
hp li gn vi gi tr trung tm hn.
( x )
2
Z2
e 22 e 2
y= =
2 2
(2.2)
lch tiu chun: T phng trnh 2.2 ta thy rng, mi gi tr lch tiu chun phi
tng ng vi ng cong phn b ca mnh. Tuy vy, c th ni rng, khng ph thuc vo
i lng , 86,30% din tch nm di ng cong trong gii hn mt lch tiu chun
(1) khi gi tr trung bnh . Do 86,30% tt c mi gi tr nm trong gii hn .
Khong 95,50% tt c mi gi tr s 2 ; 99,70% gi tr 3. Nhng gi tr (x ),
27
tng ng 1, 2 v 3 c biu th bng nhng ng thng ng t on trn
nhng ng cong pha trn ca hnh 2.4. Trn ng cong pha di nhng gi tr Z mang
n v c t trn trc honh.
N
(xi )2
= i =1 (2.4)
n
Ngi ta pht hin rng, ng dng trc tip nhng phng php thng k c in cho
mt s khng ln nhng php o song song (t 2 n 20) thng dn ti kt lun sai lm v
gi tr sai s ngu nhin c th c. Rt may l ngi ta nghin cu c nhng phng
php cho php rt ra nhng kt lun tin cy v sai s ngu nhin m ch cn hai hoc ba php
o l .
N
(xi x)2
S= i =1 (2.5)
n 1
xi xi x (xi x)2
165,4.106
S= = 6,4.103 = 0,006
5 1
S= (2.6)
d
n d n d n d
Nh thc nghim s dng nhng php tnh thng k hon thin s nh gi ca mnh v
nh hng ca sai s ngu nhin. S nh gi trong gio trnh ny bao gm:
2. S php o song song cn thit trung bnh thc nghim vi mt xc sut nht nh
ri vo khong d on xung quanh gi tr trung bnh tht.
3. Gii quyt vn , trong tnh ton mu trung bnh c nn gi li hay loi tr nhng gi
tr ri ra ngoi dy kt qu song song.
4. Xc sut v vic hai mu c phn tch bng phng php tng t nhng do kt qu
khc nhau v thnh phn, ngha l s khc nhau v kt qu thc nghim gy nn bi sai s
ngu nhin hay bi s khc nhau tht s trong thnh phn.
Khong tin cy l i lng xut pht t lch tiu chun S ca phng php o, ph
thuc vo tin cy ca cc gi tr o c v t cc gi tr ny S c xc nh. Thng nh
ho hc c quyn khng nh rng gi tr thc nghim S m h tm c l gn nht vi .
Nhng trong mt s trng hp i lng S c th cha sai s ng k. Trong nhng trng
hp khong tin cy cn phi m rng.
i vi nhng php phn tch tn nhiu cng sc, cch lm m t trn y khng th
dng c trong thc t. Nhng trong trng hp nhng d kin ca nhng mu khc
nhau c th lin kt li thu c gi tr ng tin cy hn so vi gi tr S ca mu ring l.
V mt ln na phi chp nhn rng nhng nguyn nhn ca sai s ngu nhin trong phn
tch tt c cc mu l nh nhau. S chp nhn thng ng n trong iu kin l cc mu
gn nhau v thnh phn v mi mu u c phn tch trong nhng iu kin gn ging
nhau. thu c s nh gi thng nht ngi ta bnh phng lch khi gi tr trung
bnh ca mi mu sau cng cc bnh phng lch ca tt c cc mu v chia cho s bc
t do tng ng. Ly cn bc hai thng s ta thu c i lng thng nht S. Trong mi
mu mt i mt i lng t do. Do , s bc t do tnh i lng S thng nht bng s
php o tng qut tr i s mu. Di y dn ra v d v cch tnh ton .
31
V d: ngi ta xc nh thu ngn bng phng php hp th nguyn t trong cc
mu t by con c cu c h ERI. Nhng kt qu c dn ra di y. Hy tnh lch
tiu chun ca phng php theo kt qu thng nht.
Gi tr Tng s cc
S php Kt qu
S trung bnh phng
o song
mu bnh lch khi gi tr
song (hm lng Hg) n.104 %
n.104% trung bnh
xi xi x (xi x)2
1,80 0,0161
0,127
1,58 0,0087
0,093
1,64 0,0011
0,033
3 [5,02] Tng cc bnh phng = 0,0259
xi = 1,673
Khi s bc t do ln hn 20 s nh gi S c th c xem nh rt gn vi .
32
Khong tin cy khi S rt gn vi . Nh ni trc y, chiu rng ca ng
cong phn b chun sai s c xc nh bi i lng . Z cng ng vai tr tng t
trong cc phng trnh (2.2) v (2.3). Theo phng trnh (2.2) c th tnh din tch di
ng cong phn b chun sai s theo din tch chung i vi mi gi tr Z.
50 0,67 2,00
96
68 1,00 2,58
99
80 1,29 3,00
99,7
90 1,64 3,29
99,9
95 1,96
= x Z (2.7)
Z
= x (2.8)
n
Mt ln na S = 0,10.
i vi 3 php o:
0,67 0,10
= 0,67 = (1,67 0,04).104%
3
1,96 0,10
= 1,96 = (1,67 0,11).104%
3
Nh vy: Trong 50 trng hp trong s 100, gi tr trung bnh tht s nm trong khong:
(1,63 1,71).104% Hg v trong 95 trng hp trong s 100 n s nm trong khong (1,56
1,78).104% Hg.
Z
Khong tin cy = ;
n
1,96 0,0065
0,005 ml = ; n= 6,5
n
34
Nh vy, s dng gi tr trung bnh t by php o, chng ta c th thu c th
tch trung bnh tin cy chy ra t pipet vi chnh xc n 0,005 ml vi xc sut tin cy
95%.
Gii hn tin cy khi cha bit . Thng nh ho hc bt buc phi s dng nhng
phng php phn tch khng c nghin cu trc. Ngoi ra s thiu thn thi gian v s
gii hn lng mu c giao lm kh khn cho vic xc nh chnh xc i lng .
x
t= (2.9)
S
Khc vi Z trong phng trnh (2.3), t khng ch ph thuc vo xc sut tin cy cho
m cn ph thuc s bc t do trong cng thc tnh S. Ch l khi s bc t do l v hn,
gi tr t tin ti gi tr Z c dn ra bng 2.7.
C th tnh gii hn tin cy theo gi tr t khi s dng phng trnh tng t (2.8). Nh
vy:
tS
= x (2.10)
n
Gii :
4,3 0,0050
Khong tin cy xc sut 95% = 0,084 = 0,084 0,012
3
1,96 0,0050
Khong tin cy xc sut 95% = 0,084 = 0,084 0,006
3
36
R rng l, bit gi tr s thu hp khong tin cy i mt na.
Nhiu nghin cu khoa hc v k thut c thc hin kim tra gi thuyt. hiu r
bn cht nhng quan st m t m hnh l thuyt c hnh thnh cn thc hin nhng
thc nghim kim tra ng n ca n.
Thuc cc phng php kim tra loi c phng php gi thuyt khng da trn s
so snh nhng gi tr bng s ca hai i lng thc t bng nhau. Sau ngi ta nh gi
xc sut xut hin s khc nhau quan st c do sai s ngu nhin theo nhng quy lut ca
thng k. Nu s khc nhau bng hoc ln hn s khc nhau c th xut hin 5 ln trong s
100, tu thuc vo tin cy i hi ca kt lun.
Nhng nh ho hc rt hay dng cc phng php kim tra, nh so snh hai gi tr trung
bnh ca hai mu (x1 v x2); so snh gi tr trung bnh ca php phn tch x1 v i lng
c chp nhn l tht; so snh nhng lch tiu chun S1 v S2, hoc 1 v 2 ca hai dy
o v c lch tiu chun S ca mu nh v lch tiu chun ca mu ln. Trong cc
mc tip theo chng ta s xt ti nhng phng php thc hin nhng php so snh nh vy.
tS
x = (2.11)
n
Nhng x = 0,007.
C th hy vng rng 5 ln trong s 100, trung bnh tm c bng thc nghim s sai lch
0,0059 hoc ln hn. Nh vy l nu chng ta kt lun rng, 0,007 l hiu s c ngha th
trung bnh, kt lun ng trong 95 trng hp v sai trong 5 trng hp trong s 100.
So snh hai trung bnh thc nghim. Nh ho hc thng s dng nhng s liu phn tch
khng nh tnh ng nht hay khng ca hai vt liu. Trong trng hp cn phi bit,
s khc nhau ca kt qu phn tch l do sai s ngu nhin ca c hai dy o hay l do s
khc nhau tht s ca nguyn liu gy nn. thy r chng ta gi thit rng lm n1 php
phn tch song song vt liu 1 v n2 php phn tch vt liu 2. Dng phng trnh (2.10)
chng ta c th vit:
tS
1 = x1
n1
tS
2 = x 2
n2
38
y x1 v x2 l nhng trung bnh tm c bng thc nghim. khng nh,
c tn ti hay khng s khc nhau gia x1 v x2, chng ta phi a ra gi thit khng ngha
l 1 v 2 l ng nht. Sau lm cn bng hai phng trnh ta thu c:
tS tS
x1 = = x2
n1 n2
n1 + n2
x1 x2 = tS (2.12)
n1n2
Hm lng Ti, %
4,6 + 4,0
x1 = = 4,3
2
Ch rng S , bin i phng trnh (2.12) mt cch tng ng v tin hnh tnh
ton vi xc sut tin cy 95 v 99%:
39
n1 + n2 2+5
Z = 1,96 0,35 = 0,57
n1n2 25
2+5
= 2,58 0,35 = 0,76
25
n1 + n2 6+4
tS = 2,31 0,70 = 0,10%
n1n2 64
Trong v d cui cng, xc sut tin cy 95% khng pht hin c s khc nhau c ngha
ca nhng kt qu. Cn nhn xt rng, iu khng c ngha l x1 v x2 bng nhau. Cn
phi i hi c nhng bng chng khc v s ng nht ca ru vang hai thng. V thc
cht, hon ton c kh nng, mt l vang mt l vang trng.
xn xn 1
Qtn =
xmax xmin
2
7 0,51
3 0,94
8 0,47
4 0,76
9 0,44
5 0,64
10 0,41
6 0,56
a
Theo Dean R.B., Dixon W.J. Anal.Chem. 23, 636 (1951)
V d: Khi phn tch mu canxit thu c hm lng CaO (biu din bng phn trm):
55,95; 56,00; 56,04; 56,08; 56,23. Gi tr cui cng dng nh l bt thng. Nn gi hay
nn loi tr n?
1. Kim tra cn thn tt c nhng s liu lin quan n kt qu ng nghi ng xem xt,
c phi chng cho sai s th bo xut hin kt qu ny. Qun l tt nht k phng th
nghim, ghi chp chi tit tt c mi quan st l iu rt c li.
4. Nu khng c kh nng thu c nhng s liu b sung hy ng dng tiu chun Q cho
mu v trn c s gii quyt vn v s loi tr kt qu nghi ng.
Phng php nh gi sai s h thng i vi tng hoc hiu khc vi phng php nh
gi chng i vi php nhn hoc chia.
Chng ta xt mi quan h:
y=a+bc
Tr phng trnh th hai cho phng trnh th nht c th thu c sai s trong tnh ton
kt qu, ngha l:
y = a + b c (2.13)
R rng l khi cng hoc tr, sai s tuyt i ca tng hoc hiu c xc nh bng sai
s tuyt i ca cc s hng.
+ 0,50 (+ 0,02)
+ 4,10 ( 0,03)
1,97 ( 0,05)
2,63
y = a.b
y + y = (a + a)(b + b) = ab + ab + ba + ab
y = ba + ab + ab
y a b ab
= + +
y a b ab
Thnh phn th 3 trong v phi ca phng trnh thng nh hn nhiu so vi hai thnh
phn khc bi v t s l tch ca hai s nh v mu s l tch ca hai s rt ln. V ab/ab
<< (a/b+ b/b), nn:
y a b
= + (2.14)
y a b
a
y=
b
Khi :
(a + a)
y + y =
(b + b)
yb = a
yb + by + yb + yb = a + a
y a b yb
=
y a b yb
Khi :
y a b
=
y a b
ab
y=
c
y a b c
= + (2.15)
y a b c
Nh vy, khi nhn hoc chia sai s tng i ca php nhn hoc chia c xc nh
bng sai s tng i ca cc thnh phn tham gia vo kt qu c tnh ton.
Trong trng hp ny, trong tnh ton cn phi tnh sai s tng i. Nh vy:
y = 0,0104 (+ 0,0004)
45
2.7.2 Cng sai s ngu nhin
Nh chng ta nhn xt trc y, lch tiu chun tuyt i l phng php thun
li nht nh gi sai s ngu nhin ca nhng kt qu thc nghim. Khc vi sai s h
thng khng nn ghi du cho lch tiu chun bi v n c th dng hoc m vi xc sut
nh nhau, do lch tiu chun ca kt qu tnh c nm trong mt s vng.
+ 0,50 ( 0,02)
+ 4,10 ( 0,03)
1,97 ( 0,05)
2,63
(Cc s trong ngoc l lch tiu chun). Chng ta nhn xt rng nu hai sai s u l
dng v sai s th ba l m th lch tiu chun ca kt qu phi l:
Mt khc, trong nhng tnh hung bt ng sai s tng cng c th bng khng. Kt qu s
nh th nu 3 i lng u dng:
y sa; sb; sc ... l lch tiu chun tuyt i ca nhng s tham gia vo tng hoc
hiu. Chng ta nhn thy rng tn mn tuyt i ca kt qu l tng tn mn tuyt i
thnh phn. Cng c th vit phng trnh (2.16) di dng:
ab
y=
c
46
2 2 2
sy s s s
c th vit: = a + b + c (2.17)
y a b c
T : y = 2,63 ( 0,06)
Trong trng hp ny chng ta cn phi s dng lch tiu chun tng i. nh vy:
2 2 2
0,02 0,0001 0,04
(sy )td = 2 2 2
4,10 + 0,0050 + 1,97 = (0,0049) + (0,020) + (0,020) = 0,029
Do : y = 0,0104 ( 0,0003)
y=
[14,3( 0,02) 11,6( 0,2)] 50( 0,16) = 3,191 ?
42,3( 0,4)
sy = 3,191.0,10 = 0,32
y = 3,2 ( 0,3)
y = ax
dy = xa(x1)da
dy xa(x 1)da
=
y ax
nhng:
a(x 1) 1
=
x a
a
do :
dy xda
=
y a
y a
=x (2.18)
y a
48
y y l sai s tuyt i ca php xc nh y, sinh ra do sai s a trong php
xc nh a. R rng l, sai s tng i y/y ca kt qu tnh ton l sai s tng i ca gi
tr thc nghim a/a nhn vi ch s lu tha, x. V d, sai s tng i ca s bnh phng
hai ln ln hn sai s ca php xc nh chnh s , cn sai s tng i ca mt s nm
di du cn bc 3 bng mt phn ba sai s ca php xc nh s .
iu quan trng cn ch l, quy lut lan truyn sai s ngu nhin khi tng ch s bng
lu tha khc vi quy lut lan truyn sai s khi nhn bi v trong trng hp khng tn ti
kh nng gin c tng h. Chng ta nh li rng, lch tiu chun ca hai s v c th
tnh gi tr xc sut bng cch ly cn bc hai ca tng bnh phng sai s chng ta p dng
phng php cho php nhn mt s vi chnh n (a.a). y du tt nhin l ng nht
bi v chnh nhng i lng ny l ng nht. Do sai s tng i ca php xc nh a2
phi bng hai ln sai s xc nh a. Phng trnh (2.18) cng c dng tnh sai s ngu
nhin; khi ta thay th y v a bng sy v sa.
V d 1: lch tiu chun khi o ng knh d ca qu cu bng 0,2 cm. lch tiu
chun bng bao nhiu khi tnh th tch qu cu, nu d = 10,0 cm?
3
4 10
V= = 523, 6 cm3
3 2
C th vit:
s
(sy )td = Vy = 3sdd = 3 0,2
10
= 0,06
sy = 523,6.0,06 = 31
Do :
0,4 108
(sx )td =
4,0 108
49
sy = 2,0.104.0,05 = 0,1.104
y = loga = 0,434.lna
da
dy = 0,434
a
a
y = 0,434 (2.19)
a
Gii:
a) Theo phng trnh (2.19) chng ta thy rng cn nhn lch tiu chun tng i vi
0,434, ngha l:
0,02.103
y = 0,434 = 0,004 = s y
2,00.103
50
Nh vy:
b) Bin i phng trnh (2.19) v thay th a v y bng lch tiu chun tng ng:
sa sy 0,003
= = = 0,0069
a 0,434 0,434
Nh vy:
c)
sa 0,3
= = 0,69
a 0,434
Do :
Khi nhn hoc chia cc s liu ngi ta thng chp nhn quy tc ly s ch s c ngha
ca kt qu bng s ch s c ngha ca i lng cha s ch s c ngha nh nht. V d:
52
24 0,452
= 0,108 = 0,11
100,0
0,5/24 =
> 0,5 0,108.0,02 = 0,002 0,108
0,02
<5 0,108.0,2 =0,02 0,11
5/24 = 0,2
Cn phi thn trng c bit khi lm trn logarit v antilogarit n s c ngha thch hp.
Chng ta ch ti v d dn ra trn v s lan truyn sai s php tnh logarit v
antilogarit; s lm trn tng ng ca i lng log2,00.103 dn ti kt qu 2,699. Th ra
php tnh lm tng ch s c ngha. Nhng thc cht ch s th ba xut pht t kt qu ch
ch r v tr ca du phy trong s xut pht. Thng tin v s 2,00 cho 3 ch s: 0,699. Nh
vy c s tng ng gia s ch s c ngha ca phn ca kt qu v ch s xut pht.
Khi s dng nhng phng php phn tch gii quyt nhng vn phc tp ca thc
t th cht lng ca nhng kt qu thu c bng nhng phng php ny cng nh ca
nhng dng c v thit b c s dng hon thnh cc php o cn phi c nh gi
lin tc. Chng ta thng gp 3 thut ng trong bn lun v cht lng ca php o: bo him
cht lng, kim tra cht lng v nh gi cht lng. Ba thut ng ny c Taylor nh
ngha trong bi vit ca mnh v ti cht lng ca php o nh sau:
Kim tra cht lng (QC): Nhng hot ng ca mt h thng t chc nhm kim tra
cht lng mt sn phm hoc mt dch v theo yu cu ca ngi tiu dng. C th l lm
h mn nguyn mt cch y v ng tin cy.
53
nh gi cht lng: Nhng hot ng ca mt h thng t chc m bo rng cng
vic kim tra c thc hin c hiu qu. Cng vic khng nh s nh gi tip theo l
nhng sn phm c sn xut v s thc hin ca c s sn xut c chp nhn.
Biu kim tra l th din t s bin i lin tc theo thi gian hoc trong a im
ca mt tiu chun cht lng no c trng v quan trng trong bo him cht lng.
Biu cn ch r gii hn thng k ca dao ng, l s chp nhn i vi mt php o
c th c thc hin.
Biu kim tra gim st chc nng thc hin ca mt thit b phn tch
3
GKT = +
N
3
GKD =
N
Ngoi lch chun ni trn, cn ghi ch thm rng, GKT v GKD cng l lch
chun trn mt kha cnh khc ca gi tr trung bnh, chng to thnh mt hnh lang thch hp
m trng lng a o c, hy vng nm trong khun kh ti 99,7% thi gian.
55
Hnh 2.5. Biu kim tra mt cn phn tch hin i
Hnh 2.5 l biu kim tra in hnh i vi mt cn phn tch. xy dng biu
ny, chng ti tp trung nhng s liu v trng lng o trong 20 ngy lin tc mt trng
lng chun 20,000 g do Vin Tiu chun v K thut Quc gia cung cp. thu c cc s
liu, cn c a v gi tr 0, trng lng chun c t trn a cn v trng
lng c xc nh. Ton b qu trnh c lp li 4 ln v mi ngy o li 5 ln. T
nhng thc nghim c lp, ngi ta xc nh c gi tr trung bnh = 20,000 g v
lch chun = 0,00012 g, gi tr trung bnh ca nm php o l 3.0,00012 5 = 0,00016 nn
GKT = 20,00016 g v GKD = 19,99984 g. Vi nhng gi tr v gi tr trung bnh trng
lng ca mi ngy chng ta xy dng c biu kim tra c dn ra trn hnh 2.5.
Ghi ch, gi tr trung bnh trng lng ca mi ngy c din t trn th bng mt
chm en. Theo cch , bt k mt xu hng c tnh cht h thng no trong cc php o
cng c th d dng pht hin. V trung bnh trng lng ca mu gia GKD v GKT nn cn
phn tch c coi l qua kim tra thng k. Khi gi tr trung bnh mu nm ngoi gii hn
nh xy ra trong ngy th 17, cn phn tch c coi l khng qua c kim tra. Khi mt
thit b hoc mt h thng thit b khng qua c kim tra, lc chng ta s phi c gng
tm ra nguyn nhn cho tnh hung . V d nh, trong trng hp ca ngy th 17, cn
c pht hin l khng c sch do a cn b bn v cc bc s phi thc hin m
bo s vic s khng ti din. Nhng lch c h thng do gi tr trung bnh s c pht
hin tng i d dng trn biu kim tra trong v d tip theo.
Biu kim tra trn hnh 2.6 ch r, nhng kt qu phn tch 89 sn phm thng qua
nhng php o kem cha 10% benzoyl peoxit danh nh trong nhng ngy lin tip. Mi mu
l mt i din tng trng bng gi tr trung bnh phn trm benzoyl peoxit khc nhau ca
kem thu c t nhng iu kin rt c th d thc hin.
56
Hnh 2.6
S dng biu kim tra gim st nng benzoyl peoxit trong pha ch thuc chng mn da bn
th trng
Biu kim tra cho bit, cho n ngy th 83, qua kim tra thng k vi s thay i
ngu nhin bnh thng v lng benzoyl peoxit, ngha l nm trong vng gia GKD v
GKT. Trc ngy th 83 ch c kt qu ca ngy th 26 lch khi gi tr trung bnh nng
9,94% v tin st ti gii hn kim tra vi s tng h thng t bin cao hn gii hn kim tra
trn. S tng l do iu kin c th ca sn xut gy nn, ch b loi tr khi nguyn nhn
c pht hin v t chc sa sai. Mu ny gn b vi v d v cn phn tch ni trn y,
ch r, s dng biu kim tra thun li ra sao v nhng bin php hu hiu c thc hin
bo him cht lng nhng s liu nhng tnh hung khc nhau.
*
K.Taylor, Quality Assurance of Chemical Measurements. Chelsea, MI: Lewis,1987.
57
Chng 3
G = n i i (3.1)
ni : s mol ca cht i.
T phng trnh trn, ch s hng s cn bng ca phn ng, pK, c s dng nh tiu
chun trc tip cho trng thi cn bng.
58
M
pK = l o g K = Go ;(M = log e) (3.3)
RT
a cnC a d n D
pK a = lo g (3.5)
a A n A a Bn B
a
lim =1 (3.6)
c0 c
a
Nu nng chung c ca tt c cc cht tan tin ti khng th h s hot f = t ti
c
gi tr gii hn, bng n v v hot bng nng phn t a = c. Cc cht tan dng phn
t tng tc yu vi cc ht khc trong h d mang hoc khng mang in tch. Nu nng
ca chng khng qu cao, ngi ta chp nhn f = 1 trong tnh ton. Mt cch tng t, hot
ca cht kh xp x p xut ring phn p ca n. Nu p sut chung ca hn hp kh tin
ti khng thng c th xem a = p.
Khng c kh nng xem xt ring bit h s hot ca anion (f) v cation (f+) nn
ngi ta s dng hot trung bnh (f). i vi cht in li loi AmBn, gi tr f c tnh
theo cng thc sau:
m +n m
f = f fn (3.7)
1
=
2
Z2ici (3.8)
59
Zi v ci l in tch v nng tng ng ca ion i.
Trong dung dch nc c < 0,01 20oC, c th tnh h s hot theo cng thc
Debye Huckel:
lc ion cao hn, cc cht in li khc nhau biu din nhng sai lch c bit. = 0,1
c th xc nh h s hot tin cy theo cng thc:
lo g fi = 0,5Z2i (3.10)
1+
CcnC Cd nD fcnC fd nD
pK a = l o g log (3.11)
CA n A CBnB fA n A fBnB
Ch s cn bng nng :
CcnC Cdn D
pK c = log (3.12)
CA n A CBnB
pK c = pK a + 0,5(Z A 2 + ZB2 ZC2 ZD2 ) (3.13)
1+
H 1 1
pK1 pK 2 = (3.16)
4,573 T2 T1
G = H TS (3.17)
G
= S (3.18)
T p
1. Phn ng phi hp thc. Nu ngc li s khng c c s tnh ton lng cht sinh
ra trong phn ng.
2. Phn ng phi xy ra nhanh. Nu khng nhanh, thi gian cn thit hon thnh
php phn tch s qu di. Tnh cht c bit quan trng trong cc quy trnh chun ,
bi v phn ng phi hon ton sau mi ln thm cht chun.
3. Phn ng phi nh lng. Ngha l phn ng phi t hon ton t nht l 99,9%.
Phn ng sinh ra 2 sn phm brom ho khc nhau. T s theo lng ca hai sn phm c
th bin i tu thuc vo mi trng thc nghim nhng t s 1 : 1 ca 1,3-butaien
v Br2 c s dng trong phn ng lun l mt hng s. Do c th tnh lng butaien
trong mu.
Tc phn ng
Nhiu phn ng khc ko di hng pht, hng gi, hng ngy. a s phn ng hu c
thng chm, c th ko di hng tun, hng thng. Nhng qu trnh trong v qu t c th
ko di hng vn, hng triu nm .
S nh gi nh lng trng thi cn bng qua Kc cho php bit c phn ng ho hc,
v nguyn tc c c xy ra hay khng nhng s nh gi khng cho mt thng tin no v
tc t ti cn bng. Cng khng cho bit nhng qu trnh nhit ng no s xut hin.
62
Khi nh gi kh nng xy ra phn ng cng nh khi m t trng thi cn bng
hot (ch khng phi l nng phn t) mi c ngha quyt nh. Nu h l tp hp cc
phn t th trong phn ln cc trng hp ngi ta chp nhn a c.
1 dCi 1 dC j
V= = (3.19)
n i dt n j dt
trong : i l cht tham gia vo phn ng thun; j l cht tham gia vo phn ng nghch; n
l h s hp thc.
dCA
= k CA n A CBnB k ' CCnC CDnD (3.20)
dt
dCA
= k CA n
dt
Phn ln cc phn ng xy ra theo tng nc. Quy lut thc nghim v bc phn ng t n
khng cho ta mt thng tin no v c ch phn ng .
Nu nhng cht tham gia phn ng tham d vo nhng chuyn ho khc nhau c kh
nng v mt nhit ng lm xy ra trong h ng thi nhng phn ng khng ph thuc ln
63
nhau th nhng phng trnh phn ng tr nn phc tp. Hng s tc ca mt phn ng
xc nh khng bin i do s xy ra cc phn ng song song khc. Nhng s bin i nng
cc cht phn ng do s xy ra cc phn ng khc c phn nh ln tc ca phn ng
song song.
Khi tng nhit , tc phn ng thng tng tun theo phng trnh Arrhenius:
d ln K E
= A (3.21)
dT RT2
hoc:
EA
ln K = + ln A
RT
ngha ca tc phn ng i vi ha hc
Nhng phn ng cng hng thng l ngun sai s rt ng tic, i khi c th chuyn
ho thnh nhng phn ng nh lng c li. Ch c th s dng c nhng phn ng loi
ny bng cch nghin cu ton din hiu c ch ca chng.
65
Chng 4
4.1 Mt s lun im c s
Phn ln nhng php nh lng c thc hin trong dung dch. Do , i tng ca
ho phn tch bao hm l thuyt v dung dch. Tng quan v nhng lun im c bn ca l
thuyt v dung dch c trnh by trong chng ny v cc chng tip theo.
4.1.1.1 Cc cht in li
Cht in li l nhng cht ion ho trong dung mi to thnh mi trng dn in. Cht
in li mnh ion ho hon ton, nhng cht in li yu ch ion ho mt phn. Nhng cht in
li mnh v yu in hnh c dn ra bng 4.1.
Nhiu dung mi in hnh l nhng cht in li yu, nhng phn t ca chng phn ng
vi nhau to thnh nhng ion (qu trnh c gi l qu trnh proton phn). Chng ta dn
ra mt s v d:
2H2O H3O+ + OH
HCOOH2+ + HCOO
2HCOOH
nhn mnh bn cao ca proton hirat ho n gin, khi vit phng trnh phn ng
vi s tham ra ca proton nhiu nh ho hc s dng k hiu H3O+. cho tin li nhng
ngi khc li k hiu proton bng biu tng H+ khng k ti mc hirat ho tht s ca n.
K hiu n gin ho vic vit phng trnh phn ng c proton tham gia.
67
4.1.2 Tnh cht axit - baz trong cc dung mi khc nhau
S phn loi mang tnh lch s cc cht thnh axit v baz c hnh thnh trn c s
nhng tnh cht c trng ca cc dung dch nc ca nhng hp cht y. S hin mu
hoc mu xanh ca qu, mi v xc ca dung dch axit long, v ng v tnh x phng ca
cc dung dch baz, s to mui khi tng tc axit vi kim l nhng tnh cht in hnh .
Cui th k 19, Arrhenius ngh mt cch phn loi cht ch. ng nh ngha axit l
cht cha hiro v phn li trong nc thnh ion hiro v anion; cn baz l hp cht cha
nhm hiroxyl, cho ion hiroxyl v cation khi ho tan trong nc. Khi nim rt b ch
cho php hnh thnh nhng c s nh lng ca thuyt axit - baz. C th nh gi cng
axit - baz theo mc phn li ca chng trong dung dch nc. Ngoi ra, thuyt Arrhenius
t c s cho s m t ton hc cn bng thit lp do kt qu tng tc ca axit v baz.
Cn nhn mnh rng, nhng tnh cht axit ca mt cht bt k no ch th hin khi c
mt cht nhn proton v tng t nh vy, mt cht ch th hin tnh baz khi c mt cht cho
proton.
Theo thuyt Bronsted - Lowry, c th din t phn ng trung ho bng phng trnh sau:
C2H3 O2 + H3O
+
HC2H3O2 + H2O
Mc tng tc ca axit tan (hoc baz) vi dung mi, thc cht tu thuc vo kh
nng cho hoc nhn proton ca n. V d, axit pecloric, clohiric, bromhiric trong dung
dch nc thuc loi axit mnh. Nu ly axit axetic (bng axit axetic tinh khit 100%,
thng c gi l axit axetic bng; n c kt tinh 16,7oC dng bng; lng nh tp
cht ca nc lm h im ng bng xung r rt) lm dung mi thay cho nc, l cht
nhn proton yu hn th ch c axit pecloric phn li hon ton trong n thnh ion v l axit
mnh. Qu trnh phn li c th din t bng phng trnh:
Cc axit clohiric, bromhiric trong axit axetic bng ch phn li mt phn v l cc axit
yu.
Theo thuyt ca Bronsted - Lowry, nhng cht cho proton mnh nht (ngha l nhng
axit mnh nht) cho proton to thnh nhng cht nhn proton yu nht (nhng baz lin
hp yu nht). Tr li phn ng ca axit clohiric, axit axetic v ion amoni vi nc, ta thy
rng ion clorua l baz yu nht, ion axetat l baz mnh hn, cn amoniac l baz mnh
nht.
L thuyt tng qut v dung dch bao hm khng ch cc cht c kh nng cho hoc nhn
proton (axit v baz theo Bronsted - Lowry), m cn c m rng cho c nhng hp cht
khng nht thit phi cha proton. ng dng cho nhng h nh th, l thuyt proton phn t
ra c bit c ch. Trong trng hp ny, axit l cht bt k hoc l c cha trong thnh phn
ca mnh cation c trng i vi mt dung mi nht nh hoc l phn ng vi dung mi
to thnh ion . Mt cch tng t, baz l cht cho anion c trng i vi dung mi
cho.
4.2 Phng php tnh nng cc cht trong nhng dung dch cn bng
n gin
V d, chng ta xt cn bng:
C hai phng php bin th hng s cn bng: cch biu th chnh xc (c gi l cch
biu th nhit ng hc) v cch biu th gn ng, ch ng trong iu kin rt gii hn.
71
Nhng nhng hng s gn ng li c ng dng rng ri bi v s dng chng rt n gin,
mc d c kh nng phm sai s.
Khi rt ra h thc gn ng cho hng s cn bng, ngi ta gi thit rng nng ca ion
hoc phn t l yu t ng nht th hin nh hng ca chng n trng thi cn bng, ngha
l mi ht x s mt cch c lp vi ht bn cnh. V d, trong phn ng (4.1) ngi ta gi
thit rng, nh hng ca mi ion st (III) n trng thi cn bng l ng nht trong nhng
dung dch rt long (khi m ion ch yu b bao quanh bi phn t nc trung ho) v c trong
nhng dung dch rt c (khi m ngay st ion c nhng ht tch in khc). Dung dch hoc
kh c nhng ion hoc phn t x s mt cch c lp i vi nhau c gi l dung dch l
tng hoc dung dch tht. Dung dch l tng v tnh cht l tng rt t gp trong thc t.
mM + nN pP + qQ (4.3)
y nhng ch hoa k hiu cc cht tham gia phn ng, cn nhng ch thng l h s
hp thc. Phng trnh ch r rng m mol cht M phn ng vi n mol cht N to thnh p mol
cht P v q mol cht Q. Hng s cn bng ca phn ng ny c biu din nh sau:
K=
[P ]p [Q ]q (4.4)
[ M]m [N ]n
y du ngoc vung l k hiu biu din nng phn t ca cc cht tan hoc p sut
ring phn trong kh quyn nu cht phn ng l kh.
Nng P, mol/l
[P] =
1, 00 mol/l
72
mu s l nng cht tan trng thi chun. H qu quan trng ca tnh
tng i ca [P] l tnh khng th nguyn ca i lng ny cng nh ca hng s cn bng.
Phng trnh (4.4) c th d dng rt ra t nhng khi nim nhit ng hc vi gi thit l cc
cu t ca phn ng l l tng .
Hng s cn bng nhit ng, phng trnh (4.4), c s dng xc nh thnh phn
gn ng ca cc dung dch long trng thi cn bng. nh gi chnh xc hn cn phi
s dng hng s nhit ng (hng s nhit ng c xt ti chng 5). Nhng tnh ton
theo cc hng s gn ng khng phc tp v trong nhiu trng hp cho cc nh khoa hc
thng tin kh v h.
Trong mc ny chng ta s xt nhng loi cn bng thng gp nht trong ho phn tch
v nu ln nhng c im ca nhng hng s tng ng .
4.2.4.1 S phn li ca nc
hnh dung hng s cn bng ca phn ng ny, chng ta s dng phng trnh (4.4):
H3 O+ OH
K=
[H2O]
Trong cc dung dch long trong nc, nng nc rt ln so vi cht tan nn c th
xem l hng nh. V d, nu cho 0,1 mol hiro clorua sc qua mt lt nc [1000 g : 18
g/mol = 55,6 mol H2O], cn bng (4.5) chuyn v bn tri v s mol nc khng phn li tng
t 55,6 n 55,7; nh vy, nu nng axit clohiric khng qu ln, nng nc r rng
khng bin i. Do , [H2O] trong phng trnh (4.5), trong phn ln trng hp c th xem
l i lng hng nh; khi c th vit:
Bng 4.1
Nhit , oC K H2O
0 0,114.1014
25 1,010.1014
50 5,470.1014
100 49,000.1014
V d: Tnh nng ion hiro v ion hiroxyl trong nc nguyn cht 25oC v 100oC.
[H3O +] = [OH]
V d: Tnh nng ion hiro v ion hiroxyl trong dung dch NaOH 0,200M trong nc.
khng dn n sai s ng k.
AgCl(r) AgCl(n)
AgCl(n) Ag+ + Cl
y, AgCl(n) l nhng phn t khng phn li trong dung dch. C th din t hng s
cn bng ca qu trnh u tin nh sau:
[ AgCl ]n
K= (4.7)
[ AgCl ]r
T phng trnh (4.8) r rng l nng AgCl trong dung dch bo ho l khng i
mt nhit nht nh.
Ag + Cl
K1 = (4.9)
[ AgCl ]n
AgCl(r) Ag+ + Cl
75
Cn nhc mt iu rt quan trng l, cc phng trnh (4.8) v (4.10) ch dng c cho
cc dung dch bo ho nm cn bng vi cht rn d khng tan.
Phn ln cc mui v c t tan, thc t phn li hon ton trong cc dung dch nc, do
so vi nng ca cc ion, nng ca cc phn t khng phn li gn bng khng (1). iu
kin , phn ng tng cng m t mt cch thch hp nht cn bng ca phn ng ho tan.
Do nguyn nhn ny nn i vi phn ln cc cht v c, trong cc ti liu ch dn ra mt
hng s (tch s tan) (xem mc lc). V d, khng c c s cho rng trong dung dch bo
ho bari ioat c Ba(IO3)2 hoc BaIO3+ khng phn li. Do , cn bng:
[Ba2+][ IO3 ]2 = T
V d 1: C th ho tan bao nhiu gam bari ioat trong 500 ml nc 25oC? Cho bit tch
s tan ca Ba(IO3)2 bng 1,57.109.
[Ba2+][IO3]2 = 1,57.109 = T
T phng trnh m t cn bng, mi mol Ba(IO3)2 tan, phn li to thnh mt mol Ba2+,
ngha l:
[ IO3 ] = 2[Ba2+]
Thay nng ioat bng nng Ba2+ vo phng trnh hng s cn bng ta c:
[Ba2+](2[Ba2+])2 = 1,57.109
tan = 7,3.104 M
(1)
Quan im ny rt ph bin, tuy nhin khng phi lc no cng ng. C nhiu mui t tan v t phn li. Trong s , v
d c dy sunfua.
76
bit c tan ca Ba(IO3)2 tnh bng gam trong 500 ml, ta vit:
1
tan ca Ba(IO3)2 = [ IO3 ]
2
Ba(NO3)2 v Ba(IO3)2 cng sinh ra ion bari trong dung dch. Phn ng gp ca cht th
1
nht l 0,02M, cn phn ng gp ca cht th hai bng tan phn t hoc bng [ IO3 ].
2
1
[Ba2+] = 0,02M + [ IO3 ]
2
1
(0,02 + [ IO3 ]) [ IO3 ] = 1,57.109
2
Gi thit rng:
1
[0,02 + .2,8.104 ] 0,02
2
77
khng dn ti sai lm nghim trng, bi v thnh phn th hai ch bng khong 0,7% ca
0,02. Thng gi thit loi ny c th c coi nh l ng n nu s khc bit nh hn 5
10%. Vy:
1 1
tan ca Ba(IO3)2 = [ IO3 ] = .2,8.104 = 1,4.104 M
2 2
V d 3: Ly mt v d khc phc tp hn, tnh tan ca Ba(IO3)2 trong dung dch thu
c bng cch trn 200 ml dung dch Ba(NO3)2 0,01M vi 100 ml dung dch NaIO3 0,1M.
[ IO3 ] 0,02
C th nhn c li gii s b:
T 1,57.109
tan ca Ba(IO3)2 = [Ba2+] = 2
= 2
= 3,9.106
IO3 0,02
H3 O+ NO2
Ka =
[HNO2 ]
y Ka l hng s phn li axit ca axit nitr. Hng s phn li baz ca amoniac c
biu din tng t:
NH4+ + OH
NH3 + H2O
NH4 + OH
Kb =
[ 3]
NH
Ta nhn thy rng, nng nc khng tham gia vo mt phng trnh no trong s cc
phng trnh trn. Cng nh i vi tch s ion nc, ngi ta chp nhn rng nng dung
mi l i lng ln v hng nh, do bao gm hm trong hng s cn bng Ka v Kb .
Quan h gia hng s phn li ca mt cp axit - baz lin hp. Chng ta xt biu thc
hng s phn li ca amoniac v axit lin hp ca n l ion amoni. C th vit:
NH4 + OH
Kb =
[NH3 ]
NH4+ + H2O NH3 + H3O+
[NH3 ] H3O+
Ka =
NH4 +
Bi v:
ng dng ca hng s phn li axit. Hng s phn li ca nhiu axit yu ph bin nht
c dn ra ph lc IV.
Nhng hng s ny c s dng ph bin tnh nng ion hiro v hiroxyl trong
dung dch ca cc axit v baz yu.
HA + H2O H3O+ + A
A H3 O+
Ka =
[HA ]
Ngoi ra ion hiro cn phn li t nc:
2H2O H3O+ + OH
Ngoi ra, tng nng phn t ca axit yu v baz lin hp ca n phi bng nng
ca phn t axit ban u bi v trong dung dch khng c cc cht khc cho A. Do :
Nu thay th [A] v [HA] bng cc biu thc ca chng t cc phng trnh (4.12) v
(4.14) th hng s phn li axit c dng:
80
2
H O+
Ka = 3 (4.15)
CHA H3O+
K a + (K a + 4K aCHA
H3 O+ = (4.16)
2
V d: Hy tnh nng ion hiro trong dung dch axit nitr 0,12 M trong nc. Cn
bng c bn trong dung dch:
Trong ph lc IV ta tm thy:
H3 O+ NO2
Ka = = 5,1.104
[HNO2 ]
T :
2
H3 O+
= 5,1.104
+
0,12 H3O
Bng 4.2 Sai s gy ra do gi thit cho rng H3O+ nh so vi CHA khi s dng phng
trnh (4.15)
V d: Tnh nng ion hiro trong dung dch hiroclorua anilin C6H5NH3Cl 2,0.104 M.
Trong dung dch nc, hp cht phn li hon ton ra Cl v C6H5NH3+ . Axit yu
C6 H5 NH3+ phn li nh sau:
Kb = 3,94.1010
1,00.1014
Ka = = 2,54.105
10
3,94.10
Lm nh trong v d trc:
83
[H3O+] = [C6H5NH2]
So snh nhng i lng 7,1.105 v 2,0.104 ta thy rng, khi tnh [H3O+] ta b qua
sai s ln (s dng hnh 4.1 ta tm thy sai s ln hn 20%). Sai s ln n nh vy nn phi
s dng phng trnh chnh xc hn.
2
H3 O+
= 2,54.105
2,0.104
Gii ra ta thu c:
5 5 2 9
H3 O+ = 2,54.10 + (2,54.10 ) + 4 5,08.10
2
ng dng hng s phn li ca baz yu. Nhng tnh ton dn ra trong cc phn trc
c th d dng vn dng tnh nng ion hiroxyl trong cc dung dch baz yu.
D dng ch ra rng, ht chim u th trong dung dch l NH3. Hn na, i khi ngi ta
gi nhng dung dch l dung dch hiroxit amoni theo thut ng cn c cng nhn cho
n khi NH4OH cn c coi l dng cha phn li ca baz ch khng phi l NH3. Theo
nh lut tc dng khi lng:
NH4 + OH
Kb =
[NH3 ]
84
Gi tr hng s cn bng tan khng ph thuc vo cng thc ca hp cht mu
s, l NH3 cng thc ng hn hay NH4OH l cng thc dng trc y.
NH4 + OH
= 1,76.105
[NH3 ]
T phng trnh phn li trn:
[NH4+] = [OH]
[OH]2 (7,5.102)(1,76.105)
V d: Tnh nng ion hiroxyl trong dung dch hippoclorit natri 0,01M.
c th vit:
85
[HOCl ] OH
Kb =
OCl
K n 1,00.1014
Kb = = = 3,3.107
Ka 8
3,0.10
[OH] = [HOCl]
nn:
Gi thit rng [OH] << 0,01 mol/l v thay vo phng trnh hng s cn bng ta c:
2
OH
= 3,3.107
0,01
4.2.4.4 S to phc
Phn ng to phc ca cc ion phc tan l loi phn ng phn tch quan trng. Chng ta
dn ra hai v d:
Fe(SCN)2+
K=
Fe3 + SCN
3+
1 Fe SCN
K kb = =
K Fe(SCN)2+
K = 1,4.102
ngha l:
FeSCN2+
= 1,4.102
Fe SCN
3 +
1mg 1 1
CFe3+ = = = = 1,8.105 M
1 1000mg/g 55,8g/trng lng mol
iu kin gii hn pht hin ca phc [FeSCN2+] = 6.106 M. trng thi cn bng, st
(III) hai trng thi: Fe3+ v FeSCN2+. Do :
5 3+ 2+
CFe3 + = 1,8.10 M = [Fe ] + [FeSCN ]
6.106
= 1,4.102 [SCN ] = 0,0036M
5
1,2.10 SCN
C th biu din hng s cn bng ca phn ng oxi ho kh bng phng php thng
thng. V d:
6 2
Fe3+ Cr3 +
K=
6 14
Fe2+ Cr2O72 H3 O+
Nh trc y chng ta nhn xt, nng nc khng tham gia vo phng trnh. Ni
chung, cc bng hng s cn bng ca cc phn ng oxi ho kh khng c thit lp bi v
d dng thu c cc hng s ny t cc hng s c bn hn l th in cc tiu chun.
Nhng tnh ton chi tit s c xt ti trong chng 13.
Cn mt dng cn bng na c s dng trong phn tch l s phn b cht gia hai
tng lng. V d, nu ta ly dung dch it trong nc vi mt dung mi hu c khng ho
tan trong nc nh hexan hoc clorofom th mt phn iot c chit vo lp hu c. Cui
cng cn bng c thit lp gia hai tng v c th hnh dung cn bng nh sau:
[I2 ]hc
I2 (n) I2 (hc) ; K=
[I2 ]n
Nhiu cht in li yu lin hp hoc phn li tng nc, c th vit hng s cn bng i
vi mi nc. V d, nu thm amoniac vo dung dch ca ion bc th cui cng hai cn bng
c thit lp, Ag+ v NH3 tham gia vo cc cn bng sau:
88
Ag+ + NH3 AgNH3+
AgNH3+
K1 =
Ag [NH3 ]
+
Ag(NH3 )2+
K2 =
AgNH3 [NH3 ]
+
Ag(NH3 )2+
2 = K1K 2 =
Ag [NH3 ]2
+
Cd(CN)3
3 = K1K 2K 3 =
3
Cd2+ CN
Cd(CN)24
4 = K1K 2K 3K 4 =
4
Cd2+ CN
Nhiu axit v baz rt quen bit, phn li tng nc. V d, trong dung dch axit photphoric
tn ti nhng cn bng sau y:
H2PO4 + H3O
+
H3PO4 + H2O
89
H3O+ H2PO4
K1 = = 7,11.103
[ 3 4]
H PO
H3 O+ HPO42
K2 = = 6,34.108
H2PO4
H3O+ PO34
K3 = = 4,2.1013
HPO24
Chng 5
tan ca kt ta
Nhng phn ng to nhng hp cht t tan c nhiu ng dng rng ri trong ba qu trnh
ho phn tch quan trng:
3. Trong phng php phn tch chun da trn s o th tch ca dung dch thuc th
chun tiu tn cho s kt ta nh lng cu t cn xc nh.
2HF + 2H2O
+
Ag(NH3)2
Nhng phn t amoniac lm h thp nng ion bc trong dung dch. Do cn bng ca phn
ng ho tan chuyn dch v pha phi nn tan ca bromua bc tng ln.
AB (rn) A + B
+ +
C D
AC BD
Khi m t nhng cn bng phc tp cn phi lun bit rng gi tr v dng din t hng s
ca mt cn bng cho, bng bt c cch no cng khng ph thuc vo s xy ra trong
dung dch nhng phn ng cnh tranh ph. Nh trong v d ta ang xt, tch s tan AB m t
h thc gia nhng nng cn bng A v B v khng ph thuc vo vic trong dung dch c
hay khng c nhng ion C v D. Ni cch khc, nhit khng i trong dung dch bo ho
AB, tch s [A][B] l mt i lng hng nh. Tt nhin l khi c mt C hoc D, lng AB b
ho tan tng ln nhng iu xy ra khng phi do s bin i tch s ion [A][B], m do s
chuyn mt phn kt ta thnh AC v BD.
3. Vit cc biu thc cho hng s cn bng ca tt c cc phn ng vit (im 1). Tm
cc gi tr hng s cn bng trong cc bng tng ng.
5. Vit phng trnh trung ho in. Trong mt dung dch bt k, tng s in tch dng
ca cation phi bng tng s in tch m ca anion, ngha l trung ho in. Nhng h thc
c din t bng phng trnh trung ho in (1).
(1)
Chng ta xt dung dch thu c bng cch ho tan NaCl trong nc. V ton cc, in tch ca dung
dch bng khng mc d rng trong dung dch c cc ion tch in dng v m. iu kin trung ha in
+ +
cn c thc hin trc tip t h thc: [Na ] + [H3O ] = [Cl ] + [OH ]. Dung dch NaCl trung ha, bi v
tng nng cc ht tch in dng bng tng nng cc ht tch in m. By gi chng ta xt dung dch
2+ +
nc MgCl2. i vi dung dch ny cn phi vit: 2[Mg ] + [H3O ] = [Cl ] + [OH ]. tnh in tch ion
bng hai, chng ta nhn nng ca ion magie vi 2. Cn bng in tch s c tun theo bi v nng
2+
ca ion clorua gp i nng ca ion magie ([Cl ]=2[Mg ]). Theo nguyn nhn y, nng ca ion 3 in
tch c nhn vi 3. V d, i vi dung dch cha Al2(SO4)3, MgCl2 trong nc ta c phng trnh trung
ha in nh sau:
93
6. m s n s trong cc phng trnh c thit lp theo cc im 3, 4, 5 v so snh n
s vi s phng trnh c lp. Nu s n s v s phng trnh bng nhau th c th gii
bi tp mt cch chnh xc nh nhng php tnh i s tng ng. Nu s phng trnh t hn
s n th hy th c gng thit lp nhng phng trnh c lp ph. Nu nh khng lm c
iu th cn phi tha nhn rng khng th gii chnh xc c, nhng c th gii gn
ng.
8. Gii nhng phng trnh i s tng i theo nhng nng cn bng cn phi xc
nh (im 2).
tan ca nhiu kt ta c ngha quan trng trong phn tch nh lng, ph thuc
trc ht vo nng ion hiro trong dung dch. Trong phn t ca nhng kt ta cha
hoc anion c tnh baz, hoc cation c tnh axit, hoc ng thi c hai. Baz tham gia vo
thnh phn canxi florua l ion florua, phn ng vi ion hiro to thnh axit flohiric. Do
tan ca florua canxi tng ln khi axit ho. Chng ta ly bismut ioua lm v d v hp cht
trong thnh phn c cation c tnh axit tham gia. Trong dung dch bo ho BiI3 cn bng sau
c thit lp:
Chng ta nhn thy rng, khc vi tan ca canxi florua, tan ca bismut ioua gim
khi axit tng.
3+ 2+ + +
3[Al ] + 2[Mg ] + [H3O ] = 2[SO4 ] + [HSO4 ] + [Cl ] + [OH ]
94
5.2.1 Tnh tan nng ion hiro bit
Trong thc t phn tch thng cn phi kt ta nng ion hiro xc nh cho sn.
Chng ta minh ha php tnh tan trong nhng iu kin nhng v d sau y.
V H2C2O4 l axit yu, nhng ion oxalat lin kt mt phn vi ion hiro c thm vo
to axit nu trn.
HC2O4 + H3O
+
H2C2O4 + H2O (5.3)
D dng hnh dung phng trnh (5.2) nh phn ng phn li ca HC2O4 . Do lin
h gia [ C2O24 ] v [ HC2O4 ] c th s dng gi tr K2 ca axit oxalic.
H3 O+ C2O42
K2 = (5.5)
HC2O4
H3O+ HC2O4
K1 = = 5,36.102 (5.6)
[H2C2O4 ]
95
Giai on 4. Thit lp phng trnh cn bng vt cht CaC2O4 tan l ngun duy nht ca
Ca2+ v cc dng khc ca oxalat. Do :
Giai on 8. Gii phng trnh. S thay th tng ng vo phng trnh (5.7) lin kt
[Ca ] v [ C2O42 ] l phng php thun li gii. Ban u chng ta cn din t [ HC2O4 ]
2+
(1,00.104 ) C2O42
= 5,42.105
HC2O4
T :
(1,00.104 ) C2O42
HC2O4 = = 1,84.102 C O2
5,42.10 5 2 4
Sau khi thay th cc h thc thu c v nng ion hiro vo phng trnh (5.6) ta thu
c:
Vy:
Ca2+
C2O24 =
2,84
Ca2+
Ca2+ = 2,3.109 mol / l
2,84
Nhng kt ta cha anion baz, v d canxi oxalat hoc cation axit, v d nh bismut
ioua ng gp phn ca mnh vo nng ion hiro trong dung dch nc. Do , nu
nng ion hiro khng c gi hng nh nh mt cn bng no n s ph thuc vo
tan ca kt ta. V d, dung dch bo ho ca canxi oxalat c phn ng kim v tn ti
nhng cn bng:
Khc vi trng hp trn, nng ca ion hiroxyl trong trng hp ny cha bit nn
cn thit phi thit lp phng trnh i s ph.
97
Trong phn ln trng hp khng nn b qua tng tc ca kt ta vi nc, v khng
chp nhn c nhng sai s trong cc php tnh. Theo bng 5.1, gi tr sai s ph thuc vo
tan ca kt ta v hng s phn li baz ca anion. tan ca kt ta MA c k ti phn
ng ca A vi nc c gii thiu ct th t. ct th nm dn ra nhng kt qu tnh
khng k tnh baz ca A; tan trong trng hp ny, mt cch n gin, bng cn bc hai
ca tch s tan. Nhng tnh ton c thc hin i vi hai kt ta vi tch s tan 1,0.1010
v 1,0.1020 mt gi tr hng s baz ca A. R rng l s b qua tng tc ca anion vi
nc dn ti sai s m; sai s ny cng tr thnh r rng hn khi tan ca kt ta cng ln,
ngha l T cng ln v anion ca kt ta l baz cng mnh.
tan ca MA tnh
Hng s Hng s baz tan ca MA
Tch s c khi khng k ti
phn li ca ca A tnh c,
tan MA phn ng vi nc,
HA, KHA mol/l
Kb = Kw/KHA mol/l
HCO3 OH K
= H2O = 2,13.102 (5.14)
2 K2
[CO3 ]
Ngoi ra:
0 = [OH] [ HCO3 ]
hoc l:
2
HCO3
= K H2O
2 K2
[CO3 ]
K H2O
HCO3 = CO32
K2
Phng trnh thu c cho php loi tr [ HCO3 ] ca phng trnh (5.19):
K H2O
Pb2+ = CO32 + CO32 (5.22)
K2
100
T phng trnh (5.13) chng ta thu c:
CO32 = T
Pb2+
T K H2O .T
Pb2+ = +
Pb2+ K 2 Pb2+
ng mu s v sp xp li cc thnh phn:
K H2O .T Pb2+
Pb 2+
T = 0
K2
14
CO2 = 3,3.10 = 1,7.108 M
3 1,9.106
1,00.1014
[H3O+ ] = = 5,3.109 ion.g / l
6
1,9.10
Chng ta thy rng nhng gi thit c chng ta chp nhn khng dn ti sai s ng
k. [H2CO3] bng khong 1/90 [ HCO3 ], cn [H3O+] r rng nh hn nhiu nng tng
cng ca cc ion cacbonat v hirocacbonat trong phng trnh (5.18).
V cui cng, nu nh khng k ti tnh cht baz ca CO32 chng ta thu c tan
1,8.107 ch bng mt phn mi i lng tnh bng phng php chnh xc hn.
S2 + H2O HS + OH (5.24)
1
tan = [Ag+] = [S2] + [HS] + [H2S]
2
HS OH K 14
= H2O = 1,0.10 = 8,3 (5.28)
S2 K2 1,2.1013
102
[H2S] OH K H2O 1,0.1014
= = = 1,8.107 (5.29)
HS K1 8
5,7.10
1
[Ag+] = [S2] + [HS] + [H2S] (5.30)
2
Chng ta thay [OH] trong cc phng trnh (5.28) v (5.29) bng gi tr 1,0.107:
[H2S] = 1,0.1014
= 8,3.107
S2 13 7
1,2.10 .10
[H2S] =
1,0.1014
= 1,8
HS 5,7.108.107
1
[Ag+] = [S2] + 8,3.107 [S2] + 14,9.107 [S2]
2
1
tan = [Ag+] = 1,5.1014 M
2
103
Gi thit cho rng [Ag+]nh hn nhiu so vi [H3O+] r rng l c c s. Chng ta c th
d dng tnh (2[S2] + [HS]) v khng nh c rng tng s cng nh hn [OH] rt
nhiu. T chng ta i n kt lun l nhng gi thit nu l chp nhn c v cch gii
gn ng l tho mn.
2H2O H3O+ + OH
Nu hiroxit tan kh, nng ion hiro s nh v phng trnh (5.34) c n gin
ho:
2[M2+] [OH]
T T
[M2+ ] = = = tan (5.36)
2
[OH ] 1,0.1014
lm gi thit gii.
tan = 2.1010 M
T suy ra rng:
1,00.1014
[H3 O+ ] = = 1,7.105 M
10
6.10
4.1028
[Fe3+ ] = = 4.1017 M
7 3
[1,00.10 ]
tan = 4.1017 M
Gi thit cho rng 3[Fe3+] << [H3O+] r rng l ng n. Cn nhn mnh rng, trong
php tnh u, khi a ra mt gi thit khng ng tin cy th nhn c sai s rt ln.
V d trn y ch r tan ca hiroxit kim loi c tnh ton tng t cch tnh tan
ca hp cht cha baz yu. Sau khi chp nhn mt trong hai php tnh gn ng th nhng
php tnh c th c n gin ho. Nhng chc chn l s c mt vng gi tr tch s tan,
khng mt php tnh gn ng no ng dng c v i vi trng hp cn phi
105
gii cc phng trnh (5.32), (5.33) v (5.34) theo ba n s, bng 5.2 ch ra nhng gii hn
ca vng i vi nhng kt ta loi M(OH)2.
Sai s gy ra
tan tnh tan tnh tan tnh Sai s gy ra
Gi tr T do s dng
c khng c theo c theo do s dng
c phng
s dng phng trnh phng trnh phng trnh
chp trnh
php gn
nhn
ng (5.35) (5.36) (5.36), %
(5.35), %
3
AlF6
Nh vy, ion florua y cnh tranh thng li vi ion hiroxyl phn ng vi nhm (III).
Nng ion florua cng cao th tan ca kt ta cng ln do s to thnh [AlF6]3.
+
AgNH3+ + NH3 Ag ( NH3 )2
Chng ta xc nh n s:
AgNH3+
= K = 2,0.103 (5.38)
1
Ag [NH3 ]
+
Ag ( NH )+
3 2
= K = 6,9.103 (5.39)
2
AgNH3 [NH3 ]
+
NH4+ OH
= K = 1,76.105 (5.40)
[NH3 ] b
Ngoi ra, trong tng tc ca amoniac vi nc, c mi ion NH4+ xut hin, mt ion OH
c to thnh. Nh vy:
Gi thit:
b/ [ Ag ( NH3 )2+ ] >> [ AgNH3+ ] v [Ag+]. Loi tr nhng dung dch amoniac rt long, gi
thit l c c s. iu c suy ra t gi tr hng s cn bng ca cc phng trnh
(5.38) v (5.39).
Ag ( NH )+
3 2
= K K = 1,38.107
1 2 (5.48)
Ag + [NH3 ]2
[Br ]
= 1,38.107
+ 2
[Ag ](0,10 2[Br ])
Thay th [Ag+] bng gi tr tng ng t phng trnh (5.37) vo phng trnh trn ta
c:
(1) +
Chng ta b qua [H3O ] bi v nng ca ion hidro trong dung dch amoniac 0,10 M l khng ng k.
108
[Br ]
= 1,38.107
5,2.1013
[Br ]
(
0,10 2[Br ] )
hoc:
[Br ]2
= 7,2.106
(0,10 2[Br ])
2
T :
Cc cn bng:
Hng s cn bng:
Zn(OH)24
K= = 0,13 (5.51)
2
OH
T 2
S= + K OH (5.52)
2
OH
dS 2T
= 2K OH
d OH 3
OH
Nu:
dS
=0
d OH
2T
th: = 2K OH
3
OH
T :
1/ 4
1/ 4 1,2.1017
OH = 2T = = 9,8.105
2K
0,13
Ngi ta thu c tan cc tiu khi thay th nng ion hiroxyl tnh ton c vo
phng trnh (5.52):
110
1,2.1017 5 2 9
Scc tiu = + 0,13(9,8.10 ) = 2,5.10
5 2
(9,8.10 )
Bng thc nghim ngi ta pht hin rng, kt ta thng tan trong dung dch cht in li
nhiu hn so vi trong nc, tt nhin l iu kin cht in li khng cha ion cng tn vi
kt ta. Hnh 5.1 minh ha nh hng ca cht in li n tan ca ba kt ta.
Khi tng nng kali nitrat trong dung dch t 0 n 0,02 M, tan ca bari sunfat tng
gp i. tan ca bari ioat cng khong bin i nng cht in li nh vy ch tng
1,25 ln v ca bc clorua tng 1,20 ln.
Hnh 5.1
Bng 5.3 Hng s phn li ca axit axetic trong cc dung dch natri clorua 25oC
0,00 1,75.105
0,02 2.29.105
0,11 2,85.105
0,51 3,31.105
1,01 3,16.105
cn bng th hai chuyn mnh v bn phi hn cn bng th nht (xem hnh 5.1).
iu khi qut quan trng th hai l nh hng ca cht in li trong mt khong rng
nng thc t khng ph thuc vo bn cht ca n m ch ph thuc vo thng s nng
ion ca dung dch qua lc ion :
1
Lc ion = (m1Z12 + m2Z22 + m3Z32 +.. .) (5.53)
2
112
y m1, m2, m3... l nng phn t ca cc ion khc nhau trong dung dch;
cn Z1, Z2, Z3 l in tch ca cc ion tng ng.
V d: Lc ion ca dung dch KNO3 0,1 M ca dung dch Na2SO4 0,1 M l bao nhiu?
1
= (0,1.12 + 0,1.12) = 0,1
2
1
= (0,2.12 + 0,1.22) = 0,3
2
V d: Lc ion ca dung dch KNO3 0,05 M v Na2SO4 0,1 M bng bao nhiu?
1
= (0,05.12 + 0,05.12 + 0,2.12 + 0,1.22) = 0,35
2
Ngi ta pht hin rng trong cc dung dch c lc ion nh hn 0,1, nh hng ca cht
in li khng ph thuc vo bn cht ion v c xc nh ch bng lc ion. Do , phn li
ca axit axetic l ng nht khi c mt natri clorua, kali nitrat hoc bari ioua iu kin
nng ca cc cht in li m bo lc ion ng nht. Cn nhn xt rng, quy lut
lc ion cao b ph v.
aa = [A].fA
aH + a Ax H3 O+ Ax f f
Ka = 3O
= H3O+ Ax
aHAx [HAx ] fHAx
113
y fH O+ , fAx v fHAx bin i theo s bin i ca lc ion cho Ka hng nh trong
3
Hnh 5.2
0,5085 Z2A
lg fA = (5.55)
1 + 0,3281 a A
S kim tra thc nghim nhng gi tr h s hot ca nhng ion ring bit c dn ra
bng 5.4, rt ng tic l khng th thc hin. Tt c cc phng trnh thc nghim ch cho
gi tr h s hot trung bnh ca cc ion tch in dng v m trong dung dch. Nhng cn
ch rng h s hot trung bnh tnh ton c nh cc d kin ca bng 5.4 kh ph hp
vi nhng gi tr tm c bng thc nghim.
Rb+, Cs+, Tl+, Ag+, NH4+ 2,5 0,964 0,924 0,898 0,800 0,750
Pb2+, CO32, SO32 CrO42 4,5 0,868 0,742 0,665 0,460 0,370
Al3+, Fe3+, Cr3+ La3+ Ce3+ 9 0,738 0,540 0,440 0,240 0,180
Nh cng thc Debye - Huckel v nhng d kin ca bng 5.4 c th tnh ton c h
s hot lc ion nh hn 0,1. gi tr cao hn s tnh ton theo cng thc dn ti sai
s v cn phi s dng nhng gi tr h s hot trung bnh tm c bng thc nghim.
Tnh ton tan c s dng h s hot . S dng hot thay th cho nng phn t
khi tng hng s cn bng cho php ta thu c thng bo chnh xc hn. Nu khng c
nhng quy c c bit trc nhng gi tr T trong bng thng l tch s hot . (Nhng
hng s c din t bng hot , i khi ngi ta gi l hng s nhit ng hc). Nh vy,
i vi kt ta AmBn c th vit:
hoc:
T
[A]m [B]n = = T'
m
fA fBn
V d: Hy tnh tan ca Ba(IO3)2 trong dung dch Mg(IO3)2 0,033 M. Tch s tan ng
hc ca Ba(IO3)2 bng 1,57.109.
Trc ht ta vit :
2 9
Ba2+ IO3 = 1,57.10 = T'
fBa2+ f 2
IO3
1
= m 2+ 22 + mIO 12
2 Mg 3
117
1
= [0,33.4 + 0,066.1 ] = 0,099 0,1
2
Khi tnh chng ta gi thit rng, cc ion Ba2+ v IO3 t kt ta khng th hin nh
hng ng k n lc ion ca dung dch. S n gin l c c s bi v bari ioat c
tan nh. Trong nhng trng hp, khi gi thit l khng tha mn cn tnh gn ng nng
ca c hai ion bng cch thng thng vi gi thit l hot v nng ph hp vi
nhau. Cn tnh nhng nng khi thu c nhng gi tr xc nh hn.
By gi c th vit:
1,57.109
= 6,8.109 = T'
(0,38) (0,78)
tan S = [Ba2+]
Rt l th nhn thy rng, tan tnh ton c khng k lc ion bng 3,60.107 M.
B qua h s hot trong cc php tnh cn bng. Mt cch n gin thng chng ta
b qua h s hot trong cc phng trnh cn bng, s dng nng phn t. iu lm
n gin cc php tnh v lm gim i ng k lng thng tin cn thit. Trong phn ln
trng hp sai s gy nn do vic cho h s hot bng n v khng ln n mc lm sai
lch kt qu tnh ton. Nhng t v d trn r rng l, s b qua h s hot trong cc tnh
ton loi c th dn n sai s ng k. Sai s tng i 100% hoc ln hn trong trng
hp ny khng phi l him hoi.
Sinh vin cn ch trong tnh ton bi v i khi s thay th hot bng nng c th
dn ti nhng sai s ln. S khc bit ln c quan st thy trong trng hp lc ion ln
(0,01 v ln hn) hoc ion nhiu in tch (xem bng 5.4). i vi cc dung dch long (lc
ion < 0,01) ca cc cht khng in li hoc cc ion mt in tch, vic s dng nng trong
tnh ton theo nh lut tc dng trng lng thng cho kt qu kh chnh xc.
118
Cng cn nhn mnh rng, s gim tan khi c mt ion cng tn vi ion ca kt
ta c b tr mt phn bng s tng tan ng thi do nng ln ca cc cht in li cha
ion cng tn. Hin tng c minh ha trong v d va phn tch.
Nhit , phn ln cc cht rn khi tan hp th nhit. Do , khi tng nhit thng
tan v tch s tan tng ng ca phn ln cht t tan tng ln.
Bng 5.5 tan ca canxi sunfat trong cc dung dch ru etylic trong nc
0 0,208
6,2 0,100
13,6 0,044
23,8 0,014
33,0 0,0052
41,0 0,0029
D dng tnh c nng OH nm cn bng vi 1,0.106 mol/l Fe3+ trong phng trnh
tch s tan.
[OH] = 3,4.1011
120
11 3+
Nh vy, nu gi nng OH mc 3,4.10 mol/l, nng Fe h n
1,0.106 ion.g/l. Rt l th nhn xt rng, Fe(OH)3 kt ta nh lng trong dung dch kh
axit.
Nhng php tnh thc hin ch r rng, s tch nh lng Fe(OH)3 xy ra nng OH
ln hn 3,4.1011 mol/l v cho ti khi nng OH cha t ti 1,3.105 mol/l th Mg(OH)2 s
cn cha kt ta. Do tch Fe3+ v Mg2+ cn gi nng OH khong gia cc gi tr
.
V d 2. Phn chia di dng sunfua. Trong mt lot phng trnh quan trng dng
tch cc ion kim loi, ngi ta gi nng cn thit ca cht kt ta amoni bng cch iu
chnh nng ion hiro trong dung dch. Nhng phng php nh th c sc hp dn c
bit, bi v trong cc phng php ny tng i d gi nng ion hiro mc xc nh
nh dung dch m thch hp (1). C l phng php c bit ti nhiu nht trong s cc
phng php l phng php da trn s ng dng hiro sunfua lm cht kt ta.
H3 O+ HS
K1 = = 5,7.108
H2S
HS + H2O H3O+ + S2
H3 O+ S2
K2 = = 1,2.1015
[HS ]
(1)
iu ch v tnh cht ca cc dung dch m c xt ti chng IX. Kh nng gi nng ion hidro
mc xc nh khng bin i l tnh cht quan trng ca dung dch m.
121
Cng nhng phng trnh , ta thu c phng trnh tng cng ca s phn li sunfua
hiro n ion sunfua.
H3 O+ S2
K 1K 2 = = 6,8.1023
[H2S]
Ngi ta thu c hng s ca phn ng cui cng bng cch nhn K1 vi K2.
Khi phn chia di dng sunfua, ngi ta thng lm dung dch bo ho hiro sunfua
lin tc cho ti khi phn ng kt ta kt thc. V vy, nng ca thuc th trong qu trnh
kt ta thc t l khng i. V hiro sunfua l axit yu, nng cn bng xp x bng tan
trong nc ca n, bng khong 0,1 M. Nh vy chng ta c th gi thit rng, trong qu
trnh kt ta mt sunfua no :
[H2S] 0,1 M
24
S2 = 6,8.10
2
H3 O+
Do , nng ca ion sunfua t l ngc vi bnh phng nng ion hiro. H thc
c ng dng tnh iu kin ti u cho kt ta cc cation di dng sunfua.
V d 3. Hy tm nhng iu kin tch nh lng Pb2+ v Tl+ bng cch dng H2S kt ta
t dung dch cha mi ion 0,1 mol/l.
[S2] = 7.1022
[S2] = 1.1020
Nh vy, mun phn chia cn gi nng S2 gia 7.1022 v 1.1020 mol/l. Chng ta cn
tnh nng H3O+ m nng S2 s nm trong gii hn ni trn. Thay vo h thc
rt ra trc y:
24
S2 = 6,8.10
2
H3O+
6,8.10 24
[H3O+] = = 0,97.10 2 mol / l
7.10 22
6,8.10 24
[H3O+]2 =
1.10 20
Khi gi nng [H3O+] gia 0,03 v 0,01 mol/l c th kt ta c PbS trc khi kt ta
Tl2S bt u. Nhng vi quan im thc t, tht ng ng kh nng kim tra axit chnh
xc phn chia c.
123
Chng 6
Qu trnh to thnh kt ta
Nielsen so snh nhng thi k tip xc ca nhng kt ta khc nhau theo nhng d kin
ca nhiu nh nghin cu v rt ra c phng trnh thc nghim sau:
tiCon = k (6.1)
Thi lng ca thi k tip xc khng ph thuc vo phng php quan st. Khi quan st
trc tip bng mt cng thu c kt qu ging nh khi s dng cc thit b quang hc c
nhy cao hoc o dn in. Theo cc s liu ca Johnson v ORourke, dn in trong
thi k tip xc hu nh khng bin i. Do vy, trong thi gian ch mt phn nh cht tan
dng cp ion hoc nhng lin hp ion ln hn.
Khi kt ta bari sunfat, thi lng ca thi k tip xc ph thuc vo phng php trn
thuc th. T nhng s liu ca Lamer v Dinegar c th rt ra kt lun, trong trng hp
iu ch ion sunfat trong dung dch ng th theo phn ng:
124
2 2 2 2
S2O8 + 2S2O3 2SO4 + S4O6 (6.2)
aBa2+ .aSO2
4
= 21,5
KM
Ngoi ra, nhiu bng chng ng tin cy v s to thnh nhng trung tm kt tinh l
trong cc dung dch bari clorua va mi c iu ch c cng b v s khng nh v
s gim lng, ng thi tng kch thc ht bari sunfat c to thnh khi s dng cc dung
dch bari clorua gi ha v c lc cng c xc nhn. Cn c mt nhm quan st rt
quan trng khc v s ph thuc ca kch thc v lng ht kt ta vo nng cht kt ta.
Von Weimarn hon thnh cng trnh nghin cu c in v s to thnh kt ta: o kch
thc tinh th bari sunfat thu c bng cch trn nhanh nhng dung dch bari tioxianat v
mangan(II) sunfat c nng phn t bng nhau. long 104 M, ni chung kt ta
khng xut hin. Khi tng nng trong gii hn 104 103 M, kt ta c to thnh, ban
u l nhng ht v nh hnh, sau chuyn t t thnh tinh th. Nhng nhng bin i
ny ca kt ta xy ra rt chm, n mc to thnh nhng tinh th hon chnh cn ti 6
thng. Kch thc ca nhng ht to thnh ban u tng ln cng vi s tng nng , ngc
li, kch thc ca nhng tinh th cui cng gim i khi nng ban u tng.
Tnh cht ca mt s kt ta in hnh nht trong nhng khong thi gian khc nhau tng
t t1 n t5 c dn ra trn hnh 6.1. Khi nng ban u bin i t 103 n 1 M, nhng
tinh th mi c to thnh km hon chnh, xut hin nhng tinh th ln c dng hnh kim
v hnh b khung; nng ln hn 1 M, ban u to thnh mt khi ng t, khi ny dn
dn chuyn thnh kt ta ht nh c th tch ln. T u th k 20, Weimarn khng nh
rng, nhng kt ta c gi l v nh hnh v thc cht cng ch l kt ta tinh th nhng
bao gm nhng ht cc k nh dng cha hon chnh, sau c xc nhn nh nhng
nghin cu ph Rnghen. Nhng nghin cu ny ch r rng, nhng nh Debye ca nhng
kt ta mi v nhng kt ta c gi ha thng l ng nht; s khc nhau duy nht l
nhng vch trn nh Debye ca nhng kt ta mi c c tnh khuch tn hn. Weimarn
125
khng hnh dung c mt cch r rng nhng khc nhau gia s to thnh cc ht kt ta v
nhng s bin i tip theo vi chng m ngy nay chng ta gi l hin tng gi ha.
Hnh 6.1
Oden v Werner o kch thc tinh th bari sunfat bng phng php trm tch. Cc tc gi
rt ra kt lun, trong gii hn nng 103 101, kch thc ht tng cng vi s pha long
v ng thi ng nht ca s phn b kch thc cng tng ln.
Mt khc, nhng iu kin xc nh, kch thc ht c th tng cng vi s tng nng
. Quy lut Weimarn pht hin khi kt ta t nhng dung dch rt long. ORourke v
Johnson nhn thy rng, khi trn nhanh cc dung dch bari clorua v natri sunfat gi ha,
tng lng cc ht bari sunfat to thnh khng ph thuc vo nng u ca bari sunfat trong
gii hn 2,5 25.104 M. Fisher v Rhinehammer ch r rng, khi kt ta t dung dch HCl
pH = 1, kch thc ht bari sunfat tng cng vi s tng nng trong gii hn 2,6 26.103
M. Cc tc gi nhn xt rng, trong nhng iu kin nhng tinh th kh ln (4,3 16 m)
c to thnh. nhng pH cao hn, kch thc tinh th tng ln nhng nhng tinh th ny
l nhng lin hp ln ca nhng ht nh.
Hnh 6.3
Hnh 6.3
Ni chung, tnh cht ca bari sunfat tng ng vi nhng ng cong trn hnh 6.2. Nh
ni trn y, nhng dung dch vi qu bo ho tng i ln c th tn ti trong thi
gian kh lu mi xut hin kt ta v bari sunfat thu c t dung dch rt long thc t bao
gm nhng ht tng i ln v ng nht. Trong khi bc clorua c tan tnh theo mol/l
cng gn nh th nhng biu l khuynh hng to thnh dung dch qu bo ho kh nh v
nhng ht s cp ca kt ta v c khi kt ta t dung dch long cng b khuch tn rt mn.
Chng 7
7.1 M u
Phn tch trng lng da trn php o trng lng ca hp cht c thnh phn bit,
lin quan v mt ha hc vi cu t cn xc nh. C hai nhm cc phng php phn tch
trng lng: nhm cc phng php kt ta v nhm cc phng php chng ct. Trong
nhm cc phng php kt ta, cu t cn xc nh tham gia vo phn ng ha hc vi thuc
th to thnh sn phm t tan; sau lc v thc hin nhng ng tc cn thit khc v cui
cng cn kt ta rn c thnh phn ha hc bit. Trong nhm cc phng php chng ct,
cu t cn xc nh c tch ra khi mu dng kh: trong trng hp ny, php phn tch
hoc l da trn php xc nh trng lng cht c ct ra, hoc l da trn php xc nh
trng lng cht cn li. Chng ta s ch yu xem xt phng php kt ta bi v phng
php ny thng c s dng.
Phng php phn tch trng lng bao gm hai php o thc nghim: cn mu v cn
sn phm bit thnh phn ha hc, thu c t lng mu . Trn c s ca nhng d
kin , bng nhng php tnh n gin, ta thng thu c hm lng theo phn trm ca
cu t cn xc nh.
Nu A l cu t cn xc nh th c th vit:
Trng lng A
%A = .100 (7.1)
Trng lng mu
0,2040 1
S mol AgCl = = s mol Cl2
t AgCl
Khi lng phan 2
nn:
t Cl2
1/2 trng lng phan
Trng lng ca Cl = 0,2040
Trng lng phan t AgCl
35,45
= 0,2040 = 0,2040.0,2474 = 0,0505 (g)
143,3
1 1 0,2040
Do : s phn t AlCl3 = t AgCl =
s phan
3 tAgCl
3 Trng lng phan
133,3
= 0,2040 = 0,0633 (g)
3 143,3
Chng ta nhn thy s ging nhau ca nhng php tnh dn. Trong c hai v d, trng
lng ca mt cht c din t qua tch s trng lng bit ca mt cht khc vi t s
trng lng phn t tng ng vi hai cht . T s c gi l h s chuyn. Trong v
d th hai, cn phi nhn trng lng phn t ca bc clorua vi 3 lm cho lng clorua
t s v mu s ca h s chuyn bng nhau.
Trong trng hp ny cn thit phi gi thit rng, Fe3O4 chuyn nh lng thnh Fe2O3
v c hon ton oxi chuyn:
Chng ta thy rng, t mt mol Fe3O4 thu c 3/2 mol Fe2O3. Nh vy, s mol Fe2O3
ln hn s mol Fe3O4 3/2 ln hoc l:
133
S mol Fe2O3 = 3/2 s mol Fe3O4;
t Fe2O3
3 Trng lng phan
Trng lng Fe2O3 = trng lng Fe3O4
t Fe3 O4
2 Trng lng phan
v thay cc gi tr bng s ta c:
3 159,7
Trng lng Fe2O3 = 1,63 = 1,687 = 1,69 g
2 231,5
Trong v d ny:
t Fe2O3
3 Trng lng phan
H s chuyn = = 1,035.
t Fe3 O4
2 Trng lng phan
t ca cht cn xc nh
a Trng lng phan
H s chuyn = .
b Trng lng phan t ca cht c can
By gi c th hnh dung phng trnh (7.1) di dng thun tin hn cho vic vn dng
thc t:
V d 4: Chng ta xem xt php xc nh gin tip st trong st (III) sunfat bao gm php
kt ta v php cn bari sunfat. Trong trng hp ny t s v mu s ca cng thc h s
chuyn khng c nguyn t chung v chng ta phi tm mt cch khc din t s tng
ng ha hc gia cc i lng . Chng ta nhn thy rng.
Nh vy, mc d hp cht ng trong cng thc tnh h s chuyn khng c lin quan
trc tip qua nguyn t chung, chng ta vn c th xc nh s tng ng ca chng, khi
bit quan h hp thc gia chng.
Chng ta minh ho vic p dng h s chuyn tnh kt qu phn tch qua nhng v d
sau y:
Na2C2O4 Na2CO3 + CO
Khi nung 1,3906 g natri oxalat bn thu c trng lng cht cn li l 1,1436 g. Hy xc
nh tinh khit ca mu.
Trong trng hp cho cn gi thit rng s khc nhau gia trng lng ban u v
trng lng cui cng tng ng vi s mt oxit cacbon khi nung. o lng mt i l c
s ca php phn tch. T phng trnh phn ng chng ta thy rng:
Nh vy:
hoc:
% C14H9Cl5 = 42,18.
2. D lc v d ra cc cht bn km theo.
3. Khng b tc dng ca mi trng xung quanh v c thnh phn bit sau khi sy
kh hoc sau khi nung nu cn thit.
Ch c s rt t kt ta v cht to kt ta tho mn tt c cc yu cu , do nh ha
hc thng phi s dng nhng sn phm hoc phn ng cn xa mi t tiu chun l tng
phn tch.
Kch thc ht ca tng rn quyt nh tnh d lc v tnh d tinh ch. Gia kch thc
ht v tnh d lc c mi quan h trc tip. Kt ta ht ln d b cc vt liu xp gi li; iu
m bo lc nhanh. Khi phi lc kt ta nh, phn tn phi dng giy lc mn v do tc
lc b gim xung. nh hng ca kch thc ht n tinh khit ca kt ta cn phc
tp hn. Thng khi tng kch thc ht km theo s gim bn ca kt ta.
Q S
Tnh qu bo ho tng i = (7.2)
Q
y n khong 4 v:
Q S
Tc ln ln ca ht = k2 .
Q
Hnh 7.1
S iu chnh kch thc ht. S nng nhit ( tng S), s pha long dung dch
gim Q v s thm cht to kt ta chm trong iu kin khuy mnh ( gim gi tr Q trung
bnh) l nhng iu kin thc nghim cho php lm cho qu bo ho gim n cc tiu v
cng chnh l nhng iu kin thu c kt ta tinh th.
7.5.2 Kt ta v nh hnh
Nhng ht keo ring bit nh n mc khng gi c khi lc, chuyn ng Brao cng
cn tr s kt ta chng t dng dch nh tc dng ca trng lc (s lng ng). May mn l
c th lm ng t hoc l lm ln ln nhng ht ca phn ln h keo v khi trng lng
khng phi l tinh th lng xung nhanh v d lc.
Trn hnh 7.2 dn ra hnh nh din t bng s ht keo bc clorua trong dung dch cha
d ion bc. Nhng ion bc lin kt trc tip vi b mt to thnh lp hp ph th nht. Xung
quanh ht tch in to thnh mt lp i ion, trong cha lng d ion m lm trung
140
ho in tch ca cc ion dng b hp ph trn b mt. Lp ion i c to thnh
di tc dng ca lc tnh in.
Hnh 7.2
S lm tng nng cht in li trong dung dch bng cch thm hp cht c c tnh ion
thch hp l phng php ng t hiu qu hn. Trong trng hp ny, trung ho in tch
ca ht i hi mt th tch nh dung dch cha ion tch in ngc du. Do s thm cht
in li gy nn s bp mo lp ion i v do kt qu in tch trn b mt ht c trung
ho hon ton hn. S h thp in tch hiu dng dn ti s xch li gn nhau ca cc ht.
Hnh 7.3
Cu to ca kt ta v nh hnh
Khi lc kt ta ngi ta ra bng dung dch long cht in li bay hi. Nhng ion b hp
ph trc t b tch ra khi ra bi v chng lin kt cht vi cht kt ta rn. Nhng gia
nhng ion i trong kt ta v mt trong nhng ion ca cht lng ra c th trao i. Khi k
ti tt c nhng iu , kh m hy vng rng kt ta khng b bn n mc no thm
ch c ngay sau khi ra tch cc. Sai s phn tch do nguyn nhn c th dao ng t (1
2).104% (v d nh bc nitrat cng kt trn bc clorua) n nhng i lng khng th chp
nhn c (v d nh hiroxit cc kim loi nng cng kt trn oxit hirat ha st ha tr ba
hoc nhm).
Nhng bin php lm cho ht ln v nng cao tnh d lc ca kt ta: Theo thng l, c
th lm tng kch thc ht kt ta tinh th khi gi trng thi qu bo ha tng i trong qu
143
trnh kt ta mc thp. Nh thy trn hnh 6.2, c th t ti iu bng cch h
thp Q hoc nng cao S hoc iu chnh c hai yu t .
Dng dung dch long, thm cht kt ta chm v khuy mnh ngi ta c th lm gim
s qu bo ha tng ni trong dung dch. Thng c th nng cao S khi kt ta t dung dch
nng. Nh bin php n gin , hon ton c th thnh cng v kch thc ht.
Ngi ta bit c hai loi cng kt trn kt ta tinh th: loi hp tng v loi hp lu;
chng khc bit nhau c tnh phn b tp cht bn trong tng rn. Tp cht hp tng
dng cc ion hoc phn t n l c phn b ng th trn ton tinh th. Ngc li, s hp
lu l s phn b khng ng u, nhiu ion hoc phn t tp cht ri vo tinh th do s
khng hon chnh ca mng li tinh th.
S hp lu xut hin trong nhng trng hp khi m nhng git nh hon chnh ca
dung dch cha tp cht gy bn b ko vo v b bao quanh rt nhanh chng bi s ln ln
ca tinh th. V tp cht nm bn trong tinh th nn kh tch chng bng cch ra, c th
gim mc hp lu ng k bng cch kt ta chm hn cho nhng ht nh tp cht kp
tch ra khi b mt tng rn trc khi chng b ri vo bn trong tinh th. Cn mt phng
php hiu qu hn lm gim tp cht hp lu l phng php lm gi kt ta.
S ho tan v kt tinh li khi lm gi cn to kh nng nng cao tnh d lc. S xut hin
cu gia nhng ht gn nhau dn ti s thu c nhng lin hp (chm tinh th) tinh th d
lc hn. Gi thit khng nh rng s khuy kt ta vi dung dch khi lm gi thc t
khng nh hng n tnh d lc ca kt ta.
Khi kt ta t dung dch ng th s sinh ra cht kt ta trong dung dch phi chm
s qu bo ho tng i lun lun thp. V cht kt ta c phn b u trong ton b th
tch dung dch nn s qu bo ho mt ch khng xy ra. Theo thng l, nhng kt ta c
v nh hnh v tinh th thu c t dung dch ng th c nhng tnh cht phn tch qu gi
hn so vi nhng kt ta thu c bng cch thm trc tip cht kt ta vo.
Thng thu c ion hiroxyl ng th ngi ta dng ure cho phn ng theo phng
trnh sau:
7.5.6 Sy v nung kt ta
Hnh 7.4
R rng l nhit trng lng ca canxi oxalat phc tp hn nhiu nhit trng lng
ca cc cht khc c din t trn hnh 6.4. nhit thp hn 135oC m hp ph
c tch ra, monohirat CaC2O4.H2O c to thnh v 225oC n chuyn thnh oxalat
khan. khong 450oC s bin i t ngt trng lng ch r s phn hy canxi oxalat, to
thnh canxi cacbonat v oxit cacbon. Bc cui cng trn nhit trng lng tng ng vi
s chuyn cacbonat thnh canxi oxit v kh CO2. Hin nhin l dng trng lng c s
dng i vi canxi oxalat ph thuc vo iu kin nung.
146
7.4 V thiu st ca phng php phn tch trng lng
CA = kM
Trong phn ln cc phng php phn tch cn thit phi xc nh k bng cch chun ha
hoc l bng ng chun thc nghim trong ngi ta o M i vi mt hoc mt s ln
hn mu chun c CA bit. C hai ngoi l c bit lch ra khi quy lut : phng php
phn tch in trng lng v culng (cc phng php phn tch cng c). Trong cc phng
php ny c th tnh k trc tip t nhng hng s tng qut bit. Nh vy, s cn thit phi
hiu chnh hoc chun ha khng cn na.
Trong phn tch trng lng k l yu t lng c th tnh c theo bng phn t lng.
Nh s c ch r sau y, i khi tnh hnh lm cho phn tch trng lng tr thnh
phng php hiu qu nht gii quyt nhng nhim v phn tch.
Khi cp n vn thi gian thc hnh phn tch, cn thit phi phn bit thi gian
xc nh v thi gian nh phn tch tiu ph cho php xc nh. Thi gian xc nh l s gi
hoc pht k t lc bt u phn tch n khi thu c kt qu. Cn thi gian nh phn tch
tiu ph l thi gian thc t tiu ph cho s hon thnh cc ng tc cn thit hon thnh
php phn tch v tnh ton kt qu. Khi so snh vi cc phng php khc, ta thy phng
php phn tch trng lng c c im l c s khc nhau ln gia thi gian xc nh v thi
gian nh phn tch tiu ph, bi v phn ln nhng giai on phn tch di khng cn thit phi
lun lun ch . V d, nhng ng tc nh a cht n trng lng khng i, lm bay hi
dung dch, lm gi kt ta v nung sn phm chim mt mt s gi nhng nh phn tch tiu
ph cho tt c nhng ng tc nhiu nht cng ch l mt s pht v do thi gian cn li
c th dng hon thnh nhng nhim v khc.
Nu so snh vi nhng phng php khc, v nguyn tc, vic hnh thnh mt php xc
nh no theo thi gian m nh phn tch phi tiu tn cho vic thc hin chng th phn
tch trng lng thng t ra hiu qu nht c bit l khi ch phn tch mt hoc hai mu bi
v khng cn tn thi gian cho ng chun hoc chun ha (ngha l xc nh k). Khi tng s
mu phn tch thi gian tiu tn cho ng chun tnh cho mt mu trong nhng phng
php khng trng lng tr nn ngy cng nh hn v thng khi phn tch 8 n 10 mu ni
147
chung l c th b qua. (Tt nhin l gi thit rng mt ng chun phn tch tt c cc
mu). Khi phn tch mt s ln mu, lc kt ta, ra v cn c th cn thi gian ln hn so
vi vic thc hin nhng ng tc tng ng trong cc phng php khng trng lng.
Do , nu phi phn tch mt s ln mu, phng php trng lng thng (nhng khng
phi l lun lun) khng thch hp.
Nhng phng php trng lng c nghin cu cho phn ln cc anion v cation v
c v c cho cc hp cht trung ha nh nc, ioxit lu hunh, kh CO2 v it. C mt lot
cc hp cht hu c cng d dng xc nh bng phng php trng lng, v d nh xc
nh lactoza trong cc sn phm sa, salixilat trong dc phm, phenolphtalein trong thuc
s, nicotin trong ha cht c, cholesterol trong huyt thanh v benzanehit trong dch chit
qu hnh nhn. Phn tch trng lng l mt trong nhng phng php phn tch c s
dng rng ri nht.
7.5.1 Cc cht to kt ta v c
Bng 7.3 lit k nhng cht kt ta v c thng dng nht. Nhng thuc th ny thng
c s dng iu ch nhng mui v hiroxit t tan. Hoc l chnh mui hoc l oxit c
dng lm dng cn. Nhiu hp cht c gch di trong bng ch r tnh khng chn lc
ca phn ln cc thuc th v c.
Cht kt ta Nguyn t b kt ta
(NH4)2CO3 Bi (Bi2O3)
(NH4)2SCN Cu [Cu2(SCN)2]
HNO3 Sn (SnO2)
H5IO6 Hg[Hg5(IO6)2]
Ch m k hiu trong bng 7.3 ch nguyn t hoc ion m i vi chng phng php
trng lng l phng php xc nh chim u th nht. Dng cn ca chng c ch ra
trong ngoc. Du sao c ngha l phng php trng lng t c dng. Gch di ch dng
cn thch hp nht.
C hai loi thuc th hu c. Nhng thuc th loi th nht to phc cht t tan c c
tnh kh ion ha gi l cc hp cht phi tr. Nhng thuc th loi th hai to nhng sn
149
phm trong lin kt gia nhng ion v c v thuc th mang c tnh ion mc ng
k.
Nhng thuc th hu c to nhng hp cht phi tr t tan thng cha t nht hai nhm
to phc, trong mt nhm c kh nng cho cation kim loi i in t khng phn chia.
Cht kh Nguyn t cn xc nh
SO2 Se, Au
SO2 + NH2OH Te
NH2OH Se
H2C2O4 Au
H2 Re, Ir
HCOOH Pt
NaNO2 Au
TiCl2 Rh
SnCl2 Hg
Kh bng in phn Cs, Ni, Cu, Zn, Ag, In, Sn, Sb, Cd, Re, Bi
N
OH
N Mg N
NO
OH
Khi tng tc vi coban (II) n to thnh phc vng cng ca coban (III) khng dn in
c thnh phn CoA3, y A l baz lin hp ca thuc th. Chng ta nhn thy rng, s to
kt ta km theo s oxi ha coban bng 1-nitrozo-2-naphtol nn kt ta thng b bn bi sn
phm kh ca thuc th. Do , nu chp nhn nung phc vng cng trong kh quyn oxi ha
th n Co3O4; cn nu nh dng coban trng thi nguyn t l dng cn th phi nung trong
kh quyn kh.
imetylglyoxim:
H3C C C CH3
N N
HO OH
151
l thuc th hu c c la chn rt cao. V d, trong mi trng axit ch c palai to
hp cht phi tr t tan vi thuc th ny, cn trong mi trng kim yu ch c hp cht ca
niken lng xung. Kt ta imetylglyoximat niken c mu hng ti, c cu to nh sau:
H 3C CH3
C C
O N N O
H Ni H
O N N O
C C
H 3C CH3
Benzidin:
Xc nh axit salixilic: Ha tan axit salixilic trong dung dch natri cacbonat v sau khi
thm iot vo, yn. Khi xy ra phn ng:
-
COO I I
OH
2 + 68I2 + OH
-
O O + 8I- + 2 HCO3- + 6 H2O
I I
Hai phng php trng lng ph bin nht da trn php chng ct l php xc nh
nc v php xc nh kh CO2.
Nc b tch nh lng ra khi phn ln cc cht v c khi nung chng. Phng php
xc nh trc tip da trn s tng trng lng cht lm kh ri suy ra trng lng nc.
Phng php gin tip da trn s mt trng lng mu khi nung cho kt qu km tho
mn hn. Trong trng hp ny buc phi gi thit, nc l cu t duy nht b tch. Gi thit
thng khng c c s bi v khi nung, nhiu cht b phn hy v khi dn ti s mt
trng lng khng lin quan vi s c mt ca nc.
153
Cc cacbonat thng b phn hy bi cc axit to thnh kh CO2 d dng tch ra khi
dung dch khi un nng. Nh trong phng php trc tip xc nh nc, trng lng kh
CO2 c xc nh theo s tng trng lng ca cht hp th rn. Askanit v amiang tm
kim natri c dng lm cht hp th kh CO2.
Cng c th xc nh sunfua v sunfit bng phng php chng ct. Trong trng hp
ny, sau khi ch ha mu bng axit, sunfua hiro hoc ioxit lu hunh c tch ra t dung
dch, c hp th bng cht hp th thch hp.
154
Chng 8
Trong nhiu trng hp, gii quyt nhim v phn tch, phng php phn tch trng
lng l phng php tt nht. Tuy vy, thi gian thc hin php phn tch trng lng
thng qu di nn nhiu khi khng p ng nhu cu ca sn xut cng nghip. l l do ra
i ca phng php phn tch th tch.
Phng php nh lng da trn php o th tch c gi l phng php phn tch th
tch hay phng php chun . Phng php chun c s dng rng ri hn phng
php trng lng v phng php ny nhanh hn, thun tin hn m nhy li khng thua
km.
Chun l qu trnh nh lng cht cn phn tch theo lng thuc th tiu chun tiu
tn. Php chun c thc hin bng cch thm mt cch thn trng dung dch thuc th
bit nng vo dung dch cht cn xc nh cho ti khi phn ng gia chng kt thc,
sau o th tch dung dch thuc th chun. i khi, nu iu khng thun tin hoc cn
thit, ngi ta thm d thuc th v sau chun ngc bng mt thuc th khc bit
nng xc nh lng d thuc th th nht khng tham gia phn ng.
1. Trc tip bng cch ho tan hon ton mt lng cn chnh xc thuc th chun gc v
pha long n th tch chnh xc bit bng nc ct.
1. Chng phi c tinh khit cao nht, hn na phi c nhng phng php n gin,
tin cy khng nh tinh khit ca chng.
5. C phn t gam mol cao. Khi lng cht cn thit chun ha hoc iu ch
dung dch c nng cho s cng ln nu phn t gam ca n cng ln. Khi khi lng
tng sai s ca php cn s gim, phn t gam cng cao c kh nng lm gim sai s cn cng
ln.
156
Ch c mt s t cht tha mn hoc hu nh tho mn cc yu cu v do
s cht quy cch dng lm cht chun gc b hn ch.
Trong mt s trng hp, thay th cho cht chun th nht phi dng cht km tinh khit
hn. tinh khit ca cht chun th hai cn phi c xc nh bng con ng phn
tch cn thn.
Dung dch chun l tng phn tch chun cn phi c nhng tnh cht sau:
1. Sau khi iu ch nng ca n phi khng bin i trong thi gian bo qun lu
(trong mt vi thng hoc hng nm), khng cn phi chun ha li.
2. Phn ng nhanh vi cht cn xc nh thi gian ch i sau khi thm tng phn nh
thuc th phi ngn.
hnh dung r rng hn s bin i trong vng , biu din nng khng phi
dng tuyn tnh m dng logarit s thun li hn. V chng thng nh hn n v nn s
dng logarit m l hp l v v vy hm s din t nng di dng s dng nh.
Logarit m (c s 10) ca nng phn t c bit di dng hm s p. Nhng gi tr pH
v pOH c a ra 2 ct cui ca bng 8.1.
Hnh 8.1
S bin i nng cc cht phn ng khi chun 50,00 ml dung dch HCl 0,0100 M bng dung dch NaOH 0,100 M
Hnh 8.2
160
ng chun 50,0 ml dung dch HCl 0,100 M bng dung dch NaOH 0,100 M
Chng 9
Chun kt ta
Nhng phng php chun da trn s to thnh mui bc t tan l nhng phng
php phn tch c bit t lu. Cho n by gi, nhng phng php vn thng c
s dng xc nh bc v nhng ion nh clorua, bromua, ioua v tioxianat. ng dng
nhng phng php chun kt ta trong cht chun khng phi l mui bc m l
nhng hp cht khc cn tng i hn ch.
9.1 ng chun kt ta
Trc khi nghin cu chng ny, sinh vin cn n li nhng lun im c s v tan
ca kt ta chng 5.
V d: Hy dng ng chun 50 ml dung dch KBr 0,005 M bng dung dch AgNO3
0,010 M.
im sau khi thm 5 ml thuc th: Nng ion bromua trong trng hp ny h thp do
kt ta c to thnh v do c s pha long dung dch. Do :
th
C th tnh i lng pAg mt cch thun tin khi s dng logarit m din t tch s
tan ca AgBr:
hoc
[Ag+] = [Br]
Thc hin nhng php thay th tng ng trong phng trnh tch s tan chng ta c:
im sau khi thm 25,10 ml thuc th: Trong dung dch c d AgNO3, do :
Nng thuc th: bng 9.1 dn ra nhng kt qu tnh theo phng php c phn
tch trong v d dn ra trn y. Tnh ton c tin hnh i vi 3 nng ion bromua v
ion bc khc nhau 10 ln. Nhng kt qu tnh ton pAg i vi c 3 trng hp c din t
trn hnh 9.1, minh ha r rng nh hng ca nng n ng chun . Khi tng nng
164
cht cn chun v cht chun, s bin i pAg vng gn im tng ng
tr nn r hn.
Hin tng tng t cng c quan st thy nu thay th pAg trn trc tung bng pBr.
Hnh 9.1
Bng 9.1 S bin i pAg v pBr trong qu trnh chun nhng dung dch c nng
khc nhau
Hnh 9.2
nh hng ca hon ton ca phn ng xy ra n ng chun 25,0 ml dung dch anion 0,050
M bng dung dch AgNO3 0,100 M
9.4 ng chun hn hp
V bc ioua t tan hn nhiu so vi bc clorua nn khi thm cht chun vo, u php
chun ch ring bc ioua to thnh. ng chun s tng t ng chun ioua
c m t trn hnh 9.2. Cn c bit ch n vic thit lp gii hn m , kt ta bc
ioua xy ra khi s to thnh bc clorua khng ng k.
[I ] 8,3.1017
= = 4,56.107
10
[Cl ] 1,82.10
[I] = 4,56.107.[Cl]
167
v thu c h thc
[I] = 4,56.107.[Cl]
R rng l trc khi kt ta bc clorua xut hin, nng ca ion ioua phi h thp n
gi tr ch bng mt phn rt nh nng ion clorua. Ni mt cch khc, bc clorua khng
c to thnh gn nh n chnh im tng ng ca ion ioua hoc cho ti khi thm
khong 20 ml cht chun. Trong trng hp ny nng ion clorua c k ti c s pha long
bng khong:
50,0 0,100
CCl [Cl ] = = 0,0714 mol/l
70,0
Nh vy l cho n khi nng ioua cha b chun bng khong 6.105% lng ban
u, bc clorua vn cha to thnh nn ng chun phi tng t ng chun mt
mnh ioua. Xut pht t , na u ca ng chun c dn ra bng ng m nt
trn hnh 9.3.
Ngay khi kt ta AgCl bt u xut hin, s gim nhanh chng pAg t ngt dng li.
Thun tin nht l tnh pAg t tch s tan ca bc clorua:
[Cl] 0,0714
10
Ag + = 1,82.10 = 2,55.109 mol/l
0,0714
Tip tc thm bc nitrat s lm gim nng ion clorua v ng cong chuyn thnh
ng cong c trng cho php chun mt mnh clorua. V d, sau khi thm 25,00 ml cht
chun:
[Cl] = 0,0533
1,82.1010
[Ag + ] = = 3,41.109 mol / l
0,0533
pAg = 8,47
Hnh 9.3
A+B AB
In + B InB
Tt nhin l tnh cht ca InB cn thit phi khc bit ng k vi tnh cht ca In. Ngoi
ra mt phi nhn bit c mt lng InB nh n mc l sau khi to thnh InB, s tiu tn B
khng nhn thy c v cui cng hng s cn bng ca phn ng vi s tham gia ca ch
th cn phi c mt gi tr nh th no gn im tng ng, khi [B] (hoc pB) bin
i s xy ra s bin i t ngt [InB]/[In]. iu kin cui cng d thc hin nht khi pB
bin i ln.
Chng ta xt s chun 3 dung dch (bng 9.1 v hnh 9.1) vi cht ch th bin i
hon ton mu trong vng pAg = 7 5 lm v d. R rng l chim vng pAg nu,
trong mi trng hp i hi mt th tch cht chun khc nhau. Nh, t nhng d kin ca
h chun ct th 2 bng 9.1, r rng l ch cn t hn 0,10 ml dung dch AgNO3 0,100 M,
ngha l s bin i mu bt u sau khi thm 24,95 ml cht chun v kt thc trc khi thm
vo 25,05 ml. Khi c th hy vng s bin i mu t ngt v sai s chun cc tiu.
Ngc li, khi chun bng dung dch AgNO3 0,001 M s bin i mu bt u khi thm
vo khong 24,5 ml v khi kt thc thm vo 25,8 ml. Trong trng hp ny khng c kh
nng xc nh im tng ng. Khi chun bng dung dch 0,010 M, mu bin i
im cui i hi mt lng nh hn 0,2 ml mt cht, trong trng hp ny c th dng cht
ch th nhng sai s xc nh im tng ng s kh ln.
Phng php Mohr c ng dng rng ri khi chun clorua v bromua bng dung dch
bc nitrat chun. Ion cromat c dng lm ch th, im cui php chun xut hin kt
ta bc cromat Ag2CrO4 mu gch.
[ CrO24 ][Ag+]2 T
12
Nu: CrO24 = T > 1,1.10 = 0,048 mol / l
[Ag]2 (4,78.106 )2
Nhng tnh ton ch r rng, chun chnh xc theo phng php Mohr, c th
gi nng cht ch th trong mt khong kh rng, gia 0,0008 v 0,05 M. Nhng trong
thc t nng ln hn 0,005 M mu vng m ca ion cromat s cn tr mu ca bc
cromat. Ngi ta thng s dng nng cromat nh hn 0,005 M mt cht. Khng th tnh
ton lng ti thiu cromat cn phi c to thnh m mt c th nhn bit m ch xc nh
c bng thc nghim. Trc khi pht hin mu ca bc cromat, dung dch b chun
qu trung bnh 0,05 ml dung dch 0,1 M. Ch sai s trong sai s kt qu ca php
chun , nn trong thi gian phn tch ngi ta thng lm th nghim trng. t mc
ch ngi ta xc nh s tiu tn ion bc cho mt th tch nh vy huyn ph canxi
171
cacbonat khng cha ion clo vi chnh cht ch th . Dung dch v kt ta thu c sau
php chun trng c dng lm chun rt thun tin chun lp li. Php chun ha
dung dch bc nitrat bng cch chun natri clorua tinh khit theo phng php Mohr l mt
bin php khc lm gim i ng k sai s ch th. Xc nh "nng ng lng chun
" nh vy s khng nhng gip tnh ton s tiu tn qu dung dch chun m cn cn nhc
c nhng kh nng khc xc nh s i mu ca nh phn tch.
2CrO24 + 2H Cr2O72
+
+ H2O
Nh vy, php xc nh clorua theo phng php Mohr cn phi c tin hnh trong
mi trng trung tnh hoc gn trung tnh (pH = 7 10). C th gi nng ion hiro trong
khong mt cch thun tin bng cch thm vo natri bicacbonat, canxi cacbonat hoc
natri tetraborat.
S to thnh phc mu - phng php Volhard: chun bc theo phng php Volhard
c th s dng dung dch tioxianat chun:
Ion st (III) lm cho dung dch c mu khi thm nhng git dung dch tioxianat d u
tin c dng lm ch th:
Php chun cn c thc hin trong mi trng axit ngn nga s kt ta st (III)
di dng hiroxit. C th d dng tnh c nng ch th m sai s chun tin ti
khng nh s c ch r trong v d sau y.
sai s chun bng khng, mu ca Fe(SCN)2+ cn phi xut hin nng Ag+,
cn trong dung dch bng nng tng cng ca tioxianat:
hoc:
172
T 1,1.1012
= = [SCN ] + 6,4.106
[SCN ] [SCN ]
Bin i:
Hng s bn ca Fe(SCN)2+:
[Fe(SCN)2+ ]
K = 1,4.102 =
[Fe3+ ][SCN ]
6,4.106
1,4.102 =
[Fe3+ ] 1,7.107
Khi chun theo phng php Volhard, nng khng bt buc phi cht ch. Tht
vy, nhng tnh ton tng t nh va c tin hnh ch r rng nng st (III) trong
khong 0,002 1,6 mol/l mt cch l thuyt, sai s s khng vt qu 0,1%. Trong thc t
ngi ta cng pht hin rng, nng vt qu 0,2 mol/l, mu ring ca cht ch th gy tr
ngi cho s pht hin phc tioxianat. Do ngi ta to ra nng st (III) thp hn (thng
l khong 0,01 mol/l).
gy tr ngi cho s pht hin im cui php chun theo Volhard. V vy ta quan st
thy s tiu tn qu mc ion tioxianat v xut hin sai s phn tch m. Gi tr sai s ph
thuc vo nng cht ch th.
173
trnh sai s lin quan vi phn ng gia tioxianat v bc clorua ngi ta s dng ch
yu hai bin php. Bin php th nht l to ra nng cht ch th cc i c php
(khong 0,2 M st (III)). Bin php th hai ph bin hn l tch kt ta bc clorua trc khi
chun ngc bng dung dch tioxianat. Php chun mt phn nc lc sau khi lc bc
clorua cho kt qu tt nht trong iu kin kt ta ng t tt. S tiu tn thi gian cho php
lc tt nhin l nhc im ca phng php ny. Dng nh phng php c ng dng
rng ri nht l phng php Caldwell v Moyer. Theo phng php ny, ngi ta ph ln
kt ta bc clorua mt lp nitrobenzen ngn nga n tip xc vi dung dch. C lp kt ta
bng cch lc hn hp vi mt vi mililit nitrobenzen trc khi chun ngc.
u php chun clorua bng cc ion bc theo phng php Fajans, cc anion cht
mu hu nh khng b kt ta hp ph. Thc t chng y b mt kt ta tch in m do hp
ph cc ion clorua. Sau im tng ng, nhng ht kt ta mang in tch dng do s hp
ph mnh cc ion bc d; trong nhng iu kin ion fluoretxeinat i vo lp ion i. V
vy, trn b mt kt ta xut hin mu c trng cho fluoretxeinat bc. Cn nhn mnh
rng, s bin i mu xy ra do qu trnh hp ph (ch khng phi do qu trnh kt ta), bi
v tch s tan ca fluoretxeinat bc khng t c trong thi gian chun . S hp ph l
thun nghch: cht mu b gii hp khi chun ngc bng ion clorua.
Phng php xc nh
Cu t cn xc nh Ghi ch
im cui
AsO43, Br, I,
Phng php Volhard Khng cn tch mui bc
CNO, SCN
Kt ta K+ bng lng d
Phng php Volhard B(C6H5)4 bit, thm d Ag+ to
K+
bin dng kt ta AgB(C6H5)4 v chun
ngc Ag+ d
V(OH)4+, cc axit Phng php phn tch Chun trc tip bng dung dch
bo, cc mecaptan in ha Ag+
Kt ta di dng ZnHg(SCN)4.
Phng php Volhard
Zn2+ Lc v ha tan trong axit, thm d
bin dng
Ag+; chun ngc Ag+ d
Kt ta di dng PbClF. Lc ha
Phng php Volhard
F tan trong axit thm d Ag+; chun
bin dng
ngc Ag+ d
Nhng phng php khc xc nh im cui: Trong gio trnh cc phng php phn
tch cng c c m t nhng phng php in ha pht hin im cui trong mt s phng
php chun kt ta.
ng dng ca phng php chun kt ta: Trong phn ln trng hp, php chun
kt ta da trn s s dng dung dch bc nitrat chun, i khi phng php ny gi l
phng php o bc. bng 9.2 dn ra nhng v d in hnh v ng dng phng php o
bc. Chng ta nhn thy rng, nhiu phng php xc nh trong nhng php xc nh nu
da trn php kt ta cu t cn xc nh bng mt lng d chnh xc dung dch bc nitrat
v chun tip theo bng dung dch kali tioxianat chun theo Volhard. C hai thuc th
c th dng c di dng cht chun u nhng kali tioxianat ht m mt cht gy kh
khn cho php cn m cao. Nhng dung dch bc nitrat v kali tioxianat bn trong thi
gian lu khng gii hn.
Bng 9.3 lit k nhng phng php chun khc dng cc thuc th khc thay th cho
mui bc.
Chng 10
Trong chng ny s xt nhng axit v baz n gin, chng phn li tch ra mt ion
hiro hoc mt ion hiroxyl. Trong chng 11 s bn ti nhng ng chun nhng axit
hoc baz nhiu nc v hn hp axit.
chun b cho nhng bn lun sp ti, sinh vin cn xem li nhng kin thc v axit,
baz v phng php tnh ton cn bng axit - baz (chng 4).
Trong phng php chun axit - baz, cc axit hoc baz mnh lun lun c dng
lm thuc th chun bi v phn ng vi s tham gia ca chng xy ra hon ton hn so vi
phn ng vi s tham gia ca axit hoc baz yu. Cng nh trong php chun kt ta,
phn ng xy ra cng hon ton, hm s p bin i cng ln v cng d xc nh im cui.
Nhng ch th axit - baz l nhng hp cht hu c biu l tnh axit yu hoc baz yu.
Phn ng phn li hoc lin hp ca cht ch th km theo s chuyn v cu to bn trong dn
ti s bin i mu. Chng ta a ra phn ng in hnh ca ch th axit - baz di dng sau:
hoc
In + H2O InH + OH
Trong cc dung dch axit mnh, ch th dng HIn l dng chim u th, tng ng vi
"mu axit" v In s l "mu kim" ca n. Trong cc dung dch kim, cc ht In s chim u
th tng ng vi "mu kim" ca cht ch th .
[In ] Ka [InH] Kb K [H O+ ]
= v = = b 3
[HIn] [H3 O+ ] [In ] [OH ] K H2O
Khi pH bin i, dung dch cha cht ch th bin i lin tc thnh phn phn trm dng
mu ca mnh. Nhng mt ngi rt khng nhy vi nhng bin i . Thng mt dng
phi hn t 5 n 10 ln dng kia th ngi quan st mi nhn bit c mu ca n; tip tc
tng lng d ca dng s kh nhn bit. S bin i mu ca ch th ch c nhn bit
trong vng m mt dng hn dng kia 5 10 ln. Nh vy "s bin i mu" quan st
c phn nh s chuyn dch cn bng ca ch th. Xt HIn lm v d, c th ni rng, ch th
th hin mu axit hon ton ca mnh c ngi quan st nhn bit khi:
[In ] 1 [In ] 10
v mu hon ton kim khi
[HIn] 10 [HIn] 1
[H3 O+ ] 10 K
= K a [H3O+ ] = a
1 10
Ka
t log10Ka n log = t 1 + pKa n (1) + pKa = pKa 1.
10
Danh sch nhng hp cht c tnh cht ch th axit - baz l danh sch nhng cht hu
c. Thng c th tm ch th c mu bin i trong khong pH cn thit bt k. Mt s ch
th c dn ra bng 10.1.
S bin i mu
Loi ch th
Tn Khong bin i pH a
Dng axit Dng kim
1,22,8 Vng
Timol chm 1
8,0 9,6 Vng Xanh bin
Bromtymol
6,0 7,6 Vng Xanh bin 1
xanh
Nhng ch th phtalein: Phn ln nhng ch th phtalein khng mu trong dung dch axit
v c mu trong mi trng kim. Trong mi trng kim mnh mu ca chng b mt chm.
Trong mt s trng hp iu l khng thun li. Thng nhng ch th phtalein tan va
phi trong nc. chun b dung dch ch th ngi ta thng dng etanol. C th biu din
phenolphtalein theo cng thc cu to nh sau:
181
OH OH OH OH
+ 2H2O + H3O+
C O C OH
C O C O
O
Khng mu Khng mu
OH OH O O
+ H3O+
C OH C
C O C O
O O
Khng mu
chun b cc dung dch ch th, ngi ta thng s dng mui natri ca sulfophtalein
bi v bn thn ch th c tnh axit r rt. C th iu ch dung dch trc tip t mui natri
hoc bng cch ha tan sulfophtalein trong mt th tch tng ng dung dch natri hiroxit
long trong nc.
C C
SO3 SO3
Vng
OH O O O
Ka = 10-7,9
+ H2O + H3O+
C C
SO3 SO3
Vng
Thay th cc nguyn t hiro vng phenol ca hp cht ban u bng cc halogen hoc
cc nhm alkyl s thu c nhng sunfophtalein khc nhau v mu sc v khong pH chuyn
mu.
H+
O3S N N N(CH3)2
+ H2O
H+
O3S N N N(CH3)2
O3S N N N(CH3)2 + H3O+
Vng
Metyl c c trng bng cng thc tng t cng thc ca metyl da cam, ch loi
tr nhm sunfo trong vng v thay th bng nhm cacboxyl. Thay th cc nhm th nit
183
ca nhm amino v trong vng s thu c hng lot ch th c tnh cht khc nhau mt
cht.
Sai s ngu nhin do kh nng ca ngi quan st phn bit mt cch lp li thi im
chuyn mu b hn ch l loi sai s th hai. Gi tr ca sai s ph thuc vo s bin i
pH trn mt mililit thuc th im tng ng, nng ch th v phng php nh phn
tch dng phn bit hai mu ca ch th. Khi quan st bng mt vi ch th axit - baz sai s
trung bnh khong 0,5 n v pH. So snh mu ca dung dch b chun cha lng ch th
"i chng" gi tr pH tng ng thng cho php h thp sai s n 0,1 n v pH hoc
nh hn. R rng, l nhng gi tr gn ng v mc ng k chng ph thuc vo bn
cht ca ch th cng nh vo trnh ca ngi thc hin.
Nu c cht chun v cht b chun l axit mnh v baz mnh th c th hnh dung phn
ng axit - baz tng th bng phng trnh:
H3O+ + OH = 2H2O
Nhng ion hiro trong cc dung dch nc ca axit mnh xut pht t hai ngun:
Nu nng dung dch thp hn 1.106 M, tnh [H3O+] c th s dng phng trnh
chnh xc hn, thu c t iu kin trung ha in tch:
K H2O
[H3O+] = [Cl] + [OH] = CHCl + (10.2)
[H3 O+ ]
Thnh phn u tin phn bn phi ca phng trnh l lng ion hiro to thnh do
HCl phn li, cn thnh phn th hai l lng ion hiro to thnh do nc phn li.
[OH] = CNaOH
[OH] = 2 CBa(OH)2
C th thu c phng trnh thun tin tnh pH ca cc dung dch kim bng cch ly
logarit phng trnh biu thc tch s ion nc:
V d: Hy xy dng ng chun 50,00 ml dung dch HCl 0,050 M bng dung dch
NaOH 0,100 M. Nhng gi tr pH thu c c lm trn n s l th hai sau du phy.
Bng cch tng t, ngi ta tnh pH cho n tn im tng ng. Nhng kt qu tnh
ton c gii thiu trong ct 2 ca bng 10.2.
Gi tr pH sau khi thm 25,00 ml dung dch NaOH: thi im trong dung dch
khng cn d HCl v cng khng d NaOH v pH c xc nh bng s phn li ca nc:
pOH = 3,88
Trong ct th hai ca bng 10.2 dn ra nhng d kin b sung ca php chun trn,
c tnh ton tng t.
Bng 10.2 S bin i pH khi chun axit mnh bng baz mnh
pH
Th tch dung dch
Chun 25,0 ml
NaOH, ml Chun 25,0 ml HCl 0,0005 M
HCl 0,050 M bng
bng NaOH 0,0010 M
NaOH 0,100 M
Hnh 10.1
Khi chun bng dung dch NaOH 0,100 M (ng cong 1) vng im tng ng,
quan st thy bc nhy pH ln, trong trng hp chun bng dung dch NaOH 0,001 M
bc nhy pH nh hn nhiu nhng rt cuc vn hon ton nhn thy c.
T hnh 10.1 r rng l nng cht chun 0,100 M, vic la chn ch th khng kh
khn. Trong trng hp hiu s th tch cht chun tiu tn cho php chun khi dng c ba
ch th c nu ln trn hnh v ch bng sai s c trn buret v do khng ng k. Mt
khc, bromcrezol lc r rng l khng thch hp cho php chun bng dung dch chun
187
0,001 N, khng ch v s chuyn mu ch th c quan st thy trong mt khong ln th tch
cht chun m cn v s chuyn ch th thnh dng kim thc t xy ra rt sm trc khi t
ti im tng ng v do xut hin sai s xc nh ln. Cng do chnh nguyn nhn
m ny sinh s bt ng v s s dng phenolphtalein. Trong s ba ch th xt ch c
bromtimol xanh cho php xc nh im cui vi sai s nh nht.
Tnh hnh tng t c quan st thy khi chun baz mnh bng axit mnh. gn im
tng ng, dung dch l kim mnh v nng ca ion hiroxyl bng nng ca kim
mnh cha c chun . Mt cch chnh xc, cng theo nhng nguyn nhn xt trn
y, dung dch im tng ng tr thnh trung ha. Cui cng, dung dch sau im
tng ng tr thnh axit v trng hp ny ngi ta tnh pH theo lng axit mnh d thm
vo. ng chun baz mnh bng HCl 0,100 M c gii thiu trn hnh 10.5. Ngi ta
chn ch th cng nh trng hp chun axit mnh bng baz mnh.
Khi xy dng ng chun axit yu cn phi tnh pH ca dung dch chnh axit lin
hp vi baz ca n v hn hp ca chng. Nhng tnh ton tng t cng cn thit khi xy
dng chun baz yu. Nhng phng php tnh pH ca dung dch axit yu v baz lin
hp c xem xt chng 4. Tnh pH ca cc dung dch cha mt lng ng k cp
axit - baz lin hp s c xem xt trong chng sau.
Dung dch cha mt cp axit - baz lin hp c th l axit, kim hoc trung tnh ty
thuc vo hai cn bng cnh tranh tn ti trong dung dch. i vi axit yu HA v mui natri
NaA ca n, nhng cn bng l:
[H3 O+ ][A ]
HA + H2O H3O+ + A ; K a = (10.3)
[HA]
[OH ][HA]
A+ H2O OH + HA ; Kb = (10.4)
[A ]
Nu cn bng th nht chuyn dch v bn phi mnh hn cn bng th hai th dung dch
s axit. Ngc li, nu cn bng th hai chim u th th dung dch s kim. T cc phng
trnh hng s cn bng y, r rng l nng tng i ca ion hiro v hiroxyl ph thuc
khng ch vo cc i lng Ka v Kb m cn ph thuc vo t s nng ca axit v baz
lin hp vi n.
188
Dung dch baz yu cng hon ton tng t. Trong dung dch cha amoniac
v amoni clorua, cc cn bng sau y c thit lp:
[NH4 + ][OH ]
Kb = = 1,76.105
[NH3 ]
Tnh pH ca dung dch cha axit yu v baz lin hp vi n: Chng ta xt dung dch c
nng axit chung CHA v nng baz lin hp chung CNaA. Nhng cn bng quan trng
nht v nhng h thc hng s cn bng y c m t bng cc phng trnh (10.3) v
(10.4).
nhng v:
[Na+] = CNaA
189
nn:
Thay cc phng trnh thu c vo phng trnh hng s phn li, sau khi bin i ta
c:
CHA
[H3O+ ] = K a (10.11)
CNaA
CHA
log[H3O+ ] = log K a lg
CNaA
T :
CNaA
pH = pK a + lg (10.12)
CHA
T phng trnh (10.11) ta thy rng, trong dung dch cha axit yu v baz lin hp vi
n, nng ion hiro ch ph thuc vo t s nng chung ca cc cht ny; iu ng
trong khong nng tha mn nhng gi thit, t rt ra phng trnh (10.11) cn c
ngha. Ngoi ra, gi tr h thc khng ph thuc vo s pha long dung dch, bi v khi
bin i th tch dung dch, nng ca mi cu t bin i mt s ln nh nhau. Nh vy,
nng ion hiro trong dung dch cha mt lng ng k axit yu v baz lin hp vi n,
khng ph thuc vo pha long v c xc nh ch bng t s nng chung ca c hai
cht tan. S khng ph thuc ca pH vo long l mt trong nhng biu hin tnh cht
m ca nhng dung dch .
V d: pH ca dung dch cha 0,400 M axit focmic v 1,00 M natri focmiat bng bao
nhiu ?
Nng ca ion hiro trong dung dch c xc nh bng cn bng ca phn ng:
[H3 O+ ][HCOO ]
Ka = = 1,77.104
[HCOOH]
v:
[H3 O+ ] 1,00
= 1,77.104
0,400
t :
(1)
Nu [H3O+] c gi tr ln, dung dch s axit v c th b qua gi tr [OH]. Ngc li nu
dung dch l kim s c [OH] l ch yu v c th khng cn k ti gi tr [H3O+].
191
Nu chng ta so snh pH ca dung dch vi pH ca dung dch axit focmic 0,400 M th
thy rng, khi thm natri focmiat, nh hng ca ion cng tn dn ti s tng pH t 2,08 n
4,15.
Tnh pH ca dung dch baz yu v axit lin hp vi n: Tnh pH ca mt dung dch cha
baz yu v axit lin hp vi n khng c g khc vi v d phn tch trn.
Cn bng chng ta ch l:
NH4+ + OH
NH3 + H2O
[OH ] 0,28
= 1,76.105
0,070
pH = 14 5,36 = 8,64.
1
= (0,100.12 + 1,00.12) = 0,100.
2
fH + = 0,83;
3O
fHCOO = 0,76
Nh vy:
Chng ta nhn thy rng h s hot ca HCOOH khng tch in c chp nhn
bng 1,0. Gi thit i vi ht trung ha thng l ng.
Sau ny, tnh ton chng ta s dng hng s cn bng nng Ka':
[HCOO] = 0,100 M
[HCOOH] = 0,0400 M
[H3 O+ ] 0,100
= 2,81.104
0,0400
pH = log(1,12.104) = 3,95.
2. Khi thm vo mt lng nh axit hoc baz. Dung dch c nng axit v baz lin
hp vi n cao v xp x bng nhau l tt nht.
V d: Hy tnh pH ca dung dch m c pH = 4,15 khi pha long dung dch m (xem
v d mc 10.4.1):
1. 50 ln;
2. 10.000 ln.
Gii:
[H3 O+ ] 2,00.102
= 1,77.104
8,00.103
Trong trng hp :
1,00.1014
[OH ] = = 1,41.1010 mol / l
5
7,08.10
CHCOOH = 4,00.105 M
194
4
CHCOONa = 1,00.10 M
Trong trng hp ny cn s dng phng trnh (10.5) v (10.6), chng cho nhng kt
qu chnh xc hn:
V dung dch l axit nn chc chn phi c [H3O+] >> [OH], nh vy:
v gii ra:
Nh vy, khi pha long 10.000 ln pH tng t 4,15 n 4,63 v khi pha long 50 ln pH
thc t khng bin i.
[OH ] 0,300
= 1,76.105
0,200
Hnh 10.2
NH4+ + OH
NH3 + H2O
Nng chung ca NH3 v NH4Cl sau khi thm kim vo tr thnh nh sau:
1,76.105 0,170
[OH ] = = 1,30.105 mol / l
0,230
pH = 14 (log1,30.105) = 9,11
1,76.105 0,150
[OH ] = = 1,06.105 mol / l
0,250
pH = 14 (log1,06.105) = 9,02
pH = 14 (log1,00.102) = 12,00
pH = log(1,00.102) = 2,00
pH = 2 9,07 = 7,07
197
Khi lng m: nhng v d xt ch r rng dung dch cha cp axit - baz lin hp
c kh nng gi pH n nh khi pH ca dung dch b bin i. Tnh cht gi pH n nh ca
dung dch m i vi s bin i ng k ca pH ph thuc c vo nng chung ca cc
cu t ca dung dch m c vo t s ca chng. V d, nu thm vo 400 ml dung dch m
thu c bng cch pha long 10 ln dung dch m m t trong v d trn, cng mt
lng nh th natri hiroxit hoc axit clohiric th pH ca n bin i khong 0,5 n v;
i vi dung dch m c hn, s bin i pH ch khong 0,04 n v.
Ngi ta o khi lng m ca dung dch bng s mol axit mnh hoc baz mnh cn
thit phi thm vo mt lt dung dch m lm bin i pH ca n mt n v. Chng ta
cng thy rng, khi lng m ph thuc vo nng cp axit - baz lin hp ng thi
c vo t s nng ca cp axit - baz lin hp v t ti gi tr cc i khi t s bng
n v.
Chng ta xt dung dch m cha a mol axit HA v b mol baz lin hp NaA. Nu thm
vo dung dch n mol axit mnh, nng chung ca axit v baz lin hp s nh sau:
a+n
CHA = ;
v
bn
CNaA =
v
CNaA bn
pH = pK a + log = pK a + log = pK a + log(b n) log(a + n)
CHA a+n
dpH 1 1
= 0,434 0,434
dn bn a+n
d 2 pH 1 1
= 0,434 0,434 =0
2 2
dn (b n) (a + n)2
1 1
=
2
(b n) (a + n)2
CNaA
pH = pK a + log (10.12)
CHA
K H2O 1014
[OH ] = K bCb = CNaCH3COO = 101 = 1.105,12
Ka 4,76
10
pOH = 5,12
do
CNaA 107
Ngc li, khi = = 106 th i vi h NaCH3COO - CH3COOH ta ang xt
CHA 1
10
pH s l:
pH = 2,88.
Khi sinh vin mun tnh pH im "v cng st" vi im u v im "v cng st" vi
im tng ng ca php chun axit yu bng baz mnh nhng li bng phng trnh
phng trnh Henderson-Schwazenbach th phm phi nhng sai lm nh trn.
c c t s cn trn VHA ml axit axetic vi VOH ml NaOH 0,426 M. Sau khi trn,
nng axit v baz lin hp s tng ng bng:
0,426 VOH
COAx = [OAx ]
VHA + VOH
0,500 VHA 0,426 VOH
CHOAx = [HOAx]
VHA + VOH
0,426 VOH
= 1,75
0,500 VHA 0,426 VOH
Nh vy, nu thm 57,2 ml dung dch axit axetic vo 42,8 ml dung dch NaOH th v
nguyn tc phi thu c dung dch c pH cn thit. Bng cc tnh ton loi tng t c th
hng dn vic iu ch cc dung dch m c pH xp x pH tng ng cn thit. Thng
khng nn mong i cc gi tr chnh xc bi v gi tr ca nhiu hng s phn li c sai s.
Cn mt iu quan trng hn na l lc ion ca cc dung dch m thng ln dn n mc
l khng th thu c gi tr h s hot tin cy ca cc ion trong cc dung dch t
phng trnh Debye-Huckel. Nh trong v d xt, lc ion khong 0,18 v vy hng s phn
li nng K 'a cn phi ln hn 1,75.105 ng k nhng cha c xc nh chnh xc
(khong 3.105).
xy dng ng chun axit yu (hoc baz yu) cn phi thc hin bn loi php
tnh tng ng vi bn phn ca ng cong:
1. Trc khi chun, dung dch ch cha axit yu, nn pH ca dung dch c tnh theo
nng cht b chun.
2. Sau khi thm mt phn bt k thuc th (mt lng cho ti trc im tng ng
nhng cha bng lng tng ng), cc dung dch s l mt lot h m; i vi mi h
m c th tnh pH theo nng chung ca sn phm phn ng v ca axit hoc baz
cha b chun.
Gi tr pH sau khi thm 10,00 ml cht chun: Trong trng hp ny chng ta thu c
dung dch m gm c NaOAx v HOAx. Ta phi tm nng ca c hai cu t ca dung
dch m:
[H 3 O + ] 1, 00 0
= K a = 1,75.10 5
60, 00
4, 0 00
60, 00
pH
Th tch dung dch
Chun 50,00 ml CH3COOH Chun 50,00 ml CH3COOH
NaOH ml
0,100 M bng dung dch 0,00100 M bng dung dch
NaOH 0,100 M NaOH 0,00100 M
Nhng tnh ton loi tng t, thch hp xy dng ng chun sut c vng
m. Nhng kt qu ca nhng tnh ton c gii thiu ct th hai ca bng 10.3. Ch
l nu axit b chun 50% (i vi php chun cho, iu tng ng vi s thm vo
chnh xc 25 ml dung dch kim) nng chung ca axit v baz lin hp bng nhau; trong
gii hn ca nhng gi thit thng thng, ngi ta cng nhn nng cn bng bng nhau
ca chng. Do trong phng trnh hng s phn li nhng i lng c n gin
ha v nng ion hiro bng tr s hng s phn li, ngha l pH bng pKa. Bng cch tng
t khi chun baz yu, nng ion hiroxyl thi im 50% baz c chun bng tr s
hng s phn li baz.
Gi tr pH sau khi thm 50,10 ml baz mnh: Sau khi thm 50,10 ml kim, ion hiroxyl
c to thnh do s phn li ca baz d v do tng tc ca ion axetat vi nc. S ng
gp ca phn ng sau qu nh bi v lng d baz mnh cn tr s phn li baz yu v c
th khng cn k ti n. iu tr thnh r rng khi chng ta tnh c nng ion
hiroxyl im tng ng trong php chun cho l 5,34.106 mol/l. S ng gp
[H3O+] do phn ng phn li ca axit axetic khi va xut hin lng d baz mnh s cn b
hn do :
V d: Hy tnh pH ca dung dch to thnh khi trn 50,00 ml dung dch axit axetic 0,001
M vi 10,00 ml dung dch NaOH 0,001 M.
Nu chng ta tnh [H3O+] bng chnh nhng phng trnh c s dng trong trng
hp chun bng cc dung dch thuc th 0,100 M th tm thy: [H3O+] = 7,00.105 mol/l. R
rng l gi tr [H3O+] tm c by gi c th snh vi CHOAx v CNaOAx do cn ng dng
cc phng trnh (9.5) v (9.6):
Ka =
(
[H3 O+ ] CNaA + [H3O+ ])
(CHA [H3O ])
+
i vi v d cho:
pH = 4,30
204
Gi tr pH i vi nhng thi im chun tng ng vi s thm vo t 10,00
n 49,00 ml dung dch baz mnh (bng 10.3, ct 3) c tnh ton tng t.
S din t bng th nhng d kin ca bng 10.3 c gii thiu trn hnh 10.3.
Chng ta nhn thy rng i vi dung dch long hn, gi tr pH ban u cao hn v pH
im tng thp hn so vi trng hp dung dch 0,100 M. cc im tng ng vi s
thm vo mt th tch trung gian cht chun, pH bin i t hn. Trong vng ca php
chun, dung dch m cha axit axetic v natri axetat c to thnh. Hnh 10.3 khng nh
li rng, s pha long t nh hng n pH ca dung dch m.
Trn hnh 10.4 dn ra nhng ng chun cc dung dch axit 0,100 M c cng
khc nhau. R rng l khi lm gim cng axit, s bin i pH trong vng im tng
ng tr nn t r rng hn bi v phn ng gia axit v baz xy ra km hon ton hn.
Nhng ng chun axit axetic bng dung dch nh hng ca cng axit n c im ca ng
NaOH chun .
1. Chun axit 0,100 M bng NaOH 0,100 M. Mi ng cong tng ng vi php chun 50,00 ml axit
0,1000 M bng NaOH 0,1000 M
2. Chun axit 0,00100 M bng NaOH 0,00100 M
La chn ch th: Hnh 10.3 v 10.4 ch r rng, s la chn ch th cho php chun axit
yu b hn ch hn so vi php chun axit mnh. V d, brom crezol lc hon ton khng
thch hp cho php chun axit axetic 0,100 M; c brom timol chm cng t thch hp i vi
php chun axit axetic 0,100 M bi v s bin i mu ca n c quan st thy trong
khong t 47 n 50 ml baz mnh 0,100 M. Nhng c th dng brom timol chm nu chun
205
n mu hon ton kim; bin php i hi phi dng dung dch kim chun cha cng
mt lng ch th v dung dch b chun (i chng) so snh. chun , nhng ch th
c s chuyn mu trong mi trng kim nh phenolphtalein thch hp hn.
S bin i pH im cui khi chun axit axetic 0,00100 M (ng cong 2 trn hnh
10.3) nh n mc l c th gy sai s chun ln. xc nh im cui vi lp li mt
vi phn trm cn s dng ch th vi s chuyn mu trong vng chuyn mu t
phenolphtalein n brom timol chm v ngoi ra cn dng i chng.
T hnh 10.4 r rng l, nhng vn tng t ny sinh theo mc gim cng axit.
Khi chun axit 0,100 M vi hng s phn li 108 c th thu c chnh xc 2% iu
kin c i chng thch hp. C th chun nhng dung dch c hn ca nhng axit tng i
yu vi chnh xc kh.
Sau y xin dn ra mt v d v cch tnh bc nhy pH khi chun 20,00 ml dung dch axit
0,100 M c K a = 1.108 bng dung dch NaOH 0,100 M lm minh chng.
O H = 4,74.10 4 M
Vy bc nhy c pH = 0,38.
V d: Chun 50,00 ml dung dch NaCN 0,050 M bng dung dch HCl 0,100 M. Hy tnh
pH sau khi thm:
1. Thm 0,00 ml dung dch chun. Ion xianua l baz yu; tnh pH c tin hnh nh
ch ra chng 4.
[OH ] K b CNaCN
KH2O 1,00.1014
y: Kb = = = 4,76.106
KHCN 9
2,1.10
Gi tr pH tm c l 10,69.
2. Thm 10,00 ml dung dch chun: s thm axit dn ti s to thnh dung dch m
cha:
2,1.109 1,00
60,00
[H3O+ ] = = 1,4.109 mol / l
1,500
60,00
pH = 8,85.
3. Thm 25,00 ml dung dch chun: thm vo mt th tch nh vy cht chun cho php
t ti im tng ng; by gi trong dung dch c axit yu HCN:
25,00 0,100
CHCN = = 0,03333 M v do (xem chng 4)
75,00
207
[OH ] K b CNaCN
4. Thm vo 26,00 ml cht chun: lng d axit mnh ngn cn s phn li HCN n mc
l s ng gp ca n vo gi tr pH khng ng k v do :
Trn hnh 10.5 dn ra nhng ng chun baz yu c cng baz khc nhau. R
rng l khi chun baz yu c th s dng nhng ch th vi s chuyn mu trong vng axit.
Hnh 10.5
Mi ng cong tng ng vi php chun 50,00 ml dung dch baz 0,1000 M bng HCl 0,1000 M
208
Chng 11
Trong chng ny chng ta s xem xt nhng cn bng c thit lp trong dung dch c
hai axit hoc hai baz khc nhau v hng s phn li. ng ch l hai loi dung dch:
giai on u ca php chun , nng ion hiro c din t bng phng trnh:
Gi thit rng [A] << 0,120, khi [H3O+] = 0,120 v pH = 0,92. kim tra ng
n ca gi thit trn ta tnh nng [A]:
A
= Ka 1,00.104
= = 8,33.104
[HA ] H3O+ 0,120
209
V:
nn:
A
0,080 = + A
8,33.104
V d: Tnh pH ca dung dch to thnh khi thm 29,00 ml dung dch NaOH 0,100 M vo
25,00 ml dung dch c [HCl] = 0,120 M v [HA] = 0,080 M (Ka = 1,00.104).
nn:
Ngoi ra ta c th vit:
H3 O+ A
[HA ] = (11.3)
1,00.104
H3 O+ A
+ A = 3,70.102
1,00.104
210
T ta tm c:
A = 3,70.106
H O+ + 1,00.104
3
H O+ = 1,85.103 + 3,70.106
3 H3O+ + 1,00.104
Nu lng baz thm vo tng ng vi lng axit clohiric ban u th dung dch thu
c v mi mt ng nht vi dung dch c pha ch bng cch ho tan mt lng axit yu
v natri clorua tng ng vo mt lng nc thch hp. Natri clorua khng nh hng n
pH ca dung dch v c th b qua nh hng ca lc ion ti nng ion hiro xy dng
phn tip theo ca ng chun c tnh ton tng t nh khi xy dng ng chun
axit yu long HA.
Hnh 11.1
Cc ng chun hn hp axit mnh v axit yu c hng s phn li axit hc nhau bng dung dch NaOH 0,100 M
H3 O + H2 PO4
H2PO4 K1 = = 7,11.10 3
+
H3PO4 + H2O H3O + ;
[H3 PO4 ]
H3O+ HPO42
H2PO4 + H2O +
H3O + HPO4 2
; K2 = = 6,34.108
H2PO4
H3O+ PO34
HPO24 + H2O H3O + +
PO34 ; K3 = = 4,2.1013
HPO24
HCO3 OH
CO32 HCO3 ( K b )1 = = 2,13.104
+ H2O + OH ;
CO32
[H2CO3 ] OH
HCO3 + H2O H2CO3 + OH
; ( K b )2 = = 2,25.108
HCO3
K H2O
( K b )1 = ;
( K a )2
K H2O
( K b )2 =
( K a )1
Trong dung dch mui loi NaHA c kh nng th hin c tnh axit c tnh baz.
Phngtrnh phn li axit i vi NaHA c vit nh sau:
HA + H2O A2 + H3O+
HA + H2O H2A + OH
213
mt trong hai phn ng ny, ion hiro c to thnh, cn trong phn ng cn li ion
hiroxyl c sinh ra. Dung dch HA s l axit hoc baz ty thuc vo t s hng s cn
bng ca hai qu trnh :
H3 O+ A 2
K2 = (11.4)
[HA ]
K H2O [H2 A ] OH
Kb = = (11.5)
K1 HA
Nu Kb > K2, dung dch s kim, cn trong trng hp ngc li dung dch s axit. Cht
loi NaHA c kh nng th hin c tnh axit v tnh baz c gi l cht in li lng tnh.
V nng ion natri bng nng chung ca mui nn c th chuyn phng trnh cui
cng thnh:
Thng thng i vi cc dung dch cc cht loi NaHA, khng nn b qua nng ion
hiroxyl v nng ion hiro. Do tm c gi tr ca tt c cc n s ([H3O+], [HA],
[A2], [OH]) cn phi gii h 5 phng trnh. V vy cn c tch s ion nc:
K H2O = H3 O+ OH
Tm phng trnh chnh xc tnh [H3O+] suy ra t 5 phng trnh nu trn rt phc tp
nhng c th thc hin php gn ng chnh xc tnh pH ca cc dung dch ca phn
ln cc mui loi NaHA. Gii ng thi cc phng trnh (11.6) v (11.7) ta c:
Thay th cc gi tr [H2A] v [A2] bng cc phng trnh biu din qua [HA] nh cc
phng trnh (11.4) v (11.5) vo cc phng trnh trn ta s thu c:
K H2O HA K 2 HA
= + OH H O+
K1 OH H O + 3
3
214
v v
K H2O
OH =
H O+
3
nn
H3 O+ HA K 2 HA
= + K H2O H O+
H3 O+
+ 3
K1 H3 O
HA
H3 O+ + 1 = K HA + K
2
K1
2 H2O
v t ta tm c gi tr cn tm:
Phng trnh (11.9) c ngha trong iu kin hai hng s cn bng K1 v K2 nh v nng
NaHA khng qu nh.
Thng CNaHA >> K1 v K1K H2O << K1K2CNaHA nn phng trnh (11.10) c rt gn:
H3 O+ K1K 2 (11.11)
8 13
H3 O+ = 6,34.10 4,2.10 1,0.103 + 6,34.10 22
= 8,1.1010 mol / l
1,0.10 3
3 8 2
H3 O+ = 7,11.10 6,34.10 1,0.10 = 1,6.105 mol / l
1,0.102 + 7,11.103
HA + H2O H3O+ + A2
i vi dung dch axit H2A bit nng , phng trnh cn bng vt cht c th vit
di dng:
V dung dch l axit nn c th b qua s hng cui cng trong phng trnh (11.15).
Phng trnh cui cng tng t phng trnh dn ra trc y, tnh nng ion
hiro trong dung dch n axit yu (chng 4) v cng ging nh trng hp c m t
trc y c th gii hon ton hoc gii theo cch n gin ha nu H3O+ << CH2 A .
H3 O+ HM
H2M +
H3O + HM
; = K = 1,20.102
[H2 M] 1
H3 O+ M2
HM +
H3O + M 2
; = K = 5,96.107
2
HM
B qua s phn li ca H2M giai on 2 v s dng phng trnh (11.18) tnh [H3O+]
ta c:
2
H O+
3 = K1 = 1,20.102
+
0,100 H3O
Hng s phn li th nht ca axit maleic ln n mc l phi gii hon ton phng trnh
bc 2 tm [H3O+].
pH = log2,92.102 = 1,54
chng minh rng, s phn li ca axit maleic giai on 2 trong nhng iu kin
cho tht s c th b qua ta thay [H3O+] = [HM] vo phng trnh K2:
H3 O+ M2
= 5,96.107 ; M2 = 5,9.107
HM
Axit sunfuric phn li hon ton giai on th nht v ch phn li mt phn giai on th
hai. Nu b qua s phn li giai on th hai th nng ion hiro l:
218
[H3O+] = [ HSO4 ] = 0,0400 mol/l
H3 O+ SO24
1,20.102
HSO4
(
H3 O+ H3 O+ 0,0400
)
= 1,20.102
+
0,0800 H3 O
HCO3 OH
CO32 + H2O HCO3
+ OH ; = 2,13.104
CO32
[H2CO3 ] OH
HCO3 = 2,25.108
+ H2O H2CO3 + OH ;
HCO3
[HCO3] = [OH]
[H2CO3 ] OH
= 2,25.108
HCO3
V d: Tnh nng ion hiro trong dung dch m ca axit phtaleic 0,100 M (H2P) v
kali biphtalat 0,200 M (KHP).
H3 O+ HP
H2P + H2O H3O+ + HP ; = K = 1,12.103
[H2P ] 1
nn
v do :
3
H3 O+ = 1,12.10 0,100 = 5,60.104 mol / l
0,200
Tnh [P2] c thc hin bng cch thay th [H3O+] v [HP] vo phng trnh K2. Kt
qu tnh ton ch r rng gi thit a ra l hon ton ng n.
HA + H2O H2A + OH
V d: Tnh nng ion hiro trong dung dch m kali biphtalat (KHP) 0,0500 M v kali
phtalat (K2P) 0,150 M.
221
Phng trnh phn li ca axit phtaleic giai on hai:
H3 O+ P2
K2 = = 3,91.106
+ 2
HP + H2O H3O + P ;
HP
[P2] C K 2 P = 0,150
T :
6 2
H3 O+ = 3,91.10 5.10 = 1,30.106 mol / l
1,5.101
1,3.106 0,0500
= 1,12.103
[H2P ]
Do gi thit a ra l hon ton c th ng dng c. Nng H2P nh thua rt
nhiu so vi nng HP v P2, v c th b qua phn ng phn li ca baz HP.
HM + H2O OH + H2M
V d: Xy dng ng chun 25,00 ml dung dch axit maleic 0,100 M bng dung
dch NaOH 0,100 M.
Tnh pH ca dung dch sau khi thm 5,00 ml dung dch NaOH. Sau khi thm dung dch
kim, axit maleic cha b chun H2M v baz lin hp vi n HM to thnh dung dch m.
B qua s phn li ca HM v tnh pH ging nh trng hp ca dung dch m to thnh t
n axit yu. Ta tm c nng H2M ( CH2M ) cha b chun v nng ca baz lin hp
HM (CNaHM).
[H2M] 6,67.102 M
[HM] 1,67.102 M
223
Thay th cc gi tr tm c vo phng trnh K1 ta c [H3O+] = 4,8.102 mol/l. Do ,
gi thit [H3O+] << CH2M hoc CHM u khng ng nn cn thit phi s dng nhng
phng trnh (11.7) v (11.8) chnh xc hn:
V dung dch l axit nn gi thit cho rng [OH]rt nh l hon ton ng n. Thay th
cc gi tr [HM] v [H2M] trn vo phng trnh K1:
K1 =
(
H3 O+ 1,67.102 + H3 O+
)
= 1,2.102
2 +
6,67.10 H3O
v t
pH = 1,76
H3 O+
K1K 2CHM 1,20.102 5,96.107 5,00.102
= = 7,60.105 mol / l
K1 + CHM 5,00.10 2
+ 1,20.10 2
pH = 4,12
Vng m th hai: Tip tc thm kim vo, mt dung dch m mi s hnh thnh, bao
gm axit HM cha chun ht v baz M2 lin hp vi n. Nu baz thm vo n lng
b qua phn ng ca HM vi nc to thnh OH (mt vi phn mi mililit), pH ca
dung dch c th tnh ton d dng t K2. Chng ta tnh pH ca hn hp khi thm 25,50 ml
dung dch kim lm v d:
224
( 25,50 25,00 ) 0,100 0,050
CNa2M =
50,50 50,50
H3 O+ 0,050
50,50
= K 2 = 5,96.107
2,45
50,50
im tng ng th hai: sau khi thm 50,00 ml dung dch NaOH 0,100 M vo 25,00
ml dung dch H2M 0,100 M ta thu c dung dch Na2M 0,0333 M. Trong h ny, phn ng
ca M2 vi nc l cn bng chim u th nn ch cn ch n cn bng m thi. Nh
vy l:
M2 + H2O OH + HM
K H2O 1,00.1014
Kb = =
K2 5,96.107
Hnh11.2
Hnh 11.3
ng chun dung dch axit maleic 0,100 M bng dung dch kim NaOH 0,100 M
c dn ra trn hnh 11.2. ng chun c xy dng trn c s nhng tnh ton
trong v d trn y. Nhng bc nhy tng ng vi php chun proton th nht v th hai
c phn chia rt r rng. V nguyn tc, nu chn ng ch th s xc nh c hoc mt
hoc c hai bc nhy khi chun axit maleic. Vi quan im thc t, s dng bc nhy
th 2 thun tin hn bi v s bin i pH trong vng im tng ng th hai c th
hin chnh xc hn.
Trong trng hp ca axit oxalic (ng s 2) t s K1/K2 bng khong 1000, do trong
vng im tng ng th nht, im un ca ng cong c quan st thy nhng bc
nhy nh ti mc thc t khng th xc nh c bng ch th. Kt qu l, xc nh chnh
xc oxalic ch c th s dng im tng ng th hai.
K H2O
HCO3 + H2O H2CO3 + OH ; ( K b )2 = = 2,25.108
( K a )1
Hnh 11.4
ng chun 25,00 ml dung dch natri cacbonat 0,100 M bng dung dch axit clohiric 0,100 M
229
11.5 ng chun cht in li lng tnh
K H2O
H2PO4 + H2O OH + H3PO4 ; Kb = = 1,14.1012
K1
K H2O
HPO24 + H2O OH + H2PO4 ; Kb = = 1,58.107
K2
Cc amino axit n gin nht thuc loi cc cht in li lng tnh quan trng. Tnh cht
axit - baz ca chng l do trong phn t c c nhm chc axit v nhm chc baz. Trong
dung dch nc ca aminoaxit in hnh, v d glyxerin, ba cn bng quan trng sau y c
thit lp.
Phng trnh u tin l mt bin dng ca phn ng axit - baz - phn ng axit - baz ni
phn - v v thc cht tng t phn ng ca axit cacboxilic vi cc amin:
Hng s ion ha ca nhng amin bo in hnh c c trng bng nhng i lng trong
khong 104 105. Hng s phn li ca phn ln axit cacboxilic cng nm trong khong . Do
, nhng cn bng (11.19) v (11.22) thc t chuyn dch v bn phi.
230
Cc ht amino axit mang ng thi c in tch dng v in tch m
(phng trnh 11.19) c gi l cc ion lng cc. T gi tr cc hng s cn bng (11.20)
v (11.21) th tnh cht axit ca ion lng cc glixin th hin mnh hn tnh baz v do
dung dch glixin c phn ng axit yu.
Khc vi cc ion ch c in tch dng hoc m, ion lng cc amino axit mang ng
thi c in tch dng v in tch m nn khng in chuyn ti c catt v ant trong in
trng. pH ca dung mi c nng dng anion v cation bng nhau, s in chuyn ca
amino axit trong in trng khng quan st thy. Gi tr pH c gi l im ng in
v l c tnh quan trng ca amino axit. C th d dng tm c im ng in khi bit
hng s phn li. V d nh i vi glixin:
H3 O+ H2NCH2COO
=K ;
+ a
H3 NCH2COO
OH H3+ NCH2COOH
=K
+ b
H3 NCH2COO
im ng in:
[H2NCH2COO] = [H3+NCH2COOH]
H3 O+
= Ka
OH K b
K H2O
Sau khi thay [OH] bng v bin i:
H3 O+
K a K H2O
H3 O+ =
Kb
i vi glixin, im ng in nm pH = 6,0:
10
H3 O+ = 2.10 1.1014 = 1.106
2.10 12
v theo nh ngha:
HM M2
o
[H M ]
= 2 ; = ; 2 =
1
CH2M CH2M CH2M
o + 1 + 2 = 1
Chng ta c th din t o, 1 v 2 qua [H3O+], K1, K2. Bin i cc phng trnh hng
s phn li ta c:
HM = 1 [ 2 ] ; M2 = 1 2 [ 2 ]
K H M K K H M
[H3 O+ ] 2
H3 O+
K1 H3 O+
1 = (11.24)
2
H3 O+ + K1 H3 O+ + K1K 2
K 1K 2
2 = (11.25)
+ 2
H3 O + K1 H3O+ + K1K 2
Hnh 11.5
Chng 12
chng 10 chng ta bit khng th chun c nhng axit hoc baz c hng s
phn li nh hn 1.108 bi v phn ng xy ra khng hon ton v rt kh xc nh im cui.
Nhng c th chun nhiu hp cht trong s nhng hp cht k trn trong dung mi khng
nc, bi v cc dung mi ny c kh nng lm tng tnh axit hoc tnh baz ca cc hp cht
. Nhng dung mi khng nc c s dng thnh cng chun nhiu cht kh tan
trong nc.
Dung mi lng tnh: dung mi lng tnh l nhng dung mi c c tnh axit v tnh
baz, t ion ha hoc proton phn. Mc d nc l dung mi lng tnh in hnh nht, nhiu
hp cht khc cng th hin tnh cht tng t thng qua cc phn ng.
2H2O H3O+ + OH
SH2+ + S
2SH
Dung mi KS Hng s in mi
Nc 1,01.1014 78,5
Dung mi aproton hoc dung mi tr: Nhng dung mi ny khng th hin tnh axit
hoc tnh baz v khng proton phn mc ng k. Benzen, tetraclorua cacbon, pentan
thuc loi dung mi ny.
hon ton ca phn ng axit - baz: c th hnh dung phn ng xy ra khi chun
baz yu B bng dung dch chun axit mnh trong nc dng:
BH+
K cb = = Kb (12.2)
[B] H3O+ K H2O
R rng l, hng s cn bng ca phn ng trn bng t s hng s phn li baz B v tch
s ion ca nc.
A
K cb = =
Ka
(12.3)
[HA ] OH K H2O
y HCOOH2+ l proton solvat ha, tng t nh H3O+ trong dung dch nc. Hng s
cn bng ca phn ng :
BH+
K 'b
K cb = = (12.5)
[B] HCOOH2+ KS
BH+ HCOO
B + HCOOH BH+ + HCOO; K 'b = (12.6)
[B ]
Cn KS l hng s proton phn ca axit focmic:
Chun axit yu HA bng natri etilat trong etanol, c th d dng hnh dung dng:
A
K'
K cb = = a (12.9)
[HA ] C2H5O+ K S
A C2H5 OH2+
C2H5OH2+ =
HA + C2H5OH +A ; K 'a (12.10)
[HA ]
v KS l hng s proton phn ca etanol:
T nhng bn lun trn y, r rng l nhng php chun axit - baz trong cc dung
mi c hng s proton phn thp chim u th. Ngoi ra, nhng phn ng axit - baz s xy
ra hon ton hn trong cc dung mi c gi tr K 'a v K 'b ln. Hai iu kin gii trn y
khng phi l hon ton c lp vi nhau v cng khng th c on quyt nh s la
chn dung mi lng tnh cho php chun khng nc.
nh hng ca cng axit hoc cng baz ca dung mi ln tnh cht ca cht
tan: Hng lot nhng dung mi lng tnh nh axit focmic, axetic, sunfuric d dng cho
proton hn l lin kt proton v do c xem nh nhng dung mi axit. Trong nhng
dung mi nh th, tnh baz ca cht tan c tng ln ng thi tnh axit gim xung. V
d nh, khng nn chun anilin C6H5NH2 trong dung dch nc bi v hng s baz ca
n khong 1010 nhng trong axit axetic bng, alinin l baz mnh hn nhiu bi v kh
nng tng tc vi dung mi ca n c tng cng. V d: hng s cn bng Kb ca
phn ng:
C6 H5 NH3+ + OAx
C6H5NH2 + HOAx
238
cao hn kh nhiu so vi Kb ca phn ng tng t trong nc.
C6H5NH3+ + OH
C6H5NH2 + H2O
HA + SH SH2+ + A
Mt qu trnh tng t cng c quan st thy khi ha tan baz khng tch in B:
B + SH BH+ + S
BH+ + SH SH2+ + B
A + SH HA + S
La chn dung mi lng tnh chun axit - baz: hon ton ca phn ng axit -
baz t l thun vi gi tr hng s phn li ca axit hoc baz ha tan v t l ngc vi hng
s proton phn ca dung mi. Ngoi ra, hng s phn li ph thuc vo tnh axit hoc tnh baz
v hng s in mi ca dung mi. Nh vy l, la chn thnh cng dung mi cho mt
php chun cn ch 3 yu t c lp.
1. Hng s proton phn ca dung mi. Sao cho i lng ny cng nh cng tt.
2. Tnh cht axit - baz ca dung mi. chun baz yu, dung mi c tnh cht cho
proton (ngha l dung mi axit) l thch hp. chun axit yu cn chn dung mi c tnh
cht nhn proton tt.
chun baz rt yu, nn chn axit axetic bng lm dung mi, bi v axit ny c kh
nng cho proton v lm tng cng baz ha tan. Hng s proton phn ca axit cng cn
thch hp (3,6.1015), thp hn ca nc mt cht. Nhng c lp vi nhng u th trn, axit
axetic li c hng s in mi thp. Hai u im quan trng hn mt nhc im nn axit
axetic l dung mi tt nht chun baz yu; nhng khi chun axit yu, axit axetic li
thua nc bi v c tnh cht nhn proton yu hn.
Xem xt kh nng s dng axit focmic lm dung mi axit. Tng t nh dung mi axit
axetic, nhng axit focmic c kh nng cho proton mnh hn nc. Ngoi ra, khc vi axit
axetic, axit focmic c hng s in mi gn vi nc. Phn xt theo hai tnh cht th axit
focmic dng nh s l dung mi l tng cho chun baz yu. Nhng ng tic l, hng
s proton phn ca axit focmic li ln hn nhiu so vi nc hoc axit axetic. Do , mc d
c hai phm cht rt tt, axit focmic ch c u th cc tiu so vi nc.
Khc vi s phn li ca axit benzoic, s phn li ca NH4+ trong etanol gim xung khng
ng k. Phn ng ca NH4+ vi baz mnh trong etanol xy ra hon ton hn so vi trong
nc bi v hng s proton phn ca etanol thp hn so vi nc. Do , php chun NH4+
trong etanol c ngha.
Hng s proton phn ca nc bng 1.1014, ca etanol tuyt i l 8.1020; hng s phn
li ca NH4+ bng 6.1010 trong nc v 1.1010 trong etanol tuyt i.
NH4+ + OH
NH3 + H2O
K cb =
[NH3 ] =
Ka
=
6.1010
= 6.104
NH4+ OH K H2O 1.1014
NH4+ + C2H5O
NH3 + C2H5OH
K cb =
[NH3 ] =
K a'
=
1.1010
= 1,2.109
NH4+ C2H5 O K S 8.1020
Trong c hai trng hp, im tng ng, nng chung ca NH3 s l 0,10 M. Khi
chun trong nc:
Nu gi thit rng, im tng ng, trong c hai trng hp [ NH4+ ] << [NH3] ta c:
0,10
1. 6.104 ; OH = NH4+ = 1.103 mol / l
2
OH
0,10
2. 1,2.109 ; OH = NH4+ = 9.106 mol / l
2
OH
Nhng dung mi khng lng tnh c u th l khng chy ua ginh proton vi cc cht
tham gia chun ; ni cch khc l, hng s proton phn ca nhng dung mi ny tin dn
ti khng. Do , khi chun trong nhng dung mi ny c th t ti hon ton ca
phn ng ln.
Phng php ph bin nht pht hin im cui khi chun trong dung mi khng
nc l o th ca in cc thy tinh nh hm s ca nng proton solvat ha. in cc
thy tinh s c bn chi tit trong gio trnh phng php phn tch cng c. Nhiu ch th
c ng dng khi chun trong cc dung mi nc cng thch hp trong dung mi khng
nc. Tt nhin l khng th s dng tnh cht ca ch th trong mi trng nc d on
tnh cht ca n trong dung mi khng nc. S hn ch trong thng bo v tnh cht ca ch
242
th trong dung mi khng nc dn ti vic la chn ch th, trong a s trng
hp, c thc hin mt cch thc nghim.
Chun axit - baz trong dung mi khng nc c ng dng gii quyt nhiu vn .
Trong cc mc tip theo ca chng ny s bn lun ti nhng kh nng .
y Tch l nhit ca thuc th trong thi gian chun ha, T l nhit trong thi
gian hon thnh php phn tch, V l th tch thuc th, Vhc l th tch thuc th c hiu
chun.
Pht hin im cui khi chun trong axit axetic: Tm tinh th v metyl tm l hai ch
th axit - baz thch hp cho php chun trong axit axetic. C hai ch th ny c s chuyn
mu phc tp. V d nh mu ca metyl tm, theo mc axit ha, mu ca dung dch bin
i t tm qua lc n vng. S mt mu tm ch r rng, t ti im tng ng. Mu
243
ca metyl tm bin i khng tht r rng nh mong mun, nhng khi chun baz
mnh, sai s c h thp. Khi chun nhng baz rt yu, xc nh im cui bng mt
khng chnh xc, cn xc nh bng phng php in th vi in cc thy tinh (xem
phng php phn tch cng c).
Tiu chun ha dung dch axit pecloric: tiu chun ha dung dch axit pecloric trong
axit axetic, kalibiphtalat thng c dng lm cht chun gc. Cn ch l,
kalihirobiphtalat trong axit axetic l mt baz mnh, do c th s dng n tiu
chun ha dung dch axit. Phn ng xy ra to thnh axit t phn li.
ng dng php chun trong axit axetic: S dng axit axetic khng nc lm dung
mi cho php chun nhiu hp cht v c v hu c khng th chun c trong dung
mi nc. V d, bng cch chun trong axit axetic bng c th xc nh nhng mui natri
nh clorua, bromua, ioua, nitrat, peclorat v sunfat. Dung dch axit pecloric chun trong axit
axetic bng hoc trong ioxan khng nc c dng lm cht chun. Trong dung mi ny
cng c th xc nh cc mui amoni v cc mui kim loi kim ca phn ln cc axit
cacboxilic, v d nh amoni benzoat, natri salixilat, natri axetat, kali tactrat, natri xitrat.
ng 1 trn hnh 12.1 l ng cong in hnh tng ng vi php chun dung dch natri
axetat trong axit axetic khng nc bng dung dch axit pecloric cng trong dung mi .
so snh, ng chun l thuyt (ng 2) dung dch natri axetat bng dung dch axit
pecloric cng nng vi ng 1 nhng trong nc cng c dn ra trn hnh 12.1.
Hnh 12.1
Hai ng chun dung dch natri axetat 0,075 M bng dung dch HClO4 0,100 M
1. ng chun thc nghim (cht b chun v cht chun u trong axit axetic khng
nc).
2. ng chun l thuyt ca dung dch natri axetat bng dung dch HClO4 u trong
nc.
244
Axit axetic khng nc l dung mi c bit thch hp cho chun cc cht
hu c c nhm chc amino hoc amid. Khc vi nc, dung mi ny thch hp cho chun
trc tip phn ln cc amino axit bng cc dung dch axit chun. Nh nhn xt trong
chng 11, cc amino axit tn ti ch yu dng ion lng cc l axit hoc baz khng
mnh c th chun . Nhng trong axit axetic bng, s phn li ca nhm cacboxilic thc
t hon ton b cn tr nn c th chun nhm amino bng axit pecloric.
Trong nhiu v d dn ra trn y, dung dch natri axetat trong axit axetic c s
dng lm dung dch chun trong chun ngc.
Hnh 12.2
Chng 13
Chun to phc
Ion ca nhiu kim loi phn ng vi cp in t cho t mt cht khc to thnh hp cht
phi tr hoc ion phc. Cht c kh nng cho i in t c gi l phi t (ligan), cn phi
c t nht mt i in t khng phn chia to lin kt. Cc phn t nc, amoniac v cc
ion halogenua l nhng phi t thng gp.
Chng ta xt cn bng gia ion kim loi M c s phi tr bng 4 v phi t 4 rng D, in
tch ca M v D quyt nh in tch ca sn phm phn ng nhng i vi cc bn lun tip
theo, iu khng c ngha nn in tch c b qua.
M+D MD
K=
[ MD]
[ M][D]
247
K l hng s cn bng.
M +B MB
MB + B MB2
K1 =
[ MB] v K2 =
[ MB2 ]
[ M][B] [ MB][B]
Tch s K1 v K2 cho ta phng trnh hng s cn bng ca qu trnh tng hp:
2 = K1K 2 =
[ MB] [ MB2 ] = [ MB2 ]
[ M][B] [ MB][B] [ M][B]2
M + 4A MA4
ng chun complexon
1. Chun 60,0 ml dung dch kim loi M 0,020 M bng dung dch phi t D 4 rng vi
s to thnh hp cht MD.
2. Chun bng dung dch phi t 2 rng B 0,040 M vi s to thnh hp cht MB2.
3. Chun bng dung dch phi t 1 rng A 0,080 M vi s to thnh hp cht MA4.
Khng ph thuc vo loi phn ng c s dng chun , sai s chun gim khi
hon ton ca phn ng tng ln. Vi quan im , khng cn nghi ng g na, nhng
phi t a rng c u th r rt so vi nhng phi t n rng bi v chng to vi ion kim
loi nhng phc bn hn.
Chun to phc l mt trong nhng phng php chun lu i nht. Php chun
ion ioua bng dung dch thy ngn (II) theo phn ng:
Hg2+ + 4I HgI24
13.2.1 Thuc th
Phng php chun da trn phn ng to phc ca cc ion kim loi vi nhm cc
axit aminopolicacboxilic c gi l phng php chun complexon. Cc complexon l
nhng dn xut ca cc axit aminopolicacboxilic:
V axit ny t tan trong nc nn trong thc t ngi ta thng dng dng mui inatri
(Na2H2Y hay comlexon III, trilon B).
CH2 COOH
H2C CH N
CH2 CH2 COOH
250
Cc complexon to phc bn vi nhiu ion kim loi. Cc phn ng to phc
ny tha mn tt c cc iu kin ca phn tch th tch; do , ngy nay phng php chun
complexon tr thnh mt trong nhng phng php phn tch th tch ph bin nht.
H3 Y
o
[H Y ]
= 4 ; =
1
C C
R rng l vng axit va phi (pH = 3 6) dng H2Y2 l dng chim u th, pH = 6
10 dng HY3 chim u th v ch pH > 10 th dng Y4 mi bt u chim u th.
Hnh 13.2
T th phn b trn, r rng rng nhng phn ng xy ra trong dung dch trung tnh v
kim va phi vit di dng sau:
Hnh 13.3
Men+ + Y4 MeY(n4)+
MeY (n 4)+
K MeY = (13.1)
+
Me Y
n 4
o
Bng 13.2 Hng s bn ca phc kim loi vi EDTA ( 20 C v lc ion bng 0,1)
Xy dng ng chun cho phn ng gia ion kim loi v EDTA v c bn khng
khc vic xy dng ng chun trong phng php chun axit baz, nhng trong
trng hp ny phc tp hn v trng hp chun axit baz thng ch cn nghin cu
mt cn bng, cn trong trng hp chun complexon cn nghin cu mt s cn bng ln
hn.
13.2.3.1 nh hng ca pH
S nghin cu cn bng trong dung dch cha ion kim loi v EDTA ch r rng, mc
to phc ph thuc vo pH ca dung dch. chun nhng cation to phc km bn (v
d: Mg2+, Ca2+) ngi ta phi chun trong mi trng kim. Ngc li, chun nhng
cation to phc bn hn (v d: Zn2+, Ni2+) c th thc hin thnh cng ngay c trong mi
trng axit va phi.
xy dng ng chun ion kim loi bng EDTA trong dung dch m c th s
dng gi tr 4 mt cch rt tin li:
Y 4
4 = (13.2)
C
Nh vy:
K 1K 2 K 3 K 4
4 =
4 3 2
(13.3)
H + + K 1 H + + K 1K 2 H + + K1 K 2 K 3 H + + K 1 K 2 K 3 K 4
254
Bng 13.3 Cc gi tr 4 ca EDTA cc gi tr pH
pH 4 pH 4
12,0 9,8.101
Thay [Y4] bng 4C (phng trnh (13.2)) vo phng trnh hng s bn ca phc (13.1)
ta c:
MeY (n 4)+
K 'MeY = K MeY = (13.4)
+
Me C
n
V d: V ng chun 50,0 ml dung dch Ca2+ 0,0100 M bng dung dch EDTA
0,0100 M trong dung dch m c pH = 10.
Tnh pCa trc im tng ng: Cho n trc im tng ng, nng chung
ca Ca2+ bng tng s nng ion Ca2+ cha b chun v nng Ca2+ do phc phn li ra.
Thng thng, hon ton hp l khi chng ta chp nhn rng nng ion Ca2+ do phc phn
li ra nh thua nng ion Ca2+ cha b chun nn c th b qua nng ny (Ta c chp
nhn gi thit ny bi v [Ca2+] do phc phn li ra im tng ng cn nh thua [Ca2+]
do phc phn li ra trc im tng ng v nng [Ca2+] cha b chun cn ln,
ngn cn s phn li ca phc CaY2. Khi ta tnh ton [Ca2+] im tng ng di y ta
s thy r hn iu ta gi thit trn y l hon ton ng n).
v pCa=2,48.
[Ca2+] = CEDTA
K'CaY pH = 10 l 1,75.1010
(xem mc trn)
Vy:
0,00500 0,00500
= = 1,75.1010
2 +
Ca CEDTA 2+ 2
Ca
[Ca2+] = 5,35.107 M;
do :
pCa = 6,27.
Tnh pCa sau im tng ng: Tnh nng chung ca CaY2 v EDTA sau im
tng ng rt d dng. V d, sau khi thm 60,0 ml cht chun.
50,0 0,0100
CCaY = = 4,55.103 M
110
10,0 0,0100
CEDTA = = 9,1.104 M
110
Mt cch gn ng c th vit:
4,55.103
= 1,75.1010 = K 'CaY
+
Ca 9,1.10
2 4
256
2+ 10
[Ca ] = 2,86.10 M
do :
pCa = 9,54.
T nhng tnh ton nh trn ta c th v ng chun ion Ca2+ trong nhng dung dch
m c pH khc nhau. T hnh 13.4, r rng l, s bin i pCa ch r rt im tng
ng khi pH 8 (Nhng ti sao ta khng chun pH=12 c bc nhy pCa ln nht? Cu
hi ny s c tr li mc sau ni v im cui khi chun ).
Hnh 13.4
nh hng ca pH ln ng chun dung dch Ca2+ 0,0100 M bng dung dch EDTA 0,0100
M
257
Hnh 13.5
Hnh 13.6
Gi tr pH nh nht, cn thit chun cc dung dch cation bng dung dch EDTA
Ta k hiu:
259
Men +
= (13.5)
CMe
vi CMe l nng chung ca tt c cc dng cha ion kim loi cn chun , tr loi
phc ca EDTA vi kim loi cn chun . i vi dung dch cha Zn(II) v amoniac ta c
th m t nh sau:
CMe = [Zn2+] + [Zn(NH3)2+] + [ Zn(NH3 )22+ ] + [ Zn(NH3 )32+ ] + [ Zn(NH3 )42+ ] (13.6)
Zn(NH3 )2+
K1 =
Zn [NH3 ]
2 +
v t :
[Zn(NH3)2+] = K1[Zn2+][NH3]
Mt cch tng t:
[Zn(NH3)22+] = K1K2[Zn2+][NH3]2
Gii phng trnh ny cng vi phng trnh (13.5) v cho [Men+] = [Zn2+] ta tm c:
1
= (13.7)
1 + K1 [NH3 ] + K1K 2 [NH3 ] + K1K 2K 3 [NH3 ] + K1K 2K 3 K 4 [NH3 ]
2 3 4
Cui cng gii ng thi cc phng trnh (13.4) v (13.5) ta tm c hng s cn bng
iu kin ca phn ng EDTA vi Zn2+ trong dung dch m cha amoniac v amoni clorua:
ZnY 2
K "ZnY = 4K ZnY = (13.8)
CMe .CEDTA
V d: Tnh pZn trong cc dung dch khi trn ln 40,0; 50,0; 60,0 ml dung dch EDTA
0,0010 M vi 50,0 ml dung dch Zn2+ 0,0010 M. Gi thit rng dung dch Zn2+ v dung dch
260
EDTA u cha 0,100 M NH3 v 0,176 M NH4Cl to nn gi tr pH khng i
bng 9,0. Nhng hng s bn ca cc phc amiacat Zn(II) l nh sau: K1 = 1,9.102; K2 =
2,2.102; K3 = 2,5.102; K4 = 1,1.102; KZnY = 3,2.106.
1
= = 8,0.106
4 5
1 + 19 + 420 + 1,04.10 + 1,14.10
2. Tnh pZn sau khi thm vo 40,0 ml EDTA. Nng Zn2+ cha phn ng vi EDTA
thi im ny vi s gn ng kh tt l:
do : pZn = 9,05.
3. Tnh pZn sau khi thm 50,0 ml EDTA: im tng ng [ZnY2] = 5,00.104. Tng
nng cn bng ca cc dng phc km khng cha EDTA bng tng nng cn bng ca
cc dng khng to phc vi EDTA:
CMe = CEDTA.
v:
a kt qu ny vo (13.8) ta c:
5.10.104
K"ZnY =1,33.1010 = ;
C2Me
do : pZn = 11,81
4. Tnh pZn sau khi thm 60,0 ml EDTA: trong trng hp ny dung dch c d EDTA:
4,55.104 10
1,33.1010 = CMe = 3,76.10 mol/l
9,51.105.CMe
do : pZn = 14,52.
Trn hnh 13.7 dn ra hai ng chun l thuyt Zn2+ bng dung dch EDTA pH =
9. Nng cn bng ca amoniac trong trng hp th nht l 0,100 M v trong trng hp
th hai l 0,0100 M. Hnh v ch r, amoniac lm gim bc nhy trn ng chun . V
vy, nng cht to phc ph khng c vt qu nng ti thiu, ngn nga to
hiroxit. (Chng ta nhn thy rng, gi tr khng nh hng n pZn sau im tng ng
nhng gi tr 4 v do pH ng vai tr quan trng trong s to thnh vng ny ca ng
chun ).
262
Hnh 13.7
nh hng ca nng amoniac n php chun dung dch Zn2+ 0,0010 M bng dung dch EDTA
0,0010 M. C hai php chun u c thc hin dung dch m c pH = 9.
Ch th kim loi: Trong chun bng EDTA hoc l bng nhng thuc th to phc
khc, ngi ta thng dng mt s cht ch th kim loi xc nh im cui. Nhng ch th
ny l nhng cht mu hu c to phc vng cng (chelat) vi cc cation kim loi nhng
vng pH xc nh, ty thuc vo tnh cht ca cation kim loi v ch th. Nhng phc ny c
mu kh m, c th pht hin ion kim loi trong khong nng 106 107 M. Phn ln
ch th kim loi c kh nng lin kt proton v to thnh nhng hp cht mu gn nh ging
mu phc kim loi. V vy, chng ng thi cng l ch th axit baz nn chng ch ng vai
tr ch th kim loi mt cch thun li vng pH m khng c phn ng cnh tranh ca
proton. Ericrom T l ch th c tnh cht nh nu trn v c s dng rng ri nht trong
chun complexon. Trong dung dch axit v kim va phi, cn bng sau y chim u th:
263
OH O
N Ka = 5.107 N
+ H+
N N
OH OH
O2N O2N
SO3 SO3
Xanh bin
H2In H2In + H+
Xanh bin
Hnh 13.8
Trong chun complexon, ngi ta s dng nhiu bin php khc nhau. Sau y l
nhng cch ph bin nht:
Chun trc tip: Theo Welcher, ngi ta c th chun trc tip 25 ion kim loi. Chun
trc tip ch c th thc hin vi nhng ion kim loi phn ng nhanh vi EDTA v c ch th
thch hp xc nh im cui. Trong trng hp ngc li, ngi ta c th s dng phng
php chun ngc hay chun thay th.
Chun thay th: Trong chun thay th, ngi ta a vo dung dch phn tch mt
lng d phc ca EDTA vi Mg2+ hoc Zn2+. Nu cation kim loi cn xc nh to vi
EDTA phc bn hn phc tng ng ca Zn2+ hoc Mg2+ th phn ng s din ra nh sau:
Sau ngi ta chun Mg2+ b y ra khi phc bng dung dch chun EDTA.
Chun axit baz: Trong phng php chun axit baz, ngi ta thm vo dung
dch trung tnh ca ion kim loi mt lng d EDTA. Phn ng xy ra nh sau:
Chun lng ion hiro c gii phng ra bng dung dch kim suy ra lng ion
kim loi cn xc nh.
265
Chng 14
Chun Oxi ha kh
14.1.1 nh ngha
Cht oxi ha (Ox) sau khi nhn electron tr thnh cht kh (Kh) gi l cht kh lin hp
vi n. Mi cp oxi ha kh lin hp c th biu din bng phng trnh:
Ox + ne Kh
2H+ + 2e H2 2H+/H2
Electron khng tn ti trng thi t do trong dung dch, do mt cht ch th hin tnh
oxi ha khi c cht kh cho electron ca n hay ngc li.
Phn ng trao i electron gia cc cht oxi ha v cht kh gi l phn ng oxi ha kh.
266
aOx1 + bKh2 cKh1 + dOx2
Hnh 14.1
267
H oxi ha kh ng km
i vi h n gin:
Ox + ne Kh
RT aOx
E = Eo + ln
nF aKh
Th oxi ha kh tiu chun quyt nh chiu ca phn ng oxi ha kh, nhng trong thc
t c nhng yu t nh hng rt mnh n th oxi ha kh ca cc cp oxi ha kh lin hp
v do nh hng n chiu ca phn ng. Sau y ta xt tng trng hp c th.
Vi cp ny c th xy ra phn ng:
Th oxi ha kh ca cp ny:
268
0,059 0,059 a AsO3
E = Eo + log a2 + + log 4
2 H 2 a AsO3
3
0,059 2 0,059
E' = Eo + log 108 = 0,57 + ( 8 ) 2 = +0,10(0,098)
2 2
Nh vy, pH cng tng th th chun iu kin cng gim ngha l kh nng oxi ha ca
AsO34 gim khi pH tng, cn kh nng kh ca AsO33 li tng cng vi pH. Chnh v vy
m th oxi ha chun ca cp AsO34 / AsO33 = 0,57 V khi pH = 0 nn AsO34 c th oxi ha
c I v th chun ca cp I2/2I = 0,54 V.
Khi cht oxi ha hoc cht kh ca mt cp oxi ha kh lin hp tham gia vo phn ng
to phc th th oxi ha kh cng bin i. Chng ta xt mt v d c th.
FeF63
o'
E =E = th oxi ha kh tiu chun iu kin khi =1 (3)
6
Fe2+ F
FeF63
Theo phng trnh to phc (2): = 1016 (4)
6
Fe 3+
F
Fe3 +
Chia (3) cho (4) ta c: = 1
Fe2+ 1016
Fe3 +
Eo ' = Eo + 0,059 log = 0,77 + 0,059 log 1 = 0,17 V
Fe
2 + 1016
2CuI + I2 2Cu2+ + 2I
Cu2+ + e Cu+
trong Eo = 0,17 V
Cu2+ + I + e CuI
th
E = Eo + 0,059log[Cu2+][I]
ta c:
Cu2+
= 1
Cu 1012
+
1
E' = E + 0,059 log = 0,17 + 0,059 log1012
12
10
2Cu2+ + 4I 2CuI + I2
Gi s c phn ng:
trong :
aOx1 + ne aKh1
271
bOx2 + ne bKh2
E1 = E1o +
0,059
log
[Ox1 ] a
n [Kh ]a 1
E2 = E2o +
0,059
log
[Ox2 ] b
n [Kh ]b 2
E1o +
0,059
log
[Ox1 ] = Eo + 0,059 log [Ox2 ]
a b
2
n [Kh ]a 1
n [Kh ]b 2
E1o E2o =
0,059
log
[Kh1 ] [Ox2 ] a b
n [Ox1 ]a [Kh2 ]b
[Kh1 ]a [Ox2 ]b =K
[Ox1 ]a [Kh2 ]b
log K =
(
n E1o E2o )
0,059
1,55 0,77
log K = = 13,4 K = 1013,4
0,059
V d: Tnh th ca dung dch khi chun 50 ml FeSO4 0,100 M bng dung dch
KMnO4 0,020 M [H+] lun bng 1 M. Cho bit Eo 3+ 2+ = 0,77 V; Eo 2 + = 1,51 V .
Fe / Fe MnO4 / Mn
Fe2+ e Fe3+
Fe3+
0,059 (14.1)
E = 0,77 + log
1 Fe2+
Sau khi qua im tng tng ng, lc ny cp MnO4 /Mn2+ d nn tnh th theo cp
ny da vo bn phn ng:
8
MnO H+
E = 1,51 +
0,059
log 4 (m [H+] = 1) (14.2)
5 Mn2+
Fe3+
0,059
E = 0,77 + log
1 Fe2+
8
MnO H+
5E = 5.1,51 + 0,059log 4
Mn2+
8
Fe3+ MnO4 H+
6E = 0,77 + 5.1,51 + 0,059log (14.3)
Fe Mn2+
2 +
273
Fe3+ 5 Mn2+
=
Fe2+ 5 MnO4
v do :
Fe3 + MnO4
= 1 v [H+] =1 theo gi thit.
+
Fe Mn
2 2 +
6E = 0,77 + 5.1,51
0,77 + 5.1,51
E= = 1,39
6
Bng 14.1
Lng d (ml)
Lng
Fe3+
KMnO4 MnO4
Cng thc tnh E (V)
thm vo Fe2+ Mn2+
(ml) KMnO
FeSO4
4
49,9:0,1=49 E=0,77+0,059log49
49,9 0,1 0,93
9 9
(im T)
0, 059 3
E = 1,51 + log 2.10
50,1 0,1 5 1,49
0,059 2
51,0 1,0 E = 1,51 +
5
log 2.10 1,50
Hnh 14.2
ng chun 50,00 ml dung dch Fe2+ 0,100 M bng dung dch KMnO4 0,020 M
Hnh 14.3
Eh (V) EOxoEKho
A
1,0 Kcb
A 1,20 V 8.1016 B
13
B 1,00 V 3.10
0,8
C 0,80 V 1.1010 C
0,4
E
0,2
0 10 20 30
14.2.3 Tc phn ng v th in cc
Cc dung dch c hai cht oxi ha hoc hai cht kh sinh ra cc ng chun c hai
im un nu th chun ca hai cht cn phn tch khc nhau ln. Nu s khc nhau ln
hn 0,2 V th hai im un thng c phn bit r rng xc nh ring tng hp
phn. Tnh hung hon ton ging php chun hai axit c hng s phn li khc nhau
ln hoc php chun hai ion to kt ta c tan khc nhau ln.
Phn tch chi tit ngun gc ca ng chun cho tng cht ring bit trong hn hp
ca nhng cht phn ng loi ny khng c g kh khn nu s khc bit v th chun ln.
Chng ta ly php chun dung dch cha ion st (II) v titan (III) bng kali pemanganat lm v
d. Th chun ca hai cp ng vai tr cht kh trn l:
Nhng phn thm pemanganat u tin c dng cho ion titan (III) v d dng b oxi
ha hn. Cho n khi nng ca cht ny cn ln trong dung dch, th ca h khng th
cao lm bin i nng ion st (II). Nh vy l, c th thu c nhng im to nn
phn th nht ca ng chun bng cch thay th nhng nng hp thc ca ion titan
(III) v titan (IV) vo phng trnh:
Ti3 +
E = +0,099 0,059 log
2
TiO2+ H+
Ti3+ Fe2+
2E = +0,099 + 0,77 0,059 log
2
TiO2+ Fe3 + H+
nn [Fe3+] = [Ti3+]
Fe2+
E=+
0,87 0,059
log
2 2 2
[TiO2 ] H+
Hnh 14.4
279
ng chun 50,0 ml dung dch hn hp Ti3+ 0,050 M v Fe2+ 0,200 M bng dung dch KMnO4
0,050 M. Nng H+ ca dung dch lun bng 1,0 M
Nhng ch th oxi ha kh thng thng l nhng cht chuyn mu khi b oxi ha hoc
kh. Khc vi cc cht ch th c bit c mu bin i ph thuc nhiu vo bn cht ha hc
ca cht cn phn tch v cht chun, s chuyn mu ca cc cht ch th tht s oxi ha kh
ph thuc vo s bin i th in cc ca h xut hin do s tin trin ca php chun .
Inox + ne Inkh
E = Eo
0,059
log
[ InKh ] (14.4)
n [InOx ]
Mt ngi ch c kh nng nhn bit s bin i mu khi
0,059
E = EoIn
n
280
Phng trnh trn ch r rng, mt cht ch th thng thng ch c th biu l
kh nng pht hin s chuyn th ca mnh khi cht chun gy nn s chuyn dch th ca
h t EoIn + 0,059/n n EoIn 0,059/n hoc khong (0,118/n) V. i vi nhiu ch th n = 2
v s chuyn dch 0,059 V l .
Mu
Th chuyn
Cht ch th iu kin
Dng ox dch
Dng kh
ha
Phc Fe(II)-5-nitro-
Xanh nht tm +1,25 H2SO4 1 M
1,10-phenantrolin
Axit iphenylamin
Xanh tm Khng mu +1,12 H2SO4 7 10 M
icacboxilic
Phc Fe(II)-1,10-
Xanh nht +1,11 H2SO4 1 M
phenantrolin
Phc Fe(III)-5-
metyl,1,10- Xanh nht +1,02 H2SO4 1 M
phenantrolin
iphenylamin
tm Khng mu +0,85 Axit long
sunfomic axit
Xanh nht
N N
O 2N H3C
N N
2 N N N + 2H+ + 2e
iphenylamin iphenylbenziin
(khng mu) (khng mu)
H H H H
N N N N
+ 2H+ + 2e
iphenylbenziin iphenylbenziin tm
(khng mu) (mu tm)
Phn ng th nht khng thun nghch, nhng phn ng th hai l thun nghch v to
nn phn ng ch th tht s.
Th kh ca phn ng th hai vo khong 0,76 V. Do ion hiro xut hin trong phng
trnh, s dao ng v axit c nh hng nh n gi tr th, c l do sn phm mu l cht
proton ha.
iphenylamin khng phi l cht tan nhiu trong nc, nn phi iu ch dung dch ch
th trong axit sunfuric. Cn ch l, khng c dng ch th cho cc dung dch c cha ion
wonfram v s to thnh kt ta mu tm. Ion Hg(II) cng gy cn tr v km hm phn ng
ch th.
HO3S N
14.7.2 Ch th c bit
Chng 15
Phn hy v ha tan mu
Hu ht cc php o phn tch u c thc hin trong cc dung dch (thng l dung
dch nc) ca cht cn phn tch. Trong khi mt s mu c th tan tt trong nc hoc trong
cc dung dch nc ca axit hoc baz thng thng th mt s mu li i hi cc thuc th
c tc dng mnh v cch x l chnh xc, nghim ngt. V d nh, khi cn xc nh lu
hunh hoc halogen trong mt hp cht hu c, cn phi x l mu nhit cao v bng
ha cht c tc dng mnh ph v nhng lin kt bn vng gia cc nguyn t ny vi
cacbon. Mt cch tng t, nhng iu kin m bo c tc dng mnh, c hiu qu cao cng
thng c s dng ph v cu trc silicat ca cc khong liu silic a cc cation ca
mu v trng thi t do, to iu kin thun li cho php phn tch.
Ngun sai s thng gp khi phn hy mu, v d nh nung chy nhit cao. Hn
na, ngun sai s li tr thnh mi quan tm c bit trong phn tch lng vt.
Axit nitric c v nng l mt cht oxi ha mnh, ha tan tt c cc kim loi thng
thng, tr nhm v crom tr thnh th ng vi thuc th do s to thnh oxit trn b mt.
Khi nhng hp kim cha thic wonfram hoc antimon c x l bng thuc th nng,
nhng oxit hirat ha t tan, v d nh SnO2.4H2O c to thnh. Sau khi lm ng t, c th
tch cc hp cht keo ny khi cc hp cht ca cc kim loi khc bng cch lc.
Axit nitric nng ring mt mnh, hoc vi hn hp cc axit khc v cc cht oxi ha khc
nh hiro peoxit v brom c s dng rng ri phn hy cc mu hu c trc khi xc
nh hm lng vt kim loi. Qu trnh phn hy c gi l s tro ha t, lm bin i
mu hu c thnh cacbon ioxit v nc. Nu khng thc hin trong bnh ng kn, cc
nguyn t phi kim nh halogen, lu hunh v nit s b mt i hon ton hay mt phn do
bay hi.
Nhiu vt liu b phn hy v ha tan bng axit sunfuric c nng nh tnh hiu qu ca
n nh mt dung mi im si cao (khong 340oC). Hu ht cc hp cht hu c b
ehirat ha v oxi ha nhit v sau li b loi tr khi mu dng cacbon ioxit
v nc nh php x l tro ha t . Hu ht cc kim loi v nhiu hp kim b ha tan
bng axit nng ny.
Trn nhn chai axit pecloric thng ghi hm lng t 60% n 72%. hn hp si hng
nh (72,4% HClO4) thu c 203oC.
15.2.5 Cc hn hp oxi ha
Axit fluoric c dng cng vi cc axit khc ha tan nhng thp kh tan trong cc
dung mi khc.
Hnh 15.1
Bnh un mu bng vi sng c ch to bng vt liu bn, vi sng d truyn qua. Nhng
vt liu ny cng cn phi bn nhit v chu c tc dng ca cc axit thng dng phn
hy mu. Teflon l vt liu gn nh l tng i vi nhiu axit thng dng ha tan mu.
Teflon c im nng chy khong 300oC, khng b mt axit thng thng no tc dng, cho
vi sng chuyn qua rt d dng. Nhng axit sunfuric v axit photphoric u c im si cao
hn im chy ca teflon nn cn phi kim tra nhit rt cn thn trong qu trnh phn hy.
i vi cc axit ny, bnh thch anh hoc bnh thy tinh bosilicat i khi c s dng
thay th cho bnh teflon. Nhng bnh silicat c bt li l b axit fluoric tc dng - mt axit
thng dng phn hy silicat v cc hp kim chu nhit.
15.4.3 L vi sng
Hnh 15.3
Trong 20 nm cui ca th k XX xut hin hng trm cng trnh s dng bnh ng
kn phn hy mu trong l vi sng vi cc thuc th c dn ra mc 15.2. Nhng
ng dng ny c chia lm 2 loi:
Phng php phn hy nhiu hp cht hu c nh s thiu nhit vi oxi trong bnh ng
l phng php kh tin cy. Cc sn phm phn ng c hp th trong mt dung mi thch
hp trc khi bnh phn ng c m ra. Sau , cc sn phm c phn tch bng cc
phng php thng thng.
Hnh 15.4
Sau khi lm lnh, lc bnh cn thn ri tho my, ra mt bn trong ca bnh n sch.
Php phn tch c thc hin trn dung dch thu c. Quy trnh s c p dng phn
tch halogen, lu hunh, photpho, flo, asen, bo, cacbon v nhng kim loi khc trong hp cht
hu c.
Khi c kh nng nn trnh dng cht chy do c nguy c gy bt li khi s dng chng.
V d nh, gy nhim bn mu do c tp cht trong cht chy. S nhim bn tr nn trm
trng hn do lng tng i ln ca cht chy (t nht 10 ln ln hn trng lng mu) cn
phi c mi m bo nung chy thnh cng. Hn na, dung dch nc thu c khi ha tan
mu nng chy c hm lng mui cao c th gy nhng kh khn trong nhng bc tip
294
theo ca php phn tch. Thm vo , nhit cao cn thit cho nung chy s lm
tng nguy c mt do bay hi. Cui cng, chn nung thc hin nung chy gn nh chc
chn b tn cng n mt mc no do nung chy v mt ln na nhim bn mu l kt qu.
Khi s nng chy hon thnh, lm lnh chm sn phm thu c. Ngay trc khi m
np cn phi xoay trn chn phn b cht rn nng chy trn thnh chn mt lp mng d
ly ra.
Loi tr mt t ngoi l, cc cht nung chy thng c s dng trong phn tch l cc
hp cht ca kim loi kim, cacbonat, hiroxit, peoxit v borat. Kim loi kim l cht nung
chy baz, chng ha tan cc vt liu axit. Cc cht nung chy axit l pyrosunfat, florua v
oxit bo. Nu cn cht nung chy oxi ha, c th dng natri peoxit. Cng c th dng lng
nh nitrat hoc clorat kim loi kim trn vi natri cacbonat lm cht nung chy. Tnh cht ca
cc cht nung chy ph bin c tm tt trong bng 15.1.
Natri cacbonat: C th phn hy silicat v cc vt liu chu nhit khc bng cch nung
n nhit t 1000 n 1200oC vi natri cacbonat. Php x l ni chung c th lm bin i
cc hp phn cation ca mu thnh cacbonat axit tan hoc oxit; cc hp phn phi kim c
chuyn thnh mui natri tan. Nung chy cacbonat c thc hin bnh thng trong chn
platin.
Kali pyrosunfat: Kali pyrosunfat l cht nung chy axit mnh, c s dng mt cch c
bit ha tan nhng kim loi rt kh tan. Cc php nung chy vi thuc th ny c thc
hin khong 400oC; nhit ny s bin chuyn chm ca kali pyrosunfat xy ra nh sau:
Liti metaborat: Liti metaborat LiBO2 c dng ring hoc hn hp vi liti tetraborat
c s dng nhiu ha tan silicat chu nhit, cc khong liu nhm, c bit l cho phn
tch hp th AAS v pht x tia X. Thng thng, php nung chy c thc hin trong chn
graphit hoc platin khong 900oC. Khi thy tinh sinh ra do lm lnh hn hp nng chy c
th c s dng trc tip o hunh quang tia X. Cng c th ha tan hn hp nng chy
295
sau khi lm lnh bng cc axit v c. Sau khi dung dch ca hn hp nng chy c lm bay
hi n kh vi metyl ancol v metyl borat B(OCH3) c ct loi b.
im Loi chn
Cht nung chy chy, dng Loi cht phn hy cc cht
(oC) nung chy
Na2CO3 + mt thuc
Pt (khng Cc mu i hi mi trng oxi ha.
th oxi ha nh
dng vi V d nh, cc mu cha S, Ag, Sb, Cr
KNO3, KClO3 hoc
Na2O2) Ni ...
Na2O2
Pt, Au,
Cht nung chy baz mnh cho silicat,
LiBO2 849 than thy
hu ht cc khong liu, g st, gm.
tinh
Chng 16
Loi b cc tc dng cn tr
C hai phng php tng qut rt c ch cho vic x l cc tc dng cn tr. u tin l
s dng thuc th cn tr v hiu ha cht cn tr hoc lin kt vi cht cn to thnh hp
cht mi t ng gp vo hoc t lm gim tn hiu ca cht cn phn tch. R rng l, thuc
th cn phi khng nh hng n tnh cht ca cht cn phn tch nhiu. V d nh, dng
ion florua ngn cn st (III) cn tr php o iot xc nh ng (II). y tc dng cn tr
ca ion florua l do xu hng to phc rt mnh ca n vi st (III) nhng khng to phc
vi Cu(II) gy ra. Kt qu l th in cc ca cp Fe(III)/Fe(II) gim xung, to ra iu kin
ch c cc ion Cu(II) trong mu oxi ha ioua thnh iot.
Cch x l tc dng cn tr th hai l, chuyn ha hoc cht cn phn tch hoc cht gy
cn tr vo pha tch tch ring ra. Trong chng ny chng ta ch cp ti cc phng
php tch c in, c s dng trc khi dng phng php sc k.
Tch bng kt ta
Mun tch bng kt ta, s khc nhau v tan ca cht cn phn tch v cht gy cn
tr phi ln. C s l thuyt ca phng php tch loi ny l nhng tnh ton tan,
c dn ra chng 5. ng tic l c mt s yu t cn tr s dng thnh cng phng
php kt ta tch. V d nh, hin tng cng kt c cp ti mc 7.2.4 c th
gy nhim bn mnh kt ta do mt hp phn bt thng no ngay c khi tan ca sn
phm nhim bn khng ln. Hn na, tc to thnh kt ta ca mt kt ta khc cng c
kh nng nhng li qu chm s c li cho s tch bit. Cui cng, khi kt ta to thnh
dng keo huyn ph, s keo t c th kh khn v chm, c bit l khi c nh tch lng
nh ca pha rn. Nhiu thuc th to kt ta c ng dng tch nh lng cc cht
v c. Mt s thuc th ph bin v c s dng thnh cng nht s c trnh by cc
mc di y.
1. Cc cch tch c thc hin trong dung dch axit mnh c nng tng i cao.
3. Cc cch tch c thc hin trong cc dung dch natri hoc kali hiroxit m c.
Cc hp cht to thnh
Thuc th Cc cht khng b kt ta
kt ta
Dung dch m
Cc ion mang in tch 2+
CH3COOH/NH4CH3CO Fe(III), Cr(III), Al(III)
ph bin
O
Fe(III), hu ht cc ion
Zn(II), Al(III), Cr(VI),
NaOH/Na2O2 kim loi mang in tch
V(V), U(VI)
2+, t him
Ngoi cc ion kim loi kim v kim th, hu ht cc cation u to thnh cc sunfua t
tan; tan ca cc sunfua li khc nhau rt ln. C th kim tra nng ion sunfua trong
dung dch nc kh d dng thng qua vic iu chnh pH (xem mc 5.2.2) nn tch da
trn s to thnh cc sunfua c s dng rng ri trong thc t. C th kt ta sunfua mt
cch thun tin t dung dch ng th khi c cung cp anion S2 nh s thy phn
tioaxetamit (bng 7.2). X l l thuyt cn bng ion nh hng n tan ca kt ta sunfua
c bn lun mc 5.6. Nhng mt cch x l nh vy cng c th tht bi trn ng
i ti mt kt lun hin thc v kh nng tch do cng kt v do to thnh mt s sunfua vi
tc chm gy ra. Kt qu l, cch gii quyt phi da vo kh nng quan st thc t. Bng
16.2 dn ra mt s cch tch thng gp c thc hin bng H2S thng qua kim tra pH.
iu kin khng kt
Nguyn t iu kin kt ta (1)
ta
(1)
1 = HCl 3 M; 2 = HCl 0,3 M; 3 = m pH = 6 bng CH3COOH/CH3COONa; 4 = m pH = 9 bng
NH3/(NH4)2S
299
Sn(IV) 2, 3 1, 4
Fe(II), Mn(II) 4 1, 2, 3
Clorua v sunfat u c tnh cht la chn cao nn thng c s dng trong thc t.
Clorua thng c dng tch bc ra khi hu ht cc kim loi khc v sunfat thng
c dng tch ring nhm cc kim loi ch, bari, stronti.
L thuyt
Hai thut ng c s dng din t s phn b mt cht tan gia hai dung mi
khng trn ln vo nhau l: h s phn b v t s phn b. iu quan trng l hiu r s
khc nhau gia hai i lng y :
[ A ]hc
Kd = (16.2)
[ A ]n
Khi cht tan tn ti cc dng lin hp khc nhau trong hai dung mi th cn bng tr
thnh:
(1)
E. B. Sandell v H. Onishi, Colorimetric Determination of Traces Metals, 4 th ed., pp 709-721. New York:
Interscience, 1978.
301
xAy(n) yAx(hc)
v h s phn b c dng
[ Ax ]hc
y
Kd =
[ Ay ]nx
Chc
D= (16.3)
Cn
y Chc v Cn l nng phn t phn tch ca HA trong hai pha. Trong mi trng
nc, nng phn tch ca axit bng tng nng cn bng ca axit yu v baz lin hp
ca n:
Cn = [HA]n + [A]n
Ngc li, khng c s phn li ng k ca axit xut hin trong lp hu c khng phn
cc nn nng phn tch v nng cn bng ca HA l ng nht v chng ta c th vit:
Chc = [HA]hc
Thay th hai gi tr Chc v Cn trong phng trnh (16.3) bng cc gi tr tng ng trn
y, ta c:
[HA ]hc
D= (16.4)
[HA ]n + A n
H3O+ A
n n
Ka =
[HA ]n
hoc l
A =
[HA ]n K a
n H3O+
302
Thay gi tr mi thu c ca [A ]n vo phng trnh (16.4) ta c:
S sp xp li ch r mi quan h gia D v Kd i vi HA
H3 O+
Chc n
D= = Kd (16.5)
Cn +
H3O + K a
n
Chc 800.1,00.102
D= = = 799 (16.6)
Cn 1,00.102 + 1,50.105
Tng s milimol axit c trong hai dung mi bng s molimol ban u trong dung dch
nc.
Sau khi chit, 2,50 milimol HA c phn b gia hai dung mi nn:
Trong phng trnh trn Cn v Chc l nng phn tch trong hai dung mi. Phng
trnh (16.6) ch r rng: Chc = 799Cn nn c th vit:
Cn =1,25.104 M.
Chc 800.1,00.108
D= = = 0,533
Cn 1,00.108 + 1,50.105
303
Tng t nh trong phn a, c th vit:
Cn =3,95.102 M.
a1 1 a a1
C1n = ;Chc = o
Vn Vhc
Vn
a1 = ao (16.7)
Vhc D + Vn
Vn
a2 = a1
Vhc D + Vn
Khi thay th a1 ca phng trnh trn y bng phng trnh (16.7) chng ta thu c:
2
Vn
a2 = ao
Vhc D + Vn
C th vit li phng trnh (16.8) di dng thut ng nng phn tch ban u v
cui cng ca HA trong nc bng cch thay th:
50,0
a) (Cn )1 = 3 5
.1,00.10 = 1,16.10 M
50,0.85 + 50,0
2
50,0
b) (Cn )2 = 3 7
.1,00.10 = 5,28.10 M
25,0.85 + 50,0
5
50,0
c) (Cn )5 = .1,00.103 = 5,29.1010 M
10,0.85 + 50,0
Chit n.
Hnh 16.1
B chit Soxlet
Chit ly ht cht ra khi mu: Cch chit n cn kit, cho php tch cc hp phn c
cc t s phn b tng i khng thun li (< 1) ca mt hn hp khi cc hp phn c cc
t s gn khng. Trong thit b thng dng, dung mi hu c c chuyn lin tc qua lp
nc (xem hnh 16.2). Nh vy l, vi vi trm ln chit bng dung mi mi c thc hin
trong mt gi hoc t hn trong mt thit b khng cn phi theo di thng xuyn, c th
chit ly ht cht cn quan tm ra khi mu.
Phn on ngc dng: Nhng thit b t ng cho php thc hin thnh cng hng
trm ln chit t ng. Vi nhng thit b ny s phn on din ra nh s ngc dng
trong s phn b gia nhng phn mi ca hai pha c thc hin trong hng lot cc
bc giai on. Php chit n cn kit khc vi k thut ngc ch l, nhng phn mi
ca ch mt pha c sinh ra trong pha c.
Phng php ngc dng cho php tch nhng hp phn c h s phn chia kh ng
nht. V d nh Craig ch r rng, c th tch 10 aminoaxit bng chit ngc dng ngay
c khi h s phn b ca chng ch khc nhau t hn 0,1.
306
16.4 ng dng cc quy trnh chit
Nhiu thuc th to ni phc (chelat) l nhng axit yu phn ng vi cc ion kim loi
to thnh cc phc khng tch in, tan tt trong cc dung mi hu c nh ete, hirocacbon,
xeton v cc hp cht clo ha (bao gm clorofom, tetraclorua cacbon). Mt khc, cc hp
cht ni phc kim loi thng gn nh khng tan trong nc, cn cc thuc th to phc
thng tan kh tt trong dung mi hu c nhng ch tan hn ch trong nc.
Cc thuc th vng cng c th nghim rt thnh cng tch da trn quy trnh
chit la chn cc ion kim loi t mt dung dch m trong nc vo mt dung mi hu c
c sn cc thuc th . Nh ch r trn hnh 16.3, mi qu trnh nh th, bao gm mt
vi cn bng v mt vi cht. Cc cht l phi t HQ khng phn li, baz lin hp ca n
Q, phc kim loi - phi t MQn, ion kim loi v H+. Nhng cn bng quan trng xy ra l:
[HQ]hc
HQn HQhc ; K d1 = (16.10)
[HQ]n
H3 O+ Q
+ n
HQn + H2O H3O + Q(n) ; Ka = (16.11)
[ ]n
HQ
+ [ MQm ]n
Mm
n + mQ(n) MQm(n) ; Kf = (16.12)
m
Mn + Q
n n
[ MQm ]hc
MQm(n) MQm(hc) ; K d2 = (16.13)
[ MQm ]n
Chc v Cn l nng mol phn tch ca Mm+ trong pha hu c v pha nc. Thng
thng, gi thit cho rng, [MQm]n << [Mm+]n l hp l bi v:
Hnh 16.2
iu bt ngun t ngun gc sau: D khng ph thuc vo tng lng ion kim loi
trong 2 tng nhng ph thuc vo c nng HQ trong lp hu c v nng H+ trong
dung dch nc. Nu CQ l nng phn t ban u ca HQ trong tng hu c, cn bng
khi lng i hi nh sau:
Thng thng nhng quy trnh chit c thc hin vi lng d cht to phc, v d
nh nng HQ trong lp hu c phi d nhiu so vi nng ca tt c cc cht khc c
cha Q. Nh vy l, biu thc cn bng khi lng trn y c n gin n:
CQ [HQ]hc (16.15)
308
dng li mt biu thc din t mi quan h gia D ca h ny vi nng
u ca phi t to phc trong dung dch hu c v pH ca dung dch nc, chng ta
nhn phng trnh (16.12) vi phng trnh (16.13) v sp xp li s c :
[MQm]hc = Kf K d2 [Mn+]n[Q]nm
Chc
= K f K d2 [Q ]n
m
D= (16.6)
Cn
Chia phng trnh (16.11) cho phng trnh (16.10) ta c th din t [Q]n qua [H3O+]n
v [HQ]hc:
Q = K a
[HQ]hc
n K d
(16.17)
H3 O+
1
n
(2,0.104 ).(0,0250)2
D= = 50,0
(0,500)2
H C6H5 C6H5
H5C6 N N H5C6 N N
2+
N N C H + Pb N N C Pb + 2H+
S H S
2
C ithizon v phc kim loi ca n u khng tan trong nc, nhng tan tt trong dung
mi hu c nh CCl4 v CHCl3. Dung dch thuc th c mu lc thm nhng dung dch
phc kim loi li c mu , tm, da cam hoc vng m nn xut hin nhiu phng php
o mu nhy xc nh cc ion b tch. T s phn b ca cc ithizonat kim loi c din
t bng cc phng trnh (16.18) v (16.14). Nh vy, i vi ch:
Hnh 16.3
Hiu ng pH ln phn trm chit cc cation bng dung dch ithizon trong CCl4
Hnh 16.4 ch r phn trm ch v mt s ion kim loi khc b chit vo dung dch
ithizon trong CCl4 bin i nh th no theo pH ca mi trng nc. Nhng s liu thu
310
c cho nhng ng cong ny thu c bng con ng tng t nh nhng
tnh ton c dn ra trong v d 16.3. R rng l t nhng ng cong ny tch c rt
p ng, ch v cadimi bng cch kim tra pH. Ty thuc vo ph hp th ca n, thic (II)
c th gy cn tr nh cho php xc nh ng v ch.
Bng 16.3 Chit phc clorua kim loi bng ietylete t dung dch HCl 6 M
Phn trm
Cc nguyn t v trng thi oxi ha
b chit
90 100 Fe(III) 99%; Sb(V) 99% *; Ga(III) 97%; Ti(III) 95% *; Au(III) 95%
1 50 Te(IV) 34%; Sn(II) 15 30%; Sn(IV) 17%; Ir(IV) 5%; Sb(III) 2,5% *
< 1, > 0 As(V) *; Cu(II); In(III); Hg(II), Pt(IV); Se(IV); V(V); V(IV); Zn(II)
R rng l cn bng chit ph thuc vo pH, do c th tch cc ion kim loi thng
qua s iu chnh pH ca pha nc. Nhng th nghim trong thc t chng t rng, phng
php ny rt tin dng tch lng vt cc kim loi.
niken. Hp cht b chit dng lin hp ion H3O+ FeCl4 . Phn trm st c chuyn vo
tng hu c ph thuc vo hm lng axit clohiric trong tng nc (mt phn nh c
chuyn li tng nc khi nng HCl thp hn 3 M v cao hn 9 M) v mt mc no
ph thuc vo hm lng st.
Nha trao i ion c nhiu ng dng trong ha phn tch. ng dng quan trng nht l
sc k lng hiu qu cao, s c cp n trong gio trnh cc phng php phn tch
cng c. Trong mc ny ch trnh by mt cch tm tt nhng ng dng khc trong ha phn
tch ca nha trao i ion.
Nha trao i ion c s dng loi b cc ion cn tr, c bit l nhng ion ny c
in tch tri du i vi ion cn phn tch. V d nh, st (II), nhm (III) v mt s nhng
cation khc cn tr php xc nh ion sunfat bng phng php khi lng do khuynh
hng cng kt vi bari sunfat ca chng. Cho dung dch cn phn tch chy chm qua ct
nha trao i cation, tt c cc cation b gi li v mt lng proton tng ng c gii
phng. Ion sunfat i qua ct nh vy mt cch t do v php phn tch c thc hin trn
dung dch chy ra khi ct. Bng cch tng t, ion sunfat cn tr php xc nh cc ion bari
v canxi c th b loi b bng cch cho mu chy chm qua ct nha anionit.
Cc cht trao i ion thng c dng lm giu lng vt ion t mt dung dch rt
long. V d, nha trao i cation c s dng tch gp cc nguyn t kim loi t th
tch ln nc t nhin. Sau , x l nha bng axit cc ion c gii phng, ta s thu c
dung dch m c hn nhiu phn tch.
312
16.5.3 Chuyn ha mui thnh axit hoc baz
Chng ct cho php tch cc hp phn khi t s phn b dung dch/tng hi ca chng
khc nhau ln. Nu mt hp phn c t s phn b ln so vi ch s ca cc cu t
khc ca mt hn hp th c th tch mt cch n gin. Bng 16.4 thng k mt s cc hp
cht v c c th b tch mt cch thun li bng cch chng ct n gin.
Thm H2SO4 v
H3BO3 B(OCH3)3 Dung dch baz
metanol
Ph lc
Ph lc I
CC TP CH PHN TCH LN C LU HNH RNG RI TRN TH GII
American Laboratory
The Analyst
Analitical Biochemistry
Analytical Chemistry
Analytica Chimica Acta
Analytical Instrumentation
Analytical Tetters
Applied Spectroscopy
Clinical Chemistry
Fresenins Journal of Analytical Chemistry
Journal of the Association of Official Analytical Chemists
Journal of Chromatography Science
Journal of Chromatography
Journal of Electroanalytical Chemistry and Interfacial Electrochemistry
Microchemical Journal
Microchimica Acta
Saparation Science
Spectrochimica Acta
Talanta
Zeitschrift fr Analytische Chemie
Ph lc II
NGUYN T KHI QUC T
Nguyn t K hiu Nguyn t s Nguyn t khi
Actinnium Ac 89 227
Aluminum Al 13 26,981539
Americium Am 95 243
Antimony Sb 51 121,757
314
Nguyn t K hiu Nguyn t s Nguyn t khi
Argon Ar 18 39,984
Arsenic As 33 74,92159
Astatine At 85 210
Barium Ba 86 137,327
Berkelium Bk 97 247
Beryllium Be 4 9,012182
Bismuth Bi 83 208,98037
Boron B 5 10,811
Bromine Br 35 79,904
Cadmium Cd 48 112,411
Calcium Ca 20 40,078
Califormium Cf 98 251
Carbon C 6 12,011
Cerium Ce 58 140,115
Cesium Cs 55 132,90543
Chlorine Cl 17 35,4527
Chromiun Cr 24 51,9961
Cobalt Co 27 58,93320
Copper Cu 29 63,546
Curium Cm 96 247
Dysprosium Dy 66 162,50
Einsteinium Es 99 252
Erbium Er 68 167,26
Europium Eu 63 151,965
Ferium Fm 100 257
Fluorine F 9 18,9984032
Francium Fr 87 223
Gadolinium Gd 64 157,25
Gallium Ga 31 69,723
Germanium Ge 32 72,61
Gold Au 79 196,96654
Hafnium Hf 72 178,49
Helium He 2 4,002602
Holmium Ho 67 164, 93032
315
Nguyn t K hiu Nguyn t s Nguyn t khi
Hydrogen H 1 1,00794
Indium In 49 114,82
Ioine I 53 126,90447
Iridium Ir 77 192,22
Iron Fe 26 55,847
Krypton Kr 36 83,80
Lanthanum La 57 138,9055
Lawrencium Lr 103 262
Lead Pb 82 207,2
Lithium Li 3 6,941
Lutentium Lu 71 174,967
Magnesium Mg 12 24,305
Manganese Mn 25 54,93805
Mendelevium Md 101 258
Mercury Hg 80 200,59
Molybdenum Mo 42 95,94
Neodymium Nd 60 144,24
Neon Ne 10 20,1797
Neptunium Np 93 237
Nickel Ni 28 58,6934
Niobium Nb 41 92,90638
Nitrogen N 7 14,00674
Nobelium No 102 259
Osmium Os 76 190,2
Oxygen O 8 15,9994
Palladium Pd 46 106,42
Phosphorus P 15 30,973762
Platium Pt 78 195,08
Plutonium Pu 94 244
Polonium Po 84 210
Potassium K 19 39,0983
Praseodymium Pr 59 140,90765
Promethium Pm 61 145
Protatinium Pa 91 231,03588
316
Nguyn t K hiu Nguyn t s Nguyn t khi
Radium Ra 88 226
Radon Rn 86 221
Rhenium Re 75 186,207
Rhodium Rh 45 102,90550
Rubidium Rb 37 85,4678
Ruthenium Ru 44 101,07
Samarium Sm 62 150,36
Scandium Sc 21 44,955910
Selenium Se 34 78,96
Silicon Si 14 28,0855
Silver Ag 47 107,8682
Sodium Na 11 22,989768
Strontium Sr 38 87,62
Sulfur S 16 32,066
Tantalum Ta 73 180,9479
Technetium Tc 43 98
Tellurium Te 52 127,60
Terbium Tb 65 158,92534
Thallium Tl 81 204,3833
Thorium Th 90 232,0381
Thulium Tm 69 168,93421
Tin Sn 50 118,710
Titanium Ti 22 47,88
Tungsten W 74 183,85
Uranium U 92 238,0289
Vanadium V 23 50,9415
Xenon Xe 54 131,29
Ytterbium Yb 70 173,04
Yttrium Y 39 88,90585
Zinc Zn 30 65,39
Zirconium Zr 40 91,224
317
Ph lc III
PHN T LNG CA MT S HP CHT THNG DNG
Hp cht Phn t lng Hp cht Phn t lng
AgBr 187,772 Hg2Cl2 472,09
AgCl 143,321 HgCl2 271,50
Ag2CrO4 331,730 KBr 119,002
AgI 234,773 KBrO3 167,001
AgNO3 169,873 KCl 74,551
AgSCN 165,952 KClO3 122,519
Al3O3 101,961 KCN 65,116
Al2(SO4)3 342,154 K2CrO4 194,190
As2O3 197,841 K2Cr2O7 294,185
B2O3 69,620 K3Fe(CN)6 329,248
BaCO3 197,336 K4Fe(CN)6 368,347
BaCl2.2H2O 244,263 KHC8H4O4 204,224
BaCrO4 253,321 KH(IO3)2 389,912
Ba(IO3)2 487,132 K2HPO4 174,176
Ba(OH)2 171,342 KH2PO4 136,086
BaSO4 233,391 KHSO4 136,170
Bi2O3 465,959 KI 166,003
CO2 44,010 KIO3 214,001
CaCO3 100,087 KIO4 230,000
CaC2O4 128,098 KMnO4 158,034
CaF2 78,075 KNO3 101,103
CaO 56,077 KOH 56,106
CaSO4 136,142 KSCN 97,182
Ce(HSO4)4 528,401 K2SO4 174,260
CeO2 172,114 La(IO3)3 663,614
Ce(SO4)2 332,242 Mg(C9H6NO)2 312,611
(NH4)2Ce(NO3)6 548,222 MgCO3 84,314
(NH4)4Ce(SO4)4.2H2O 632,554 MgNH4PO4 137,315
Cr2O3 151,990 MgO 40,304
CuO 79,545 Mg2P2O3 222,553
Cu2O 143,091 MgSO4 120,369
318
Hp cht Phn t lng Hp cht Phn t lng
CuSO4 159,610 MnO2 86,939
Fe(NH4)2(SO4)2.6H2O 392,143 Mn2O3 157,874
FeO 71,846 Mn3O4 228,812
Fe2O3 159,692 Na2B4O7.10H2O 381,372
Fe3O4 231,539 NaBr 102,894
HBr 80,912 NaC2H3O2 82,034
HC2H3O2 60,053 Na2C2O4 133,999
HC7H5O2 122,123 NaCl 58,442
(HOCH2)3CNH2(Tris) 121,136 NaCN 49,008
HCL 36,461 Na2CO3 105,989
HCLO4 100,458 NaHCO3 84,007
H2C2O4.2H2O 126,066 Na2H2EDTA.2H2O 372,240
H5IO6 227,941 Na2O2 77,978
HNO3 63,013 NaOH 39,997
H2O 18,015 NaSCN 31,074
H2O2 34,015 Na2SO4 142,043
H3PO4 97,995 Na2S2O3.5H2O 248,186
H2S 34,082 NH4Cl 58,491
H2SO3 82,080 (NH4)2C2O4.H2O 142,112
H2SO4 98,079 NH4NO3 80,043
HgO 216,59 (NH4)2SO4 132,141
(NH4)S2O8 228,204 P2O5 141,945
NH4VO3 116,978 Sb2S3 339,712
Ni(C4H7O2N2)2 228,917 SiO2 60,084
PbCrO4 323,2 SnCl2 189,615
PbO 223,2 SnO2 130,709
PbO2 239,2 SO2 64,065
PbSO4 303,3 SO3 80,064
Zn2P2O7 304,72
319
Ph lc IV
TCH S TAN 25OC
Hp cht Cng thc T Ghi
ch
Nhm hiroxit Al(OH)3 3.10
34
CoS 3.10
26
*
Ch oxit PbO 7,4. V
+ 2+ 14
PbO(r) H2O Pb + 10 ng
2OH
*
PbO 5.10
+ 2+ 16
PbO(r) H2O Pb +
2OH
Ch ioua PbI2 7,9. V
9
10 ng
Ch oxalat PbC2O4 8,5. =
9
10 0,05
Ch sunfat PbSO4 1,6.
8
10
Ch sunfit PbS 3.10
28
NiS 1,3.
25
10
Bc asenat Ag2AsO4 6.10
23
ZnS 3.10
23
324
Ph lc V
CC HNG S PHN LI AXIT 25OC
Ph lc VII
MT S TH IN CC CHUN V HNH THC
o * +
Na phn ng E ,V Th hnh thc, V
Nhm
3+
Al + 3e = Al(r) 1,662
Antimon
+ +
Sb2O5(r) + 6H 4e = 2SbO + 3H2O +0,581
Asen
+
H3AsO4 + 2H + 2e = H3AsO3 + H2O +0,559 0,577 trong HCl.HClO4
Bari
2+
Ba + 2e = Ba(r) 2,906
Bismut
+ +
BiO + 2H 3e = Bi(s) + H2O +0,320
329
o * +
Na phn ng E ,V Th hnh thc, V
BiCl4 + 3e = Bi(s) + 4 Cl +0,16
Brom
Br2(l) + 2e = 2Br +1,065 1,05 trong HCl 4 M
Br2(n) + 2e = 2Br +1,087
BrO3 + 6 H + 5 e = Br2(l) + 3H2O +1,52
BrO3 + 6H + 6e = Br + 3H2O +1,44
Cadimi
2+
Cd + 2e = Cd(s) 0,403
Canxi
2+
Ca + 2e = Ca(s) 2,866
Cacbon
+ +0,696 trong HCl, HClO4, H2SO4 1
C6H4O2 (quinon) + 2H 2e = C6H4(OH)2 +0,699
M
+
2CO2(g) + 2H + 2e = H2C2O4 0,49
Xeri
4+ 3+ +1,70 trong HClO4 1 M, +1,61 trong
Ce + e = Ce
HNO3 1 M, +1,44 trong H2SO4
Clo
Cl2(k) + 2e = 2Cl +1,359
HCl + H e = 1/2Cl2(k) + H2O +1,63
ClO3 + 6H 5e = 1/2Cl2(k) + 3H2O +1,47
Crom
3 2
Cr + e = Cr 0,408
3
Cr + 3e = Cr(r) 0,744
2 3+
Cr2O7 + 14H + 6e = 2Cr + 7H2O +1,33
Coban
2+
Co + 2e = Co(r) 0,277
3 2+
Co + e = Co +1,808
ng
2+
Cu + 2e = Cu(r) +0,337
2+ +
Cu + e = Cu +0,153
+
Cu + e = Cu(r) +0,521
2+
Cu + I + e = CuI(r) +0,86
CuI(r) + e = Cu(r) + I 1,85
330
o * +
Na phn ng E ,V Th hnh thc, V
Flo
+
F2(k) + 2H + 2e = 2HF(n) +3,06
Hiro
+ +
2H + 2e = H2(k) 0,000 0,005 trong HCl, HClO4
Io
I2(s) + 2e = 2I +0,5355
I2(n) + 2e = 2I +0,615
I3 + 2e = 3I +0,536
ICl2 + e = 1/2I2(s) + 2Cl +1,056
+
IO3 + 6H + 5e = 1/2I2(r) + H2O +1,196
+
IO3 + 6H + 5e = 1/2I2(n) + 3H2O +1,178
+
IO3 + 2Cl + 6H + 4e = ICl2 + H2O +1,24
+
H5IO6 + H + 2e = IO3 + 3H2O +1,601
St
2+
Fe + 2e = Fe(r) 0,440
3+ 2+ 0,700 trong HCl 1 M; 0,732 trong
Fe + e = Fe +0,771
HClO4 1 M, 0,68 trong H2SO4 1 M
3 2 0,71 trong HCl 1 M; 0,72 trong
Fe(CN) + e = Fe(CN)6 +0,36
HClO4 1 M, H2SO4
Ch
2+ 0,14 trong HClO4 1 M; 0,29 trong
Pb + 2e = Pb(r) 0,126
H2SO4 1 M
+ 2+
PbO2(r) + 4H + 2e = Pb + 2H2O +1,455
2
PbSO4(r) + 2e = Pb(r) + SO3 0,350
Liti
+
Li + e = Li(r) 3,045
Magie
2+
Mg + 2e = Mg(r) 2,363
Mangan
2+
Mn + 2e = Mn(r) 1,180
3+ 2+
Mn + e = Mn 1,51 trong H2SO4 7,5 M
+ 2+
MnO2(s) + 4H + 2e = Mn + 2H2O +1,23
+ 2+
MnO4 + 8H + 5e = Mn + 4H2O +1,51
+
MnO4 + 4H + 3e = MnO2(r) + H2O +1,695
2
MnO4 + e = MnO4 +0,564
331
o * +
Na phn ng E ,V Th hnh thc, V
Thy ngn
2+ 0,274 trong HCl; 0,776 trong HClO4;
Hg2 + 2e = 2Hg(l) +0,788
0,67 trong H2SO4
2+ 2+
2Hg + 2e = Hg2 +0,920 0,907 trong HClO4
2+
Hg + 2e = Hg(l) +0,854
0,244 trong KCl bo ha; 0,282 trong
Hg2Cl2(r) +2e =2Hg(l) + 2Cl +0,268
KCl; 0,334 trong KCl
2
Hg2SO4(r) +2e =2Hg(l) + SO4 +0,165
Nicken
2+
Ni + 2e = Ni(s) 0,250
Nit
+ +
N2(k) + 5H + 4e = N2H5 0,23
+
HNO2 + H + e = NO(k) + H2O +1,00
+
NO3 + 3H + 2e = HNO2 + H2O +0,94 0,92 trong HNO3
Oxi
+
H2O2 + 2H + 2e = 2H2O +1,776
HO2 + H2O + 2e = 3OH +0,88
+
O2(k) + 4H + 4e = 2H2O +1,229
+
O2(k) + 2H + 2e = H2O2 +0,682
+
O3(k) + 2H + 2e = O2(k) + H2O +2,07
Paladi
2+
Pd + 2e = Pd(r) +0,987
Ptatin
2+
PtCl3 + 2e = Pt(r) + 4 Cl +0,73
2 2
PtCl6 + 2e = PtCl3 + 2Cl +0,68
Kali
+
K + e = K(r) 2,925
Selen
+
H2SeO3 + 4H + 4e = Se(k) +3H2O +0,740
2 +
SeO3 + 4H + 2e = H2SeO3 + H2O +1,15
Bc
+ 0,228 trong HCl; 0,792 trong HClO4;
Ag + e = Ag(r) +0,799
0,77 trong H2SO4
AgBr(r) + e = Ag(r) + Br +0,073
AgCl(r) + e = Ag(r) + Cl +0,222 0,228 trong KCl
332
o * +
Na phn ng E ,V Th hnh thc, V
AgCl(r) + e = Ag(r) + 2CN 0,31
2
Ag2CrO4(r) + 2e = 2Ag(r) + CrO4 +0,446
AgI(r) +e = Ag(r) + I 0,151
2
AgI(r) + e = Ag(r) + 2S2O3 +0,017
Natri
+
Na + e = Na(r) 2,714
Sulfua
+
S(r) + 2H 2e = H2S(k) +0,141
H2SO3 + 4H + 4e = S(r) + 3H2O +0,450
2 +
SO4 + 4H + 2e = H2SO3 + H3O +0,172
2 2
S4O6 + 2e = 2S2O3 +0,08
2 2
S2O8 + 2e = 2SO +2,01
Tali
0,551 trong HCl; 0,33 trong
Tl + e = Tl(r) 0,336
HVlO4, H2SO4
3+ +
Tl + 2e = Tl +1,25 0,77 trong HCl
Thic
2
Sn + 2e = Sn(r) 0,136 0,16 trong HClO4
4+ 2+
Sn + 2e = Sn +0,154 0,14 trong HCl
Titan
3 2+
Ti + e = Ti 0,369
2+ + 3+
TiO + 2H + e = Ti + H2O +0,099 0,04 trong H2SO4
Uran
2+ 4+
UO3 + 4H + 2e = U + 2H2O +0,334
Vanadium
3 2+
V +e =V 0,256 0,21 trong HClO4
2+ 3
VO + 2H + e = V + H2O +0,359
+ + 2+
V(OH)4 + 2H + e = VO + 3H2O +1,00 1,02 trong HCl, HClO4
Km
2+
Zn + 2e = Zn(r) 0,763
+
Nhng th ny l gi nh bi v chng tng ng vi dung dch Br2 hoc I2 bng
1,00 M. tan tng ng ca hai hp cht ny 25oC l 0,18 M v 0,0020 M. Trong cc
dung dch bo ha cha lng d Br2 lng hoc I2 rn th chun ca na phn ng:
333
Br2(lng) + 2e = 2Br
I2(rn) + 2e = 2I
vn c s dng. Ngc li nng Br2 v I2 thp hn nng bo ha, nhng th in
cc gi nh cng c s dng.
* Th hnh thc l th in cc ca mt cp c nng phn tch ca tt c cc cht
tham gia bng n v v nng cc cht khc trong dung dch c nh r.
G. Milazzo, S. Caroli, K. Sharma, Tables of Standard Electrode Potentials, London:
Willey, 1978.
E. H. Swift and E. A. Butler, Quantitive Measurement and Chemical Equilibria, New
York: Freeman, 1972.
Ph lc VIII
CC CHT C KHUYN DNG IU CH CC DUNG DCH
CHUN CHO NHNG NGUYN T THNG DNG
*
Nu khng c ghi ch g c bit khc, cc cht s c lm kh n khi lng khng i
110oC.
* Nu khng c ghi ch g c bit khc, cc axit u l axit c tinh khit phn tch.
a. Ph hp vi cc tiu chun c lit k mc 7.2 v t cht lng chun
b. c tnh cao
c. Mt 1/2H2O 110oC. Sau khi lm kh khi lng phn t = 324,92 g. Hp cht
kh c cn li nhanh sau khi ly khi bnh phng m.
335
d. C hiu lc nh mt tiu chun c bn ca vin Quc gia v tiu chun v cng
ngh.
e. H3BO3 c cn trc tip trong mt cc cn, mt 1 mol H2O 100oC, kh lm kh
n khi lng khng i.
f. Hp th CO2 v H2O. Nung ngay trc khi s dng
g. C th lm kh 110oC m khng mt nc
h. Mt c hai phn t nc. Khi lng phn t = 293,82. Gi trong bnh
i. Tiu chun c bn
j. HF c c tnh cao v ha tan thy tinh
Ph lc IX
H M pH
HN HP M TRONG VNG pH = 2,2 8,0