Hoa Phan Tich Bo Y Te VinaEbookChemistryHere PDF

Bo Y te - Hoa phan tich
Page 1 of 239
B Y T
HA PHN TCH
TP 1
(DNG CHO O TO DC S I HC) M S : .20.Y.14
NH XUT BN GIO DC H NI 2007
Ch o bin son : V KHOA HC V O TO B Y T Ch bin :
file://C:\WINDOWS\Temp\kgpwyiypbu\hoa_phan_tich.htm
11/25/2010
Page 2 of 239
PGS. TS. V TH BCH HU Nhng ngi bin son : PGS. TS. V TH BCH HU ThS. PHNG TH NG ThS. TRN TH TRC THANH ThS. PHAN THANH DNG ThS. NGUYN HU LC THU Tham gia t chc bn tho : ThS. PH VN THM TS. NGUYN MNH PHA
Bn quyn thuc B Y t (V Khoa hc v o to)

874 - 2007/CXB/ 5 - 1918/GD M s : 7K725 M7 - DAI
Li gii thiu
Thc hin mt s iu ca Lut Gio dc, B Gio dc & o to v B Y t ban hnh chng trnh khung o to Dc s i hc. B Y t t chc bin son ti liu dy - hc cc mn c s v chuyn mn theo chng trnh trn nhm tng bc xy dng b sch t chun chuyn mn trong cng tc o to nhn lc y t. Sch HO PHN TCH c bin son da trn chng trnh gio dc ca Trng i hc Y Dc Thnh ph H Ch Minh trn c s chng trnh khung c ph duyt. Sch c cc tc gi PGS.TS. V Th Bch Hu, ThS. Phng Th ng, ThS. Trn Th Trc Thanh, ThS. Phan Thanh Dng, ThS. Nguyn Hu Lc Thy bin son theo phng chm : Kin thc c bn, h thng ; ni dung chnh xc, khoa hc ; cp nht cc tin b khoa hc, k thut hin i v thc tin Vit Nam. Sch HO PHN TCH c Hi ng chuyn mn thm nh sch v ti liu dy - hc chuyn ngnh Dc s i hc ca B Y t thm nh nm 2007. B Y t quyt nh ban hnh l ti liu dy -
11/25/2010
Page 3 of 239
hc t chun chuyn mn ca ngnh trong giai on hin nay. Trong thi gian t 3 n 5 nm, sch phi c chnh l, b sung v cp nht. B Y t xin chn thnh cm n cc tc gi v Hi ng chuyn mn thm nh gip hon thnh cun sch ; Cm n GS.TS. T Vng Nghi, PGS.TS. Trn T An c v phn bin cun sch sm hon thnh kp thi phc v cho cng tc o to nhn lc y t. Ln u xut bn, chng ti mong nhn c kin ng gp ca ng nghip, cc bn sinh vin v cc c gi ln xut bn sau sch c hon thin hn. V KHOA HC V O TO - B Y T
LI NI U
HO PHN TCH l mt mn hc dnh cho cc hc vin thuc ngnh Ho. khoa Dc ca Trng i hc Y Dc Thnh ph H Ch Minh, mn ny c ging dy cho: - sinh vin Dc nm th 3 (h chnh quy 5 nm) - sinh vin Dc nm th 2 (h tp trung 4 nm) nhm trang b cc kin thc c bn v ho hc phn tch t sinh vin Dc hiu r hn cc mn Bo ch, Dc liu, Ho dc, Dc lc, Kim nghim thuc l cc mn nghip v s c hc tp cc nm k tip. Ho phn tch cng l mt trong nhng mn hc nhm cung cp cc kin thc nn tng rt quan trng sau khi tt nghip, d lm vic bt k cc v tr no th Dc s cng xc nh c nhim v ca mnh l trc tip hay gin tip gp phn lm cho thuc phi ng v cht lng v v s lng khi ti tay ngi s dng. Vi mc ch trn, b mn Ho Phn tch Kim nghim bin son sch Ho phn tch, tp 1, cho sinh vin ngnh Dc theo ch o ca B Y t v B gio dc o to. Ni dung sch Ho phn tch, tp 1, gm cc phn sau: Phn I: l phn i cng gm cc chng tng qut cp n: - i tng, chc nng v phn loi ca ho hc phn tch. - Cc loi phn ng ho hc, khi nim v cc yu t nh hng n cn bng ho hc, hng s cn bng v nh ngha v hot , nng . - Cc khi nim v sai s v ng dng ton thng k x l cc kt qu thu c t thc nghim nhm m bo chnh xc theo yu cu ca ngnh Dc. Phn II: l phn nh lng gm cc chng vit v:
11/25/2010
Page 4 of 239
- Cch biu th v tnh ton nng dung dch ca mt cht c s dng thng xuyn khi phn tch. - Nguyn tc v cch th hin cc bc tin hnh phn tch khi lng. - Nguyn tc, phn loi, gii thch cc khi nim, c ch cng nh cc ng dng ca cc phng php phn tch th tch: acid base; oxy ho kh; kt ta v to phc ch yu s dng trong ngnh Dc. Cc cn b ging ca b mn c gng cp nht ho kin thc bin son v vn lun mong gio trnh s mang li cho hc vin kin thc b ch, chnh xc. Chng ti knh mong qu thy c, qu ng nghip, qu c gi v cc sinh vin c k v nu nhng kin ng gp, ch gip cc thiu st chng ti hon thin hn ti liu ging dy ny. Chn thnh cm n v mong nhn c nhng kin ng gp qu bu ca qu v. Ch bin PGS.TS. V TH BCH HU
Phn I
I CNG
Chng 1 I CNG HO PHN TCH

MC TIU
Trnh by c i tng, chc nng v phn loi ca ho hc phn tch. Nu c ni dung ca ho hc phn tch. Gii thch c cc bc thc hin ca quy trnh phn tch.
11/25/2010
Page 5 of 239
NI DUNG 1. M U Ho phn tch l khoa hc v cc phng php xc nh thnh phn ho hc ca cht v cu trc ca cc hp phn c trong cht phn tch. Cc phng php ca Ho phn tch cho php xc nh nh tnh mt cht, ngha l c th xc nh xem cht phn tch c cu to bi nhng nguyn t no, nhm chc no, v phn tch xem cc nguyn t v cc nhm chc c sp xp v lin kt vi nhau nh th no (phn tch cu trc). Ho phn tch nghin cu cc phng php phn tch nh lng, dng cc phng php xc nh thnh phn nh lng ca cc nguyn t, cc hp cht ho hc trong cht phn tch. Ni v Ho phn tch, ngi ta cho rng y l khoa hc v cc phng php v phng tin ca phn tch ho hc v trong mc nht nh xc nh cu trc ho hc. V phng tin c th hiu l: dng c, thuc th, cht chun, ... Phng php v phng tin ca phn tch thay i thng a ra nhng hng mi, s dng nhng nguyn tc mi, c nhng hin tng t nhng lnh vc c t xa xa. Th d, trong thc nghim phn tch ho hc hin nay phng php vt l gi vai tr quan trng l phng php quang ph v vt l ht nhn. Cn phn bit khi nim "ho hc phn tch" v "phn tch ho hc". Ho phn tch l khoa hc v cc phng php phn tch, cn phn tch ho hc l nhng phng php c dng trong thc t xc nh thnh phn ho hc ca cht phn tch. Ngi ta cn phn bit khi nim k thut phn tch v phng php phn tch. K thut phn tch l da trn cc hin tng khoa hc thu thp thng tin v thnh phn ho hc ca cht phn tch. Th d nh k thut sc k lng hiu nng cao, k thut cc ph. Phng php phn tch l ng dng c th ca mt k thut phn tch gii quyt mt vn phn tch. Phng php ca phn tch l phng cch (cch) xc nh, lun chng r rng, nh gi ton din c cn c xc nh thnh phn ca i tng phn tch. Th d phng php phn tch vitamin C bng k thut cc ph, phng php xc nh phenol trong nc sng dng k thut sc k. 2. CHC NNG CA HO PHN TCH HIN I C th chia ra lm 3 chc nng (lnh vc khoa hc): 2.1. Gii quyt cc vn chung ca phn tch Th d: pht trin v hon thin nhng lun thuyt v cc phng php phn tch. 2.2. Nghin cu cc phng php phn tch 2.3. Gii quyt cc nhim v c th ca phn tch Th d: s thnh lp chuyn ngnh Ho phn tch v thuc phng chng dch bnh. Cu trc su ca mn hc ny c th chia ra phn tch nh tnh v phn tch nh lng. Phn tch nh tnh gii quyt vn l cc hp phn no c trong i tng phn tch, phn tch nh lng cho bit v hm lng ca tt c hay ca tng hp phn. 3. PHN LOI
11/25/2010
Page 6 of 239
3.1. Phn loi theo ng li phn tch - Tng th - Cc b - Phn hy - Khng phn hy - Trc tip - Gin tip - Gin on - Lin tc
3.2. Phn loi da theo th tch v khi lng cht phn tch - Phn tch th: lng mu th cht rn 0,1 - 1 g, lng mu th dung dch t 1 - 100 ml. - Phn tch bn vi lng: lng mu th t 0.01 - 0,1 g, dung dch t 0,1- 0,3 ml. - Phn tch vi lng: lng mu th t 10-3 -10-2 g, dung dch t 10-2 - 10-1 ml. - Phn tch siu vi lng: lng mu th t 10-6 - 10-12 g, dung dch t 10-3 - 10-6 ml. 3.3. Phn loi da trn bn cht ca cc hp phn ca cht cn xc nh - Phn tch ng v: chuyn ngnh trong phn tch t s dng, nhng phn tch ny thng dng trong vt l, m, sinh hc. Th d nh: xc nh nc deuterium trong nc thng, cng nh ca oxy "nng" (ng v oxy 18) trong hn hp vi s ng v ph bin oxy 16. Phn tch ng v cn thit khi nghin cu cc nguyn t nhn to. - Phn tch nguyn t (nguyn t - ion): phn tch nhng nguyn t no c trong i tng nghin cu, hm lng l bao nhiu. - Phn tch phn t: y l s pht hin v xc nh hp cht ho hc c c trng bng khi lng phn t xc nh. Th d: phn tch hn hp kh, xc nh trong khng kh nhng thnh phn chnh (N2, O2, CO2, O3, kh tr). Mt trong nhng phng php phn tch phn t ngi ta s dng phng php sc k. - Phn tch nhm chc: i vi phn tch ho hu c cn c mt dng phn tch gia phn tch nguyn t v phn t - l phn tch nhm chc. Phn tch ny trc ht xc nh nhm chc, ngha l xc nh tng nhm hu c ring bit nh nhm carboxyl, hydroxyl, amin,... - Phn tch cht: Trong phn tch cht ngi ta xc nh trong dng no c mt hp phn ta quan tm trong i tng phn tch ny v hm lng ca nhng dng ny. Th d: trong mc no ca s oxy ho c mt nguyn t As(III) hay As (V), trong trng thi ho hc no c mt nguyn t (th d ng trong khong cht c th dng oxyd hay sulfit hay hn hp nhng hp cht ny). Phn tch cht c nhiu ci chung vi phn tch phn t hay tng. - Phn tch tng (pha): l phn tch i tng trong h d th. Th d: sunfit v oxyd km phn b trong khong cht khng ng th m to nhng tng khc nhau. Ngi ta dng cc phng php khc nhau tch v xc nh cc h d th tham gia trong thnh phn cu trc (cc tng) ring bit, khc nhau v tnh cht, v cu trc vt l v phn tch nhau bi gii hn b mt. 3.4. PHN LOI THEO BN CHT CA PHNG PHP Xc nh theo c tnh ca tnh cht o hay theo kh nng ghi nhn tn hiu tng ng. C th chia ra: - Phng php ho hc: l phng php da trn nhng phn ng ho hc. Th d: phn ng acid-
11/25/2010
Page 7 of 239
base, oxy ho - kh, kt ta - ha tan, to phc. - Phng php ho l, vt l: phng php vt l da trn nhng hin tng v qu trnh vt l nh phng php quang ph, phng php so mu, vt l ht nhn,... - Phng php sinh hc: da trn nhng hin tng ca cuc sng (trao i cht, tng trng, c ch ca vi sinh vt...), th d nh phng php phn tch vi sinh vt l da vo qu trnh trao i cht ca vi sinh vt. Bng phng php vi sinh vt ngi ta nh lng cc thuc khng sinh, khng nm, vitamin,... 4. PHN TCH NH TNH V PHN TCH NH LNG 4.1. Phn tch nh tnh Phn tch nh tnh l xc nh cc nguyn t, cc ion, cc phn t c trong thnh phn cht phn tch. tin hnh phng php nh tnh ngi ta dng nhiu phng php c bn cht khc nhau, cc k thut, cc ng li khc nhau: phng php ho hc, vt l v ho l. 4.1.1. Phng php ho hc Phng php ho hc l nhng phng php nh tnh da trn cc phn ng ho hc. Nhng phng php trong phn tch c s dng rng ri trong thc t, phng php ny khng i hi trang b phc tp nhng cn c mt s nhc im l: trong trng hp cn phi tch cht ra khi cc tp cht v phi tch dng tinh khit thng rt kh khn, i khi khng thc hin c, khng pht hin c nhng lng cht rt nh. 4.1.2. Phng php vt l v ho l Phng php vt l v ho l l nhng phng php da trn cc tnh cht vt l ca cc cht cn phn tch. Th d: S nhum mu ngn la n kh khng mu thnh mu c trng do cc hp cht bay hi ca mt s nguyn t ho hc Na+, K+,... Phng php so mu ngn la: Ngn la Na+ c mu vng, K+ c mu tm, Ba2+ c mu xanh lc nht. Phng php phn tch quang ph hng ngoi, phng php o quang (quang ph hp th), phng php cc ph, phng php sc k v.v... Dng phng php vt l v ho l c th tch c cc nguyn t m chng kh b tch bi cc phng php ho hc, phng php vt l v ho l c nhy v chnh xc cao nhng phi c trang b phc tp, my mc t tin khng phi tt c cc c s u trang b c nn phng php ho hc vn ng vai tr quan trng trong cng tc phn tch. 4.2. Phn tch nh lng Phn tch nh lng cho php xc nh thnh phn v lng cc hp phn ca hp cht cho hoc ca hn hp cc cht. Khc vi phn tch nh tnh, phn tch nh lng cho kh nng xc nh hm lng ca cc hp phn ring r ca cht phn tch hoc hm lng chung ca cht cn xc nh trong cht nghin cu. Cc phng php dng trong phn tch nh lng:
11/25/2010
Page 8 of 239
4.2.1. Phng php phn tch ho hc - Phn tch trng lng (phn tch khi lng) Phng php ny da vo phn ng kt ta cc cht cn nh lng vi thuc th. Kt ta c tch ra khi dung dch, ra tht sch ri nung hoc lm kh sau em cn. T khi lng ca kt ta ta xc nh c khi lng ca cht cn nh lng. Phng php ny mt nhiu thi gian nhng kh chnh xc. - Phn tch th tch (chun ) Phng php ny da trn s o th tch dung dch thuc th bit chnh xc nng cn dng cho phn ng vi cht cn nh lng. Phng php ny rt ph bin, da trn cc phn ng trung ha, to phc, to kt ta, oxy ho - kh,... 4.2.2. Phng php phn tch vt l v ho l (phng php phn tch dng c) - Phng php phn tch vt l Cc phng php phn tch nh lng cho php xc nh thnh phn ca cht cn phn tch khng dng n cc phn ng ho hc. xc nh thnh phn cht cn phn tch c th o cc ch s v cc tnh cht vt l nh: h s khc x, dn in, nhit,... - Phng php ho l Cc phng php phn tch da trn s thay i tnh cht vt l ca mt h cn phn tch, s thay i xy ra do cc phn ng ho hc xc nh. Cc phng php vt l, ho l thng dng: cc phng php sc k, cc phng php o quang, phng php in ho, cc ph, in di,... 5. CC BC THC HIN CA MT QUY TRNH PHN TCH 5.1. Mu th - xc nh i tng u tin phi xc nh r mc tiu (cn nhng thng tin g) v yu cu phn tch (nh tnh hay nh lng). Thu thp thng tin v mu th: bn cht, ngun gc, cch ly mu, tnh trng mu v bo qun mu. 5.2. La chn phng php La chn phng php phn tch da trn nhng thng tin c trc nh: c mu phn tch, phng tin phn tch, yu cu phn tch,.. t kt qu phn tch tt ph thuc nhiu vo s la chn phng php. 5.3. Ly mu th y l bc quan trng nht trong c quy trnh phn tch. Chn mu i din c thnh phn phn nh ng thnh phn mu cn phn tch. T mu i din chn v chun b mu lm th nghim v phn tch theo yu cu. 5.4. X l mu th phn tch, mu th phi c x l l tch cc cht cn tr ra khi hn hp trc khi o. y l giai on quan trng trong phn tch.
11/25/2010
Page 9 of 239
5.5. Tin hnh o cc cht phn tch S dng nhng dng c, my mc thch hp o cht cn phn tch. 5.6. Tnh ton - x l kt qu phn tch Cc d liu thu c x l theo ton thng k nh gi tin cy ca kt qu o c. Cc bc trn lin quan mt thit vi nhau v nh hng ln nhau. Trong thc t, tu theo tng trng hp c th, cc bc tin hnh trn c n gin ho hoc b qua mt s bc, hoc thc hin ng cc bc trn. 6. HO PHN TCH LIN QUAN TI CC KHOA HC KHC Ho phn tch khng th v khng ch l mt phn ca ngnh ho hc m n lin quan mt thit vi cc ngnh khc nh: vt l v k thut. Phn tch ho hc phn ln da trn cc thnh tu ca quang ph (quang hc, phng x...), vt l ht nhn v nhiu phn khc ca vt l. Cc phng php phn tch ho hc c s dng trn nn tng cc thnh tu ca cc ngnh ho khc nh: l thuyt v cn bng ho hc, in ho, ng ho hc, ho v c, ho hu c, ho keo. Ngoi ra Ho phn tch cn lin quan ti ton hc v sinh hc. Nh vy c th ni rng Ho phn tch l c trng ca khoa hc gm nhiu ngnh, khoa hc lin quan. 7. HO PHN TCH VI NGNH DC Trong ngnh Dc, Ho hc phn tch gi vai tr quan trng. N c mt trong sut qu trnh sn xut (kim nghim nguyn liu, bn thnh phm, v sn phm cui cng), bo qun, lu thng v s dng thuc. Cc phng php phn tch s dng rt phong ph v a dng thuc cc lnh vc: vt l, ho hc v sinh hc. Hin nay ngi ta cn quan tm nhiu ti cc phng php kim nghim dng trong i tng sinh hc, (th d nh phn tch mu, nc bt, dch no ty, gp phn vo cc nghin cu sinh dc hc v dc ng hc). 8. NG DNG V HNG PHT TRIN CA HO PHN TCH 8.1. ng dng Ho phn tch ng vai tr quan trng trong s pht trin khoa hc k thut v nhiu mn khoa hc t nhin: ho hc, a cht, a l, khong vt hc, vt l, sinh hc, sinh ho, nng ho, y dc hc. Trong nhng lnh vc ny thc hin cc cng trnh nghin cu khoa hc u i hi phi p dng cc phng php phn tch. Da vo cc thng tin ca phn tch ho hc m cc nh a cht tm kim cc khong cht. Da vo kt qu phn tch mu cc thy thuc chn on c tnh trng sc khe ca con ngi. S nh lng cc ion K+, Ca2+, Na+ trong dch t bo ng vt cho php cc nh sinh l hc nghin cu vai tr ca cc ion ny trong s dn truyn lung thn kinh cng nh trong c ch co v dui ca cc c. Cc nh ho hc gii thch cc c ch phn ng ho hc nh vo vic nghin cu vn tc phn ng, nh c cc phng php phn tch hin i m ngi ta tng hp c cc cht ho hc mi, ... 8.2. Hng pht trin Ngy nay vi s pht trin ca khoa hc k thut tin tin i hi chuyn ngnh Ho phn tch ngy mt hon thin, p ng nhu cu trn Ho phn tch tin ti phi gii quyt c 5 vn sau:
11/25/2010
Page 10 of 239
8.2.1. Xc nh v gii quyt nhng kh khn trong Ho phn tch Cn phi xc nh cc thng tin c th (nh tnh, nh lng, tnh cht, chc nng). Xc nh tnh hung c th. 8.2.2. Thit k mt quy trnh phn tch Thit lp tiu chun cho mt quy trnh phn tch ( chnh xc, ng, nhy, chi ph, quy m thc hin, tin thc hin...) Xc nh cc yu t cn tr. La chn phng php. Thit lp cc tiu chun thm nh. Cch ly mu. 8.2.3. Thc hin v thu thp d liu Kim nh dng c v trang thit b. Chun ho thuc th. Thu thp d liu. 8.2.4. X l d liu - Gim hoc bin i d liu. - Phn tch thng k. - nh gi kt qu. - Biu th kt qu.
8.2.5. Thc hin nh gi ca c s bn ngoi Kim tra nh gi li kt qu phng th nghim ca c s bn ngoi. Tu iu kin thc t, tnh hnh c th ca c s c th khng gii quyt c ngay ht cc vn m tng bc gii quyt tin ti hon chnh nh cc yu cu t ra. Hin nay nc ta ngnh Dc ang pht trin, cc x nghip Dc c phn trong nc v lin doanh ra i, bn cnh cc phng bo ch cc khoa Dc cc bnh vin cng pht trin khng ngng, ngoi ra cc ngun thuc nhp khu cng rt phong ph t cc nc pht trin v ang pht trin. m bo cht lng thuc sn xut v thuc xut nhp khu n tay ngi tiu dng, cng tc kim nghim thuc ngy cng c quan tm, v vy ngi Dc s cn trang b nhng kin thc vng vng v Ho hc phn tch. Ngoi cng tc kim nghim thuc, cc cng tc khc trong cc phng th nghim ho dc, dc l, dc liu, dc lm sng, sinh ho, c cht,... cng i hi nhng kin thc v Ho hc phn tch. T KHO - Ho hc phn tch - Phn tch nh lng - Phn tch phn t - Phn tch nh tnh - Phn tch cht - Phn tch vi lng, bn vi lng, siu vi lng - Phn tch nguyn t - Quy trnh phn tch
11/25/2010
Page 11 of 239
CU HI LNG GI 1. Cho bit i tng ca ho hc phn tch. S lin quan ca ho hc phn tch vi ngnh Dc v cc mn khoa hc khc. 2. Th no l phn tch nh tnh? Nu cc phng php phn tch trong phn tch nh tnh. 3. Nu cc phng php dng phn tch nh lng. 4. Trnh by cc bc thc hin ca mt quy trnh phn tch. CU HI TRC NGHIM Hy chn t ng thch hp in vo ch trng trong cc cu 1 v 2 sao cho ph hp: 1. Ho phn tch l khoa hc v s xc nh......... ca cht phn tch a. phn ng ho hc b. thnh phn ho hc c. thnh phn d. nhm chc e. tnh cht ho hc
2. Phn tch nh lng cho php xc nh..... ca cc hp phn trong cht nghin cu: a. cu trc b. thnh phn c. th tch d. trng lng e. hm lng
3. Phng php ho hc l phng php da trn a. tnh cht ho hc b. thnh phn ho hc c. phn ng ho hc d. hin tng ho hc e. cu trc ho hc
4. Ho phn tch ng vai tr quan trng trong s pht trin ca mn khoa hc a. y dc hc b. a cht c. khong vt hc d. tt c cc cu trn e. ch cu a,b
5. C my bc ch yu ca mt quy trnh phn tch a. 3 b. 4 c. 5 d. 6 e. 7
Chng 2
11/25/2010
Page 12 of 239
CN BNG HO HC
MC TIU
Trnh by c nh ngha v phn loi phn ng ho hc. Trnh by c khi nim v s cn bng ho hc. Trnh by c cch tnh cc hng s cn bng ho hc. Din t c s khc bit gia hot v nng . Gii c mt s bi tp cn bng ho hc.
NI DUNG 1. PHN NG HO HC 1.1. nh ngha Phn ng ho hc l phn ng khi lin kt mt hay nhiu hn 2 nguyn t th cc lin kt ho hc trong cht tham gia phn ng thay i v to ra cht mi (sn phm). Qu trnh ny lun km theo 1 s thay i nng lng v tun theo nh lut bo ton nng lng. Phn ng ho hc kt thc khi c s cn bng phn ng ho hc hay cc cht tham gia phn ng c chuyn i hon ton. 1.2. Cc loi phn ng ho hc Cc ti liu v phn ng ho hc hin nay phn loi nhiu kiu phn ng theo cc c ch nhng ch yu tp trung cc loi sau: 1.2.1. Phn ng kt hp (synthesis reaction) Trong phn ng ny, 2 hay nhiu cht n gin s kt hp to nn cht phc tp hn. Dng c bn: A + X AX Th d: kh hydro kt hp vi kh oxy c th to nn cht phc tp hn l nc 2H2 + O2 H2O Th d 1: kim loi + oxy oxid kim loi*: 2Mg(r) + O2(k) 2MgO(r) Th d 2: phi kim + oxy oxid phi kim: C(r) + O2(k) CO2(k) Th d 3: oxid kim loi + nc hydroxid kim loi
11/25/2010
Page 13 of 239
MgO(r) + H2O(l) Mg(OH)2(r) Th d 4: oxid phi kim + nc acid: CO2(k) + H2O(l) H2CO3(nc) Th d 5: kim loi + phi kim mui: 2 Na(r) + Cl (k) 2NaCl(r) 2 Th d 6: Vi phi kim kt hp vi nhng cht khc: 2P(r) + 3Cl2(k) 2PCl3(k) C 2 phn ng thuc loi ny cn ghi nh N2(k) + 3H2(k) 2NH3(k) NH3(k) + H2O(l) NH4OH(nc) 1.2.2. Phn ng phn hy (decomposition reaction) Phn ng phn hy l mt phn ng ho hc tch ri do mt cht t hy hay chia ra thnh cc n cht* Dng c bn: AX A + X 2H2O 2H2 + O2 Th d 1: carbonat kim loi, khi un nng to thnh cc oxid kim loi v kh CO2(k). CaCO3(r) CaO(r) + CO2(k) Th d 2: Hu ht cc hydroxid kim loi, khi un nng phn hy thnh oxid kim loi v nc. Ca(OH)2(r) CaO(r) + H2O(k)
*
K hiu (k = th kh = gaz); (l = th lng = liquid); (r = th rn = solid); (nc = dung mi, nc = aqueous)
Th d 3: Cc clorat kim loi khi un nng phn hy thnh clorid kim loi v oxy. 2KClO3(r) 2KCl(r) + 3O2(k) Th d 4: Mt s acid khi un nng phn hy thnh oxid phi kim v nc H2SO4 H2O(l) + SO3(k) Th d 5: Mt s oxid khi un nng phn hy: 2HgO(r) 2Hg(l) + O2(k) Th d 6: Mt s phn ng phn hy c sn xut do in phn
11/25/2010
Page 14 of 239
2H2O(l) 2H2(k) + O2(k) 2NaCl(l) 2Na(r) + Cl2(k) 1.2.3. Phn ng trao i (replacement reaction) Dng c bn: A + BX AX + B hay AX + Y AY + X Th d 1: Trao i 1 kim loi ca 1 cht bng kim loi c hot tnh hn Fe(r) + CuSO (nc) FeSO (nc) + Cu(r) 4 4 Th d 2: Trao i nguyn t hydro c trong nc bng kim loi c hot tnh 2Na(r) + 2H2O(l) 2NaOH(nc) + H2(k) Mg(r) + H2O(k) MgO(r) + H2(k) Th d 3: Trao i nguyn t hydro c trong acid bng kim loi c hot tnh Zn(r) + 2HCl(nc) ZnCl2(nc) + H2(k) Th d 4: Trao i phi kim bng kim loi c hot tnh hn. Cl (k) + 2NaBr(nc) 2NaCl(nc) + Br (l) 2 2 a) Phn ng trao i n (single replacement reaction) Phn ng trao i n l mt phn ng ho hc ca mt n cht vi acid. Trong phn ng trao i n th mt nguyn t khng kt hp s thay th nguyn t khc trong mt hp cht. Hai cht tham gia phn ng nhng ch cho 2 sn phm. Th d: Natri kt hp vi acid hydrochloric th natri s thay th hydro 2Na + 2HCl 2NaCl + H2 b) Phn ng trao i kp (double replacement reaction) Trong phn ng trao i kp th 2 hp cht chuyn v tr to thnh 2 hp cht mi. Hai cht tham gia phn ng nhng ch cho 2 sn phm mi. Th d: Bc nitrat kt hp vi natri clorid s to 2 hp cht mi l bc clorid v natri nitrat AgNO3 + NaCl AgCl + NaNO3 Fe2O3 + 6HCl 2FeCl3 + 3H2O c) Phn ng trao i ion Phn ng trao i ion l phn ng ho hc xy ra gia cc ion trong dung dch nc. Mt phn ng s xy ra khi cp ion cng nhau trao i to thnh t nht mt trong nhng cht sau: kt ta, kh, nc hay cht khng ion ho khc. Dng c bn: AX + BY AY + BX
11/25/2010
Page 15 of 239
Th d 1: Phn ng to ta NaCl (nc) + AgNO3(nc) NaNO3(nc) + AgCl(r) BaCl2(nc) + Na2 SO4(nc) 2NaCl(nc) + BaSO4(r) Th d 2: Phn ng to kh HCl(nc) + FeS(r) FeCl2(nc) + H2S(k) Th d 3: Phn ng to nc. (Nu phn ng gia acid v base th gi l phn ng trung ha) HCl(nc) + NaOH(nc) NaCl(nc) + H2O(l) Th d 4: Phn ng to ra mt sn phm phn hy CaCO3(r) + HCl(nc) CaCl2(nc) + CO2(k) + H2O(l) 1.2.4. Phn ng oxy ho kh Cht tham gia phn ng b oxy ho (mt mt hay nhiu electron) v cc cht tham gia khc b kh (nhn mt hay nhiu electron). Cc th d chung ca cc phn ng oxy ho - kh lin quan n oxy l s st r ca kim loi nh st (cc kim loi b oxy ho bi oxy ca kh quyn), s t chy v chuyn ho nng lng trong c th. C10H8+ 12O2 10CO2 + 4H2O + nhit CH2S + 6F2 CF4 + 2HF + SF6 + nhit Mt th d ca phn ng oxy ho - kh khng lin quan n oxy ca kh quyn l phn ng to in trong bnh acquy: Pb + PbO + 4H+ + 2SO 2 2PbSO + 2H O 2 4 4 2 2. KHI NIM V S CN BNG HO HC Khi kho st cc phn ng ho hc ngi ta nhn thy c rt t phn ng ho hc di chuyn ch theo mt chiu. a s cc phn ng ho hc u di chuyn thun nghch. Khi bt u c s to thnh sn phm l c phn ng theo chiu ngc li hay c th ni ngay t lc c nhng phn t sn phm xut hin l bt u c phn ng nghch. Khi tc ca phn ng di chuyn theo chiu thun v theo chiu nghch bng nhau v nng ca cht tham gia phn ng v ca nng sn phm khng thay i theo thi gian na l cn bng ho hc t n. Cn bng ho hc l mt qu trnh cn bng ng. Hy tng tng nh nhng ngi ang trt tuyt trn 1 dc thoi. Lng ngi ang i ln v trt xung lin tc ni tip nhau thay i nhng tng s ngi tham d trt tuyt t nh ti chn dc khng thay i. Khi ni n cn bng ho hc l ni n c t nht 2 cht khc nhau: cht tham gia phn ng v sn phm. Khi ni n cn bng vt l l ch cp n mt cht c trong 2 pha (th) khc nhau v s thay i sn phm ch l thay i v l tnh. Th d trong s bay hi nc s mol H2O thot ra khi th lng
11/25/2010
Page 16 of 239
bng vi s mol H2O chuyn thnh th kh: H2O (l) N2O4 (k) H2O (k) 2NO2 (k)
Mt th d in hnh ca cn bng ho hc l phn ng: (2.1)
y l phn ng to thnh kh nit dioxyd (NO2) t kh dinit tetraoxyd (N2O4). C th theo di din bin ca phn ng ny d dng do N2O4 l kh khng c mu trong khi NO2 c mu nu m. Nu bm mt lng chnh xc N2O4 vo mt bnh cu trong l chn khng th mu nu ca s xut hin ngay chng t l NO2 c mt. Mu nu s m dn do N2O4 t phn ly. n khi t cn bng th mu khng i na. i vi phn ng ngc vi phn ng (2.1) 2NO2(k) N2O4 (k) (2.2)
Trong cc hnh minh ha 2.1 v 2.2 vng mu nu en i din cho kh NO2 v vng trng i din cho kh N2O4. Nu bt u vi NO2, c th minh ha cn bng t n nh sau:
Hnh 2.1. Chuyn 2NO2 (k)
N2O4 (k), h thng cn bng cc 4, 5 v 6
Nu bt u vi N2O4, cng nhit c th minh ha cn bng t n l
Hnh 2.2. Chuyn N2O4 (k)
2NO2 (k), h thng cn bng cc 10, 11 v 12
Tu theo nhit v khi lng ban u ca N2O4 (c th c ln NO2 hay khng) s dng m nng ca NO2 v N2O4 trng thi cn bng ca h ny s khc h khc. Ch : - Mt h thng cn bng khng cn bt c nng lng no duy tr s cn bng. - Khng nn ln ln trng thi cn bng v trng thi tnh. Trng thi tnh l trng thi m cc nng u khng i theo thi gian.
11/25/2010
Page 17 of 239
- Cn bng ho hc l trng thi ng trong cht tham gia phn ng v sn phm chuyn i lin tc cho nhau. Tc mt i v xut hin ca chng bng nhau. Bng 2.1 nu vi d liu thc nghim lin quan n phn ng ny 25 C. Nng ca kh c din t bng nng mol v c tnh t s phn t ca kh c mt t lc phn ng bt u cho n lc phn ng cn bng xy ra trong 1 th tch ca bnh cu (tnh bng lt). Phn tch cc d liu t s cn bng s cho thy trong khi t s i th t s li gn nh hng nh v trung bnh l 4,63 x 10-3. cho nhng gi tr thay
Gi tr trung bnh ny gi l hng s cn bng K i vi phn ng ny 25 C. Biu thc ton hc ca hng s cn bng i vi h NO2 - N2O4 l
Cng cn ch l s m 2 ca [NO2] trong biu thc trn bng h s cn bng t lng ca NO2 trong phng trnh (2.1). Khi nim ny thu c khi xt phng trnh ca phn ng thun nghch: A+B A, B: Cc cht tham gia phn ng C, D: Sn phm to thnh. Phng trnh (2.3) l biu thc ton hc tun theo nh lut tc dng khi lng.
B ng 2.1. Gi tr cc t s nng ca NO2 v N2O4 Nng ban u (M) [NO2] 0,000 0,0500 0,0300 0,0400 0,200 [N2O4] 0,670 0,446 0,500 0,600 0,000 Nng cn bng (M) [NO2] 0,0547 0,0457 0,0475 0,0523 0,0204 [N2O4] 0,643 0,448 0,491 0,594 0,0898 0,0851 0,102 0,0967 0,0880 0,227 4,65 10-3 4,66 10-3 4,60 10-3 4,60 10-3 4,63 10-3 Gi tr cc t s nng
C+D
(2.3)
11/25/2010
Page 18 of 239
Hnh 2.3. Bin i nng ca NO2 v N2O4 theo thi gian a) Lc u ch c NO2; b) Lc u ch c N2O4; c) Lc u c hn hp NO2 v N2O4
3. HOT V NNG Khi ni n hot v nng cn xc nh r 2 loi nng : - Nng mol/l (phn t gam / l) ch s phn t gam cht tan (cht tan c th l phn t, ion) c trong mt 1000 ml dung dch. - Nng molan ch s phn t gam cht tan c trong mt 1000 gam dung dch. Khi nim hot v h s hot do nh ho l ngi Hoa K Lewis a ra (1907). hiu r hn s xt th d bng 2.2 Biu thc tnh pH l pH= - lg[H+] (l mt cng thc rt quen thuc din t s lin quan gia pH v nng mol ca ion H+). Theo bng 2.2, nu so snh pH tnh ton theo cng thc v pH o c qua thc nghim th s nhn thy c sai s gia gi tr pH l thuyt v thc nghim. L do c sai s nh thy l do biu thc pH= - lg[H+] ch chnh xc trong mt gii hn pha long v pH tht s tnh theo hot ion hydro ch khng tnh theo nng . Ngha l pH= -lg aH+
Hot aH+ ca ion hydro c trong mt dung dch cho c th c xc nh bng cch n gin l o pH.
B ng 2.2. S khc bit v pH tnh theo l thuyt v thc nghim Nng mol ca HCl 0,00050 0,0100 0,100 0,4 pH theo l thuyt 3,30103 2 1 0,39794 pH theo thc nghim 3,31 2,04 1,10 0,52 Sai s pH -0,00897 -0.04 -0,1 -0,12206
Mt cch tng qut, gia hot v nng c mi lin quan theo cng thc: a=C hay a=fC
vi a: hot ; (hoc f): h s hot ; C: nng mol;
11/25/2010
Page 19 of 239
Hot da trn cc nng cho c p dng tt i vi cc dung dch khng in ly (hay cc hp cht phn t). Trong dung dch pha long, h s hot thng = 1 cho nn hot = nng . Trong dung dch in ly, do cc tc ng tng h ca in tch nn cn quan tm n vi yu t c bit tnh c h s hot nh: - Lc ion: Khi bn n dung dch ion th t nht phi bit v lc ion ca dung dch ny v ngi ta tin rng lc ion s nh hng n hot ion. i lng ny c k hiu l I Mt cht in ly MxXm c phn ly thnh: MxXm = x Mm+ + m XxCc ion dng Mm+ v cc ion m Xx- phi cng c mt trong mt dung dch v khng c cch no tch ring hot ca cc ion dng v m. Do vy, thng dng i lng hot ion trung bnh (a) a = C (MmXx)-(m+x) i vi c 2 ion dng v m, C l nng t lng ca cht in ly (stoichiometric concentration). Trng hp ny h s hot trung bnh c tnh theo biu thc:
Trong + v - ln lt l s cation v anion trong 1 n v cng thc ca cht in ly. Ngoi ra, phng trnh Debye Huckel m rng (ci tin t nh lut gii hn ca Debye Huckel) cng l biu thc c c s chc chn lm nh i cch tnh nng khi tnh theo h s hot trung bnh:
Trong A l hng s tu thuc vo tnh cht ca dung mi (A= 0,5085 i vi nc 25oC), z+ v z- l cc in tch ion, I l lc ion c xc nh theo phng trnh: I = zi2mi trong mi l nng ca ion i. Tm li, I c tnh n tt c cc ion c th c trong dung dch ny. i vi cc dung dch m c, vic s dng nng tnh theo trng lng ca dung mi (nng molan) thng c th cung cp mt c lng tt hn l dng nng tnh theo th tch (nng mol). 4. HNG S CN BNG (HSCB) 4.1. Cch tnh hng s cn bng nh lut tc dng khi lng l nh lut biu din mi lin quan gia nng (hot ) ca cc cht phn ng v ca sn phm phn ng trng thi cn bng. nh lut tc dng khi lng ch p dng c vi cc dung dch l tng l dung dch ca cc
11/25/2010
Page 20 of 239
cht khng in ly v cc cht in ly yu vi nng rt long (hot ). Trong thc t, thng thng nng ca cc dung dch khng tun theo pha long mt cch chnh xc. Trong trng hp cc cht in ly mnh hoc cc cht in ly yu nhng nng cao th s sai lch rt ln, y l gii hn ca nh lut tc dng khi lng. V th khi p dng nh lut tc dng khi lng ch nhn c cc kt qu gn ng. Tuy vy, trong nhiu trng hp chnh xc ny vn chp nhn c vi cc mc ch thc tin. Th d: i vi phn ng trng thi cn bng mA + nB Nu tnh theo hot Khi mt phn ng t trng thi cn bng th t s gia tch cc hot ca cc sn phm phn ng (c nng lu tha vi s m bng h s t lng trong phng trnh phn ng) v tch tng ng ca cc cht phn ng l mt hng s ( nhit cho sn). Khi t cn bng th t s (2.5) Ka c gi l HSCB, trong aA, aB, aC, aD l hot cn bng ca cc cht phn ng (A, B) v cc sn phm phn ng (C, D); m, n, p, q l cc h s t lng tng ng. Nu tnh theo nng Thay cho hot , HSCB cng c th biu din qua nng Ci, p sut ring Pi hoc phn mol Xi ca cc cu t i tng ng. Trong cc trng hp ny HSCB c k hiu Kc, Kp, Kx. Kc - hng s cn bng: (2.6) Trong phng trnh 2.6 [A], [B], [C], [D]: nng cn bng tng ng ca cht phn ng v sn phm, m, n, p, q: cc h s cn bng (cc h s t lng tng ng). Nu coi (2.4) l phn ng c bn (xy ra trong mt giai on, mt va chm) theo chiu t tri sang phi th tc phn ng theo chiu thun c biu din bng phng trnh: (2.7) Trong , V1 l tc phn ng; m, n l cc h s t lng; K1: hng s tc ; [A] v [B] l nng tng ng ca cht phn ng A v B thi im kho st. Nu coi (2.4) l phn ng c bn hai chiu, thun v nghch, V2 l tc phn ng xy ra theo chiu ngc li. Phn ng c c trng bng hai hng s tc K1 v K2 vi (2.8) pC +qD (2.4)
11/25/2010
Page 21 of 239
Khi phn ng t ti trng thi cn bng th V1 = V2 Ngha l K1[A]m[B]n = K2[C]p[D]q (2.9) Trn thc t, (2.4) thng biu din mt phn ng phc tp (bao gm nhiu giai on, qua nhiu va chm) th biu thc (2.6) ni chung khng ng. Trong trng hp ny hm tc phn ng ph thuc nng c dng phc tp. Ch trong mt s trng hp tc phn ng c th biu din bng hm m: (2.10) Trong n1 v n2 tng ng l bc phn ng theo cc cu t 1 v 2. C: nng ca cc cht tham gia hoc sn phm to thnh sau phn ng. Nh vy, n1 m v n2 n. Bc phn ng l i lng c xc nh bng thc nghim, khng lin quan n cc h s t lng. Bc c th l s nguyn, phn s hay s khng. 4.2. Hng s cn bng ca cc phn ng hay s dng trong ho hc phn tch 4.2.1. Hng s cn bng ca cc phn ng phn ly (HSPL) L hng s cn bng ca phn ng phn ly mt cht. Th d: i vi phn ng phn ly acid yu HA: HA = H+ + A-
Ka c gi l HSPL nhit ng; a: hot ca ion hoc phn t; g: h s hot . Trong nhng trng hp, khi c th chp nhn h s hot khng i:
K'a c gi l HSPL iu kin. Ka ph thuc nhit , khng ph thuc nng ; cn K'a ph thuc c nng v nhit . Bn cnh Ka ngi ta cn dng khi nim pKa = - lgKa. Th d. i vi acid acetic CH COOH 25oC, K = 1,754. 10-5 v pK = 4,76. 3 a a Trong hng s phn ly ngi ta c th lm r hn vi hng s khc l: a) Hng s phn ly acid (phn ng acid base) Phn ng ca mt acid vi dung mi (nh nc) c gi l phn ng phn ly acid. Acid chia lm 2 loi: - Acid mnh nh l HCl chuyn ht proton ca n cho dung mi.
11/25/2010
Page 22 of 239
- Acid yu nh acid acetic khng th cho ht proton acid ca n cho dung mi. Thay vo hu ht acid cn li khng phn ly, ch mt phn nh hin din di dng base lin hp CH3COOH (nc) + H2O (l) 10-5 H3O+ (nc) + CH3COO- (nc) (2.11)
Hng s cn bng ca phn ng ny c gi hng s phn ly acid Ka. Ka ca acid acetic l 1,75 x
Ch : nng ca nc c th b qua trong biu thc tnh Ka v gi tr qu ln khng b nh hng bi phn ng phn ly. ln ca Ka cung cp thng tin v lc tng i ca acid vi Ka cng nh th acid cng yu. (trnh by trong chng 7) b) Hng s phn ly base (phn ng acid base): Hng s phn ly base l hng s cn bng gia base yu v proton m base nhn to nn acid v acid . Th d gia NH3 v proton to nn acid NH4+ v acid , c cn bng: NH3 + H+ Vi hng s cn bng NH4+
Kb c gi l hng s phn ly base. V cng ca base c biu th bng Kb nn Kb cng ln, base kt hp vi proton cng nhiu, ngha l base cng mnh. Th d NH3 c Kb = 1,76.10-5 mnh hn base CH3COO- c Kb = 1,74.10-9. c) Hng s khng bn ca phc cht (HSKB) Hng s cn bng gia phc cht v cc tiu phn (ion, phn t) to nn phc cht . Th d: gia ion phc Ag(NH3)2+ v Ag+, NH3 (do ion phc phn ly) c cn bng:
Hng s cn bng Kb ny c gi l HSKB ca ion phc Ag(NH3)2+; v Kb cng ln, ion phc phn li cng nhiu nn Kb cn c gi l hng s phn ly ca phc cht. (trnh by trong chng 10). 4.2.2. Hng s cn bng ca cc phn ng kt hp (HSKH) L hng s cn bng gia ion t do v cp ion (do hai ion khc du kt hp vi nhau to thnh).
11/25/2010
Page 23 of 239
Th d: i vi KCl (kali clorid) gia cc ion t do K+, Cl- v cp ion K+Cl- c cn bng:
HSKH ph thuc vo hng s in mi D ca dung mi v nng cht tan: Kkh ca KCl 0,1 M trong acid acetic vi D = 6,2 l 106,9 v trong metanol vi D = 32,6 l 101,15. Trong dung mi c D cng nh, Kkh cng cao; trong benzen, clorofom hu nh khng c ion t do, v D rt nh. Trong hng s kt hp ngi ta c th lm r hn hng s khc nh: a) Hng s bn (HSB = K) (Phn ng to phc) . Hng s bn l hng s cn bng gia cc tiu phn (ion, phn t) to nn phc cht v phc cht Th d: gia Ag+ v NH3 to nn ion phc Ag(NH3)2+ v ion phc c cn bng Ag+ + 2HN3 vi hng s cn bng Ag(NH3)2+
Hng s cn bng K cng c gi l HSB ca ion phc Ag(NH3)2+; v K cng ln, Ag(NH3)2+ c to nn cng nhiu nn K cn c gi l hng s to thnh phc cht. (trnh by trong chng 10) b) Hng s bn iu kin (Phn ng to phc) (trnh by trong chng 10) 4.2.3. Hng s cn bng ca cc phn ng trao i Tch s tan (Phn ng to ta) Phn ng to ta xy ra khi c 2 hay nhiu cht ha tan kt hp vi nhau to thnh cht khng tan gi l ta. Phn ng kt ta chung nht l phn ng hon v m trong 2 hp cht ion ho tan trao i cc phn. Th d: Pb2+ (nc) + 2Cl (nc) PbCl2 (r)
Tuy nhin, trong vic x l s cn bng ca s kt ta, cng thng xuyn gp phn ng ngc chiu m t s phn ly ca ta ny. PbCl (r) 2 Pb2+ (nc) + 2Cl (nc)
Trong phn ng ny c mt hng s c gi l tch s tan (solubility product, Ksp) l tch nng cc ion ca hp cht t tan trong dung dch bo ho cht TST ca PbCl2 = Ksp = [Pb2+] [Cl-]2 = 1.7 10-5 i vi cc cht tan kh, c nng bo ho ln, khng p dng tch s nng , m phi tnh theo tch s hot a (trnh by trong chng 9)
11/25/2010
Page 24 of 239
4.2.4. Hng s cn bng ca cc phn ng oxy ho - kh Khng ging nh cc phn ng c xt, v tr cn bng ca phn ng oxy ho - kh him c din t bng hng s cn bng. V phn ng oxy ho - kh lin quan n s di chuyn electron t tc nhn kh sang tc nhn oxy ho nn xt nhit ng hc ca phn ng v mt electron li thch hp hn (trnh by trong chng 8). Nhit ng hc l khoa hc nghin cu s tng tc ca nhit vi s bin thin nng lng v quan trng hn c i vi lnh vc ho hc l nghin cu s thay i nng lng trong qu trnh phn ng. Nhit ng hc ho hc phn tch cc yu t xc nh im cn bng ca phn ng. Hng s cn bng K c th suy ra t l thuyt nhit ng hc. K ph thuc vo bn cht ca cht phn ng, nhit v p sut. nhit v p sut hng nh, nng lng t do Gibb biu din theo cng thc G = H T. S Trong : - T l nhit Kelvin; G: l bin thin v nng lng t do Gibb - H: l bin thin enthalpy; S: l bin thin entropy Bin thin nng lng G lin quan n hng s cn bng K ca phn ng ho hc G = Go + RTlnK 4.3. ng dng ca hng s cn bng K Hng s K cho bit v chiu mc hon ton ca phn ng. Nu K ln rt nhiu hn 1 (K>>1) th phn ng s chim u th to ra C v D; K cng ln, phn ng theo chiu thun cng hon ton. Nu K nh rt nhiu so vi 1 (K< 0,1) th phn ng khng hon ton, K qu nh th phn ng to C v D hu nh khng xy ra. V K l mt hng s do nu thay i mt tha s [A] hoc [B] hoc [C] hoc [D] th s ko theo s thay i mt hay nhiu tha s khc. Nh vy, mun quyt nh chiu ca phn ng ta c th thay i nng ca cc cht. Khi bit hng s cn bng ho hc K, ta c th tnh ton: - Nng cn bng ca cc ion cht in ly yu, nu bit nng ban u ca chng. - Nng cn bng ca ca cc cht tham gia phn ng hoc sn phm to thnh ca cc phn ng ho hc. - Nng cn bng cc ion hydro, hydroxyd, in ly ca cht in ly trong cc dung dch nc ca cc acid hoc baz yu, cc mui thu phn, dung dch m... - Nng cn bng ca cc cation, anion v tan ca cht in ly t tan trong nc. 5. CC YU T NH HNG N CN BNG HO HC Theo nguyn l Le Chatelier Khi tc ng ln mt h th bn thn h s t iu chnh hn ch
11/25/2010
Page 25 of 239
nh hng ca tc ng . C rt nhiu yu t nh hng n hng s cn bng ca phn ng. 5.1. nh hng ca nhit Xt phn ng thun nghch sau y: N2 + 3H2 2NH3 (2.12)
Phn ng thun to nhit, phn ng nghch thu nhit. Do , nu ta tng nhit ca h thng th cn bng s dch chuyn theo hng lm gim nhit tc l chuyn v pha phn ng nghch, v nu gim nhit ca h thng th phn ng s xy ra theo chiu thun. 5.2. nh hng ca p sut S tng hay gim p sut ring phn ca cht kh cng tng t nh s thay i nng . Xt phn ng th kh: H2 + Cl2 2HCl
S phn t kh hai v bng nhau do khi thay i v p sut s khng lm thay i trng thi cn bng. Nhng i vi phn ng tng hp NH3 (phng trnh 2.12) trn th hn hp s gim th tch, do khi tng p sut th h thng cn bng s dch chuyn theo chiu thun. V nng ca cc cc cht kh tu thuc p sut ring phn ca chng v khng ph thuc vo tng p sut ca h thng, do khi thm hay b mt lng kh tr s khng lm thay i cn bng phn ng ca cht kh . 5.3. nh hng ca dung mi Hu ht phn ng c s tham gia ca cht phn ng v sn phm dng phn tn trong dung mi. Nu lng dung mi thay i th nng ca tt c cc cht phn ng v sn phm s thay i. Th d: phn ng to phc Bc-amoniac trong nc: Ag+ + 2NH3 Ag(NH3)2+
Hng s cn bng ca phn ng ny l (2.13) Nu mt phn ca phn ng ny c pha long vi ng th tch nc, nng ca cc cht trong phng trnh (2.13) u gim mt na. Do h s phn ng s l
Hoc c th vit l
V Q ln hn 2, cn bng phi c ti lp bng cch dch chuyn sang tri v lm gim nng
11/25/2010
Page 26 of 239
ca Ag(NH3)2+. Hn na, v tr cn bng mi s hng v pha c s cht tan nhiu nht. Nu dung dch Ag(NH3)2+ c c m c, bng cch lm bay hi th cn bng c ti lp theo hng ngc li. Kt lun tng qut ny c th p dng vi bt k phn ng no, bt k pha rn, lng hay kh. Vic gia tng th tch lun lm phn ng din ra u tin theo hng c s phn t nhiu nht v s gim th tch th thc y phn ng theo hng c t phn t nht. Nu s phn t c hai v phng trnh l nh nhau cn bng ca phn ng khng b nh hng bi s thay i th tch. 5.4. nh hng ca nng cc cht tham gia phn ng v sn phm to thnh - H thng cn bng ca phn ng b ph v trc tip Vi phn ng phn ly ca acid acetic, (phng trnh 2.11) mt nhit hng nh, cc dung dch khc nhau ca acid acetic s c cc gi tr khc nhau cho nng H3O+, acetat, v acid acetic, nhng lun c cng gi tr Ka. Ti thi im cn bng nu thm vo dung dch natri acetat, nng acetat tng ln, c kh nng lm tng gi tr ca Ka. Tuy nhin, v gi tr Ka gi nguyn khng i, do nng ca c ba phn t trong phng trnh (2.11) phi thay i phc hi Ka v gi tr nguyn thu ca n. Trong trng hp ny, cn bng c ti lp bng phn ng mt phn ca acetat v H3O+ to thm acid acetic. Nh vy, h thng cn bng ca phn ng s b ph v khi thay i nng ca cht tham gia phn ng hay sn phm to thnh. - H thng cng c th ph v mt cch gin tip Th d s phn ly ca AgCl AgCl Ag+ + Cl(2.14)
nh hng trn tan ca AgCl bng cch thm AgNO3 th r rng, nu thm vo mt cht c th to phc bn v tan c vi Ag+ nh amoniac th s xy ra phn ng sau: Ag+ + 2NH3 (2.15)
Thm amoniac lm gim nng Ag+ di dng ion phc . V s gim nng Ag+ lm tng tan ca AgCl v phn ng (2.15) ti lp im cn bng. T cc phn ng (2.14) v (2.15) s lm r tc ng ca amoniac trn tan ca AgCl v amoniac cng l mt cht tham gia phn ng. AgCl + 2NH3 + Cl(2.16)
Th d: Nu thm HNO3 vo th cn bng ca phng trnh (2.16) s thay i nh th no? Gii: HNO3 l acid mnh, acid ny s phn ng vi NH3 Khi thm t HNO3 vo s lm gim NH3. Vic gim nng NH3 s lm phn ng (2.16) xy ra theo chiu to ra cht phn ng, gim tan AgCl.
11/25/2010
Page 27 of 239
6. BI TP V CN BNG HO HC 6.2. X l cc hng s cn bng thun tin cho vic tnh ton cc hng s cn bng ngi ta c th x l cc hng s cn bng theo cc cch sau y: - T phn ng cho nu ta o ngc phn ng th hng s cn bng ca phn ng mi s l nghch o ca phn ng u. Th d, hng s cn bng cho phn ng
L nghch o ca phn ng
- Nu cng hai phn ng vi nhau to ra phn ng mi th hng s cn bng ca phn ng mi l tch s ca hng s cn bng ca cc phn ng ban u.
6.2. Bi tp v tnh p sut cn bng ring phn Hng s cn bng KP i vi phn ng sau PCl5(k) PCl3(k) + Cl2(k)
l 1,05 250 C. Nu p sut ring phn trng thi cn bng ca PCl5 v PCl3 ln lt l 0, 875 atm v 0,463 atm th p sut ring phn trng thi cn bng ca Cl2 250 C l bao nhiu? Gii: trc tin tnh KP
6.3. Bi tp v chuyn i KC thnh KP Kc : hng s cn bng theo nng . Kp : hng s cn bng theo p sut tng phn ca kh .
11/25/2010
Page 28 of 239
Ch : theo phng trnh: aA (k) Theo phn ng N2 (k) + 3H2(k)
bB (k) th KC = 2NH3(k)
v KP =
Gi tr ca K = 4,3.10-4 375 C. Hy tnh K . p c
v T0 = 293 Kelvin v n = s mol sn phm kh s mol cht kh tham gia. Nn ta c T0 = 648 Kelvin v n = 2- 4 = -2
6.4. Bi tp v d on chiu ca phn ng Mt phn ng cho lc bt u c 0,249 mol kh N2; 3,21.10-2 mol kh H2 v 6,42.10-4 mol NH3 trong mt bnh cha 3,5 lt 375 C. Nu hng s cn bng KC i vi phn ng N2 (k) +3 H2 (k) 2NH3 (k) c gi tr l 1,2 nhit ny th: a) Hy gii thch l h thng ny c cn bng hay khng? b) Nu khng th phn ng s c khuynh hng di chuyn theo chiu no? Cc bc tin hnh Gi QC (Quotient ractionnel) l i lng thu c khi s dng cc nng ban u trong biu thc hng s cn bng. xc nh chiu phn ng th so snh QC v KC. C 3 trng hp xy ra: - QC > KC: T s gia cc nng ban u ca sn phm v cht tham gia qu ln. t c cn bng, mt lng no ca sn phm phi chuyn thnh cht tham gia. Phn ng di chuyn theo chiu tri. - QC > KC: Phn ng ang thi im cn bng . - QC < KC: T s gia cc nng ban u ca sn phm v cht tham gia qu nh. t c cn bng, mt lng no ca cht tham gia phi chuyn thnh sn phm. Phn ng di chuyn theo chiu phi. Nu trng hp hng s s dng l KP th tnh QP. Gii
11/25/2010
Page 29 of 239
- QC < KC H khng cn bng v phn ng di chuyn theo chiu phi. 6.5. Bi tp v tnh hng s cn bng Mt h gm mt cp ng phn hnh hc trong mt dung mi hu c m hng s cn bng KC = 24,0 200 C Cis stilben Trans - stilben Gi d rng lc u ch c Cis stilben c mt v nng l 0,850 mol/l. Hy tnh nng ca 2 ng phn ny thi im cn bng. Cc bc tin hnh: Bc 1: Din t nng cn bng ca tt c cc cht theo nng ban u v ch bng mt n s. Bc 2: Din t hng s cn bng theo nng cn bng. Gi tr ca hng s cn bng bit c s dng gii phng trnh theo x. Bc 3: Sau khi xc nh gi tr x, tnh nng cn bng ca tt c cc cht Cis stilben Nng ban u (M) Thay i v nng (M) Nng cn bng 0,850 -x 0,850 -x Trans stilben 0 +x x
Thay i (+) chng t s tng ln v thay i (-) chng t s gim nng . Tip n l vit biu thc hng s cn bng theo nng cn bng:
x = 0,816 M
11/25/2010
Page 30 of 239
p s: a) [Cis stilben] = 0,034M; b) [Trans stilben] = 0,816M 6.6. Bi tp v tnh tan ca mt cht trong nc Khi mt hp cht khng tan nh Pb(IO3)2 c cho vo dung dch, mt phn cht rn s tan ra. Cn bng t c khi nng Pb2+ v tha mn tan sn phm i vi Pb(IO3)2. im cn v bng, dung dch b bo ha bi Pb(IO3)2. Lm th no xc nh c nng ca Pb2+ v tan ca Pb(IO3)2 trong dung dch bo ha khi cho Pb(IO3)2 vo nc ct. tin hnh gii bi ton ny ta vit phn ng cn bng: Pb(IO3)2 Pb2+ + 2 (2.17)
V hng s cn bng ca n (2.18) Khi cn bng c thit lp, hai ion c to ra tng ng vi mi ion Pb2+. Nu chng ta gi l 2x. + 2 0 +2x 0 + 2x = 2x nh nng mol ca Pb2+ im cn bng l x th nng ca PbI2 Nng ban u Thay i v nng Nng cn bng Cht rn Cht rn Cht rn Pb2+ 0 +x 0+x=x
Th nng cn bng vo phng trnh (2.18) (x)(2x)2 = 2,5 x 10-13 4x3 = 2,5 x 10-13 x = 3,97 x 10-5 Do nng cn bng ca Pb2+ v [Pb2+] = x = 4,0 x 10-5 M [I-] = 2x = 7,9 x 10-5 M V mt mol Pb(IO ) cha mt mol Pb2+, tan ca Pb(IO ) bng nng ca Pb2+; theo 3 2 3 2 5 tan ca Pb(IO3)2 l 4,0 10 M. 6.7. Bi tp tnh tan ca mt cht trong dung dch c ion cng tn Trng hp trn l tnh ton tan ca Pb(IO3)2 trc tip trong nc ct v cht rn l ngun duy nht cung cp Pb2+ v cho dung dch. tan ca Pb(IO3)2 s b nh hng nh th no nu chng l
11/25/2010
Page 31 of 239
ta thm n vo dung dch Pb(NO3)2 0,1M? Thit lp bng theo di nng ca Pb2+ v PbI2 Nng ban u Thay i v nng Nng cn bng Cht rn Cht rn Cht rn trong h thng. Pb2+ 0,10 +x 0,10 + x + 2 0 +2x 0 + 2x = 2x
Th nng cn bng vo biu thc tan sn phm ca phng trnh (2.18) (0,10 + x)(2x)2 = 2,5 x 10-13 hay 4x3 + 0,40x2 = 2,5 x 10-13 (2.19)
Chng ta s vn dng hiu bit v ho hc n gin ho phng trnh. T nguyn l Le Chatelier, on rng nng Pb2+ ln ban u s lm gim tan ca Pb(IO ) . Trong trng hp ny c th suy 3 2 on nng cn bng ca Pb2+ s rt gn vi nng ban u ca n; theo s c tnh sau y v nng cn bng ca Pb2+ l hp l [Pb2+] = 0,10 + x 0,10 M th vo phng trnh (2.19) (0,10)(2x)2 = 2,5 x 10-13 0,4x2 = 2,5 x 10-13 v gii thu c x l x = 7,91 x 10-7 Trc khi chp nhn nghim ny, hy kim tra xem s c lng c hp l khng. Trong trng hp ny c lng 0,1 + x = 0,1 dng nh hp l v s khc nhau gia hai gi tr c th b qua. Do nng cn bng ca Pb2+ v l [Pb2+] = 0,10 + x 0,10 M [I] = 2x = 1,6 x 10-6 tan ca Pb(IO ) bng s b sung ca Pb2+ trong dung dch hay 7,9 10-7 mol/l. ng nh suy 3 2 on, tan ca Pb(IO3)2 b gim trong dung dch c cha mt trong nhng ion ca n. iu ny c gi l hiu ng ion chung. 7. KT LUN Chng ny trnh by cc loi phn ng, khi nim v s cn bng ho hc, hng s cn bng, hot , nng m rng hiu bit v cn bng ho hc. T chng ny hc vin s c th hiu mt cch tng qut cn bng ho hc ca cc phng php s dng trong ho hc phn tch vn dng trong tnh ton. T KHO
11/25/2010
Page 32 of 239
Phn ng ho hc Cn bng ho hc Hng s cn bng Hot CU HI LNG GI
Nng H s hot Hng s phn ly Hng s bn
1. Nu nh ngha phn ng ho hc v trnh by cc loi phn ng ho hc? 2. Th no l cn bng ho hc? Cn bng vt l? Nu th d c th v gii thch. 3. Ti sao ngi ta cho rng cn bng ho hc l cn bng ng? 4. Nng l g? Hot l g? Trong trng hp no 2 i lng ny ging nhau? 5. Nu ngha ca h s hot . 6. Trnh by cc cng thc tnh hng s cn bng theo hot , theo nng . 7. Nu cc yu t nh hng n h thng cn bng ho hc. CU HI TRC NGHIM 1. Phn ng thun nghch: a. c th xy ra th kh hoc lng b. c th xy ra th rn hoc lng d. ch a v c ng e. c ba cu u ng
c. nhit , p sut nht nh th thnh phn hn hp trng thi cn bng l khng i 2. Cch thng thng biu din nng lng t do ca phn ng bng hm s a. nng lng t do Gibb b. bin thin enthalpy c. bin thin entropy d. T student
3. Cc yu t nh hng n hng s cn bng ca phn ng l: a. nng cc cht tham gia phn ng. b. nhit , p sut. c. dung mi. d. nng ca sn phm to thnh. e. tt c u ng 4. x l cc hng s cn bng ta c th lm theo cc cch: a. o ngc phn ng th hng s cn bng ca phn ng mi s l nghch o ca phn ng u. b. cng hai phn ng vi nhau to ra phn ng mi th hng s cn bng ca phn ng mi l tch s ca hng s cn bng ca cc phn ng ban u.
11/25/2010
Page 33 of 239
c. Nhn hai phn ng vi nhau th hng s cn bng mi s l tng ca cc hng s cn bng ban u. d. a v b 5. Cn bng ho hc l trng thi.......... m trong cht tham gia phn ng v sn phm chuyn i lin tc cho nhau. Tc mt i v xut hin ca chng bng nhau. a. ng b. ng yn BI TP Nu hng s cn bng KC i vi phn ng 2NO(k) + Cl2(k) 2NOCl(k) c gi tr l 6,5 104 35oC. Gi s ngi ta trn 2,0 x 10-2 mol ca NO; 8,3 10-3 mol ca Cl2 v 6,8 mol NOCl trong mt bnh cu 2 lt th phn ng t n cn bng di chuyn theo chiu no? c. tnh d. kh e. lng
Chng 3 S DNG THNG K TRONG PHN TCH S LIU

MC TIU
Trnh by c khi nim v sai s, cc i lng c trng ca ton thng k. ng dng ton thng k x l cc kt qu thu c t thc nghim. Trnh by kt qu phn tch m bo c mc chnh xc theo yu cu.
NI DUNG 1. M U Khi tin hnh php phn tch vi mt mu bt k, qua bao gi chng ta cng c c cc kt qu (s liu) t thc nghim. Cu hi c t ra l: s liu thu c c gn vi gi tr thc c ca mu khng? Qu trnh phn tch c mc phi sai s khng? Gi tr thc nm khong no ca cc s liu thc nghim? v.v Sai s trong phn tch l khng th trnh khi, tuy nhin trong qu trnh phn tch cn khng ch sai s mc thp nht c th, c ngha l kt qu thu c khi tin hnh mt php phn tch lun lun mc phi sai s. Gi tr thc ca mu o l i lng khng th xc nh, nhng nu xc nh c cc sai s
11/25/2010
Page 34 of 239
trong qu trnh phn tch th c th c lng gi tr thc nm trong khong no ca gi tr thc nghim. V vy vic x l kt qu sau qu trnh phn tch l lun lun cn thc hin, qua nh gi kt qu thu c ng v chnh xc n mc no. Thng thng cn tin hnh phn tch nhiu ln v p dng ton thng k nh gi tin cy ca s liu vi mc xc sut c n nh trc. 2. MT S I LNG C TRNG TRONG THNG K 2.1. Gi tr trung bnh (Xtb)
(3.1) Trong : n: l tng s ln o; i : gi tr o c th i (i = 1, 2, 3, , n) Th d 1: hm lng ca dung dch KMnO4 c xc nh sau 7 ln chun : 3,080; 3,094; 3,107; 3,056; 3,112; 3,174; 3,198 (g/l)
2.2. Phng sai S2 (VARIANCE) Mi ln o chng ta s c 1 gi tr xi v gi tr ny c th nh hn hay ln hn so vi gi tr trung bnh Xtb. Hiu ca hai gi tr ny c th l mt s m hay dng v khi tng cc hiu li c th bng s khng. Nu gi tr tuyt i ca hiu cng ln th s bnh phng s cng ln v cng cho thy lch cng nhiu. Do vy i lng phng sai c cp
(3.2) 2.3. lch chun (sd: standard deviation) lch chun l i lng cho bit mc dao ng gia cc gi tr xi so vi gi tr trung bnh Xtb. y l i lng c trng cho phn tn ca s liu (xi) v th hin mc ca sai s ngu nhin. Cng thc tnh:
(3.3) SD: lch chun; n: s ln thc nghim; (n 1) c gi l bc t do. 2.4. lch chun tng i (RSD: relative standard deviation) lch chun tng i l t s gia lch chun so vi gi tr trung bnh. RSD th hin gi tr
11/25/2010
Page 35 of 239
lch r hn SD v c so snh vi gi tr trung bnh Xtb. Cng thc tnh: (3.4) RSD c th c tnh bng t l phn trm RSD% hay cn gi l h s bin thin CV (Coefficient of Variation): (3.5) Nh vy, ta c th tnh CV da trn lch chun v ngc li. Th d: theo th d 1, n = 7, Xtb = 3,117
2.5 Gii hn tin cy v khong tin cy S ln o n cng ln th gi tr Xtb cng gn vi gi tr thc M, nhng trong thc t ta ch thc hin n ln o v trong thng k th xc sut bt gp thng n nh trc l 95%, nn gi tr Xtb s nm trong gii hn c th chp nhn c gi l gii hn tin cy. - Gii hn tin cy e (Confidence Limit). Hay ni cch khc e l gii hn hai bn ca Xtb c cha gi tr M mc tin cy 95%. (3.6) Trong t c tra t bng Student (3.1). Gi tr t ph thuc vo s bc t do k = n 1 v vo mc xc sut c n nh P. S ln thc nghim cng nh, xc sut P cng ln th gi tr t cng cao.
B ng 3.1. Bng gi tr ca chun Student t t do 1 90% 0,10 6,31 95% 0,05 12,71 98% 0,02 31,82 99% 0,01 63,66
11/25/2010
Page 36 of 239
2 3 4 5 6 7 8 9 10 12 14 16 18 20 30 50
2,92 2,35 2,13 2,02 1,94 1,89 1,86 1,83 1,81 1,78 1,76 1,75 1,73 1,72 1,70 1,68 1,64
4,30 3,18 2,78 2,57 2,45 2,36 2,31 2,26 2,23 2,18 2,14 2,12 2,10 2,09 2,04 2,01 1,96
6,96 4,54 3,75 3,36 3,14 3,00 2,90 2,82 2,76 2,68 2,62 2,58 2,55 2,53 2,46 2,40 2,33
9,92 5,84 4,60 4,03 3,71 3,50 3,36 3,25 3,17 3,05 2,98 2,92 2,88 2,85 2,75 2,68 2,58
Nh vy gi tr Xtb cn cch gi tr thc M mt gii hn e hay cn gi l khong tin cy (Confidence Intervals): (3.7)
Th d: vi th d 1, gi tr e c tnh:
ng vi P = 0,95 v n = 7 th tlt = 2,45 nn hm lng KMnO4 nm trong khong 3,117 0,047 (g/l) tc gi tr thc M nm trong gii hn 3,070 3,164 (g/l). 3. SAI S TRONG PHN TCH Vi mt mu c gi tr thc l M, v cc nguyn nhn khc nhau ta khng th xc nh ng gi tr M m ch xc nh c gi tr trung bnh gia cc ln o lp li. Thut ng sai s c dng din t mc sai lch ca php o, n th hin lch gia cc gi tr thc nghim xi vi nhau, vi gi tr trung bnh v vi gi tr thc ca mu. Trong phn tch ta ch c gng thc hin sao cho sai s l nh nht, cc gi tr thu c t thc nghim nm trong khong chp nhn ch khng th loi tr c hon
11/25/2010
Page 37 of 239
ton sai s. Khi trnh by v kt qu bng s liu, cc ti liu c th cp n 2 loi l sai s tuyt i v sai s tng i. 3.1. Sai s tuyt i Vi M l gi tr thc ca mu th cn xc nh, xi l gi tr o c t thc nghim: Gi tr Xtb thng khc vi gi tr thc M ca mu o. Khi n th Xtb M. Sai s tuyt i l hiu gia gi tr trung bnh Xtb v gi tr thc M. Thng thng khng th xc nh c gi tr thc m ch chp nhn gi tr ng tin cy nht trong dy s liu l Xtb hay mt cch gn ng l hiu ca gi tr o c v Xtb. M: gi tr thc ca mu o : sai s tuyt i (3.8)
Cng thc tnh sai s tuyt i: = Xtb - M hay = xi - Xtb Sai s tuyt i c th l s m cng c th l s dng. 3.2. Sai s tng i S
Sai s tng i S l t s gia sai s tuyt i v gi tr thc M hoc gi tr trung bnh Xtb. Thng thng sai s tng i c biu th di dng phn trm. (3.9) Th d: hm lng thc ca Paracetamol trong vin nn l 500,2 mg; Codein l 30 mg. Sau khi tin hnh xc nh theo phng php sc k lng hiu nng cao cho thy hm lng Paracetamol l 500,9 mg v Codein l 30,7 mg.
Sai s tuyt i khi xc nh hai hot cht trn l nh nhau: + 0,7 mg.
Sai s tng i th khc nhau:
Nh vy sai s tng i th hin r hn ng ca phng php, vi th d trn cho thy phng php ny xc nh hm lng Paracetamol ng hn hm lng ca Codein phosphat. Khi trnh by v nguyn nhn dn n cc kt qu thu c trong qu trnh thc nghim b lch nhau. Cc ti liu thng cp n 3 loi sai s: sai s ngu nhin, sai s h thng, sai s th. 3.3. Sai s ngu nhin (random error) Sai s ngu nhin hay cn gi l sai s khng xc nh l sai s gy nn bi nhng nguyn nhn khng xc nh c, khng bit trc, khng c nh, thay i khng theo quy lut nn khng th hiu chnh hay loi tr m ch c th hn ch bng cch tng s ln phn tch v thao tc mt cch cn thn, ng thi nh gi cc s liu thc nghim bng ton hc thng k.
11/25/2010
Page 38 of 239
3.4. Sai s h thng (systematic error) Sai s h thng hay cn gi l sai s xc nh l sai s bit r nguyn nhn v c th hiu chnh c. Sai s ny thng do cc nguyn nhn sau: - Sai s do mu o: gy ra khi mu phn tch khng i din. Vic ly mu l tp hp cc thao tc nhm ly mt lng mu i din tin hnh phn tch, ng thi vic ly mu cn tun theo cc th tc quy nh. - Sai s do dng c: d t hay nhiu th tt c cc dng c o lng lun c sai s h thng. Sai s ny l do qu trnh ch to v chun ho dng c v.v Th d: - Cc dng c o lng thng thng nh pipet chnh xc, buret, bnh nh mc l cc dng c dng ly th tch chnh xc nhng do trong qu trnh ch to hoc s dng khng ng quy nh c th gy ra mt sai s: th tch ca mt buret 25 ml c sai s l 0,03 ml c ngha l th tch tht s ca buret l nm trong khong [24,97 25,03] ml; bnh nh mc c th tch l 100ml nhng nu thc t ch c 99,90 ml th sai s l 99,90 100,00 = - 0,10 ml. Sai s dng c thng d pht hin v hiu chnh c bng cch nh k chun ho cc dng c trong phng th nghim. - Sai s do phng php o: phng php o lng cng gy ra sai s h thng. V vy, khi p dng mt phng php mi phn tch lun lun phi xy dng v thm nh quy trnh chng minh mt cch khoa hc rng sai s ca phng php l rt thp v c th chp nhn c. Sai s do phng php thng kh pht hin v l nguyn nhn chnh gy ra sai s h thng. Thng thng pht hin sai s phng php c th tin hnh theo cc cch sau: - Thc hin song song mu trng loi cc p ng gy ra do cc cht khng cn phn tch. - Phn tch mu chun kim tra ng ca phng php. - Phn tch cng mt mu nhng bng phng php d kin v thc hin song song vi t nht mt phng php khc v so snh hai kt qu. - Sai s do ngi lm cng tc phn tch: ngi lm cng tc phn tch i hi phi c k nng ngh nghip v kinh nghim phn tch. Sai s do tng c nhn l iu khng trnh khi, mi c nhn c mt kh nng ring v quan st s thay i mu ca dung dch; quan st im tng ng trong chun ; c v tr mc nc gia hai vch; c tn hiu o c t my mc; hoc do cu th; do nh kin u dn n sai s. Sai s do c nhn c th khc phc c khi thao tc ng theo quy nh v nhiu kim nghim vin thc hin trn cng mt mu th. XC NH SAI S H THNG Bng cch xc nh mu chun bit hm lng, gi tr M coi nh bit trc, Xtb thu c t thc nghim. so snh s khc bit gia gi tr M v Xtb (trong trng hp thm nh phng php mi) thng s dng thng k tnh gi tr ttn ri so snh vi tlt theo bng (3.1) cn c vo bc t do (n 1) v xc xut P (95%). Nu ttn < tlt, kt lun khng tm thy sai s h thng Nu ttn > tlt, kt lun phng php c sai s h thng
11/25/2010
Page 39 of 239
(3.10) Th d: gi s mu th KMnO4 trong th d 1 c hm lng tht M l 3,110 mg. Hy xt xem phng php c sai s h thng khng?
ttn = 0,3786 < tlt = 2,45 nn kt lun phng php khng c sai s h thng (P = 95%). Th d: trc khi phn tch xc nh hm lng ca Na2CO3 c trong mu th, mt sinh vin c tng kim tra li quy trnh phn tch xem c sai s h thng hay khng bng cch phn tch mt mu bit hm lng M = 98,76%. Cc kt qu thu c sau 5 ln thc hin: 98,71(%) 98,59(%) 98,62(%) 98,44(%) 98,58(%)
Nh vy tlt = 2,78 < ttn = 3,91, kt lun phng php c sai s h thng (P=95%). 3.5. Sai s th (gross error) Ngoi ra cn c sai s th l sai s khi kt qu gia cc ln o lp li khc hn so vi cc gi tr trung bnh hay gi tr thc ca mu. Sai s th do nhiu nguyn nhn khc nhau: do c kt qu o sai, ly nhm qu cn, v.v pht hin v loi tr sai s th cn phi tin hnh phn tch nhiu ln trn mt mu o (n > 6) v loi i nhng gi tr bt thng theo nhng quy tc nht nh. Loi tr sai s th Thc t sau khi tin hnh phn tch thng thu c mt dy cc s liu, i khi c mt vi s liu c gi tr khc hn: hoc cao qu hoc thp qu, nhng s liu ny c gi l sai s th hay s liu xu. C hai cch gip chng ta kim tra xem nn gi li hay loi b chng: dng chun Dixon v dng bng kim nh T. 3.5.1. Phng php dng chun Dixon (chun Q) S dng khi n < 10, gm cc bc nh sau: - Bc 1: sp xp cc s liu theo th t tng dn hoc gim dn: x1, x2, x3,..., xn trong x1 l s liu nghi ng ln nht (max) hay nh nht (min), x2 l s liu ln cn ca s liu nghi ng. - Bc 2: dng test Q tnh gi tr Qtn: - Bc 3: so snh gi tr Qtn vi Qlt: Qlt > Qtn th x1 c gi li Qlt < Qtn th x1 b loi b (3.11)
11/25/2010
Page 40 of 239
Qlt c tra t bng (3.2) vi s ln o n v xc sut bt gp P thng thng l 95%.

B ng 3.2. Bng kim nh Q chun DIXON P 0,1 (90%) 0,941 0,765 0,642 0,560 0,507 0,468 0,437 0,412 0,05 (95%) 0,970 0,829 0,710 0,625 0,568 0,526 0,498 0,466 0,01 (99%) 0,994 0,926 0,821 0,740 0,680 0,634 0,598 0,568
n 3 4 5 6 7 8 9 10
Th d: ta c dy s liu sau 17,61 16,86 16,93 16,84 16,95 16,91 Bc 1: sp xp theo th t 16,84 16,86 16,91 16,93 16,95 17,61; ta thy s liu nh nht l 16,84 (ln cn l 16,86) v s liu ln nht l 17,61 (ln cn l 16,95) thng l hai s liu ng nghi ng. Bc 2: tnh gi tr Qtn Bc 3: tra bng (3.2) vi n = 6; P = 0,95 Qlt (= 0,625) < Qtn (= 0,86) nn gi tr 17,61 b loi b Qlt (= 0,625) > Qtn (= 0,03) nn gi tr 16,84 c gi li 3.5.2. Phng php dng bng kim nh T S dng vi n bt k. Sai s th thng ri vo cc gi tr cc i hay cc tiu ca dy s liu, ta tnh Ttn theo cng thc sau: (3.12) (3.13) Cn c vo s ln o n v vo xc sut n nh trc P, tra Tlt theo bng (3.3). Tlt < Ttn th s liu nghi ng l sai s th b loi b Tlt > Ttn th s liu nghi ng l sai s th c gi li
B ng 3.3. Gi tr t ca bng kim nh T vi P = 95%
11/25/2010
Page 41 of 239
n 3 4 5 6 7 8 9 10
Tlt 1,412 1,689 1,869 1,996 2,093 2,172 2,237 2,294
n 11 12 13 14 15 16 17 18
Tlt 2,343 2,387 2,426 2,462 2,493 2,523 2,551 2,623
Th d: vi dy s liu 16,84 16,86 16,91 16,93 16,95 17,61 Vi n = 6; Xtb = 17,02; SD = 0,292; P = 0,95 ta c Tlt = 1,996
Tlt (= 1,996) < Ttn (= 2,02) nn gi tr 17,61 b loi b. Tlt (= 1,996) > Ttn (= 0,61) nn gi tr 16,84 c gi li. 4. TM TT CC BC TIN HNH KHI X L S LIU Bc 1: sp xp dy s liu thu c theo th t tng hoc gim dn. Bc 2: loi cc gi tr khng ph hp, loi sai s th. Bc 3: tnh gi tr Xtb; lch chun SD, RSD%, xt sai s h thng. Bc 4: xc nh gii hn tin cy e v khong tin cy. Bc 5: bo co kt qu. Th d: theo s liu ca th d 1, cc bc tin hnh nh sau: Bc 1: 3,056; 3,080; 3,094; 3,107; 3,112; 3,174; 3,198 (g/l). Bc 2: loi sai s th theo chun Q hoc T: khng loi b gi tr no. Bc 3: Xtb = 3,117; SD = 0,05; RSD = 1,63%
Bc 4: ng vi P = 95% v n = 7
tlt = 2,45 tnh e = 0,047.
Bc 5: hm lng KMnO4 trong khong 3,117 0,047 (g/l) vi tin cy P = 95%.
11/25/2010
Page 42 of 239
5. SO SNH CC DY S LIU Kt qu thu c t o lng thc nghim thng mc phi cc sai s hoc ngu nhin hoc h thng. Gi tr trung bnh X thng ch st gn vi gi tr thc M, gi tr ny li nm trong khong tin cy no vi xc sut bt gp mong mun. Vic so snh gia cc dy s liu c thc hin nh cc bng chun xem cc dy s liu ny l ng nht hay khc nhau c ngha gip cho vic so snh gia cc phng php, gia cc ngi phn tch v gia cc l sn xut. Cc vn thng gp trong thc nghim l : - C hai gi tr trung bnh XnA v XnB thu c t 2 dy o c lp nhau, mt dy c nA kt qu, dy kia c nB kt qu. Hai gi tr trung bnh sai khc khng nhiu. Phi kt lun sai khc ny c ng k khng? - C mt gi tr phn tch X ca sn phm c bit trc qua nhiu ln lm thc nghim. Ngi thc hin phn tch lp li phng php v cn so snh kt qu o c Xi vi gi tr bit trc X xem khc nhau c ngha hay khng? - C mt l thuc c thc hin nh lng vi 2 phng php khc nhau v cho 2 dy kt qu khc nhau. Cc nh phn tch cn phi so snh kt qu o c trn cng mu bng 2 phng php khc nhau xem c khc nhau hay khng? - Trong trng hp so snh hai dy kt qu: S dng th nghim F (F-test) kim tra chnh xc hay lp li ca hai dy kt qu xem c ng nht hay khng. S dng th nghim t ( t-test) so snh hai gi tr trung bnh xem s khc nhau gia hai gi tr ny c ngha hay khng. 5.1. So snh hai phng sai S dng chun F so snh chnh xc ( lp li) ca hai dy th nghim A v B vi nA, nB l s ln thc hin ca A v B. Phng sai tng ng v . Quy c : (3.14) So snh Ftn vi Flt c tra t bng (3.4). Flt ph thuc vo bc t do ca hai th nghim A, B v ph thuc vo mc xc sut cho trc thng thng l P = 95%.
B ng 3.4. Gi tr F ca chun F (P = 95%)
11/25/2010
Page 43 of 239
Bc t do ca A: nA -1; bc t do ca B: nB 1 Nu Flt > Ftn: khng c s khc bit v lp li ca A v B. Nu Flt < Ftn: lp li ca hai th nghim A v B khc nhau. Th d: kt qu 7 ln phn tch hm lng aspirin bng phng php A c phn tch bng phng php B l ging nhau khng? = 0,00259. Theo 6 ln = 0,00138. Hy xt xem chnh xc ca hai phng php c
Do Flt = 6,978 > Ftn = 1,88: chnh xc ca hai phng php l nh nhau (P = 95%). 5.2. So snh hai s trung bnh Trong phn sai s h thng chng ta bit kt qu phn tch b nh hng chnh bi ba nguyn nhn chnh: do mu, do phng php, do kim nghim vin. Thc hin nhng cp th nghim song song tm ra nguyn nhn gy sai s trong ch mt yu t thay i. Th d nh cng thc hin song song hai phng php khc nhau trn cng mt mu th, cng mt kim nghim vin ri so snh c hay khng c s khc bit gia hai gi tr trung bnh ca hai phng php ny. Tng t nh vy so snh hai gi tr trung bnh ca hai kim nghim vin hoc ca hai mu o
11/25/2010
Page 44 of 239
S dng php th t (t test) thc hin cng vic ny nh sau: Kt qu phn tch bng phng php A c: XtbA; SDA; Kt qu phn tch bng phng php B c: XtbB; SDB; Bc 1: so snh hai phng sai (php th F; F test) Bc 2: c hai trng hp Trng hp 1: phng sai v khng khc nhau, ttn c tnh: (3.15) (3.16) tlt c tra t bng (3.1) vi t do (nA + nB -2), P = 95%. Trng hp 2: phng sai v khc nhau, ttn c tnh: (3.17) tlt c tra t bng (3.1) vi P = 95% v t do c tnh theo cng thc sau: ; nA (s ln thc hin ca A). ; nB (s ln thc hin ca B)
(3.18)
t do lun l s nguyn nn gi tr tnh c t cng thc (3.18) c gi tr gn s nguyn k cn nht. Th d: = 5,4 th t do l 5; = 5,9 t do l 6. Bc 3: kt lun c hay khng c s khc nhau ca hai phng php o. Cho d ttn c tnh theo cng thc (3.15) hay (3.17): Nu ttn < tlt kt lun hai phng php cho kt qu khng khc nhau. Nu ttn > tlt kt lun hai phng php cho kt qu khc nhau. Th d: hm lng ca dung dch KMnO4 c xc nh bng hai phng php A v B, kt qu: A: 3,080; 3,094; 3,107; 3,056; 3,112; 3,174; 3,198 (g/l) B: 3,052; 3,141; 3,083; 3,083; 3,048 (g/l) So snh hai phng sai v (chun F) khng khc nhau.
Tnh Schung theo cng thc (3.16):
11/25/2010
Page 45 of 239
tlt c tra t bng (3.1), t do n = (7 + 5 - 2) = 10; ttn = 1,34 < tlt = 2,23 nn kt lun hai phng php A v B cho kt qu khng khc nhau (P = 95%). Th d: hm lng ca Na2CO3 (%kl/kl) c hai kim nghim vin C v D chun bng phng php acid-base cho ln lt kt qu nh sau:
C 86,82 87,04 86,93 97,01 86,20 87,00 XtbC = 86,83% SC = 0,32 D 81,01 86,15 81,73 83,19 80,27 83,94 XtbD = 82,71% SD = 2,16
Do Ftn = 45,6 > Flt = 7,15 nn hai phng sai C v D khc nhau.
t do :
Do ttn = 4,62 > tlt = 2,57, nn kt lun kt qu phn tch ca C v D khc nhau (P= 95%). 6. CH S C NGHA S liu thu uc t thc nghim c th l s o trc tip khi c trn thang o ca cc dng c o lng hoc s o gin tip l s o tnh c t mt hoc vi s o trc tip thng qua cng thc ton hc. Cc s liu ny phi c th hin sao cho ngi c hiu c mc chnh xc ca chng, v vy
11/25/2010
Page 46 of 239
khi ghi kt qu phi tun theo quy tc v ch s c ngha. 6.1. Ch s c ngha (CSCN) trong s o trc tip Mt s o trc tip c th c nhiu CSCN tin cy (ch s chc chn) nhng duy nht ch c mt CSCN khng tin cy (ch s nghi ng) ng sau cng k t tri sang phi. CSCN phn nh mc chnh xc ca dng c o lng. Th d: - Trn thang o ca buret c th tch l 25ml, vch chia nh nht l 0,1ml. Gi s th tch ti im tng ng khi chun l V = 18,75 ml, nh vy c 4 ch s c ngha l 1; 8; 7 v 5. Trong 1; 8; 7 l cc ch s chc chn v ch s 5 l ch s nghi ng hay cn gi l ch s khng tin cy. Ch s 5 cn ty thuc vo kh nng c lng ca ngi quan st: c th c l 2 hoc 4 hoc 7 v.v 9. - Khi cn trn cn phn tch c nhy l 0,1 mg, kt qu c c l 1,2326 g, nh vy c 5 ch s c ngha trong ch s 6 cui cng l ch s nghi ng. - S lng CSCN ca mt s o c tnh t ch s u tin khc 0 k t tri sang phi. Mi ch s 0 sau CSCN u tin bt k v tr no u l CSCN. Hay ni cch khc, ch s 0 ng trc ch s khc 0 u tin ca mt s o khng phi l CSCN. Ch s 0 ng gia hai ch s khc 0 hoc ng sau cng u l CSCN. Th d: V = 18,75 ml : c 4 CSCN, 5 l CSCN khng tin cy. M = 0,0020 g : c 2 CSCN, 0 l CSCN khng tin cy. M = 5,06 g : c 3 CSCN, 6 l CSCN khng tin cy. M = 0,15 (M/l): c 2 CSCN, 5 l CSCN khng tin cy. Khi mun chuyn i n v o lng thun li cho vic tnh ton kt qu o cui cng, s lng CSCN ca s o phi c gi nguyn. Th d: chuyn 0,28 g ra n v mg. Ta thy 0,28 g c 2 CSCN nn khng th chuyn thnh 280 mg (3 CSCN) m phi l 0,28.103 mg hoc bng 2,8.102 mg. 6.2. Ch s c ngha trong s o gin tip Nh nh ngha, s o gin tip l s o tnh c t cc s o trc tip thng qua mt hoc vi biu thc ton hc no . Sai s ca s o trc tip c nh hng n kt qu ca s o gin tip nn s o gin tip cng phi c ghi chp theo nguyn tc ca CSCN. - i vi php cng v tr: CSCN ca kt qu cui c cng s ch s bn phi ca du thp phn c s CSCN t nht. Th d: tnh phn t lng ca phn t BaO2 vi Ba = 137,34; O = 15,9994 137,34 + 15,9994 + 15,9994 = 169,3388 c lm trn 169,34 - i vi php nhn v chia: s lng CSCN ca kt qu cui cng bng s lng CSCN ca s o c CSCN t nht. Th d: - ly chnh xc 10,00 ml dung dch acid hydroclorid cha bit nng em chun bng dung dch chun natri hydroxid 0,09876 M. Th tch NaOH cn dng l 9,58 ml. Tnh MHCl.
11/25/2010
Page 47 of 239
- i vi kt qu phi tnh ton qua nhiu bc: th ch c lm trn kt qu cui cng m khng lm trn cc bc trung gian. Th d: - pha dung dch chun HCl c nng xp x 0,1N dng chun dung dch NH4OH cn c cc bc nh sau: pha dung dch chun HCl c nng xp x 0,1 N, sau dng dung dch gc Na2B4O7 0,1N xc nh li nng HCl. Ly chnh xc 10ml dung dch Na2B4O7 em chun bng dung dch chun HCl trn vi ch th Helianthin n khi mu chuyn t vng sang cam. Th tch HCl cn dng l 9,75 ml, nng chnh xc ca dung dch acid c tnh nh sau:
Dng acid HCl ny nh lng dung dch NH4OH cha bit nng : ly chnh xc 10 ml NH4OH v vi git ch th Tashri, nh HCl n khi mu chuyn t xanh l sang tm. Th tch HCl cn dng l 9,8 ml, nng dung dch NH4OH c tnh nh sau:
6.3. Cch lm trn s o gin tip Cch lm trn s phi tun theo quy tc ch s c ngha. Cch thc lm trn CSCN cui cng ca php tnh ty thuc vo gi tr ca ch s nghi ng ng sau n. - CSCN sau cng ca s o gin tip c tng mt n v nu ng sau n l ch s nghi ng ln hn 5; nu nh hn 5 th vn gi nguyn. Th d: 71,56 lm trn thnh 71,6 71,54 lm trn thnh 71,5 - Khi ch s nghi ng ny bng 5 th CSCN sau cng ca s o gin tip c tng mt n v nu n l mt ch s l; nu n l mt ch s chn (k c s 0) th vn gi nguyn. Th d: 71,55 lm trn thnh 71,6 71,05 lm trn thnh 71,0 71,25 lm trn thnh 71,2 T KHO
Sai s h thng, ngu nhin

Sai s th Gi tr trung bnh CU HI LNG GI
Sai s tng i, sai s tuyt i lch chun, lch chun tng i Gii hn tin cy, khong tin cy
11/25/2010
Page 48 of 239
i.
1. Gii thch s khc nhau gia: sai s h thng v sai s ngu nhin; sai s tuyt i v sai s tng
2. Trnh by cc khi nim v cng thc tnh cc i lng trong ton thng k: gi tr trung bnh, lch chun, gii hn tin cy v khong tin cy v.v 3. Nu cc bc x l kt qu phn tch; ng dng vo bi tp sau: Sau 6 ln xc nh hm lng (mg) ca mt hot cht trong ch phm thu c kt qu nh sau: 116,0 ; 97,9 ; 114,2 ; 100,6 ; 108,3 ; 104,5. Hm lng thc ca mu phn tch nm trong gii hn no? Gi s hm lng thc ca mu M = 100,0; hy tm xem phng php c sai s h thng hay khng? CU HI TRC NGHIM 1. Khi tin hnh phn tch 1 mu bt k thng mc phi cc loi sai s: a. Sai s h thng b. Sai s ngu nhin c. Sai s th 2. Sai s do phng php o dn n: a. Sai s th b. Sai s ngu nhin c. Sai s h thng 3. Mt kim nghim vin c nhm th tch ti im tng ung khi nh lng, vy trong phn tnh ton kt qu ngi ny mc phi: a. Sai s tng i b. Sai s tuyt i c. Sai s th 4. Loi sai s no c th hiu chnh v loi tr khi tin hnh phn tch mu? a. Sai s th b. Sai s ngu nhin c. Sai s h thng 5. Loi sai s no th hin ng ca phng php phn tch? a. Sai s th b. Sai s ngu nhin c. Sai s tuyt i 6. Loi sai s no th hin chnh xc ca phng php phn tch? d. Sai s h thng e. Cu b v d ng d. Sai s tuyt i e. Sai s tng i d. Sai s h thng e. Khng cu no ng d. Sai s tuyt i e. Sai s tng i d. C a, b, c u ng e. Ch b, c ng
11/25/2010
Page 49 of 239
a. Sai s th b. Sai s ngu nhin c. Sai s tuyt i 7. Loi tr sai s th bng cch: a. Tra bng Student tm Ttn v Tlt b. Dng phng php chun Dixon (test Q) c. Dng phng php kim nh T (test T)
d. Sai s h thng e. Sai s tng i
d. Cu a v c ng e. Cu b v c ng
8. Ch s c ngha (CSCN) trong s o trc tip bao gm: a. Nhiu ch s tin cy v nhiu ch s nghi ng b. Ch c ch s tin cy c. Nhiu ch s tin cy v duy nht mt ch s nghi ng 9. Kt qu nh lng sau cng l M = 0,0020 g, s o ny bao gm ch s c ngha: a. 5 ch s c ngha b. 4 ch s c ngha c. 2 ch s c ngha 10. Kt qu nh lng sau cng l M = 0,0025 g, ch s 5 l ch s: a. Ch s c ngha tin cy b. Ch s c ngha khng tin cy c. Cu a v b u ng d. Khng cu no ng d. 1 ch s c ngha e. Khng cu no ng d. Cu a v c ng e. Khng cu no ng
Phn II
PHN TCH KHI LNG V PHN TCH TH TCH
Chng 4 NNG DUNG DCH
11/25/2010
Page 50 of 239
MC TIU
Trnh by c cc cch biu th nng dung dch. Tnh c ng lng ca mt cht trong phn ng. Gii c cc bi ton v nng dung dch.
NI DUNG 1. M U Dung dch l mt h ng th gm hai hay nhiu cu t (phn t hay ion). Mt dung dch bt k u gm cht tan v dung mi. Thnh phn ca cht tan trong dung dch c biu din bng nng . Nng l mt c tnh nh lng c bn ca dung dch. Ngi ta biu th nng ca dung dch bng lng cht tan c ho tan trong mt lng xc nh dung dch hay dung mi. 2. CC CCH BIU TH NNG 2.1. Nng phn trm (nng bch phn) 2.1.1. Nng phn trm theo khi lng: C%(kl/ kl) Biu th bng s gam cht tan c trong 100 gam dung dch K hiu: C% (kl/kl) Cng thc (4.1) m: khi lng ca cht tan (gam). m1: khi lng ca dung dch (gam). V: th tch dung dch (ml). d: khi lng ring ca dung dch. Th d: Dung dch amoniac 25% (kl/kl) c ngha l trong 100g dung dch c cha 25g amoniac T cng thc (4.1), suy ra lng cht tan cn thit (4.2) Trng hp pha mt dung dch trong ho tan m gam cht tan vo b gam dung mi th nng phn trm ca dung dch l:
11/25/2010
Page 51 of 239
(4.3) Th d 1: Tnh nng phn trm C% (kl/kl) ca dung dch natri carbonat nu cn 25 g Na2CO3 pha trong 250 ml nc Gii: Trong bi ton ny, m: khi lng cht tan = 25 g b: khi lng dung mi = V.d = 250 1 = 250 (g) m + b: khi lng dung dch = 25 g + 250 (g) Nng phn trm ca natri cacbonat:
Th d 2: Alizarin c dng lm thuc th. Khi pha ngi ta ho tan 0,25 g trong 100 ml nc, nh vy nng phn trm C%(kl/kl) ca alizarin s l:
Trong ho phn tch, nng phn trm c coi l gn ng, ho cht c cn trn cn k thut. 2.1.2. Nng phn trm khi lng theo th tch: C%(kl/ tt) Biu th s gam cht tan trong 100 ml dung dch K hiu: C% (kl/tt) Cng thc (4.4) Khi lng cht tan c tnh (4.5) Th d 1: Khi pha mt dung dch glucose u trng, nu s dng 200 g glucose pha thnh 1000 ml, nng dung dch glucose tnh theo nng phn trm:
Th d 2: pha 1 lt dung dch tim truyn NaCl 0,9%, lng NaCl c tnh theo cng thc:
11/25/2010
Page 52 of 239
2.1.3. Nng phn trm theo th tch: C% (tt/ tt) Biu th s mililt (ml) cht tan c trong 100 ml dung dch K hiu: C% (tt/tt) Cng thc (4.6) V: th tch ca cht tan. V1: th tch ca dung dch. Th d: Ngi ta ly 960 ml ethanol tuyt i pha thnh 1000 ml dung dch. Nh vy nng ca dung dch cn l:
3. NNG PHN T (NNG MOL) CM Biu th s mol ca cht tan c trong 1 lt (1000 ml) dung dch K hiu: CM Cng thc (4.7) (4.8) m: khi lng ca cht tan (gam) M: khi lng mol (khi lng phn t) ca cht tan. V: th tch ca dung dch cn pha. S mol ca dung dch c tnh: (4.9)
11/25/2010
Page 53 of 239
Th d 1: Tnh nng mol ca dung dch H2SO4, bit rng pha mt dung dch c th tch l 500 ml, lng H2SO4 m c cn dng l 49 gam. Khi lng mol ca H2SO4 (M = 98 g) Gii
Th d 2: Nc bin tiu chun cha 2,7 g mui NaCl trong mi 100 ml dung dch. Xc nh nng mol ca NaCl trong nc bin. Gii: Khi lng NaCl: m = 2,7 (g) Khi lng mol ca NaCl M = 58,5 g Th tch ca dung dch V = 100 ml
Mt dung dch cha mt phn t gam cht tan trong mt lt dung dch c gi l dung dch phn t. T dung dch phn t c ly lm n v, ngi ta so snh dung dch m c hn: 2M, 3M... hay dung dch long hn: 0,1M (decimol), 0,01M (centimol), 0,001M (milimol)... 3.1. Nng ng lng Cch biu th nng ng lng do nh ho hc ngi c Karl Friedrich Mohr pht biu mc ch n gin ho cc php tnh. Cch biu th nng ny da trn khi nim khi lng ng lng (ng lng gam) ca mt cht. 3.1.1. ng lng gam K hiu E gam ng lng gam ca mt cht c tnh tu thuc vo bn cht ca phn ng ho hc. 3.1.1.1. Trng hp phn ng acid base
i vi mt acid: ng lng gam l phn t mol ca acid chia cho s proton hot tnh (H+) Th d 1: ng lng gam ca acid hydrochloric trong phn ng trung ho l: HCl + NaOH NaCl + H2O
Th d 2: ng lng gam ca acid sulfuric c tnh trong trng hp phn ng vi NaOH
11/25/2010
Page 54 of 239
H2SO4 + 2NaOH Na2SO4 + 2 H2O
i vi mt base, ng lng gam l phn t gam ca base chia cho s proton hot tnh (H+) cn thit trung ho n. Th d: ng lng gam ca natri hydroxyd c tnh khi phn ng vi HCl
3.1.1.2. Trng hp phn ng oxy ho kh i vi phn ng oxy ho ng lng gam ca bt k cht no a vo phn ng cng l khi lng mol ca cht chia cho s electron (n) cho hay nhn trong qu trnh phn ng
Th d 1: Trong phn ng oxy ho gia st (II) v kali permanganat
Th d 2: Phn ng oxy ho gia Cr3+ vi Sn2+
3.1.1.3. Trng hp phn ng ta v phc cht ng lng gam ca mt cation c tnh bng cch ly khi lng gam ca cation chia cho in tch ca cation
ng lng gam ca mt anion l khi lng gam ca anion chia cho s ng lng ca ion kim loi tng ng to ta hoc phc cht. Th d: - Trng hp 1. Cation v anion c cng s in tch
11/25/2010
Page 55 of 239
- Trng hp 2. Cation v anion c s in tch khc nhau
- Trng hp 3. Trng hp to phc gia cation v anion
3.1.2. S ng lng gam S ng lng gam ca cht A bng s gam cht A chia cho ng lng gam ca cht (4.10) 3.1.3. Nng ng lng Nng ng lng c biu din bng s ng lng gam ca cht tan c trong 1 lt (1000 ml) dung dch. K hiu: CN Cng thc: (4.11) (4.12) (4.13)
11/25/2010
Page 56 of 239
Th d: Xc nh nng ng lng ca dung dch nitrat bc khi ho tan 1,35 g AgNO3 thnh 250 ml dung dch. Bit khi lng mol AgNO3 = 108, ng lng gam AgNO3 = 108 (s in tch Ag+ = 1). Nng ng lng ca dung dch AgNO3:
Mt dung dch cha mt khi lng ng lng ca cht tan c go l dung dch c nng nguyn chun N. Bn cnh nng nguyn chun, ngi ta cn s dng bi s ca N nh dung dch 2N, 4N..., c s ca N nh dung dch 0,1N, dung dch 0,01N... tnh ton lng cht tan A cn thit pha dung dch ng lng cho bit trc, ngi ta suy lng m t cng thc (4.13)
(4.14) 3.1.4. Cng thc tnh nng ng lng Cc tnh ton trong cch chun theo nng ng lng gn ging vi cch tnh ton trong chun theo nng phn t. C mt s khc bit l ti im tng ng tch ca cc th tch (tnh bng ml) ca cc dung dch cc cht phn ng vi nng ng lng th bng nhau ml A. NA = ml B. NB VA.NA = VB.NB Hay ti im tng ng cc th tch dung dch thuc th v ca cc cht cn xc nh phn ng vi nhau t l nghch vi nng ng lng ca chng.
Quy tc ny gi l quy tc hp thc (stochiomtrie stoichiometry) Th d: Dung dch acid hydrochloric c xc nh nng bng cch em chun vi dung dch chun natri hydroxyd. Nu sau khi phn ng kt thc, 25,00 ml dung dch HCl c trung ho cn mt th tch NaOH 0,0950 N l 32,20 ml. Tnh nng ng lng ca dung dch acid hydrochloric. Gii: p dng phng trnh trn, ta c: NAVA = NBVB Vi VA: th tch ca dung dch HCl cn chun , VA = 25,00 ml.
11/25/2010
Page 57 of 239
NA: nng ca HCl. VB: th tch ca dung dch chun NaOH, VB = 32,20 ml. NB: nng ca NaOH Nng ca dung dch acid hydrocloric: NB = 0,0950 N
4. MT S CCH BIU TH NNG KHC 4.1. Nng gam 4.1.1. Nng g/l Biu th bng s gam cht tan c trong 1 lt dung dch. K hiu: g/l Cng thc: (4.15) m: khi lng ca cht tan (gam). V: th tch dung dch cho tnh bng ml. Loi nng ny thng dng trong mt s thuc th acid hay base. Th d: Nc thch cao hay dung dch CaSO4 bo ho c nng 2 g/l. 4.1.2. chun Biu th s gam hay miligam cht tan c trong 1 mililt dung dch K hiu: T (4.16) (4.16a) Th d: Acid nitric m c l acid c chun T = 1,40 g/ml. Trong thc t, ngi ta thng dng nhng dung dch chun c nng chn sao cho c 1 ml dung dch chun tng ng vi mt lng cht cn nh lng tnh ton c d dng. Th d: xc nh cng ca nc, ngi ta nh lng nc bng dung dch complexon III chun 0,01M vi ch th en Eriocrom T. Khi phn ng kt thc, c s th tch ml dung dch complexon III s dng. Tnh kt qu: 1 ml complexon III ng vi 0,561 mg CaO, nh vy ng vi V ml ngi ta tnh c hm lng Ca2+ c trong nc.
11/25/2010
Page 58 of 239
Ngi ta cn dng chun trong chuyn i t nng ny sang nng khc. Th d: Tnh nng phn trm C%(kl/tt) ca dung dch H2SO4 2M. T dung dch H2SO4 2M, p dng cng thc tnh CM suy ra khi lng
Nng phn trm C% (kl/tt) ca H2SO4 = 0,196 100 = 19,6% 4.2. Nng ion gam Biu th s ion gam cht tan c trong 1 lt dung dch. K hiu: ion gam/l. Th d: Dung dch FeSO4 c cha 5,6 g Fe2+ nng ion gam ca Fe2+ l 0,1 ion g/l v 1 ion gam Fe2+ = 56. 4.3. Nng phn triu (ppm: parts per million) i vi nhng dung dch c nng rt long, ngi ta thng s dng nng phn triu (ppm). Nng phn triu biu th s gam cht tan c trong 106 gam dung dch hay hn hp. Ngi ta cn biu th s microgam ca cht tan c trong 1 ml dung dch hay s miligam cht tan c trong 1 lt dung dch. K hiu: ppm Cng thc: (4.17) (4.18) (4.19) V khi lng ring ca nc l 1, khi mt dung dch c lng cht tan qu t so vi lng dung mi, ngi ta quy c 1 ml dung dch = 1 g, v l , dung dch c nng 1 ppm tng ng vi 1g cht tan c trong 1 ml dung dch hay 1,00 mg/1 lt dung dch Th d: TCVN 5501 - 1991 quy nh gii hn nng nitrat c trong nc ung l 5ppm. 4.4. Nng phn t (ppb: parts per billion)
11/25/2010
Page 59 of 239
Nng ppb hay nng phn t biu th s gam ca cht tan c trong 109 gam ca dung dch hay hn hp. K hiu: ppb Cng thc: (4.20) (4.21) Dung dch 1 ppb ca mt cht tng ng vi 1 mg cht trong 1 ml dung dch hay 1 g trong 1 lt dung dch. Trng hp biu th nng ca cht kh, ngi ta thng dng n v cht kh trong mt th tch hn l trong khi lng. Th d: 8ppb monoxyd carbon trong khng kh c ngha l 8l CO c trong 1 lt khng kh. 5. H THC LIN LC GIA CC NNG 5.1. Nng phn trm (C%) v nng mol (CM) (4.22) (4.23) Th d 1: Tnh nng phn trm ca dung dch NH4OH 14,8M, bit rng khi lng ring l 0,899 g/ml, khi lng mol phn t l 17,03. Gii p dng cng thc (4.22)
Th d 2: Tnh nng mol ca dung dch H2SO4 98% (d = 1,84 g/ml), phn t gam = 98. Gii
Nng mol v nng ng lng (4.24) (4.25)
11/25/2010
Page 60 of 239
n c tnh tu theo bn cht ca phn ng ho hc. 6. MT S BI TON V NNG 6.1. Pha thuc th c nng long t dung dch m c Th d 1: Cn bao nhiu ml acid hydrocloric m c 12,1 N pha long thnh 1 lt dung dch HCl c nng 0,1 N? Gii p dng cng thc VANA = VBNB Hay Vm c Nm c = Vpha long Npha long Ly 8,26 ml dung dch HCl 12,1 N pha trong nc c 1 lt dung dch HCl 0,1 N
Th d 2: Dung dch amoniac m c cha 28 % (kl/kl) NH3, khi lng ring 0,899. Tnh th tch ca dung dch ny cn dng pha 500 ml dung dch c nng 0,25M. Phn t mol ca NH3 l 17,03. Gii - Tnh khi lng gam ca NH3 c trong mt lt dung dch: T cng thc (4.23) suy ra: - Nng mol ca dung dch:
- Tnh th tch ca dung dch 14,8 M pha long thnh 500 ml dung dch nng 0,25 M p dng cng thc Vm c . Nm c = Vpha long . Npha long Trong Nm c = 14,8 M. Vm c =? Vpha long = 500 ml, Npha long = 0,25 M Nh vy:
Ly 8,45 ml dung dch amoniac 14,8 M pha vi nc thnh 500 ml dung dch
11/25/2010
Page 61 of 239
6.2. Tnh nng mol ca mt dung dch Th d: Tnh nng mol ca acid nitric (M = 63) trong mt dung dch, bit rng khi lng ring l 1,42 v cha 70% (kl/kl) HNO3. Gii T cng thc (4.23) suy ra nng mol ca acid nitric:
T KHA
nng mol nng phn trm nng nguyn chun
nng ng lng ng lng gam quy tc hp thc
CU HI LNG GI 1. Phn bit cc loi nng : nng phn trm, nng mol, nng nguyn chun v nng ng lng. 2. Tnh nng mol ca cc dung dch sau: AgNO3, 117,4g/l KSCN, 0,972g/100ml BaCl2 , 2 H2O, 200mg/l Na2SO4, 720mg/72ml
3. Tnh ng lng gam ca cc ion theo cc phn ng di y: a) 2NaOH + b) 2FeCl3 + H2C2O4 SnCl2 2NaCN Na2C2O4 2FeCl2 + + + 2H2O SnCl4 2Na+ +
c) AgNO3 +
Ag(CN)2-
4. Tnh nng ng lng ca dung dch Na2CO3 khi s dng mt th tch HCl 0,1 N l 30,60ml trung ho 150 mg mu th. 5. Ngi ta dng nng ppm trong trng hp no? CU HI TRC NGHIM
11/25/2010
Page 62 of 239
1. Nng phn trm C% (kl/kl) c biu th: a. s gam cht tan / 100 ml dung dch b. s mg cht tan / 100 ml dung dch c. s gam cht tan / 100 g dung dch 2. Nng phn trm C% (tt/kl) c biu th a. s mg cht tan / 100 g dung dch b. s ml cht tan / 100 ml dung dch c. s lt cht tan / 100 g dung dch 3. Nng phn trm C% (tt/tt) c biu th a. s ml cht tan / 100 ml dung dch b. s ml cht tan / 1000 ml dung dch c. s mg cht tan / 100 ml dung dch 4. Nng gam/ lt c biu th a. s gam cht tan / 1000 ml dung dch b. s mg cht tan / 1000 ml dung dch c. s ml cht tan / 100 ml dung dch 5. S gam kali dicromat cn thit pha 250 ml dung dch kali dicromat 2M l a. 138 g b. 142 g c. 147 g d. 151 g e. 159 g d. s ml cht tan / 1000 ml dung dch e. s ml cht tan 100 lt dung dch d. s ml cht tan / 100 g dung dch e. s ml cht tan / 10 g dung dch d. s ml cht tan / 1000 g dung dch e. s ml cht tan / 100 g dung dch d. s mg cht tan / 100 g dung dch e. s gam cht tan / 1000 g dung dch
6. Tnh nng mol ca mt dung dch ethanol (C2H5OH = 46). Bit rng trong 85,0 ml dung dch c cha 1,7 g ethanol. a. 0,45 M b. 0,55 M c. 0,67 M d. 0,85 M e. 1,0 M
7. Cho bit nng ng lng ca dung dch H2SO4 98% c d = 1,84 g/ml a. 36,8 N b. 35,3 N c. 28,5 N d. 45 N e. 42 N
Chng 5
file://C:\WINDOWS\Temp\kgpwyiypbu\hoa_phan_tich.htm 11/25/2010
Page 63 of 239
PHNG PHP PHN TCH KHI LNG

MC TIU
Nu c nguyn tc v phn loi c cc phng php phn tch khi lng. Trnh by c cc bc tin hnh phn tch khi lng.
NI DUNG 1. LCH S Thodore W. Richards (1868 1928), cng vi cc sinh vin Trng i hc Harvard pht trin v ci tin nhiu k thut phn tch khi lng, xc nh c khi lng nguyn t ca 25 nguyn t. V l nm 1914 ng l ngi M u tin nhn gii Nobel v ho hc. 2. NGUYN TC C s ca phng php phn tch khi lng l nh lut thnh phn khng i v nh lut ng lng. Trong nh lut thnh phn khng i, t s khi lng cc nguyn t c trong thnh phn mt cht lun lun nh nhau. Cn vi nh lut ng lng, khi lng cc nguyn t tham gia phn ng lun lun khng i v t s gia chng khng thay i. Phng php phn tch khi lng da trn vic o lng khi lng c thc hin nh cn phn tch, mt dng c cung cp cc kt qu rt ng v chnh xc. Trong phng php ny, cht cn xc nh c tch ra di dng nguyn cht hay di dng hp cht c thnh phn xc nh. T hp cht thu c ny, sau khi cn trn cn phn tch, ngi ta tnh c khi lng ca cu t cn xc nh v hm lng phn trm ca n. Th d: xc nh hm lng bc trong bc nitrat, ngi ta ly chnh xc khong 0,2549 g AgNO3, ho tan trong nc v kt ta ion bc bng acid hydrocloric AgNO3 + HCl AgCl + HNO3 Sau khi x l thch hp kt ta thu c, v cn trn cn phn tch, khi lng ta AgCl thu c l 0, 2148 g. Tm khi lng bc trong kt ta. Gii: Da vo phng trnh ho hc trn ta c: c mt phn t AgCl (M =143,35 g) th lng bc tng ng l 107,90 g. Nh vy khi thu c 0,2148 g s suy ra hm lng ca bc 143,35g AgCl 107,90g Ag 0,2148g AgCl x?
Kt qu: vi lng mu l 0,2148 g bc clorid, suy ra lng bc l 0,1617g. Hm lng bc trong bc nitrat c tnh nh sau:
11/25/2010
Page 64 of 239
0,2549 g 100g
AgNO3
cha 0,1617 g Ag cha y g Ag
3. PHN LOI Phng php phn tch khi lng bao gm phng php tch, phng php ct v phng php kt ta. 3.1. Phng php tch Trong phng php ny, cht cn xc nh c tch ra t cht phn tch di dng t do v c cn trn cn phn tch. 3.1.1. Phng php xc nh trng lng tro Mu rn c t chy v nung n trng lng khng i. Tro thu c em cn. Da vo trng lng ca tro ngi ta tnh hm lng phn trm ca n trong mu cho. Th d: xc nh hm lng tro sulfat ca terpin hydrat, ngi ta cn 1 g ch phm (cn chnh xc) em nung vi acid sulfuric. Tro thu c em cn trn cn phn tch. Dc in Vit Nam III quy nh, lng tro sulfat khng c qu 0,1%. 3.1.2. Phng php tch Dng tch n cht ra khi hn hp. Th d nh lng vng v ng trong hp kim. Trc ht ngi ta ho tan mt lng cn xc nh ca hp kim trong nc cng thu (hn hp acid nitric v acid sulfuric), sau thm dung dch hydro peroxyd mc ch kh ion vng n vng nguyn t. Lc vng c tch ra, ra loi tp cht, sy v nung, ngui, em cn. Da vo khi lng vng c tch ra, ngi ta suy ra hm lng vng c trong mu. 3.1.3. Phng php in trng lng (Electrogravimetry) Cht cn xc nh c dng in tch ra v bm trn mt in cc bng platin (catod). Da vo khi lng tng ln ca catod, ngi ta suy ra hm lng. Th d: Khi cho dng in mt chiu i qua mt dung dch c cha ion ng, trong nhng iu kin xc nh th ng s tch ra, bm ln catod. Cn catod trc v sau th nghim s suy ra hm lng ng trong hn hp. 3.2. Phng php lm bay hi (phng php ct) Ngi ta tch mt cch nh lng cht cn phn tch di dng mt hp cht bay hi. Trong phng php ny, cht phn tch hay cc hp cht b bin i c lm bay hi mt nhit thch hp hay do tc dng vi mt thuc th thch hp. Cht bay hi c thu hi v cn. Khi lng ca mu c xc nh mt cch gin tip t s mt trng lng. Cc phng php lm bay hi thng l phng php trc tip v phng php gin tip. 3.2.1. Phng php trc tip Cht sau khi lm bay hi c hp th bng mt cht thch hp c xc nh khi lng. S chnh lch v khi lng ca cht hp th trc v sau phn ng l khi lng ca cht cn xc nh.
11/25/2010
Page 65 of 239
Th d: nh lng natri hydrocarbonat trong vin thuc khng acid. Ngi ta cn mt lng mu t thuc vin nghin mn v x l bng acid sulfuric long bin i hydrocarbonat thnh dioxyt carbon: NaHCO3 + H2SO4 CO2 + H2O + NaHSO4
Kh CO2 bay ra c cho vo bnh c cha cht hp th Ascarit II cu to bi silicat mn ph NaOH, trong cht hp th ngi ta thm CaSO4 gi nc c to ra trong qu trnh hp th. CO2 + 2NaOH Na2CO3 + 2H2O Cn bnh trc v sau phn ng suy ra hm lng ca CO2.
Hnh 5.1. Thit b dng xc nh lng natri hydrocarbonat trong thuc vin khng acid bng phng php lm bay hi
3.2.2. Phng php gin tip Trong phng php ny, ngi ta xc nh khi lng cn cn li ca cht sau khi tch hon ton cht cn xc nh. Hiu s khi lng trc v sau khi ct cht cn xc nh cho ta kh nng tnh c hm lng ca cht. Th d: BaCl2 ngm 2H2O. xc nh lng nc kt tinh, ngi ta cn mt lng mu, em sy nhit 100 - 105oC. ngui, cn mu ln hai xc nh lng nc mt.
Phng php xc nh khi lng gin tip c s dng khi xc nh m ca mu, xc nh nc kt tinh trong cc loi tinh th hydrat, xc nh lng mt khi nung. 3.3. Phng php lm kt ta Trong phng php khi lng da trn s to ta, cht phn tch c tc dng vi thuc th thch hp to thnh hp cht t tan, sau c lc, ra, sy v nung. Cht ny c cn trn cn phn tch. Qu trnh nung c th gy ra s bin i v mt ho hc ca ta, v vy trong phn tch ngi ta phn bit dng kt ta v dng cn.
11/25/2010
Page 66 of 239
Dng kt ta: dng to thnh khi cho cht cn phn tch tc dng vi thuc th thch hp. Th d: Khi xc nh ion thnh l BaSO4. trong dung dch Na2SO4, ngi ta dng ion Ba2+ kt ta. Ta to
Dng cn: dng to thnh sau khi c x l bng nhit (sy v nung) c cn xc nh hm lng. Dng cn cng c th l dng kt ta th d nh trng hp ca BaSO4, ta to thnh sau phn ng, khng b bin i sau khi sy v nung, sn phm em cn l BaSO4 ngi ta gi dng ta ging dng cn.
Cht cn xc nh
Dng ta
Dng cn
C nhiu trng hp dng ta khc dng cn, th d nh trong trng hp nh lng ion Ca2+ bng thuc th (NH4)2C2O4, dng ta thu c l calci oxalat theo phn ng sau: Ca2+ + + 2H2O CaC2O4 . 2H2O
Nhng dng cn li l calci oxyt v calci oxalat b phn hy sau khi nung, phn ng c th vit: CaC2O4.2H2O CaC2O4 CaO + CO + CO2 4. C IM Phng php phn tch khi lng l mt trong s t k thut o lng da trn nn tng ca n v SI nh khi lng v mol, c hng s xc nh nh s Avogadro v khi lng ca 12C, cho php xc nh hm lng ca cc cu t ring bit trong mt mu cho ca cht phn tch. Thng c dng khi nh gi thnh phn ca mu. Xc nh cc kim loi (cc cation), cc phi kim loi (cc anion), thnh phn ca hp kim, cc hp cht hu c... Nhc im ca phng php ny l thi gian xc nh ko di, di hn so vi phng php phn tch chun . 5. CCH TNH KT QU Cc kt qu trong phn tch khi lng thng c tnh t hai s o thc nghim: khi lng mu th v khi lng ca sn phm c thnh phn xc nh. Hm lng phn trm ca sn phm c tnh bng cng thc:
A: cht cn nh lng. Th d: xc nh lng piperazin c trong sn phm thng mi, ngi ta c th to ta piperazin diacetat bng acid acetic. Cn sn phm to thnh, tnh hm lng ca piperazin tinh khit. thc hin ngi ta cn mt lng mu 0,3126 g ho trong 25 ml aceton, thm 1ml acid acetic.
11/25/2010
Page 67 of 239
yn 5 pht, sau lc ta, ra bng aceton, sy kh 110C, em cn thu c mt lng 0,7121 g. Tnh hm lng phn trm ca piperazin? Gii
Phn t lng ca piperazin: 86,137 g Phn t lng ca acid acetic: 60,053 g Phn t lng ca piperazin diacetat: 206,243 g Theo phng trnh, mt mol piperazin s to ra mt mol sn phm, s mol ca sn phm to thnh:
5.1. Phng php ct hay tch Khi xc nh trc tip, cc sn phm d bay hi thng c tch ra di dng hp cht bay hi c thnh phn xc nh. Cc tinh th hydrat b phn hy tch ra nc, cc carbonat b phn hy to thnh CO2... V vy ngi ta tnh lng cht cn xc nh theo s tng khi lng ca b phn hp th. Hm lng phn trm ca hp cht bay hi c tnh xut pht t t l tng ng.
p: khi lng dng cn cht cn xc nh theo s gia tng khi lng ca cht hp th. a: lng cn ca mu. 5.2. Phng php lm kt ta Hm lng phn trm ca cht cn xc nh c tnh theo cng thc sau: Mu ban u l cht rn. Vi a gam mu A, sau khi kt ta, khi lng dng cn thu c l p gam.
F: tha s chuyn (tha s phn tch)
m, n: s mol ca cht A v cht cn xc nh.
11/25/2010
Page 68 of 239
MA: khi lng phn t ca cht cn xc nh. MB: khi lng mol ca dng cn. F: h s chuyn, dng chuyn t khi lng mol dng cn sang khi lng nguyn t cn phn tch. Th d: Mt cht ty ra thng mi cha phosphat c khi lng 0,3516 g. Ngi ta ph hy cc hp cht hu c bng cch un nng n . Cn thu c cho tc dng vi HCl chuyn P thnh H3PO4. Ion to thnh phn ng vi Mg2+ v NH4OH cho kt ta MgNH4PO4.6H2O. Ta ny sau khi lc, ra v nung chuyn thnh dng cn l Mg2P2O7 (M = 222,57 g) c khi lng cn 0,2161g. Hy tnh khi lng phn trm ca P (P = 30,974 g). Gii Trong 222,57 g Mg2P2O7 th c 2 30,974 g P Vy trong 0,1261 g Mg2P2O7 c P? Khi lng ca cht phn tch P c tnh:
Hm lng phn trm ca P c tnh bng cch p dng cng thc:
y khi lng ca cht phn tch l P c tnh bng cch nhn khi lng ca dng cn vi mt hng s. Hng s ny c cu to bi cht cn phn tch v dng cn. Hng s ny c gi l tha s chuyn hay yu t khi lng, k hiu F Nh vy F c tnh:
Khi lng P c th c vit
Mt phn t mol Mg2P2O7 (n = 1) thu c 2 nguyn t P (m = 2)
11/25/2010
Page 69 of 239
Mt mol Mg2P2O7 (n = 1) thu c 2 nguyn t P (m = 2) 6. CC GIAI ON CA PHNG PHP PHN TCH KHI LNG BNG CCH TO TA 6.1. Xc nh lng mu Hm lng ca dng cn ph thuc vo lng cht nghin cu. Lng cht nghin cu c nh hng n chnh xc ca s phn tch. Lng cn cht phn tch cng ln th chnh xc cng cao, tuy nhin nu lng cn qu ln gy bt li trong qu trnh lc, ra. Ngc li nu lng cn qu nh s dn n sai s ln. Lng mu cn thit lm kt ta c tnh t phng trnh ca phn ng gia cht cn phn tch v thuc th. 6.1.1. i vi kt ta dng tinh th Lng mu cn thit c tnh theo cng thc:
MA: khi lng mol ca cht cn xc nh MB: khi lng mol ca dng cn m, n: h s cn bng ca phng trnh phn ng 0,5: tm c bng thc nghim, p dng cho cc kt ta tinh th Th d: tnh lng Ca2+ trong CaCO3 bng cch to ta CaC2O4, ngi ta tnh lng mu cn thit cn c vo phng trnh phn ng:
6.1.2. i vi kt ta dng v nh hnh
Th d: Tnh lng mu cn thit ca Fe(NO3)3.9H2O khi tin hnh phn tch khi lng. Bit rng dng cn l Fe2O3.
11/25/2010
Page 70 of 239
Gii Phng trnh phn ng c th vit nh sau:
6.1.3. Chuyn mu v dng ho tan Cc phn ng thng xy ra trong dung dch, do mu th phi c ho tan trong dung mi thch hp trc khi cho tc dng vi thuc th to ta. Cn ch n cc yu t nh hng nh cu to cht, nhit , mi trng. Th d trng hp cht khng tan trong nc nhit thng, cn un nng bng cch cch thy hay cht tan c khi c s hin din ca acid... 6.2. Thuc th Thuc th gm thuc th to ta v c v hu c. 6.2.1. Thuc th v c Cc thuc th ny to vi cht cn phn tch thnh cc mui hoc cc oxit rt kh tan. Thuc th v c to ta chn lc nhng khng c hiu. Mt s thuc th v c To ta cc cation v c. Cc cation v c thng c kt ta di dng cromat, halogenid, hydroxyd, oxalat.
Thuc th dng to ta cc cation v c Cht phn tch Ba2+ Pb2+ Pb2+ Ag+ Al3+ Be2+ Fe3+ Ca2+ Thuc th (NH4)2CrO4 K2CrO4 H2SO4 HCl NH3 NH3 NH3 (NH4)2C2O4 Dng ta BaCrO4 PbCrO4 PbSO4 AgCl Al(OH)3 Be(OH)2 Fe(OH)3 CaC2O4 Dng cn BaCrO4 PbCrO4 PbSO4 AgCl Al2O3 BeO Fe2O3 CaCO3 hay CaO
11/25/2010
Page 71 of 239
Mg2+ Zn2+ Sr2+
(NH4)2HPO4 (NH4)2HPO4 KH2PO4
NH4MgPO4 NH4ZnPO4 SrHPO4
Mg2 P2O7 Zn2 P2O7 Sr2P2O7
To ta cc anion v c Mt s anion v c c th c kt ta bng cch s dng cc phn ng dng trong to kt ta cc cation nh bng trn, ch i ngc cht phn tch thnh cht to kt ta (thuc th). Th d nh ion cromat c th c xc nh bng cch cho tc dng vi dung dch BaCl2. Ngoi ra cn c th s dng cc thuc th sau:
Cht phn tch CN I Br Cl Thuc th AgNO3 AgNO3 AgNO3 AgNO3 FeSO4/AgNO3 SCN SO2/CuSO4 BaCl2 Dng ta AgCN AgI AgBr AgCl AgCl CuSCN BaSO4 Dng cn AgCN AgI AgBr AgCl AgCl CuSCN BaSO4
6.2.2. Thuc th hu c Thuc th hu c c tnh chn lc cao hn thuc th v c. Thuc th c hai loi, loi to vi cht phn tch thnh cht khng ion ho, rt t tan gi l cc hp cht kt hp, loi th hai to thnh cc cht trong c lin kt gia cht v c vi thuc th l lin kt ion. Mt s thuc th hu c
Thuc th Cupron Dimetylglyoxim Natri tetraphenylborat Na[B(C6H5)]4 Cupferon 1 nitroso 2 naphtol Cht cn phn tch Cu2+ Ni2+ K+ Fe3+ Co2+ Dng ta CuC14H11O2N Ni(C4H7O2N2)2 K[B(C6H5)]4 Fe(C6H5N2O2)3 Co(C10H6O2N)3 Dng cn CuC14H11O2N Ni(C4H7O2N2)2 K[B(C6H5)]4 Fe2O3 Co hoc CoSO4
Ngoi ra c nhiu thuc th phn ng mt cch chn lc vi cc nhm chc hu c, c th dng
11/25/2010
Page 72 of 239
nh lng cc hp cht ny bng phng php phn tch khi lng. Cc cht ny cng c th dng trong phng php phn tch th tch v phng php quang ph.
Thuc th Dinitro 2,4 phnylhydrazin Quinolin Metyl iodid/Ag+ BaCl2/HNO3 Sn Cu Nhm chc hu c cn phn tch Carbonyl RCHO Carbonyl thm ArCHO Methoxy ROCH3, ethoxyROC2H5 A. sulfamic RNHSO3H Nitro thm RNO2 Hp cht azo Dng cn R CH=NNHC6H3(NO2)2 CO2 AgI BaSO4 Sn4+ Cu2+
6.3. S kt ta Sn phm l tng ca mt phn tch khi lng l khng tan, d lc, d lm sch v c thnh phn xc nh. Mc d c t cht t nhng yu cu ny, nu s dng nhng k thut thch hp cng c th p ng c. Th d mt ta c tan gim khi trong dung dch lnh v tnh tan ca hu ht cc hp cht u gim nhit thp. Cc tiu phn ca cht kt ta phi ln c th tch d dng khi lc, khng c qu nh lm tc lc hoc i qua giy lc. Kch thc ta ln hn ch c s bm cc cht l ln ta. Ngoi ra, ta cn hin din dng hn tng keo, kch thc cc tiu phn trong khong 1 1000 nm qua c hu ht cc lc. 6.3.1. Cc yu cu i vi dng ta v dng cn
Dng ta
- Ta phi c tan nh ta c hon ton. - C tinh khit cao, t hp ph hay ln cht bn. - Ta cn c tinh th ln t b tan trong qu trnh lc, ra. - Ta phi chuyn sang dng cn mt cch d dng v hon ton.
Dng cn
- Dng cn phi bn vi mi trng, khng b ht m, khng b ph hy. - Phi c cng thc xc nh tnh F ng. - Tha s chuyn F ng vi dng cn cng nh cng tt. Th d: xc nh Cr 3+ (Cr = 52) trong mt mu, ngi ta c th s dng hai dng cn Cr2O3 v BaCrO4. c th chn dng cn thch hp ngi ta tnh F:
11/25/2010
Page 73 of 239
Gi s khi lng ca Cr2O3 v BaCrO4 thu c l nh nhau bng 1 mg. Sai s i vi Cr dng BaCrO4 nh hn so vi dng Cr2O3 l = 3,5 ln.
So snh 2 gi tr ca F, ngi ta thy 0,2 nh hn 0,7 do dng cn c chn l BaCrO4. 6.3.2. Chn thuc th v lng thuc th Cc yu cu i vi dng ta v dng cn nh hng n yu cu i vi cht lm kt ta (thuc th). Yu cu chn thuc th: L tng nht, mt thuc th to ta khi lng phi tc dng mt cch c hiu hay t nht mt cch chn lc vi cht cn phn tch. Trn thc t, cc thuc th chuyn bit hay c hiu ch phn ng vi mt loi cht ho hc th rt him. Cc thuc th chn lc c th tc dng vi vi mt s gii hn loi cht ho hc ph bin hn. Th d nh AgNO3 l thuc th chn lc v to ta vi ion Cl, Br, I v SCN trong mi trng acid. Tri li dimetylglyoxim l thuc th chuyn bit v ch to kt ta vi Ni2+ trong mi trng kim. Thuc th to kt ta l tng v tnh chuyn bit hay tnh chn lc phi tc dng vi cht cn phn tch to ra sn phm c tnh cht sau: a) D lc v d ra loi cc cht nhim bn. b) C tan thp khng mt ta mt cch nh lng khi lc v ra. c) Tr vi cc cu t ca mi trng. d) C thnh phn xc nh sau khi lm kh v sau khi nung (nu cn). Lng thuc th. m bo kt ta c hon ton cht cn phn tch, lng thuc th s c cho vi lng d t 10 15% so vi lng c tnh t phn ng. i vi nhng thuc th c tnh bay hi, lng thuc th gp 2 3 ln so vi l thuyt. Ch : Trong mt s trng hp, lng tha thuc th c tc dng lm tan ta to thnh. Th d: nh lng ion Hg2+, ngi ta s dng KI to kt ta HgI2. Nhng vi lng KI d HgI2 s to phc K2[HgI4] tan: Hg2+ + K HgI2 + KI tha K2[HgI4] tan 6.3.3. Cc yu t nh hng n qu trnh kt ta Trong giai on to kt ta nu dung dch m c s hnh thnh cc kt ta c tinh th nh. Tri li i vi cc ta v nh hnh, s tng nng s dn n s chuyn cc dng keo khng bn sang cc kt ta. Trong qu trnh ta c hnh thnh thng km theo cht bn. Nguyn nhn ca s lm bn ta l
11/25/2010
Page 74 of 239
s cng kt. Cng kt l hin tng khi kt ta lng xung mang theo cc tp cht khc m trong iu kin ring l th cc tp cht ny khng th kt ta c. Th d: FeCl3 khng ta vi H2SO4 nhng nu kt ta BaCl2 bng H2SO4 vi s c mt ca FeCl3 th bn cnh ta BaSO4 c ln c ta Fe2(SO4)3. Sau khi nung Fe2(SO4)3 s chuyn thnh Fe2O3 c mu , lm ta BaSO4 c mu. S cng kt c nhiu nguyn nhn khc nhau, ngi ta phn bit 3 dng cng kt: hp ph, hp lu v ni hp. Ngoi ra s hu ta cng l nguyn nhn gy bn ta. Hp ph (adsorption) Hp ph l hin tng cc ion hoc cc phn t cht bn trong dung dch bm dnh ln b mt ta mi to thnh. Tinh th cng nh hp ph bn cng nhiu. Nng cht bn trong dung dch cng ln, s hp ph cng mnh v nhit cng thp bn cng d b hp ph ln b mt ta. Hp ph l mt hin tng thun nghch v cng to ra s gii hp ph. S hin din ng thi ca 2 hin tng i nghch ny dn n mt trng thi cn bng ng, ngi ta gi l cn bng hp ph. Trong trng hp ny, c th x l bng cch to tinh th ln nu l ta tinh th v thng c th loi b bn bng cch ra. Hp lu (Occlution) l s gi cc tp cht tan trong mi trng vo bn trong ta do ta to thnh qu nhanh, cc tinh th mi to thnh c th bc ly cht bn pha trong. Hp lu ch xy ra i vi ta tinh th. Ni hp (Inclusion) l hin tng m cc ion tp kt ta vo cc tinh th li ca ta to thnh tinh th hn hp. Hin tng ny xy ra khi cc ion ca tp c cng kch thc v cng in tch vi ta do to thnh cc ion ng hnh. Ngoi ra hai mui ny cn phi c cng lp tinh th. Th d ta BaSO4 c hnh thnh khi thm dung dch BaCl2 vo dung dch cha ion sulfat, c s hin din ca ch. Nhng ion ch thay th mt phn ion bari trong tinh th to thnh tinh th hn hp vi BaSO4. S to thnh tinh th hn hp ny rt kh trnh khi mt s ion kt hp hin din trong mu. Trng hp ny cng xy ra i vi ta keo. Bin php tt nht l chn thuc th khc khng gy ra s to thnh tinh th hn hp. Hu ta (posprecipitation) Hin tng ny xy ra nu ta tip xc lu vi dung dch, th d nh ta HgS nu tip xc lu trong dung dch c cha Zn2+, mc d mi trng acid mnh vn c th xut hin ta ZnS trn b mt ca HgS. Thng hay gp nht l ta CaC2O4 c hu ta l MgC2O4. 6.3.4. To kt ta Vi ta tinh th. Nhiu ta tinh th nh BaCrO4, BaSO4, CaC2O4... thnh thong thu c di dng nhng tinh th rt mn c th qua c l lc gy ra s mt khi lng ca dng ta trong qu trnh x l. Hin tng bn ta l mt trong nhng yu t ngn cn s kt ta. hn ch cc yu t nh hng n kt qu phn tch, vic to cc kt ta tinh th cn tun theo cc iu kin sau: - Tin hnh kt ta vi dung dch mu v thuc th long.
11/25/2010
Page 75 of 239
- Thm dung dch thuc th vo chm v khuy trong qu trnh to ta. - Thc hin kt ta vi dung dch cht kt ta nhit cao. Trong mt s trng hp, cn thm vo cht lm tng tan v trnh hin tng cng kt. Th d to ta BaSO4 ngi ta thm HCl gim ta ph BaCO3 v gim cng kt Ba(OH)2. Ch thi gian trnh bn do hu ta Vi ta v nh hnh. Cc kt ta v nh hnh c khuynh hng hp ph v to thnh dung dch keo, do khi kt ta, cn tin hnh ta t dung dch nng v c mt ca cht in ly. ngn cn hin tng hp ph, nn tin hnh ta t dung dch c, khuy mnh v sau khi ta hnh thnh, tin hnh lc, ra ta bng nc nng. Khng nn ta tip xc vi dung dch mt thi gian di. 6.4. Lc v ra ta Lc v ra ta l 2 k thut rt quan trng trong phng php to thnh kt ta. S chnh xc ca kt qu ph thuc vo thao tc giai on ny. 6.4.1. Lc ta Lc l giai on tch kt ta ra khi dung dch to ta. Tu theo lng ta v cch chuyn t dng ta sang dng cn, ngi ta c th s dng dng c lc thch hp nh giy lc hay phu lc. Giy lc lc ly ta ngi ta s dng giy lc khng tro. Giy lc ny sau khi t chy v nung, li khi lng tro rt nh, c th b qua. Giy lc khng tro c mn khc nhau. Tu theo kch thc ca cc ht kt ta, ngi ta s dng cc loi giy lc mng hay dy, c phn bit bng mt di bng c mu bao chung quanh hp giy lc. Giy lc bng c dng trong trng hp lc cc kt ta dng keo v nh hnh. lc phn ln cc kt ta, c th s dng loi bng mu trng c mn trung bnh, cui cng lc cc kt ta tinh th nh nh BaSO4 hay CaC2O4, ngi ta dng giy lc mn nht (bng mu xanh bin). Khi tin hnh lc, iu quan trng nht l phi ch n lng ta cn lc chn kch thc ca giy lc ph hp. Ta khng c chim hn 1/3 chiu cao ca giy lc m bo ta s c ra sch sau khi lc. Phu lc Phu lc xp hin nay c dng ph bin trong cc phng th nghim. Phu lc lm bng s, lc di p sut gim. Loi lc ny chu c nhit cao nhng li c nhc im l ht m. 6.4.2. Ra ta Mc ch ca ra ta l loi cc cht bn bm trn b mt ca kt ta. Cc cht bn hp ph ny trng thi cn bng vi cc ion tng ng trong dung dch. V vy khi ra, ngi ta ra bng nc hay mt dung dch no m nng ca ion coi nh bng 0, hin tng gii hp phi tri hn hin tng hp ph ta loi c cc cht bn v cui cng thu c mt kt ta tinh khit. Khi ra ta cn phi bit loi dung dch ra thch hp i vi kt ta. Ngi ta phn bit 4 loi dung dch ra:
11/25/2010
Page 76 of 239
a) Ra bng dung dch ca cht to kt ta. Rt t kt ta thu c c tan nh ngi ta c th b qua khi lng ta b mt trong qu trnh ra ta. Phn ln trng hp lng ta b mt do ra vt qu gii hn ca sai s cho php. hn ch s mt ny, kt ta sau khi c to thnh s c ra bng dung dch long ca cht to ta. Th d ra 0,1 g ta CaC2O4 thu c, nu dng 200 ml nc ra th lng ta b mt l 1,3% trong khi nu ra ta bng 200 ml dung dch (NH4) 2C2O4,0,01M, lng ta b hao ht l 0,0067%. Cht to ta thm vo phi l cht bay hi lng tha ca cht ny c th b loi sau khi nung. b) Ra ta bng dung dch cht in ly. C nhiu cht kt ta khi ra vi nc s to hin tng pepti ho, tr thnh dng keo v i qua c lc nh trng hp ca ta AgCl (AgCl: Ag+.....NO3-), ngi ta x l bng cch ra ta keo ny vi dung dch c cha cht in ly bay hi c th loi sau khi nung nh HNO3 hay NH4NO3. c) Ra ta bng dung dch ngn cn s thu phn. i vi cc kt ta khi ra bng nc s xy ra hin tng thu phn, iu ny a n vic dng cn thu c khng cn l hp cht c thnh phn xc nh na, ngi ta ra ta bng mt dung dch c tnh cht ngn cn s thu phn. Th d ta MgNH4PO4 nu ra vi nc, hin tng thu phn xy ra theo phn ng: MgNH4PO4 + H2O MgHPO4 + NH4OH Nu dng nc ra l NH4OH, cn bng s dch chuyn v bn tri, lm gim s thu phn. NH4OH b loi d dng sau khi nung kt ta. d) Ra ta vi nc n thun. p dng i vi cc kt ta khi ra vi nc, s mt ta khng ng k. Trng hp ny cn n nhit ca nc ra, nu ta tan trong nc nng th phi ra ta bng nc lnh. 6.5. Sy v nung Sau khi lc, ngi ta sy ta cho n khi lng khng i. S sy c tc dng loi dung mi v tt c cc cht c th bay hi. Nhit v phng php sy ph thuc vo phng php lc v dng ta thch hp. Trong mt s trng hp ngi ta nung sn phm chuyn thnh dng cn c thnh phn xc nh. Nhit i hi thu c sn phm thch hp tu thuc vo cc cht kt ta. nhit 110C, loi nc v cht cht bn d bay hi. sy sn phm ngi ta c th dng t sy, n Bunsen hoc n Meker. Hnh 5.2 cho thy s mt khi lng theo nhit ca mt vi cht kt ta thng dng nh bc clorid, calci oxalat v nhm oxit. S sy ca 3 ta ny n gin l loi nc v cc cht bn d bay hi bm vo ta. Nhit s dng rt khc nhau to ra mt ta khan c khi lng khng i. i vi bc clorid, nhit cn loi nc ht m l trn 110C trong khi loi nc hon ton nh trng hp ca nhm oxit, nhit phi trn 1000C. ng biu din nhit khi lng ca calci oxalat kh phc tp. Di 135C, mt phn t nc b loi to thnh
11/25/2010
Page 77 of 239
CaC2O4.H2O. Hp cht ny sau chuyn thnh oxalat khan 225C. S thay i t ngt v khi lng nhit 450C cho thy l c s phn hy calci oxalat thnh calci carbonat v monoxyt carbon. Nc cui cng ca ng biu din tng ng vi s bin i calci carbonat thnh calci oxit v CO2. Nh vy, khi nh lng Ca2+ bng phng php phn tch khi lng vi ta oxalat, bn cht ca dng cn ph thuc nhiu vo nhit .
Hnh 5.2.Tc dng ca nhit ln khi lng ta
Khi nung kt ta giy lc chy thnh than, than to thnh c th kh mt s cht khi nung. Trong trng hp ny cn phi dng phu lc s thay cho giy lc. 6.6. Cn Giai on xc nh lng cn thu c. Dng cn c sy v nung em cn trn cn phn tch. lu dng cn phn tch cn c n 0,1 mg. 7. NG DNG 7.1. Xc nh nc kt tinh v ht m Dc in Vit Nam III c tiu chun "Gim khi lng do sy kh" trong cc chuyn lun xc nh nc ht m hoc c nc ht m v nc kt tinh vi nhit nh sau: 105oC 5oC: Nhit thch hp xc nh m. 120oC 200oC: Nhit thch hp loi nc kt tinh. tnh kt qu, p dng cng thc:
Th d: Dc in Vit nam III, trang 39 c chuyn lun Cafein ngm mt phn t nc (C8H10O2N4.H2O), c phn t lng l 212,21. em sy 80oC, n khi lng khng i, nc ht m v nc kt tinh mt i. Cn mu trc v sau khi sy ri tnh ra t l phn trm khi lng b gim. Tnh theo ng cng thc th hm lng nc kt tinh trong cafein l 8,48% nhng v c nc ht m nn Dc in cho php ti a l 9%. 7.2. Xc nh hm lng Ba2+ hay
11/25/2010
Page 78 of 239
7.2.1. Nguyn tc to ta BaSO4 dng dung dch H2SO4 hay mui sulfat nu mu l Ba2+. Dng dung dch BaCl2 nu mu l 7.2.2. Cch tin hnh - Cn mu. - Chuyn mu v dng ho tan. Thm dung dch thuc th c nng thch hp un nng kt hp khuy. un cch thu. yn cho ta kt tinh lc. Ra ta bng nc nng. Nung - cn - tnh kt qu. 7.3. nh lng clorid, bromid v iodid 7.3.1. Nguyn tc Cho dung dch AgNO3 vo mt dung dch cha ion Cl-, Br-, I- s thu c cc ta bc halogenid. Ra ta, sy v cn kt qu. Th d: nh lng NaCl c trong dung dch mu. NaCl phn ng vi AgNO3 theo phng trnh: NaCl + AgNO3 AgCl + NaNO3 7.3.2. Cch tin hnh Thm nc vo mu, thm HNO3. Cho dung dch AgNO3 khuy mnh. un cch thu ri yn trong bng ti. Lc v ra ta trc tin bng dung dch HNO3 sau bng nc nng. Sy ta v tnh kt qu. 7.3.3. Nhn xt Sy ta nhit 1300C. Ta bc d b phn hy, trnh nh sng. Ta AgCl d b hp th Ag+ to ra lp in kp trong trng hp trong dung dch c lng tha AgNO3 thm HNO3 ion ph lp in kp. T kha .
11/25/2010
Page 79 of 239
- Phn tch khi lng - Phng php ct - Phng php lm kt ta - Hp lu
- Ni hp - Hu ta - L c t a - Ra ta
CU HI LNG GI 1. Nu nguyn tc ca phng php phn tch khi lng. 2. Phn loi cc phng php phn tch khi lng. 3. Trnh by cc giai on tin hnh phn tch khi lng. Nu cch tnh kt qu. 4. K vi ng dng ca phng php phn tch khi lng. 5. Nu nguyn nhn lm bn ta v cch x l. CU HI TRC NGHIM 1. i tng ca phng php phn tch khi lng l a. cht rn b. cht lng c. cht lng v cht kh d. cht rn v cht lng e. cht rn, cht lng v cht kh 2. Phng php phn tch khi lng da vo s o chnh xc: a) th tch ca cht rn cn xc nh. b) khi lng ca cht rn cn xc nh. c) khi lng n cht c tch ra t mt hn hp rn. d) khi lng hp cht c thnh phn khng i. e) khi lng ca cht rn cn xc nh hoc thnh phn ca n c tch ra dng tinh khit hay hp cht c thnh phn xc nh. 3. Phng php p dng khi mu c lm bay hi nhit thch hp, kh bay ra c hp th bng mt cht bit trc khi lng c gi l phng php a. tch b. ct c. kt ta d. tro e. in trng lng
4. Phng php kt ta l phng php da trn nguyn tc l mu a) tc dng vi thuc th to cht t tan.
11/25/2010
Page 80 of 239
b) b bin i thnh cn khi tip xc vi nhit. c) c tch ra di dng t do hay hp cht bn. d) c tch ra v b in cc. e) c tch ra v bm vo hn hp vi xt. 5. Biu th kt qu trong phn tch khi lng thng c tnh theo a) P (g/l) b) C% (kl/ kl) c) hm lng phn trm dng ta theo khi lng mu. d) hm lng phn trm dng cn theo khi lng mu. e) hm lng phn trm ca cht tch ra di dng t do theo khi lng mu. 6. Lng thuc th cn dng phi cho tha................................ so vi tnh ton theo l thuyt l a. 5 - 10 % b. 10 15% c. 15 20% d. 20 25 % e. 25 30%
7. Bn ta thng gp trong kt ta v nh hnh l do hin tng a. cng kt. b. hp th. c. hp ph. d. hp lu. e. ni hp.
Chng 6 PHNG PHP PHN TCH TH TCH

MC TIU
Trnh by c nguyn tc ca phng php phn tch th tch. Phn bit c im tng ng v im kt thc. Phn loi c cc phng php phn tch th tch. Tnh c kt qu sau khi chun th tch.
NI DUNG
11/25/2010
Page 81 of 239
1. M U Ngi t c s cho phng php phn tch th tch l nh bc hc L.J. Gay - Lussac (Louis Joseph GAY LUSSAC) 1778 - 1850. Phng php chun th tch l phng php phn tch nh lng trong ch yu l s o chnh xc th tch ca dung dch c nng xc nh cn thit phn ng hon ton vi cht phn tch. S chun c thc hin bng cch thm t t mt dung dch chun vo dung dch ca cht cn phn tch bng buret cho n khi ngi ta nhn thy phn ng gia cht chun v cht phn tch xy ra hon ton. Th tch ca thuc th dng trong nh lng c xc nh bng s chnh lch th tch ca cht chun gia hai giai on, u v cui phn ng. Phng php th tch c s dng rng ri trong phn tch v nhanh chng v n gin. 2. MT VI KHI NIM CHUNG V PHNG PHP PHN TCH TH TCH 2.1. nh ngha 2.1.1. im tng ng S chun t n im tng ng l khi ti im lng cht chun thm vo tng ng ho hc vi lng cht phn tch c trong mu. Th d: Trong s chun natri clorid bng bc nitrat, ngi ta t n im tng ng sau khi thm chnh xc mt mol ion bc cho mi mol ion clorid hin din trong mu. NaCl + AgNO3 AgCl + NaNO3 1 mol 1 mol im tng ng l mt im l thuyt, khng th xc nh bng thc nghim. 2.1.2. im kt thc L thi im gy ra s bin i tnh cht vt l hay s i mu ca cht ch th. Thng c s sai bit v th tch hay khi lng gia im tng ng v im kt thc, ngi ta gi l sai s trong chun . Trong cc phng php th tch, sai s trong chun Et c xc nh: Et = Veq - Vfin Veq: th tch l thuyt ca thuc th cn thit t n im tng ng. Vfin: th tch tht s s dng pht hin im kt thc ca phn ng. 2.1.3. Cht chun ho hc bc mt (s cp) Hp cht c tinh khit rt cao c dng lm cht gc trong cc phng php th tch v phng php khi lng. Tnh chnh xc ca phng php ph thuc vo cch nh gi cht lng ca hp cht ny. Mt cht chun bc mt phi t cc tiu chun sau: tinh khit cao 99,95%
11/25/2010
Page 82 of 239
Tnh n nh trong khng kh. Khng c nc hydrat ho thnh phn cht rn khng thay i khi c s thay i m tng i. C tnh tan tt (thch hp) trong mi trng khi thc hin chun . Khi lng phn t tng i cao hn ch sai s tng i khi cn mu (sai s <0,1%). Trn thc t ch c rt t hp cht t c cc tiu chun trn. Th d: - Kali naphtalat (M = 204,22 g), mui lun lun dng khan, ch cha ti a 0,003% nc. KHCO3 (M = 100,11 g) Acid benzoic C6H5COOH (M = 122,15 g) 2.1.4. Cht chun ho hc bc hai (th cp) Hp cht c tinh khit phi c xc nh bng phn tch ho hc. Th d: - Natri borat ngm 10 phn t nc Na2B4O7.10 H2O (M = 381,24 g). Trc khi pha thnh dung dch chun cn sy sn phm nhit t 170 - 440C trong 1 gi. Acid oxalic ngm 2 phn t nc C2H2O4.2 H2O (M = 252 g). 2.2. Cc dung dch chun Dung dch chun l mt thuc th c nng bit trc c dng chun trong cc phng php phn tch th tch. Cc dung dch chun gi mt vai tr ch yu trong tt c cc phng php chun , v vy cn thit phi kim tra nhng tnh cht cn phi c trong dung dch, cch pha v biu th nng ca cc dung dch ny. 2.2.1. iu kin ca mt dung dch chun Dung dch chun l tng phi t cc tiu chun sau: - bn khng phi xc nh li nng sau khi pha. - Tc dng nhanh vi cht cn phn tch. - Phn ng phi hon ton t c im kt thc ng. 2.2.2. Phng php xc nh nng ca mt dung dch chun Phng php phn tch th tch chnh xc khi nng ca dung dch chun chnh xc. C hai phng php c bn xc nh nng ca dung dch chun. Phng php trc tip: Trong phng php ny, mt lng cn chnh xc cht chun ho hc bc 1 (s cp) c ho tan trong mt dung mi thch hp v pha long trong bnh nh mc n th tch
11/25/2010
Page 83 of 239
chnh xc. Phng php so vi mu chun (etalonnage): dung dch dng lm chun c so bng cch chun vi - mt khi lng cht chun ho hc s cp. - mt khi lng cht chun ho hc th cp. - mt th tch ca mt dung dch chun khc. Phn ln dung dch dng lm chun c xc nh nng bng phng php ny do cc thuc th khng t c tiu chun ca cht chun ho hc s cp. 2.2.3. Cch biu th nng ca cc dung dch chun Nng ca dung dch chun thng c biu th l nng mol v nng ng lng. Nng mol cho bit s mol ca thuc th cha trong mt lt dung dch. Nng ng lng biu th s ng lng gam ca thuc th c trong mt lt dung dch. 2.3. Cc phng php xc nh im tng ng xc nh m tng ng, ngi ta s dng cht ch th ho hc hay ch th l ho. 2.3.1. Cht ch th ho hc Ch th l cht c cho vo dung dch khi tin hnh nh lng. S thay i v pH, th oxy ho kh... s lm thay i mu ca ch th. Cc ch th thng dng trong phng php phn tch th tch: a) Ch th ni: ch th cho vo dung dch khi tin hnh nh lng. Ch th mu: metyl da cam, phenolphtalein. Ch th to ta: kali cromat. Ch th to hunh quang: fluorescein. b) Ch th ngoi: ch th ngoi, dng dng c nh a thu tinh ly dung dch ri cho tc dng vi thuc th nh trng hp dng giy tm h tinh bt. Ch th c th l: Mt cht: metyl. Hai cht: thuc th Tashiri ( metyl v xanh metylen). Nhiu cht: thuc th vn nng. 2.3.2. Ch th l ho o s i mu ca dung dch bng phng php quang ph, phng php in ho nh o in th, o cng dng in hay o d dn in. 3. PHN LOI CC PHNG PHP PHN TCH TH TCH
11/25/2010
Page 84 of 239
Ngi ta thng da trn c s phn ng phn loi cc phng php phn tch th tch. 3.1. Phng php trung ho Phng php dng nh lng cc acid, base v mt s mui trong mi trng l nc hay mi trng khan. Phng php ny da trn s trao i proton H+ Th d: nh lng acid hydrocloric bng natri hydroxyd HCl 3.2. Phng php oxy ho kh Da trn phn ng oxy ho kh tng ng vi s trao i electron gia hai cht: mt cht cho mt hoc nhiu electron, cht th hai nhn electron. Th d: nh lng st III clorid bng dung dch thic 2FeCl3 3.3. Phng php kt ta Cn c trn cc phn ng gia cht cn inh lng vi thuc th to ra hp cht t tan. Th d: phng php bc s dng thuc th bc nitrat nh lng cc halogenid. 3.4. Phng php to phc Da vo phn ng to thnh phc cht. Phng php complexon c s dng ph bin dng nh lng cc ion kim loi nh nh lng calci v magnesi trong nc vi thuc th l EDTA. 4. K THUT CHUN K thut chun trong phng php th tch ni chung rt n gin. K thut thng ch cn o th tch ca cc dung dch vi nhng dng c chnh xc nh pipet, buret, bnh nh mc. Cc dng c km chnh xc nh ng ong ch dng ly th tch thuc th dng iu chnh mi trng phn ng. Cc phng php c dng trong phn tch th tch l phng php trc tip v phng php gin tip. 4.1. Phng php trc tip Cht cn nh lng phn ng vi dung dch chun. 4.1.1. Chun trc tip Phng php chun n gin nht l t buret hiu chnh chnh xc, ngi ta nh tng git dung dch chun B vo mt th tch xc nh dung dch hay mt lng cn xc nh cht A ha tan trong dung mi thch hp. Khi phn ng kt thc, bit lng dung dch chun B dng phn ng vi cht cn nh lng A th c th tnh hm lng ca cht A. + SnCl2 2FeCl2 + SnCl4 + NaOH NaCl + H2O
11/25/2010
Page 85 of 239
Chun trc tip thng dng nh lng mt acid bng mt base hay ngc la. Th d: nh lng HCl bng dung dch chun NaOH vi ch th l phenolphtalein. Dung dch acid hydrocloric c cha trong bnh nn, dung dch natri hydroxyd chun c thm t t tng git bng buret cho n khi phn ng kt thc c nhn bit nh vo s i mu ca ch th. 4.1.2. Chun ngc hay chun tha tr Chun ny p dng trong trng hp khng th thc hin chun trc tip. Ngi ta thm mt th tch chnh xc, d dung dch chun B vo mt th tch xc nh dung dch hoc mt lng cn xc nh A ha tan vo dung mi thch hp. Khi phn ng kt thc, lng d thuc th B khng tham gia phn ng c chun bng dung dch thuc th h tr khc, bit nng chnh xc. Th tch thuc th B trong chun ny khng c t hn 15 20 ml trong phng php a lng. Th d: nh lng Mg2+ bng phng php complexon: Phng php ny c li trong cc trng hp: Khng chn c ch th kim loi thch hp cho ion cn xc nh. Chng hn khng th chun trc tip Co2+, Al3+ vi ch th en eriocrom T c v ch th ny to vi Co2+, Al3+ phc bn vng n ni khng b EDTA ph v. Ion cn xc nh nm trong ta BaSO4, PbSO4... lm phn ng vi EDTA xy ra chm. Cht cn nh lng khng tan. pH mi trng tng k vi phng php trc tip. Minh ha: nh lng Ba2+, ngi ta cho lng chnh xc complexon III c d, nh lng d complexon bng MgCl2 chun.
4.2. Chun gin tip (th) Ngi ta dng phng php ny khi cht cn nh lng khng phn ng vi dung dch chun nn cn c mt cht trung gian. Th d: Dung dch natri thiosulphat l mt cht kh tt c dng chun cc cht oxy ho yu nh iod nhng khng chun c cc cht oxy ho mnh nh KMnO4, K2Cr2O7. V vy trc ht cho K2Cr2O7 tc dng vi thuc th trung gian KI (B1) trong mi trng acid gii phng iod, iod tch ra tng ng nh lng theo t l vi K2Cr2O7. Nu chun iod c gii phng ra [thay cho K2Cr2O7,(A1)] bng dung dch chun chnh Na2S2O3 (B) th c th tnh ra lng K2Cr2O7 (A).
11/25/2010
Page 86 of 239
5. DNG C DNG TRONG CHUN BNG PHNG PHP TH TCH 5.1. Dng c cha Bnh nn, becher dng ng mu. 5.2. Dng c khc ng ong. Pipet khc . Dng ly mt th tch dung dch gn ng. 5.3. Dng c chnh xc Pipet chnh xc mt vch, pipet hai vch, phn phi mt th tch dung dch chnh xc c nh. Buret dng ong mt th tch chnh xc thay i. Bnh nh mc dng pha mt dung dch c th tch chnh xc, thng dng pha dung dch chun, pha long dung dch. Th tch cht lng trong bnh c biu din bng mililt. Trn bnh c ghi dung tch v nhit (thng l 20C). Cc bnh nh mc thng c dung tch khc nhau t 25 2000 ml. Dng c chnh xc bng thu tinh c chia thnh 2 loi: Loi A: Loi B: Sai s trong o lng thng nh hn 2%. Nhng dng c ny ch dng trong pha ch m thi. Th d 1: - Pipet chnh xc loi A 20 ml c dung sai 0,02ml c ngha l pipet c th phn phi mt th tch l 19,980 ml < th tch phn phi theo l thuyt < 20,020ml. Nh vy dung sai s l
Pipet chnh xc loi B 20 ml c dung sai 0,04 ml 0,2% Bnh nh mc 100 ml loi A c dung sai l 0,1 ml 0,1%
11/25/2010
Page 87 of 239
Hnh 6.1. Mt s dng c s dng trong chun th tch
5.3.1. Dung sai ca mt s dng c loi A, B

Dng c Th tch (ml) 1 Pipet chnh xc 2 5 10 25 Buret 50 10 Bnh nh mc 50 100 Loi A 0,006 0,006 0,01 0,02 0,03 0,05 0,02 0,05 0,08 0,04 0,10 0,16 Loi B
6. CCH TNH KT QU
11/25/2010
Page 88 of 239
tnh c kt qu trong phng php phn tch th tch cn phi bit th tch v nng ca cht chun. 6.1. Tnh kt qu trng hp dng nng ng lng i vi nng ng lng, ngi ta kt thc chun ti ln cn im tng ng, s ng lng (hay mili ng lng) thuc th bng s ng lng (hay mili ng lng) ca cht cn xc nh. Ly VB ml dung dch cht B (cht chun) c nng xc nh NB dng chun ti im kt thc ht VA ml cht cn nh lng c nng NA. tnh nng ca cht A, p dng quy tc: ti im tng ng, tch cc th tch (ml) ca cc dung dch cht phn ng vi nng nguyn chun ca chng th bng nhau: VANA = VBNB Nng cht A c suy ra t cng thc:
Th d:
Dung dch acid hydrocloric c chun ho bng dung dch natri hydroxyd chun. Nu trung ha 25 ml dung dch HCl ngi ta s dng 32,20 ml dung dch NaOH 0,0950N. Tnh nng ng lng ca HCl. T nng c xc nh, tnh c: - Hm lng gam /lt Pg/l = NA EA EA: ng lng gam ca cht cn nh lng. NA: nng ca cht A. Hm lng tnh theo phn trm C%:
mgA: khi lng ca A tnh bng mg. T KHA - Phn tch th tch - im tng ng - Dung dch chun - Cht ch th
11/25/2010
Page 89 of 239
- im kt thc - Cht chun CU HI LNG GI
- K thut chun - Dng c chnh xc
1. Trnh by nguyn tc ca phng php phn tch th tch. 2. Phn bit: - im tng ng v im kt thc. - Cht chun bc mt v bc hai. 3. Nu th d minh ha cc k thut chun . 4. Vit cng thc tnh kt qu trong phng php phn tch th tch. CU HI TRC NGHIM 1. Phng php phn tch th tch l phng php da trn vic xc nh a) khi lng ca cht chun khi phn ng vi cht phn tch. b) th tch cht chun. c) lng cht chun bc 1. d) lng cht chun bc 2. e) th tch cht chun bc 1. 2. Phng php phn tch th tch c s dng rng ri v a) t tn thi gian, t tn km, k thut n gin. b) t tn thi gian, t tn km, k thut n gin, chnh xc. c) nhanh, tin li, chnh xc v c th t ng ho. d) tin li, k thut n gin, t tn km v c th t ng ho. e) nhanh, tin li, chnh xc v t tn km. 3. Vic chun c thc hin bng cch thm............ vo dung dch phn tch cho n khi phn ng xy ra hon ton. a) dung dch chun b) cht chun bc 1 c) cht chun bc 2 d) thuc th e) cht ch th 4. c im ca mt dung dch chun: a) bn, c cng thc xc nh. b) khng b ht m, khi lng phn t kh ln.
11/25/2010
Page 90 of 239
c) c nng xc nh. d) bn, phn ng nhanh, hon ton v phn ng chn lc i vi mu. e) bn, phn ng nhanh, hon ton, phn ng chn lc v c nng xc nh, t tn thi gian, t tn km, k thut n gin.
Chng 7 PHNG PHP ACID BASE

MC TIU - Nu c cc khi nim v acid base theo cc thuyt Lewis, Bronsted. - Trnh by c phn ng acid base xy ra trong cc dung mi c proton hot ng. - S dng c cc cng thc tnh pH ca cc dung dch c tnh acid -base. - Trnh by c ngha ca phng php chun trung ho v bit cch chn cc ch th mu. - Nu nh ngha, thnh phn, c ch v mc ch s dng dung dch m. - Vn dng cc kin thc gii thch phn ng acid - base trong mi trng khan v mi trng c nc. - ng dng phng php acid base nh lng cc hot cht c trong dc phm.
NI DUNG 1. MT S KHI NIM C BN - Theo Lewis: acid l cht c kh nng nhn i electron cn base l cht c kh nng nhng i electron t do. - Theo Bronsted: acid l cht c kh nng cho H+ v base l cht c kh nng nhn H+.
Gio trnh ny c vit theo thuyt acid base ca Bronsted 1.1. Thuyt BRONSTED
11/25/2010
Page 91 of 239
Acid l cht cho proton Base l cht nhn proton
HA B + H+
A + H+ HB+
(7.1) (7.2)
Theo (7.1), nu phn ng theo chiu t tri sang phi th HA l acid (cho H+) v nu theo chiu ngc li th A- l base (nhn H+). Tng t, theo (7.2) th B l cht nhn H+: base v HB+ l cht cho H+: acid. Trong (7.1) HA / A- to thnh 1 cp acid base lin hp v trong (7.2) l cp BH+ / B. Vit gp (7.1) v (7.2) li thnh: HA acid 1 + B base 2 HB+ acid 2 + A base1
1.2. Kt qu ca thuyt BRONSTED a) Tng qut ho khi nim acid base: khng xem acid hay base l nhng cht hin din ring r nhng l 1 cp acid base lin hp v nu c acid l c base. Th d : HCl Cl + H+ (acid hydrocloric HCl lin hp vi base clorid Cl-) NH4+ (base amoniac NH3 lin hp vi acid amonium NH4+)
NH3 + H+
b) M rng khi nim: acid v base c th l phn t m cng c th l ion
2. PHN NG ACID BASE / DUNG MI C H+ HOT NG Dung mi c proton hot ng l dung mi c tnh acid hay base v c th tc ng ln cc cht tan acid hay base c trong dung dch. 2.1. Phn ng ca acid-base vi dung mi (thuyt Bronsted) Khi dung mi c proton hot ng th n s nh hng n cht tan v lc y dung mi s ng vai tr ca mt acid hay 1 base. Th d: Dung mi nc c th hoc l 1 acid hoc l 1 base. Nu nc l 1 acid hay nc l base H2O H2O + H+ OH + H+ H3O+ (ion hydroxonium) HCONH + H+
Tng t, nu dung mi l formamid hay cn: Nu formamid l acid hay formamid l base HCONH2 HCONH2 + H+
11/25/2010
Page 92 of 239
Nu cn l acid hay cn l base
ROH ROH + H+
RO + H+
Nhng H+ khng bao gi hin hu trng thi t do m phi c 1 cp cho v 1 cp nhn. Th d: HF + H2O F + H3O+
(HF v H3O: cho H+, H2O v F: nhn H+) + acid 1 H2O base 2 NH3 base 1 + H3O+ acid 2
(NH4+ v H3O+: cho H+, H2O v NH3: nhn H+) 2.2. S phn ly ca dung mi SH: K hiu ca dung mi c H+ hot ng (S: solvent) Do c th cho hoc nhn proton m dung mi khi l acid khi l base. SH + acid 1 SH base 2 S+ base 1 SH2+ acid 2 (7.3)
SH / S- : cp acid v base lin hp: Th d : Theo (7.3): 2 H2O H3O+ + OH- (H2O / OH-) (7.4)
Thc t [SH] hoc [H2O] c xem nh l mt hng s v c rt t phn t chu s phn ly. Th d: Trong 1 lt nc c 107 phn t gam (hoc 1,8 g nc) b phn ly thnh 100 g H+ (dng H3O+) v 1,7 g OH. V dung mi t phn ly nn nng dung mi coi nh khng thay i v t (7.4) ngi ta c th vit: (7.5) Hng s Ki ny l tch nng ion b phn ly ca dung mi: hng s ion ho ca dung mi c th nh hoc ln hn hng s ion ho ca nc. Th d:
11/25/2010
Page 93 of 239
Ch - Thay v vit [H3O+] ngi ta vit [H+]. - Khi dung mi nc tinh khit th [H3O+] = [OH-] = - Khi mt dung mi bt k tinh khit th [S-] = - Ki thay i theo nhit .
B ng 7.1. Hng s ion ho ca nc nhit khc nhau Nhit 18oC 23oC Knc 0,62 1014 1,00 1014 [H+] 0,79 107 1,00 107 Nhit 25oC 100oC Knc 1,2 1014 58 1014 [H+] 1,1 107 7,6 107
2.3. Lc ca acid hoc base trong dung mi c H+ hot ng - Trng hp 1 acid HA + SH A + [ ]
acid + dung mi
base +
proton c solvat ho (7.6)
pKa = - lgKa; pKa l hng s phn ly ni ln lc acid hoc base ca mt cht. Kt qu: tnh acid ca cht tan cng mnh th cng d phng thch H+, [SH2+] cng ln, Ka cng ln v pKa cng nh. Lc ca base lin hp A cng yu khi acid cng mnh. Hng s pKa dng xc nh lc ca cp acid base - Trng hp 1 base B Base 1 V + SH dung mi acid BH+ acid 1 + Sbase t dung mi (7.7)
11/25/2010
Page 94 of 239
Theo (7.5) c v theo (7.6) :
Do , Kb lin quan vi Ka bng h thc trn nn khi cp n lc ca acid base s ch ni n Ka v khng bn n Kb. 2.4. D on phn ng
Xt pK ca 2 cp acid - base
Th d: Acid acetic tc ng trn amoniac trong dung mi l nc. Cp acid acetic / acetat: pKa = 4,74 v cp ion amoni / amoniac: pKa = 9,2. Phn ng xy ra : CH3COOH + NH3 CH3COO- + (7.8)
Trong nc, acid acetic b phn ly v amoniac cng b phn ly theo phn ng cn bng c hng s: (7.9) (7.10) Hng s ca phn ng gia amoniac v acid acetic trong nc d dng tnh v
Kt qu: phn ng (7.8) cng dch chuyn v pha phi th l cng ln.
cng ln hay
cng nh, ngha
2.5. Biu thc bng s ca
11/25/2010
Page 95 of 239
Khi nim pH ca Henderson -Hasselbalch
Trong thc t, thay v s dng [H+] ca dung mi (*), ngi ta s dng lg[H+] = pH gi l th hydrogen ca dung mi hay l pH. (7.11) Khi nim pH c Henderson Hasselbalch cp khi thc hin ch trong dung mi nc s c tng qut ho cho mi dung mi min l dung mi ny phn ly ging nh nc. nh lut tc ng v khi lng din t theo hot ch khng phi theo nng v pH tng ng vi hot ca H+ trong dung mi. 2.5.1. Thay i pH theo acid hay theo base Hng s ion ho c tun theo trong dung mi tinh khit v trong cc dung dch: - Nu nc tinh khit, mt phn t dung mi khi phn ly phng thch 1 H+ v 1 OH . - [H+] = [OH-] = 10 7, do vy pH ca nc tinh khit l 7. - Nu trong nc c acid th s c H+ chuyn t acid vo nc ngha l c xut hin nhng ion H3O+ ph. Do vy [H3O+] hay [H+] > 10-7 v pH < 7, nng acid cng ln th pH cng nh. - Ngc li, khi cho 1 base vo nc, base ny b phn ly to OH- v v Knc = [H+] [OH-] nn [OH-] tng th [H+] phi gim. Do vy [H+] < 10-7 v pH > 7. 1.1.1. ng cong pH
Hnh 7.1. pH theo s pha long dung dch HCl (3 < pH < 7)
Hnh 7.2. pH bin thin theo s pha long dung dch HCl (0 < pH < 7)
Cc ng cong ny minh ha s bin i pH theo [H+] ca mi trng tnh bng ion cho php hiu rng : - Khi pH thay i 1 n v th [H+] thay i 10 ln (hnh 7.1). - vng pH nh (khong 0 - 2), [H+] thay i nhiu m pH thay i khng ng k. Ngc li khi tin gn n s trung ho, [H+] chnh lch t cng lm pH thay i nhiu (hnh 7.2).
11/25/2010
Page 96 of 239
2.5.3. Thay i pH theo nhit

B ng 7.2. Bin i gi tr pH ca nc theo nhit Nhit (oC) pH 0 7,45 15 7,12 23 7,00 30 6,86 37 6,65
Ch : bin i ny rt quan trng nht l trong lnh vc sinh hc. Gi tr pH bnh thng ca mu o c 37oC: 7,35 < pH < 7,45. Do vy, khi o phi k n sai s khi thay i nhit . 2.6. Yu t bn ngoi nh hng n tnh acid v tnh base 2.6.1. Pht hin tnh acid v xc nh lc acid ca cht tan Ho acid HA vo dung mi no c H+ hot ng. Nu dung mi c kh nng nhn H+ ca acid cng cao th cng d pht hin c lc acid ca cht tan HA. Th d: HCl yu trong dung mi acid acetic nhng HCl mnh trong pyridin v pyridin c kh nng nhn H+ t HCl cao hn kh nng nhn H+ ca acid acetic.
Nh vy, dung mi c kh nng nhn H+ cng cao (c tnh base) th cn bng ca 2 phng trnh trn cng dch sang phi : Ka cng ln pKa cng nh acid cng mnh. Trong cc dung mi c tnh acid th lc ca cc cht ho tan l base yu s tng ln v nhiu base yu li tr thnh base mnh (gii thch tng t cho dung mi c tnh base). Th d: Acid formic l dung mi t c tnh base hn nc v l acid nn kh nng nhn H+ yu, kh pht hin tnh acid HCl trong acid formic l 1 acid yu. Ngc li formamid c tnh base nhiu hn nc - v l base nn pht hin tnh acid tt hn. V vy acid acetic yu trong nc li c coi nh l 1 acid mnh trong formamid. 2.6.2. Pht hin tnh base v xc nh lc base ca cht tan Mt dung mi cho H+ l v kh nng nhn H+ ca n yu hn kh nng nhn H+ ca base ho tan. S khc bit kh nng nhn H+ ca dung mi v cht tan base cng ln th tnh cht base ca cht tan cng cao. Th d: Amin, alcaloid c coi nh l base mnh trong acid formic (hoc trong acid acetic khan) nhng l base yu trong nc. Ur coi nh l base mnh trong acid chloracetic v yu trong acid acetic v acid chloracetic c kh nng nhn H+ thp hn kh nng nhn H+ ca acid acetic.
11/25/2010
Page 97 of 239
2.6.3. Tnh tng i ca khi nim acid-base Mt cht c th l 1 acid hay base ty theo dung mi m n c ho tan: trong dung mi c kh nng nhn H+ mnh th cht tan nhng proton v c coi l acid. Ngc li, trong dung mi acid (cho proton) th cht tan c th nhn proton v c coi l base. - Th d 1: Alcaloid l mt base yu khi ho vo nc nhng li l base mnh khi ho vo acid acetic khan.
Hnh 7.3. Thang biu din kh nng cho v nhn H+ca mt s dung mi
- Th d 2: HCl lun lun l 1 acid trong dung mi acid formic (HCOOH) v kh nng cho H+ ln hn ca dung mi nhng nc trong acid formic lun lun l 1 base v nc nhn H+ ca dung mi.
Hnh 7.4. Tnh acid ca HCl v nc trong dung mi HCOOH
Th d 3: Khi dung mi l amoniac th nc li l 1 acid
Hnh 7.5. Tnh acid ca HCl v nc trong dung mi NH3
Nh vy: - Dung mi nhn H+ mnh nht (c tnh base mnh) th cc cht tan s l acid. - Dung mi cho H+ tt nht (c tnh acid mnh) th cc cht kho st s l base. 2.7. Lin quan gia pH v pKa 2.7.1. Cng thc tng qut: theo (7.11)
y l cng thc c th dng trong mi tnh hung. Nhng trong nhiu trng hp ngi ta c th dng cc cng thc gn ng, nht l tnh pH ca dung dch acid hay base bit c pKa. 2.7.2. Cng thc gn ng tnh gi tr pH
11/25/2010
Page 98 of 239
Cc cng thc ny ch c gi tr i vi nhng cht phn ly H+ yu trong dung mi phn ly kho st. t cc k hiu: HA: acid mnh; B: base mnh; Ha: acid yu; b: base yu.
pH ca 1 acid yu
Cho 1 acid yu Ha, nng ban u l c trong dung mi nc: Acid phn ly tng phn theo phng trnh: Ha Hng s ion ho ca phng trnh trn l (7.12) Nc ion ho theo phng trnh: H2O H+ + OH H+ + a
m [H+][OH] = Ka = 10-14. Vy c hai cn bng sau : c = [Ha] + [a] (7.13) (7.14) - Theo (7.13): trong nhng phn t Ha cho vo u tin c cc phn t khng phn ly: nng l [Ha]; 1 s phn t khc b phn ly cho a: nng l [a-]. - Theo (7.14): H+ l ca: Hoc nhng phn t nc b phn ly ( Hoc nhng phn t acid b phn ly ([H+]Ha) C 2 c lng sau: - Ha xem nh l acid yu (ngha l km phn ly) s phn t b phn ly c th b qua so vi s phn t khng phn ly. Nh vy, c th b [a-] trong (7.13) v vit: c = [Ha] + [a-] [Ha] - S H+ do nc phn ly xem nh c th b qua so vi s H+ trong (7.14) do acid phn ly (gi s acid khng qu yu). Do vy, c th b so vi [H+]Ha v vit: )
(do mi phn t Ha b phn ly gii phng a- ng thi vi H+). Kt qu: (7.12) c vit :
Vit theo khi nim p:
pH = 1/2pKa 1/2lg c
pH ca mui ca acid mnh v base yu
11/25/2010
Page 99 of 239
Mt acid mnh phn ng vi base yu to nn mt mui: HA + b bH+A (7.15)
A l base lin hp vi acid mnh HA nn c lc coi nh b b qua, coi nh l bng khng. Nh vy base ny khng phn ng c vi bH+ v phng trnh (7.15) khng cn bng. Mui bH+A khi cho vo dung mi phn ly c th xem nh b phn ly hon ton. bH+ A bH+ + A Trong dung dch lc ny cn acid bH+ c lc tht s (nhng cng ch l mt acid yu do lin hp vi 1 base yu) c nng c (tnh bng mol/l) ca mui v 1 base A (c lc = 0). Nh vy ch l dung dch acid yu v c tnh theo cng thc tnh pH ca dung dch acid yu: pH = 1/2pKa 1/2lg c
pH ca mt base yu
Khi p dng cho 1 dung dch nc ca base b (nng u = c) c th suy lun ging nh trng hp pH ca 1 acid yu. Phng trnh din t s phn ly ca base v nc: b + H2O bH+ OH + bH+ ; H2O H+ + OH
b + H+ v hng s ion ho
; Knc = [H+][OH ] = 10-14.
Ngi ta c :
tnh gn ng, ngi ta c : c = [b] + [bH+] [b] Biu thc Ka :
pH ca mui ca mt acid yu v base mnh

Mui ny to thnh theo phn ng: Ha + B BH+ + a Ging nh mi trng hp khc, khi ho tan hon ton mui ny b phn ly thnh BH+ v a. BH+ l acid lin hp vi 1 base mnh B nn coi nh acid c lc b qua. Base a lin hp vi mt acid yu Ha c coi nh 1 base c lc tht s (cng ch l mt base yu), trong dung dch ch c mi base a l c lc tht s.
11/25/2010
Page 100 of 239
Dung dch base a- th hin l base yu pH > 7 rt r rng. Nh vy ch l dung dch base yu v tnh theo pH ca dung dch base yu:
Th d : dung dch mui kali carbonat, natri borat. Ch : Dung mi H2O b thy phn thnh OH v H+, H+ s phn ng vi a- to Ha ngha l ac phn t ho (molarisation) tr li bi H+ ca dung mi. a + H2O Ha + OH
pH ca mui ca acid yu v base yu

Mui ny phn ly hon ton trong dung dch ging vi trng hp trc: b + Ha bHa bH+ + a bH+ (lin hp vi base yu b ban u) l acid c lc tht s d ch l acid yu. a- (lin hp vi Ha ban u) l base c lc tht s d ch l base yu. Nh vy lc ny dung dch cha ng thi mt acid yu v mt base yu v cc cht ny phn ng vi dung mi nh sau:
Hng s ion ho ca dung mi Ki = [SH+2 ] [S] c tun theo. Hai hng s Ka v khng c lp v nng [H+] tm thy trong c hai phng trnh. V do vy c th lin kt thnh mt biu thc duy nht: (7.16) Nu mui trong dung dch c nng c th : c = [bH+] + [b] c = [a] + [Ha] y cn minh ha mt c lng ph nh sau: Gi s acid bH+ v base a- b phn ly theo t l rt gn, th [b] [Ha] v iu kin ny: [bH+] = c [b] v [a-] = c [Ha]. Do vy [bH+] [a-].
11/25/2010
Page 101 of 239
Phng trnh (7.16) c n gin ho : KaKbH+ =[H+]2 hay
2.7.3. Kt qu thc nghim ca kho st lin quan gia pH v pK - S dch chuyn tng h gia acid v base: mt acid mnh ui mt acid yu t mui ca n v mt base mnh ui mt base yu ra khi mui ca n. Th d: HCl + C6H5COONa C6H5COOH + NaCl NaOH + NH4Cl NH3 + H2O + NaCl Hin tng ny c m t nh sau: mui b phn ly hon ton trong dung dch v cc ion c phng thch phi tha mn c nhng cn bng lin quan n hoc acid hoc base yu tng ng. Th d: Mui BH+a- b phn ly thnh B + Ha v Ha b phn ly thnh H+ + a- th gi tr ca hng s ion ho Ka phi tun theo
Khi thm 1 acid mnh HA, acid ny b phn ly hon ton s lm tng [H+] v gi nguyn Ka c l do a- ca mui b phn ly s kt hp vi H+ ca acid mnh HA to nn phn t Ha. Nh vy iu ny s a tr li s li ion ho (reculisation) acid Ha. 2.8. Nhng cht lng tnh / dung mi phn ly 2.8.1. nh ngha Cht lng tnh (ampholyte = amphotre) l cht cng lc c th coi nh va l 1 acid va l 1 base, th d nh nc. Ngoi ra cng cn nhiu kiu cht lng tnh khc nh: - Cc anion c H+ (l dn cht ca polyacid): carbonat acid - Cc hydroxyd kim loi: Zn(OH)2, Al(OH)3. - Cc phn t hu c mang cng lc nhng nhm cho H+: COOH, SO3H, phenol v nhng nhm nhn H+: amin. Nhng cht c bit nhiu nht l cc amino acid NH2CHRCOOH m tm quan trng sinh hc rt ln. Cht n gin nht l acid aminoacetic hay glycin. Ngoi ra cng cn nhiu phn t nh acid paraaminobenzoic v nhng dn xut sulfonic nh taurin (NH2CH2CH2SO3H) s dng nhiu trong ngnh Dc. 2.8.2. Tnh cht ca cht lng tnh , phosphat v .
11/25/2010
Page 102 of 239
Mt cht lng tnh c th c xc nh bng 2 hng s Ka1 v Ka2 tng ng vi tnh cht acid v tnh cht base. nh du s lin quan ca 2 tnh cht ny, cht lng tnh c tng trng bi HAB (HAB vit hoa khng biu th g v lc acid hay lc base).
Tnh acid ca cht lng tnh
Ngi ta nh ngha hng s
ca HAB nh sau:
Th d: Glycine NH2 CH2 COOH (tnh acid) c th phn ng vi nc theo: NH2 CH2 COOH + H2O NH2 CH2 COO + H3O+ (7.17) Tnh base ca cht lng tnh Cht lng tnh HAB phn ng vi dung mi theo phng trnh: HAB + SH S + HABH+
Vy, cp acid v base HABH+ / HAB c hng s Ka2 l: (7.18) Ly li th d ca glycine (tnh base) c th tc ng vi nc theo: NH2CH2COOH + H2O NH3+CH2COOH+OH
Ch : Trong trng hp ca nhiu mui, hng s Ka2 c xc nh ging vi hng s
Lin quan gia hai tnh cht

Ging nh trng hp 1 mui ca acid yu v base yu, tnh cht acid v base cng c mt trong cng mt dung dch v khng kho st chng mt cch c lp. Xt mt hng s mi l hng s ca hai hng s trc:
Sau khi n gin ho, phng trnh tr thnh:
11/25/2010
Page 103 of 239
(7.19) (7.20) a) pH ng in (pHi) L pH m dung dch cha [HABH+ ]= [BA-]. Gi tr pH ny d suy ra t phng trnh (7.20) v khi phn t th hai trit tiu th
Khi nu pH < pHi, ion HABH+ chim u th v theo (3.7.a) nu pH gim th [H+] tng v lc [BA-] phi gim v [HABH+] tng. Ngc li, pH> pHi th ion BA- chim nhiu hn. Ch : cng thc tnh pH dnh cho pH ng in ging vi cng thc tnh pH gn ng cho dung dch mui ca mt acid yu v base yu v pHi th dung dch cha cng nng acid v base (ging nh trng hp ca mt mui bH+a-). b) Amphion
L nhng cht lng tnh c hai nhm chc kiu acid amin. pH ng in, dung dch ch yu khng nhng cha cc dng NH3+CH2COOH v NH2CH2COO- m cn cha nhng ion ng thi mang in tch dng v in tch m: NH3+CH2COO-. Ion ny gi l amphion hay zwitterion. c) pH ca dung dch lng tnh Theo phng trnh (7.11) pH ph thuc vo nng ca mi mt trong hai ion acid v base. Do vy lut trung ho in tch chng t rng d phn ng phn ly sn sinh mt hay nhiu cht in ly, phn ng vn trung ho in. Biu thc tng qut l: in tch m = in tch dng Trong tt c anion v cation b phng thch u can thip vo. Trong trng hp hin ti, t nhng phng trnh: HAB HAB + + SH SH SH2+ S + BA (dung mi l base) (dung mi l acid)
+ HABH+
11/25/2010
Page 104 of 239
c th vit: hoc:
[HABH+] + [ SH2+] = [ S] + [BA] [BA] = [HABH+] + [ SH2+] [ S] S- + SH2+
(lut trung ho in tch) (7.21)
Nng [SH2+] v [S-] khng qu quan trng v phi tun theo cn bng tng i ca dung mi v hng s ion ho ca dung mi Ki : 2SH Mt cht lng tnh c tnh cht acid hoc base nhiu hay t hn do ph thuc vo pH ca dung dch s tm thy mt gi tr gn vi .
Th d: trong nc pH ny thng l 7 3 tng ng vi gi tr: khi pH = 4 th [H3O+] = 10-4 v [OH-] = 1010 khi pH = 10 th [H3O+] = 10-10 v [OH-] = 104 Nng [BA-] v [HABH+] thng > 10-4 v < 10-10. Trong (7.21) c th b qua hiu s ca [SH2+] - [S-] v vit [BA-] [HABH+] Nh vy, pH ca dung dch l: pH= 1/2 pKa1 + 1/2pKa2 = pHi Trong thc t, cng thc ny ch ng trong phm vi hp ca cc acid amin. 3. S TRUNG HO ACID - BASE 3.1. nh ngha S trung ho l mt thao tc c bn trong phn tch nh lng xc nh nng ca dung dch acid hay base. Khi X ml dung dch acid c trung ho bng Y ml dung dch base v khi bit nng chnh xc ca mt trong hai dung dch th d dng suy ra nng ca cht cn li. im tng ng c nh gi bng cch quan st s bin i nng acid hay base khi tin gn n s trung ho. 3.2. Phng php nh gi im tng ng C hai kh nng nh gi, ch yu l dng ch th mang mu v ch th in th. 3.2.1. Ch th mang mu Ch th mang mu l cht cho vo dung dch d dng nhn bit c im kt thc ca phn ng khi thy s thay i mu. Theo Kolthoff (1926): Ch th pH l nhng acid hay base yu m dng ion ca n c cu trc v mu sc khc bit vi dng khng b ion ho. Thun li: Khi thm mt lng nh ca cht ch th ny vo dung dch c nh lng th mu ca ch th bin i tc th gia hai gi tr pH no . Th d: Phtaleine ch c mt cu trc phn t nn khng mu trong mi trng acid (hnh 7.6), cn trong mi trng kim (pH = 8,3 - 10) n c nhiu dng ng phn di dng ion nn xut hin mu (hnh 7.7).
11/25/2010
Page 105 of 239
Hnh 7.6. Dng lacton khng mu trong mi trng trung tnh hay acid (a)
Hnh 7.7. Dng quinon ca phtalein c mu trong mi trng kim (b,c,d)
Hnh 7.8. Dng phenat ca phtaleine khng mu c th thy c trong mi trng qu kim.
Nhng cht c s dng lm ch th u tin l nhng cht mu thc vt nh cc anthocyan. Hin nay c nhiu ch th mu tng hp. 3.2.2. C ch i mu ca ch th Cu trc electron ca mt hp cht hu c c th thay i bng cch thm hay mt i mt H+ hay mt nhm OH : Qua th d trn, c th khng nh rng nhng ch th ny ch yu l nhng h thng cho hay nhn H+. Nhng ch th theo pH trong dy sau (bng 7.3) cho nhng dng ng phn quang hc (vng thm). Quan trng nht l: - Phtalein: phenolphtalein, thymolphtalein - Sulfon phtalein: thymol sulfon phtalein, phenol sulfon phtalein, bromophenol sulfon phtalein. (hnh 7.9). - Cc azoic nh Helianthin. (hnh 7.10).
Hnh 7.9. Sulfon phtalein
11/25/2010
Page 106 of 239
Hnh 7.10. Cc azoic
Trong mi trng acid: dung dch azoic c mu v hai dng ng phn c c do proton ho nit amin. Trong mi trng kim: dung dch azoic c mu vng v cn c mt lot nhng ni i lin hp nhng c nhiu kh nng hy ti ch nhng ni i ny. - Dn cht anthraquinon (alizarin sulfonat Natri). Nitrophenol (hnh 7.11).
Hnh 7.11. Nitrophenol mu vng trong mi trng acid v trong kim
Thng thng, c th s dng th mu sc hay chuyn i thun nghch. 3.2.3. Vng chuyn mu ca ch th mu trong mi trng nc mt pH nht nh, khng c ch th mang mu no thay i mu t ngt. S thay i ny xy ra gia 2 pH xc nh vng chuyn mu hay khong i mu.
B ng 7.3. pH v vng chuyn mu ca mt vi ch th Tn ch th mu Xanh thymol Xanh bromophenol Methyldacam (Helianthin) Xanh (l) bromocresol methyl Tm bromocresol Xanh bromothymol phenol cresol Xanh thymol Cresolphtalein Phenolphtalein Mu vng vng vng vng vng vng vng khng mu khng mu Mu vng xanh vng xanh vng tm xanh xanh pH ca vng chuyn mu 1,2 3,0 3,1 3,8 4,4 5,2 6,0 6,8 7,0 8,0 8,2 8,3 2,8 4,6 4,4 5,4 6,0 6,8 7,6 8,0 8,8 9,6 9.8 10
Nu gi ch th mang mu dng acid l IA, ch th dng base l IB, th : H2O + IA IB + H3O+ v i IA= HIB
11/25/2010
Page 107 of 239
hoc pH = pKa +
khi [IB ] = [IA] ; pH= pKA
Khi pH= pKA th mu sc ca cht ch th c phn chia gia hai dng, lc mu sc ca n nhy nht. D cho pH l bao nhiu, cng c th vit: Nu pH = (pKA + 1) th = 1 v = 10 = pH pKa
[IB ] = 10 [IA]. Lc ny trong thc t mu ca dung dch l mu ca dng base. Nu pH = (pKA 1) th [IB ] = = 1 v = 0,1
[IA]. Lc ny trong thc t, mu ca dung dch l mu ca dng acid.
Do vy: gii hn ca vng chuyn mu ca ch th khong: pH = pKa 1. Nu dng ch th cho chun m vng i mu khng nm trong vng thay i t ngt ca pH th s dn n sai s v kh nhn bit. 3.2.4. Chn ch th mu trong phng php - acid base Th d: khi trung ho HCl 1N bi NaOH 1N th lc ti im tng ng vng pH thay i t ngt rt rng, pH t 3 11. Do c th la chn mt s cht ch th nh sau: Ch th - Helianthin - Giy qu - Phenolphtalein pH ca vng chuyn mu 3,1 4,4 gn vng trung tnh t 8,3 10
Nu trung ho mt base yu bng mt acid mnh hay trung ho mt base mnh bi mt acid yu th khong pH thay i t ngt s b gim i.
Ch :
- Khi nh lng, nu khong pH chuyn mu ca ch th cng nh th s chuyn mu cng r, khong ny thng l hai n v pH. - Ngc li trong trng hp o mu theo pH: nu s chuyn mu cng tri ra mt vng pH ln th php o cng d thc hin. Th d: xanh bromothymol chuyn mu vng pH = 5.8; vng lc pH = 6.2; xanh l pH = 7; xanh dng pH = 8.
11/25/2010
Page 108 of 239
a) Ch th c th s dng trong nhng vng pH qu cao hay qu thp Cc loi ch th ny cho php thc hin khi nng acid hay base ln. Ch yu lin quan n cc php phn tch nh lng. Th d: mi trng acid c nng hoc pH khc nhau tm tinh th s c mu khc nhau: trong dung dch acid mnh 5N acid 2N acid 0,3N 0,5N tm tinh th c mu vng xanh l dng lc trong dung dch pH = 1 pH = 2 tm tinh th c mu xanh dng tm
Ngc li trong mi trng rt kim pH = 12, tropeoline chuyn mu vng gch. b) Ch th hn hp Nguyn tc: khi thm vo mt mu h tr s lm thay i s chuyn mu ca ch th chnh. Th d:
Ch th Tashiri
- Dung dch A: -Xanh methylen 1% / EtOH - methylen 1% /EtOH 25ml 100ml (mu h tr)
- iu ch ch th Tashiri: dung dch A: 100 ml; EtOH: 100 ml; nc: 200 ml. Thm NaOH long n khi mt mu ; pH t 5,45 5,50 mu hng xanh l. Ch th ny thch hp nh lng amoniac.
Ch th hn hp hai phtalein
- Phenolphtalein 1% / EtOH 50% 20 ml 10 ml - Naphtolphtalein 1% / EtOH 50%
pH t 9,6 9,7, mu t hng tm. Ch th ny thch hp nh lng chc acid th hai ca acid phosphoric. 3.2.5. Nng ch th mu c s dng
Ty theo ch th ch c mt dng c mu (phtalein) hay 2 dng c mu (helianthin).
Trng hp ch th c mt nhm mang mu (monochrom)

Th d: phenolphtalein [IB ] mu v [IA] khng mu. [IB ] = [IA]
pH cho: nu nng ca ch th dng khng mu [IA] cng ln th khi thay i pH, s
11/25/2010
Page 109 of 239
chuyn mu ca ch th cng d thy u im: c th cho 1 lng tng i ln cht ch th. Thng thng ch dng dung dch ch th 23% (khong 10 mg) trnh trng hp cht ch th c th tiu th nhiu thuc th chun . Trng hp ch th c nhiu nhm mang mu (polychrom) Th d: helianthin [IA] mu v [IB ] mu vng. 1 pH xc nh, thnh phn ca hai dng mu ny khng i. Do vy khi cho 1 lng tha cht ch th cng s khng lm bin i t l v li cng kh thy chuyn mu nn khng c li.
Trong thc hnh, thng thm 1 git dung dch 2% (khong 0,1 mg v l 100 ln t hn trng hp thm phenolphtalein). 3.3. Trung ho mt acid mnh HA bng base mnh B 3.3.1. Bin i pH (S bin thin ca pH trong qu trnh chun ) S trung ho dung dch HCl bng dung dch NaOH vi cng th tch, cng nng cho thy s bin i nh sau: - Lc bt u : dung dch ch c acid HA. Gi c l nng ca dung dch acid HA b phn ly hon ton th [H+] = c hoc pH = .
- Trong lc chun : hn hp lc ny gm mt dung dch acid HA cha b trung ho v mui BHA do acid b trung ho. V mui BHA c pH ging pH ca nc tinh khit nn hn hp ny cui cng c th xem nh l mt dung dch acid HA c nng gim dn. pH c tnh theo th tch ca dung dch acid cn li. - Ti im tng ng: hn hp c c l dung dch ca mui BHA, pH = 7. 3.3.2. Th d c th (trung ho bng dung dch chun N) Trung ho 100 ml HCl 1N bng NaOH 1N. Kho st s bin i v tnh [H+], pH trong c hai trng hp khng k s pha long v c k s pha long.
Hnh 7.12. Bc nhy pH
Hnh 7.13. Trung ho acid mnh (0,1N) bng
11/25/2010
Page 110 of 239
base mnh (0,1N)
Nhn xt: (trng hp c tnh n s pha long) - Nh t 0 - 90ml NaOH 1N vo: pH bin i chm (t 0 1,3); - Nh t 90 - 99ml NaOH 1N vo: pH bin i nhanh hn (t 1,3 2,3); - Nh t 99 99,9ml NaOH 1N vo: pH bin i rt nhanh (t 2,3 3,3); - Nh t 99,9 100ml NaOH 1N vo: (khong 2 git = 0,1ml): pH bin i t ngt (t 3,3 7); pH = 3,7. 3,7. - Khi thm vo mt lng rt nh NaOH 1N (khong 1 git), pH tng rt nhanh t 7 10,7 ; pH = Gii:
B ng 7.4. Bin i [H+ ] v pH khi trung ho 100ml HCl 1N bng NaOH 1N tnh acid ca dung dch [H+ ] 1 5.10-1 1.10-1 1.10-2 1.10-3 1.10-7 0,1 1 1.10-11 1.10-12 0 0,3 1 2 3 7 11 12 pH = 8 pH [H+ ] 1 3,33. 10-1 5,27.10-2 5,03.10-3 5,01.10-4 1.10-7 2.10-11 2.10-12 0 0,5 1,3 2,3 3,3 7 10,7 11,7 pH = 7,4 pH
base thm vo (ml) 0 50 90 99 99,9 100 100,1 101
acid cn li (ml) 100 50 10 1 0,1 0 tha base
khng k s pha long
c k s pha long
Nh vy khi trung ho mt acid mnh bng mt base mnh s c mt bin i pH t ngt cn im tng ng. Kho st ng cong chun s thy im tng ng tng ng vi im un. 3.3.3. nh hng ca nng acid Khi trung ho dung dch HCl bng dung dch NaOH c nng long hn trng hp trn th s thy khong bin i pH t ngt thu ngn li. Th d c th: Trung ho 100 ml HCl 0,1N bng NaOH 0,1N. Kho st s bin i v tnh [H+], pH trong c hai trng hp khng k s pha long v c k s pha long. ng cong chun thu c ging trng hp trn vi s chnh lch mt n v pH. Kt qu l s bin i pH cn im tng ng lun nhanh nhng bao ph mt vng pH nh hn : pH = 5,4. (bng 7.5, hnh 7.14, 7.15)
Bng 7.5. Bin i [H+] v pH khi chun HCl 0,1N bng NaOH 0,1N
11/25/2010
Page 111 of 239
base thm vo (ml) 0 50 90 99 99,9 100 100,1 101
acid cn li (ml) 100 50 10 1 0,1 0 tha base 0,1 1
tnh acid ca dung dch [H+] 1. 10-1 5.10-2 1.10-2 1.10-3 1.10-4 1.10-7 1.10-10 1.10-11 1 1,3 2 3 4 7 10 11 pH = 6 pH [H+] 1.10-1 3,33. 10-2 5,27.10-3 5,03.10-4 5,01.10-5 1.10-7 2.10-10 2.10-11 1 1,5 2,3 3,3 4,3 7,0 9,7 10,7 pH = 5,4 pH khng k s pha long c k s pha long
Hnh 7.14. Trung ho acid mnh (0,1N) bng base mnh (0,1N) hoc ngc li
Hnh 7.15. Trung ho acid mnh (c) bng base mnh (c) vi cc nng khc nhau
3.3.4. nh hng ca bn cht acid mnh cng nng , ng cong chun ca cc acid mnh khc nhau nh HCl, H2SO4 li ging nhau v nhng acid ny phn ly hon ton. 3.4. Trung ho mt base mnh B bng mt acid mnh HA ng cong chun ca trng hp ny s i xng vi trng hp trung ho mt acid mnh HA bng mt base mnh B v bin i pH cng c quan st gn im tng ng. 3.5. Trung ho mt acid yu bng mt base mnh B 3.5.1. Bin i pH
11/25/2010
Page 112 of 239
S trung ho dung dch CH3COOH (Ha) bng dung dch NaOH vi cng th tch, cng nng cho thy s bin i nh sau: - Lc bt u : dung dch ch c acid yu. Gi c l nng ban u ca dung dch Ha. pH c tnh theo cng thc tng qut : - Trong lc chun : hn hp gm mt dung dch acid Ha cha b trung ho v mui BHa do acid b trung ho, ngha l mt dung dch acid Ha (nng gim dn) v base lin hp [a-] (nng tng dn). Nng [Ha] v [a-] lin quan bi cng thc : (7.22) Tnh [a], xt cc phng trnh: BH+a a + H2O Ha H2O BH+ + a (phn ly hon ton) OH + Ha H+ + a H+ + OH (7.23)
C th vit: [BH+] + [H+ ] = [a-] + [OH] (lut trung ho in tch)
Mui BH+ a- l kt qu do trung ho acid Ha bi 1 base B thm vo v phn ly hon ton, ta c: [BH+] = [B] vi [B] l nng base cho vo mi trng. V Ha l acid yu - phn ly t cho nn [H+ ] <<< [BH+] v [OH] <<< [a-] (mui phn ly hon ton) nn nu b qua [H+] v [OH] trc [BH+] v [a-] th biu thc (7.23) tr thnh: [a-] [BH+] = [B] Tnh [Ha]: Lc u, Ha c nng c. mt thi im chun no Ha s tm c di dng a hoc Ha. Nh vy: c = [Ha] + [a-] hoc [Ha] = [c] [a-] Th [a-] bng gi tr tm thy trong (7.24) th [Ha] [c] [B] Tnh pH : phng trnh (7.22) c th thay th Ha v a-: (7.25) (7.24)
11/25/2010
Page 113 of 239
Khi [B] = c/2 (lc phn na [Ha] c trung ho) th: bit ny ca pH (gi l pH bn trung ho) khng lin quan n nng acid.
; v pH = pKa. Gi tr c
Ch : thng th c lng b qua [H+] v [OH] ch c th chp nhn khi pH gia pH = 4 v pH = 10. - Ti im tng ng: hn hp thu c l mt dung dch mui BHa coi nh l mt dung dch base a- c pH c cho theo cng thc tng qut :
3.5.2. Th d c th (trung ho bng dung dch chun N) Trung ho 100 ml CH3COOH 0,1N bng NaOH 1N. Kho st s bin i v tnh [H+], pH. (pKa ca acid acetic = 4,74) Gii:
B ng 7.6. Bin i pH khi chun CH3COOH 0,1N bng NaOH 0,1N base thm vo (ml) 0 50 90 99 99,9 100 100,1 101 acid cn li (ml) 100 50 10 1 0,1 0 tha base pH ca hn hp
2,87 4,74 5,69 6,73 7,73 8,73 0,1 9,7 1 10,7
pH=1
Hnh 7.16. Trung ho acid yu (0,1N) bng base mnh(0,1N)
Theo bng 7.6, so vi vic trung ho HCl 0,1N bng NaOH 0,1N, bin i pH nh sau: Trnh t bin i pH % acid c trung ho bng 7.6 (pH) 1,87 3,86 1 1 1 thay v bng 7.5 (pH) 0,5 2,3 1 2,7 2,7
- Lc bt u pH bin i nhanh 0 - 50% hn: 0 - 99% - K pH bin i tng t - Yu hn khi ti st s trung ho: 99 - 99,9% 99,9 - 100% 100 - 100,1%
11/25/2010
Page 114 of 239
Ch : khi tha base mnh B th pH thay i ging trng hp ca vic nh lng acid mnh bng base mnh (bng 7.5) v hn hp lc ny l dung dch ca 1 base mnh B v base yu a-. C th coi nh ch c base mnh B. Nhn xt: Khi trung ho mt acid yu bng mt base mnh th s thay i pH cn im tng ng s t hn trong trng hp trung ho mt acid mnh bng mt base mnh.
Hnh 7.17. Trung ho:
a) mt acid mnh bng 1 base mnh. b) mt acid yu bng 1 base mnh.
Thm 0,1 ml dung dch chun quanh gi tr l thuyt 100 ml, pH bin i l 2 (i vi trng hp trung ho acid mnh bng mt base mnh pH bin i l 5,4). ng cong chun ging nhng trng hp trc. Ch : im tng ng lun lun l im un ca ng cong chun nhng gi tr pH 7. Mt khc, khi trung ho 50% acid th ng cong ny c mt im un th hai tng ng v lc pH = pKa (hnh 7.18). nh hng ca nng acid: cng thc (7.23) chng t rng: - pH giai on bn trung ho: c lp vi [Ha] - pH ca dung dch u v pH ti im tng ng: ph thuc vo [Ha] Kt qu: ng cong ca mt acid yu vi cc pha long khc nhau khi chun u i qua im un: pH = pKa (bn trung ho). (hnh 7.19)
11/25/2010
Page 115 of 239
Hnh 7.18. Trung ho acid yu (c) c nng khc nhau bng base mnh (c)
Hnh 7.19. Trung ho cc acid yu (1N) c K khc nhau bng base mnh (c)
3.5.3. nh hng ca loi acid yu Cc gi tr pH ph thuc pKa ca acid. Acid cng yu pKa cng ln, ng cong trong thang pH cng cao, pH im tng ng cng cao v bc nhy pH cn im tng ng tri ra trn mt vng nh. (hnh 7.19) 3.6. Trung ho mt base yu bng mt acid mnh ng cong i xng vi trng hp 3.5. v bc nhy pH cn im tng ng cng c quan st tng t. Trng hp ny pH thp hn 7 : pH = pKa lgC
Hnh 7.20. Trung ho base yu (0,1N) bng acid mnh (c) v ngc li
3.7. Trung ho mt acid mnh HA bng mt base yu
11/25/2010
Page 116 of 239
- Trong lc chun , hn hp gm mt dung dch acid mnh HA v acid yu bH+ (do s phn ly mui bHA v vi mt c lng chp nhn th dung dch c coi nh ch c acid mnh HA). - Trc khi n im tng ng, ng cong tng ng khc rt t vi ng cong trung ho mt acid mnh bi mt base mnh, nhng sau im tng ng th bin i pH t ngt km th hn. - Nh vy, bc nhy pH cn im tng ng tri trn mt vng pH nh hn trng hp trung ho acid mnh bi mt base mnh.(hnh 7.21) 3.8. Trung ho mt acid yu bng mt base yu 3.8.1. Bin i pH - Lc bt u: gi c l nng ban u ca dung dch acid HA, pH theo cng thc tng qut: pH =1/2 pKa 1/2 log c. - Trong lc chun : bin i pH hi khc vi trng hp trung ho acid yu bng base mnh. - Ti im tng ng: hn hp gm dung dch ca mui bHa m pH theo cng thc tng qut: pH = pK + pKbH+ a Gi tr ny c lp vi nng , gn bng 7 khi lc ca acid v base ging nhau. 3.8.2. c im ca ng cong trung ho - Trc im tng ng: ng cong trung ho hi khc vi trng hp trung ho mt acid yu bng mt base mnh. - Sau im tng ng: hi khc vi trng hp trung ho mt base yu bng mt acid mnh. Kt qu: Bin i pH cn im tng ng km th hn trong trng hp trung ho bng mt base mnh. Bc nhy pH ch tri trn 1 vng rt nh. Nu acid v base kh yu th im tng ng khng nh du c bng im un na nn rt kh xc nh (hnh 7.22).
Hnh 7.21. ng cong chun khi trung ho 1 acid mnh bng 1 base yu
Hnh 7.22. ng cong chun khi trung ho 1 acid yu bng 1 base yu
3.9. Trung ho acid a chc (polyprotic acid) Vn t ra l cc lc acid khc nhau ca cc chc acid trong mt acid a chc c th c xc nh c khi trung ho hay khng ngha l nu ng cong chun trung ho c nhiu im un th cc im un ny s tng ng vi tng im tng ng ca cc chc acid hay khng.
11/25/2010
Page 117 of 239
3.9.1. Cc chc acid c lc mnh ng cong trung ho 1 acid mnh (cho tt c acid a chc hay n chc c lc mnh) bng 1 base mnh lun ging nhau. Kt qu l trong lc chun khng th phn bit nhiu chc acid khc nhau ca mt acid a chc (polyprotic acid). Nh vy, trong mi trng nc th ng cong trung ho ca HCl 1N bng NaOH 1N ging nh trng hp chun H2SO4 1N bng NaOH 1N v php nh lng khng tch bit c hai chc acid ca H2SO4. 3.9.2. Cc chc acid c lc khc nhau C th phn bit nhng im tng ng khc nhau vi iu kin l lc ca cc chc acid trong mt acid a chc phi khc. Th d: c th phn bit lc ca ba chc acid khc nhau ca acid phosphoric H3PO4.
Ngi ta c th tnh gi tr pH tng ng nhng im khc nhau ca ng cong trung ho H3PO4 0,1M bng NaOH 0,1N khi b qua s pha long (hnh 7.23)
Hnh 7.23. Trung ho acid a chc yu bng base mnh
- Lc bt u: (ch xt chc acid th nht, nhng chc acid sau c lc yu, c th b qua).
11/25/2010
Page 118 of 239
- giai on bn trung ho ca chc acid th nht: pH = = 2,1; yu, gi tr pH nh. ,
im tng ng th nht (xem nh hn hp lc ny l dung dch ca cht lng tnh b qua chc acid th ba do lc yu nht).
- giai on bn trung ho ca chc acid th hai : pH =
= 7,2 ):
im tng ng th hai (xem nh hn hp lc ny l dung dch ca cht lng tnh
- Bn trung ho ca chc acid th ba : pH =
= 12,4 ):
im tng ng th ba (xem nh hn hp lc ny l dung dch ca base
Nh vy, c th xc nh r hai im tng ng u tin nh lng hai chc acid u tin. Ngc li, im tng ng th ba khng th nh gi trn ng cong v chc acid th ba c lc qu yu. 3.9.3. Cc chc acid ca mt acid a chc c cc pKa gn nhau phn bit c r rng hai im tng ng thng phi xt: Th d : Acid tartric pK1= 2,5; pK2= 4,2 khng th xc nh r 2 im tng ng. 3.10. Kt qu thc nghim trong phn tch chun Khi tng kt cc ng cong chun , ngi ta thy c nhng nt chung : - im tng ng l im un ca ng chun . - Cc ng chun c th khc nhau v dng lc gn n im tng ng ngha l khi c s thay i v pH. + Nu acid v base mnh: Thay i ny rt t ngt v ph mt vng pH rng ln. + Nu mt trong nhng cht i khng yu v cht kia mnh: thay i km t ngt hn nhng ph mt vng pH cn c th nh gi c. + Nu acid v base u l hai cht yu: Thay i t t v kh phn bit c vng thay i pH. V im tng ng c nh gi theo s thay i pH ngi ta c th kt lun: - nh lng c th t n s chnh xc ln nu hai cht i khng u mnh. - nh lng c th thc hin chnh xc khi mt trong nhng cht i khng yu.
11/25/2010
Page 119 of 239
- nh lng s km chnh xc nu 2 cht i khng u yu. Ch : nh gi im tng ng d hn, c th v ng o hm bc nht im un tng ng vi mt cc i ca ng o hm ny. a) Chn thuc th chun : chn nhng cht phn ly H+ mnh trong dung mi kho st. b) Chn nng thuc th : khi pha long 1/10 dung dch cht kho st, bin i pH gim 2 n v. Do d dng kt lun l khi thc hnh vi dung dch m c N hay N/10 thch hp hn l dung dch qu long (v s km chnh xc). c) Chn dung mi - Ho tan nht. Th d : acid bo mch di ho tan trong ethanol d hn trong nc. - Pht hin tt nht tnh acid (hay base): th d: trong acid acetic, nh lng alcaloid d hn trong nc. 3.11. Thun li ca ng chun trung ho a) nh gi lc ca acid hay base Dng ca ng cong v v tr ca n s cho tng v lc ca acid hay base. Nh vy acid cng yu th ng chun cng cao v base cng yu th ng chun cng thp. b) Xc nh pKa - o pH lc bn trung ho s xc nh dc pKa v lc pH= pKa. - o nhiu pH trong khi trung ho. Tht vy, pKa c tnh theo pH sau khi thm base chun [B] vo acid c nng c : nhau, th d: [B] = c/10, 2c/10, 3c/10 - Trung bnh nhng kt qu ny c th c c pKa kh chnh xc. 4. DUNG DCH M Tm quan trng ca dung dch m th hin trn mi lnh vc khoa hc ca i sng v bt k mt h thng sinh hc no cng ph thuc vo pH. Th d: khi cho 1ml HCl 10M vo mt lt dung dch NaCl 0,15M, pH = 7 th dung dch mi s c pH = 2 nhng khi thm 1ml HCl 10M vo mt lt huyt tng c pH = 7,4 th dung dch ny s c pH =7,2 (do trong huyt tng c h m). 4.1. nh ngha Dung dch m l dung dch khng li s thay i pH khi thm acid hay base mnh vo dung dch hoc l dung dch m khi pha long th pH ca dung dch thay i t. S thay i ny thng trong mt vng gii hn pH. 4.2. Thnh phn . Tnh pKa bng cch o pH nhng gi tr [B] khc . M i
11/25/2010
Page 120 of 239
Dung dch m l dung dch cha trong mt dung mi phn ly (nh nc), hoc mt acid yu v mui ca mt acid yu (= acid yu v base lin hp ca n). Dung dch m ny thng c pH acid. Hoc mt base yu v mui ca mt base yu (= base yu v acid lin hp ca n). Dung dch m ny thng c pH kim. 4.3. C ch ca hiu ng m Xt mt dung dch hn hp ca acid (hay base) yu v mui ca base (hay acid) mnh nh dung dch acid acetic (Ha) v mui acetat Na (BHa) trong nc. Mui ho tan trong nc phn ly hon ton: BH+ a- BH+ + aTrng hp acid trong nc: Ha + H2O H3O+ + a(7.26) (7.27) (7.28) Trong cc biu thc trn: - a- c c t mui BH+ a- (7.26) m cng c c t acid Ha, do [a- ] tng t l thun vi [Ha] (7.27). - duy tr gi tr Ka n nh th khi [a-] tng [Ha] cng phi tng (7.28) m khi [Ha] tng th acid s khng b phn ly (ngha l khng ion ho c) v nh vy s c s li ion ho (reticulation) ca acid. iu ny li cng phi ch khi cho acetat [a-] t mui (7.26) vo vi lng cng ln v [a-] li kt hp vi [H+] ca (7.27) to Ha. Lc y pH s ph thuc vo t l tng i ca acid Ha v ca mui BH+ a- (cc bng 7.7; 7.8; 7.9). Nh vy, khi trong dung dch c cc ion BH+, a- v H+ cng lc th: - Nu thm acid mnh AH: acid ny khi phn ly s tng thm H+ nhng a s H+ ny tc ng vi a to thnh nhng phn t Ha l acid yu. Do vy pH thay i t. - Nu thm base mnh B: base s gn vi H+ to acid BH+ (l acid c lc gn nh bng 0). Acid BH+ tip tc phn ng vi a- to mui BH+ a-. Phn ng (7.26) li pht trin v pha s phn ly v to thnh base yu a- v BH+ l acid c lc gn nh bng 0. Base mnh B b th bng mt base yu a-, t b phn ly. Kt qu l pH thay i t. - Gii hn ca tc ng m: Nu tip tc thm vo dung dch m hoc acid mnh hoc base mnh th s n lc hu nh ton b a- c trung tnh ho bng acid (hay ngc li nhng phn t Ha s c trung tnh ho bng base). K t lc ny, thm mt lng mi nhng cht phn ly H+ vo na s dn n thay i pH t ngt v tc ng m b hy.
Ch :
c tc ng m, cn phi c cng lc mt acid yu v mt base yu lin hp. Do vy, theo l thuyt th khng th m vi ch mt acid yu hay ch mt base yu. Tuy nhin i khi trong thc t cng m mt dung dch acid mnh bng mt base yu. Th d: trong thc hnh, khi m mt dung dch nitric bng lng tha acetat Na th trc tin acid mnh tc ng ton phn trn acetat to thnh acid acetic, k trong dung dch c mt acid yu (l acid acetic) v base lin hp (acetat) ca n. y chnh l thnh phn ca dung dch m.
11/25/2010
Page 121 of 239
4.4. D on kh nng m nh vo ng cong chun trung ho - Kh nng m: khong pH m trong dung dch m cn nng lc m (phn ng cho hay nhn proton m khng c bin i quan trng v pH).
Hnh 7.24. ng cong chun biu din kh nng m
Khong bin i gii hn ca pH ny gn nh nm ngang v th hin bng mt dc rt nh trn ng cong chun (hnh 7.16). Trn hnh 7.24, ta thy giai on bn trung ho pH = pKa th c kh nng m. 4.5. nh gi kh nng m Kh nng m cng ln khi mt s lng ln dung dch m c cho vo dung dch kho st. mt nng xc nh ca dung dch m th kh nng m l ln nht khi c mt acid v base lin hp ca m vi nng tng ng (equimolar). chnh l v tr im un ca ng chun (hnh 7.24). Khi thc hnh, dung dch m cn hiu qu, ngi ta nhn thy nng acid yu [Ha] hay [bH+] bng t nht l 10% [base] (v ngc li). pH ca m c tnh theo cng thc tng qut lin quan n pH v pKa:
Nh vy: - nu [base] gp 10 ln [acid] th pH = pKa + 1 - nu [acid] gp 10 ln [base] th pH = pKa 1 kh nng m: pH = pKa 1 Nh vy, khi c qu nhiu acid hay base thm vo th pH s vt ra ngoi vng m v pH s tng hay gim nhanh. Kh nng m lin quan n lng cht c th thm vo dung dch m khng gy ra mt s thay i hot ion c ngha no.
11/25/2010
Page 122 of 239
- Dung lng m (buffer capacity) acid base ca mt dung dch cn duy tr pH: l s lng (mmol) ca acid mnh hay base mnh thm vo 1 lt dung dch ny (mmol/l hay mM) lm thay i 1 n v pH. 4.6. Kh nng m pH rt thp (hay rt cao) Khi trung ho mt dung dch acid mnh (HCl) trong nc bng mt dung dch chun base mnh (NaOH hay KOH) s nhn thy ng cong gn nh bng phng gia pH = 0 v pH = 2 ngha l c mt kh nng m (d khng c im un nh giai on bn trung ho). Hin tng ny c m t khi xt mt acid mnh v mt base c lc gn nh bng 0 (Th d: cp HCl/ Cl-). Trong trng hp acid mnh mt cch l tng, tc ng m vn hin hu v n dng chnh cp dung mi H3O+ / H2O.
B ng 7.7. m KCl HCl gia pH = 1,0 v pH = 2,2 (theo Clark v Clubs) Dung dch KCl 0,2N (ml) HCl 0,2N Nc va pH 200C (ml) (ml) 25 48,50 100 1,0 25 32,25 100 1,2 25 20,75 100 1,4 25 13,15 100 1,6 25 8,40 100 1,8 25 5,30 100 2.0 25 3,35 100 2,2
4.7. Tnh pH ca dung dch m Phn bit hai trng hp Dung dch m cha acid yu v base lin hp ca n: nu hn hp m gm acid yu Ha v base lin hp ca n (di dng mui Ma) th trong dung dch c cc qu trnh in ly:
Trng hp acid trong nc: Ha + H2O

Ma
H3O+ M
+ a+ a-
Hng s in ly ca acid Ha c biu din bng h thc: trong CH+, Ca CHa l nng cc ion H+, a- v Ha lc cn bng.
Ly logarit v o v, ta c: (7.29)
11/25/2010
Page 123 of 239
H thc ny cho php tnh pH ca dung dch m cha acid yu v mui ca n. Dung dch m cha base yu v acid lin hp ca n (di dng mui Ma) :
Trng hp base trong nc:
a- + H2O Ma
OH- + Ha M+ + a-
Hng s in ly ca base a- c biu din bng h thc:
Ly logarit o 2 v, ta c: (7.30) m pH + pOH =14 pOH = 14 - pH
H thc ny cho php tnh pH ca dung dch m cha base yu v mui ca n, trong COH-, CaCHa l nng cc ion OH-, a- v ca Ha lc cn bng. pH ny ch ph thuc vo t s nng acid hoc base yu v mui ca n ch khng ph thuc pha long hn hp. 4.8. ng dng ca dung dch m - Thit lp v duy tr hot ion hydro chun ho my o pH: cc dung dch m hay c s dng c pH: 4,01: 7,00: 9.00 - Lm n nh pH trong thnh phn pha ch ca cc quy trnh nh lng o quang ph UV- Vis. - Lm n nh pH trong thnh phn ca mt s pha ng khi trin khai sc k lng hiu nng cao. (th d: h m phosphat...) - iu ch cc dng nh lng gn vi im ng in (approach isotonicity). - Thc hnh trong cc quy trnh phn tch, nht l khi phn tch cc dch sinh hc. Cc dung dch m c dng trong cc h thng sinh l c chn cn thn khng can thip vo hot tnh dc lc ca thuc hay chc nng bnh thng ca c th. Nhiu th nghim v quy trnh nh lng trong Dc in i hi phi iu chnh n pH mong mun hay duy tr pH chuyn bit bng cch thm dung dch m. Khi o pH, cn phi c dung dch m chun. Cc dung dch m ch yu c dng trong phn tch ho hc phi tng thch vi cc cht xc nh v thuc th s dng. 4.9. Vi cng thc pha ch dung dch m theo pH yu cu
11/25/2010
Page 124 of 239
4.9.1. m ca acid yu + mui ca acid yu v base mnh

B ng 7.8. Cng thc pha m aceto acetic c pH = 3,6 - 5,6 Dd a. acetic N (ml) Dd acetat Na M (ml) Nc ct v. (ml) pH 18,5 1,5 100 3,6 17,6 2,4 100 3,8 16,4 3,6 100 4,0 14,7 5,3 100 4,2 12,6 7,4 100 4,4 10,2 9,8 100 4,6 8,0 12 100 4,8 5,9 14,1 100 5,0 4,2 15,8 100 5,2 2,9 17,1 100 5,4 1,9 18,1 100 5,6
B ng 7.9. Cng thc pha m acid citric phosphat dinatri c pH = 2,2 - 8,0 Acid citric 0,1M Phosphat dinatri 0,1M v. (ml) pH 21oC 98 100 2,2 93,8 100 2,4 89,1 100 2,6 84,15 100 2,8 79,45 100 3,0 75,3 100 3,2 71,5 100 3,4 67,8 100 3,6 64,5 100 3,8
Acid citric 0,1M Phosphat dinatri 0,1M v. (ml) pH 21oC Acid citric 0,1M Phosphat dinatri 0,1M v. (ml) pH 21oC
61,45 58,60 55,90 53,25 50,70 48,50 46,40 44,25 100 4,0 36,85 100 6,0 100 4,2 100 4,4 100 4,6 100 4,8 100 5,0 100 5,2
42 39,55 100 5,8
100 100 5,4 5,6
33,90 30,75 27,25 100 6,2 100 6,4 100 6,6
22,75 18,15 100 6,8 100 7,0
13,05 9,15 6,35 4,30 2,75 100 7,2 100 7,4 100 7,6 100 7,8 100 8,0
4.9.2. m ca base yu + mui ca acid mnh v base yu

B ng 7.10. Cng thc pha m tris hay THAM Tris 0,2M (24,20g/l) HCl 0,2N Nc ct v. (ml) pH 230C 25 22,1 100 7,2 25 20,7 100 7,4 25 19,2 100 7,6 25 16,3 100 7,6 25 13,4 100 8,0 25 11,0 100 8,2 25 8,3 100 8,4 25 6,1 100 8,6 25 4,1 100 8,8 25 2,5 100 9,0
Tris (hydroxymethyl) amino methan c pH = 7,2 - 9,0 Trong cc th d trn, nhiu cp acid - base lin hp c vn dng nh: acid citric v cc ion citrat; phosphat diacid - phosphat monoacid. Ngoi ra trong cc dc in (USP, BP....) cng c nu cch pha ch nhng cng thc m chun thng dng khc.
11/25/2010
Page 125 of 239
5. NG DNG CA PHNG PHP ACID -BASE 5.1. nh lng acid 5.1.1. nh lng acid mnh trong nc Nu nh lng mt acid mnh bng base mnh vi nng cao th bc nhy pH di, do hu ht ch th u s dng c. Khi dung dch c pha long (0,01N) pH thay i yu hn nn chn la ch th phi gii hn.
B ng 7.11. pK ca vi acid trong nc. acid v c sulfuric sulfur phosphoric arsenic hydrofluoric nitr carbonic sulfur boric cyanhydric H2SO4 H2SO3 H3PO4 H3AsO4 HF HNO2 H2CO3 H 2S H3BO3 HCN 1,8 2,1 2,2 3,2 3,3 6,4 7,0 9,1 9,4 10,3 13,8 12,7 13,8 pK1 pK2 1,9 7,2 7,2 7,0 12,4 11,5 pK3 acid hu c oxalic tartric citric formic lactic benzoic acetic diethylmalonylur phenol 9,9 pK1 1.2 2,5 3,1 3,8 3,9 4,2 4,7 7,4 pK2 4,3 4,2 4,8 6,4 pK3
5.1.2. nh lng acid yu trong nc Khi nh lng cc acid mch thng c trng lng phn t hi cao nh cc acid alcol (acid lactic, acid tartric, acid citric) bng kim th s chuyn mu xy ra trong vng kim. Dung dch chun khng c c carbonat (baryt). Nu nng acid qu thp, vng chuyn mu ko di nn thch hp hn l phi thay i dung mi. 5.1.3. nh lng acid rt yu trong nc (acid bo nng, acid boric) im tng ng c tm thy pH rt cao nn ch th s dng khng chuyn mu hon ton. Phi kch thch tnh acid bng cch s dng mt trong nhng phng php sau: - Ho tan acid rt yu trong mt dung mi tr nhn proton (butylamin, ethylen diamin, dimethyl formamid, pyridin, tetrahydrofuran) v dung dch chun l natri methylat hay hydroxyd tetrabutylammonium. Trong trng hp ny, anhydrid carbonic c vai tr mt acid mnh do phi thc hin trong kh quyn nit. - Ho tan acid rt yu trong mt dung mi khc tt hn nc: c th dng cn tinh khit thu c dung dch c nng m c nhm nh lng tt nht. Th d: acid bo dy di, t tan trong nc nhng tan trong cn.
11/25/2010
Page 126 of 239
Hnh 7.25. Lin kt ca boric vi nc
Hnh 7.26. Chun ch acid boric (1) v chun acid boric khi c mt mannitol (2)
- To phc c th lm tng tnh acid: Th d: acid boric (pK = 9,2) nu c mt polyol (glycerol hay mannitol) s to phc. Phc polyol-boric c pKa = 4 d nh lng bng NaOH. 5.1.4. nh lng mui ca acid mnh v base yu Acid bH+ c th nh lng khi lc kh mnh. Th d: NH4+ c lc rt gn acid boric. Nu base b rt yu (alcaloid), acid lin hp bH+ c lc tht s v c th nh lng trc tip (s dng acid acetic lm dung mi). Nu base b mnh hn, bH+ c lc rt yu v thng dng phng php chun ngc sau khi phng thch base v chit bng dung mi (th d nh cc alcaloid). 5.2. nh lng base 5.2.1. nh lng base mnh trong nc Ging nh trng hp nh lng mt acid mnh 5.2.2. nh lng base yu trong nc
B ng 7.12. pKa ca vi base trong nc Base Guanidin Dibutylamin Triethylamin Methylamin Ethylen-diamin Piperazin 6,8 5,7 pK1 pK2 13,5 11,5 10,9 10,7 9,9 9,8 Base Ethanolamin Ephedrin Amoniac Hydroxylamin Pyridin Hexamethylentetramin pK2 9,5 9,5 9,256,0 5,2 5,1 Base Quinolein Anilin Dicloroanilin Acetoxim Diphenylamin Ur pK2 5,0 4,6 2,1 1,8 0,8 0,4
Phi nh lng bng acid mnh, pH im tng ng s nh hn 7. Vic chn ch th ty vo pKa ca acid lin hp vi base chun . Amoniac l trng hp c bit quan trng.
11/25/2010
Page 127 of 239
5.2.3. nh lng base rt yu trong nc pH ca dung dch c chun thng di 10. Th d: amin dc dng: amphetamin, alcaloid v amid. Cc phng php nh lng sau y thng c kho st: - nh lng trc tip: ch thc hin c khi pKa cao v base c th tan trong nc. Phi dng mt dung dch m c v ch th chuyn mu trong mi trng rt acid (xanh thymol pH = 2,8 -1,2) nu khng th s c s thy phn mui to thnh v s chuyn mu ko di ra. - nh lng bng phng php tha tr: p dng i vi alcaloid, dng base gn vo alcaloid v chit bng dung mi hu c. Sau chuyn alcaloid base sang dng acid bng mt dung dch acid bit chun v th tch, lng tha acid c nh lng v dng ch th mu trong vng acid (nu khng th acid bH+ to thnh s tc ng tr li). - nh lng trong mi trng cn nc: mc d kh lc in ly ca cn thp hn nc, tc ng ca cn c th chim u th vi iu kin: - Base kh mnh. - Pha long nhiu im tng ng nng cao kh lc in ly. - nh lng trong mt dung mi sinh proton hn Th d: dung mi l acid acetic s lm tng tnh base ca cafein (alcaloid) v do d chun cafein bng acid percloric. Ngoi ra khi nh lng alcaloid cng c th dng acid formic t phn ly hay hn hp hai dung mi ny acid acetic v acid formic. 5.2.4. nh lng mui ca acid yu v base mnh a- l base to thnh s c nh lng (Natri acetat, natri carbonat) nh lng nhng carbonat trong mt hydroxyd a) B b) c) + H3O+ + H3O+ + H3O+ CO2 BH+ + H2O im tng ng pH = 11,0
+ H2O im tng ng pH = 8,3 + 2H2O im tng ng pH = 3,5
Hai phng trnh sau s dng cng mt lng acid, nh vy c th phn bit base v carbonat. 5.2.5. nh lng mui ca acid mnh v base mnh; mui ca acid yu v base yu v cht lng tnh - Mui ca acid mnh v base mnh khng c tnh acid hoc base v cc anion v cation c lc coi nh b b qua. - Mui ca acid yu v base yu to nn cng lc cc acid v base c lc. Khng th nh lng trc tip bng php o acid base. Trong thc t khng th nh lng acetat alcaloid trong mi trng nc. Nhng c th s dng cc tc ng sau: a) Tc ng ca dung mi; c th gim lc ca 1 trong nhng cu t hay tng lc ca cc cht ho tan bng tc ng a proton ca dung mi.
11/25/2010
Page 128 of 239
b) Tc ng ho hc:
) nh lng mui amoniac: thm formol vo dung dch to thnh hexamethylen tetramin khng c tnh base trong nc:
4 lc acid yu + 6HCHO + 4H2O (CH2)6N4 + 4H3O+ + 6H2O c chuyn thnh acid mnh H3O+
) nh lng nhng amino acid (phng php Sorensen) Ging nh trng hp ca mui amoniac: vi formol to mt base Schiff.
Base ny rt yu v khng cn tr vic nh lng carboxyl. ) nh lng nhng halogenid trong mi trng acid acetic. (alcaloid hay ion kim) - Trong mi trng nc, ngi ta c: bH+X ; X l 1 base c lc bng 0, bH+ l acid tht s. - Trong mi trng acid acetic khan, bH+ tr thnh BH+ ; X l base c lc tht s v lin hp vi acid yu trong mi trng ny. Vic nh lng base yu ny kh v km chnh xc. Do vy, ngi ta kh ion X thnh dng phc thy ngn. Acetat thy ngn chnh l mt phc cht (khng phng thch ion acetat mang tnh base) s tc ng trn halogenid cho mt phc cht bn hn. Hg(CH3COO)2 + 2X [HgX2]2CH3COO Base X yu c th bng base mnh CH3COO. 5.3. Xc nh mt s nguyn t Vi nguyn t nh C, N, S, Cl, Br, F .... c nh lng bng phng php trung ho. Ty tng trng hp, nhng nguyn t ny c chuyn thnh acid hay base v c c chun . 5.3.1. Nitrogen Thng c trong acid amin, protein, thuc nhum. Phng php chung xc nh nit hu c: Phng php Kjeldahl. - Nguyn tc: Mu th c phn hy bng H2SO4 m c, nng. Nit phn hy thnh ion amonium. Dung dch cha ion ny c lm lnh, pha long, em chng ct. Amoniac phng thch ra c cho vo dung dch cha acid v xc nh bng phng php chun trung ho. C nhiu phng php thu kh amoniac v nh lng amoniac. Hai phng php chnh l: Phng php 1 Amoniac c phng thch s c vo 1 th tch acid bit chnh xc nng . nh lng acid tha bng base chun. Ch th chuyn mu vng acid do tnh acid ca ion ammonium c mt im
11/25/2010
Page 129 of 239
tng ng. Phng php 2 Amoniac c phng thch vo mt lng tha acid boric Ion dihydrogen borat c sinh ra l 1 base mnh c th c chun bng dung dch chun HCl Ch th: Bromocresol lc chuyn mu trong vng acid 5.3.2. nh lng Sulfur Sulfur trong nhng cht sinh hc c xc nh bng cch t chy trong kh H2 S SO2 (hoc SO3) thu thp v chng ct SO2 (kh) + H2O2 H SO 2 4 Chun H2SO4 bng base chun 5.4. nh lng cc hp cht v c 5.4.1. nh lng mui amoniac Dng base mnh y amoniac ra ri chng ct bng dng c Kjeldahl. 5.4.2. nh lng nitrat v nitrit Dng hp kim Devarda (50% Cu, 45% Al, 5% Zn) kh nhng ion ny thnh ion ammonium ri chng ct hon ton ly amoniac v nh lng. Ngoi ra, hp kim Arnd (60% Cu, Mg 40%) cng c s dng. 5.4.3. nh lng carbonat v hn hp carbonat Trong phng php chun trung ho th vic nh tnh, nh lng cc dung dch cha Na2CO3, NaHCO3, NaOH dng ring hay dng hn hp cho nhng th d rt ng quan tm: do phn ng loi i cht th ba nn trong 1 lng thch hp ca bt k dung dch no cng ch cha 2 trong 3 thnh phn: NaOH + NaHCO3 Na2CO3 (n khi mt hay c hai cht phn ng ban u c dng ht). - Nu NaOH c tiu th th dung dch ch cn Na2CO3 v NaOH. - Nu lng NaHCO3 b yu i th cn Na2CO3 v NaOH. - Nu lng NaHCO3v NaOH tng ng c trn ln th cht tan ch yu s l Na2CO3 . Vic phn tch tin hnh qua 2 bc: - Bc 1 vi ch th vng kim: phenolphtalein (K hiu l ) - Bc 2 vi ch th vng acid: bromocresol lc (vit tt l bcg: Bromocresol green)
11/25/2010
Page 130 of 239
Khi chun cc mu c th tch bng nhau th c th suy ra c thnh phn ca dung dch da vo th tch tng i ca acid cn chun.
B ng 7.13. Chun cc dung dch cha Na2CO3, NaHCO3, NaOH Thnh phn trong mu NaOH Na2CO3 NaHCO3 NaOH, Na2CO3 Na2CO3, NaHCO3 Lin quan gia V v Vbcg khi chun th tch mu bng nhau V = Vbcg V = 1/2Vbcg V = 0; Vbcg > 0 V > 1/2 Vbcg V < 1/2 Vbcg
V : th tch s dng chun vi ch th l phenolphtalein. Vbcg: th tch s dng chun vi ch th l bromocresol lc. Kt qu s c sai s 1% . 5.5. nh lng cc nhm chc hu c C th chun trc tip hoc gin tip 5.5.1. nh lng nhm acid sulfonic v carboxylic Acid sulfonic l acid mnh, d ho vo nc ri chun thng bng base. C nhiu acid carboxylic khng ho tan nhiu trong nc nn khng nh lng trc tip c. Trong trng hp ny, acid c ho trong EtOH v chun bng nc kim hoc acid ny c ho trong mt lng base tha chun ri nh lng kim tha bng dung dch acid bit nng . 5.5.2. nh lng nhm amin - Amin dy thng thng c hng s phn ly 10-5. Do c chun thng bng acid mnh. - Amin thm - (anilin v dn cht) thng rt yu trong mi trng nc (Kb 10-10) c th chun bng phng php tha tr hoc nh lng trong mi trng khan. - Amin vng thm pyridin cng ging amin thm. - Amin vng bo ho piperidin c khuynh hng kt hp vi amin thng v c chun trong mi trng nc. C nhiu amin qu yu / nc phi c chun trong mi trng khan nh acid acetic tng tnh kim. 5.5.3. nh lng nhm ester
11/25/2010
Page 131 of 239
Ester thng c xc nh bng cch x phng ho vi mt lng base chnh xc bit chun. R1COOR2 + OH R1COO + HOR2 Lng base tha c chun bng acid chun. Cc ester thay i nhiu theo tc x phng ho. C ester cn vi gi un nng hon tt qu trnh. Mt t ester tc ng nhanh cho php chun trc tip bng base. Thng thng, tin hnh bng cch un ester v KOH 0,5M hi lu trong 1-2 gi. Sau khi lm lnh, lng base tha c chun bng acid. Trong dc in cc nc c trnh by "Ch s ester hay ch s x phng ho": S miligram KOH cn thit trung ho acid t do v x phng ho cc ester c trong 1 gam cht kho st. 5.5.4. nh lng nhm hydroxyl Nhm OH trong nhng hp cht hu c c th c xc nh bng cch ester ho vi cc anhydrid carboxylic hay chlorid khc nhau. Hai thuc th thng dng l: anhydrid acetic v anhydrid phtalic. Vi anhydrid acetic th phn ng s l: (CH3COO)2O + ROH CH COOR + CH COOH 3 3 S acetyl ho thng c thc hin bng cch trn cn thn mu th vi mt th tch bit anhydrid acetic bit trong pyridin. Sau khi un nng, thm nc vo thy phn nhng anhydrid khng phn ng: (CH3COO)2O + H2O 2CH3COOH Sau chun acid acetic bng dung dch KOH hay NaOH / cn. Song song thc hin mu trng. Nu c amin th chuyn sang amid bng anhydrid acetic. Trong cc dc in c trnh by Ch s acetyl hay ch s acetyl ho pyridin l s miligam acid acetic cn ester ho nhng sn phm c nhm chc hydroxyl OH trong mt gam cht kho st. 5.5.5. nh lng nhm carbonyl Nhiu aldehyd v ceton c th c xc nh bng dung dch hydroxylamin hydrocloric. Phn ng ny to oxim.
R2 c th l nguyn t H. Sau phn ng, HCl phng thch c chun bng base. y, cc iu kin phn ng cng thay i ty cht. Th d, i vi aldehyd ch cn 30 pht l . Nhiu ceton khc phi un hi lu vi thuc th trong 1 gi - Ch s hydroxylamin: Ch s ny c din t bng s miligam KOH cn trung ho cc acid sinh ra do phn ng ca mt lng tha chlorhydrat hydroxylamin vi 1 gam cht kho st. 5.5.6. nh lng mui Lng mui ton phn trong mt dung dch c th c xc nh chnh xc bng dung dch chun acid base. Khi cho qua ct trao i nha ion, mui ny chuyn thnh mt ng lng acid hay base v c th nh lng bng phng php trung ho.
11/25/2010
Page 132 of 239
Acid chun hay base chun cng c iu ch bng nha trao i ion. Ngi ta dng mt dung dch cha mt lng mui tinh khit bit nh l NaCl c ra qua ct nha v pha long n mt th tch bit c. Mui ny phng thch mt lng ng lng acid hay base t nha trao i s cho php tnh s mol thuc th bng phng php trung ho. 6. NH LNG TRONG MI TRNG KHAN C 2 loi cht cn c chun trong mi trng khan: - Acid hay base hu c c trng lng phn t cao v ho tan gii hn trong nc. - Nhng hp cht hu c c tnh acid hay base rt yu (Ka hay Kb < 108) nh amin thm, phenol, mui ca acid carboxylic v acid v c kh thy im kt thc trong mi trng nc nhng nu tng tnh acid hay base ca n bng cch thay i dung mi th li d thy im kt thc. Bt li khi chun trong mi trng khan: Dung mi t tin, bay hi v c. - a s dung mi u c h s dn n ln hn nc nn phi c cha trong bnh c kim tra nhit ca thuc th trnh sai s khi o th tch. 6.1. C ch Trong dung mi khan (l dung mi khng ion ho), acid cng cho H+ v c solvat ho nhng v hng s in ly ca dung mi ny thp nn H+ solvat ho ch yu hin din dng cp ion vi anion acid: HA + S SH+ BH+A A + S
Sau base B s tc ng vi cp ion ny to thnh: SH+A + B
Phn ng ny xy ra l v B l base mnh hn dung mi S 6.2. Dung mi chun trong mi trng khan Thng dng nhng dung mi lng tnh (amphiprotic) v qua giai on t phn ly nh ba dung mi lng tnh hay dng acid acetic khan, ethanol, ethylendiamin.
6.3. Tnh hon ton ca phn ng Ph thuc vo: - lc ca cht phn tch (acid hay base). - tnh acid hay base vn c ca dung mi.
11/25/2010
Page 133 of 239
- hng s in ly ca dung mi. 6.3.1. nh hng ca lc ca cht phn tch Trong mi trng nc Trong mi trng khan CH3COOH+ l proton b solvat ho v c to thnh cp ion khi HClO4 ho vo acid acetic khan HClO4 + CH3COOH CH3COOH2+ClO4
- Khi chun base b yu bng HA trong mi trng nc: - Khi chun base b yu bng HClO4 trong mi trng khan vi dung mi l CH3COOH H3O+ + b bH+ + H2O Nu k y l phi tnh lc ca nc CH3COOH2+ClO4 + b bH+ClO4 + CH3COOH
CH3COOH2+ (mi trng khan) H3O+ (mi trng nc)
(7.32) Nh vy cc phng trnh (7.31) v (7.32) cho thy tnh y ca phn ng acid, base t l thun vi hng s t phn ca acid yu v t l nghch vi hng s t phn ca dung mi. Phng trnh ny c ngha: Phn ng trung ho l cnh tranh H+ gia dung mi v acid (hoc base). 6.3.2. nh hng ca tnh acid hay base ca dung mi Acid formic, acid acetic, acid sulfuric cho H+ tt hn l nhn H+. Trong loi dung mi ny tnh base ca cht tan c nng ln. Th d: Anilin C6H5NH2 trong nc c hng s phn ly K=106,9 nn rt kh chun nhng li c th l base mnh hn trong acid acetic khan v dung mi ny cho H+ d hn nc. Ethylendiamin, amoniac lng c i lc nhiu i vi H+ (kh nng nhn H+ nhiu hn) do vy l dung mi base. Trong loi dung mi ny, tnh acid ca cht tan s nng ln. Th d: Phenol c hng s phn ly K =10-10 yu trong nc li mnh trong ethylendiamin v c chun bng base chun. 6.3.3. nh hng ca hng s in ly ca dung mi Hng s in ly ca dung mi o lng kh nng to ra nhng cu t c in tch i khng tch
11/25/2010
Page 134 of 239
tiu phn ny vi tiu phn kia. Th d: nc c hng s in ly cao ( = 78,5) nn ch cn mt nng lng nh l tch ion mang in tch (+) ra khi ion mang in tch (-). Acid acetic c hng s in ly thp ( c qu trnh in ly. = 6,2) nn cn phi c nhiu nng lng mi thc hin
MeOH, EtOH (DMeOH = 33, DEtOH = 24) l dung mi c hng s in ly trung bnh. Dung mi c hng s in ly thp phi chu mt bt li khi dng lm mi trng chun acidbase v s phn ly l to ra 2 ion c in tch i khng nhng do dung mi in ly yu nn kh nng tch ion ca dung mi b gii hn lm s phn ly gim i ng k. Khi s phn ly khng cn tch nhng cu t tch in th s in ly ca dung mi t c tc ng ln phn ly ca mt acid hay mt base. Th d: tc ng in ly ca cn i vi amoniac l ti thiu i vi phn ng phn ly: C2H5OH + NH4+ 6.4. Dung dch chun trong mi trng khan 6.4.1. Dung dch acid Dung dch chun acid percloric 0,1N trong acid acetic khan y l mt monoacid (E = M = 100,45) rt mnh, nht l trong mi trng acetic khan. Acid percloric khan - km bn v d n - c bn trn th trng di dng dung dch nc khong 72%. Nh vy n khng phi l cht chun. Cch iu ch dung dch ny thnh acid chun : - Ho long 14,5 gam acid percloric 70% - 72% (8,5ml) trong khong 900 cm3 acid acetic bng dng phn tch. - Kh nc c trong dung dch ny bng cch thm 29 -30 gam anhydrid acetic. Cht ny phn ng vi nc cho hai phn t acid acetic. - Sau khi ngui, thm acid acetic khan n vch 1000 cm3 v lc. Chuyn vo l c nt mi v cho nc t phn hy trong 48 gi. Chun dung dch ny bng mt dung dch mui chun pha trong acid acetic khan. Bo qun trnh m. Ch : khng c cho tha nhiu anhydrid acetic v gy nguy c to nn sai s dn n t nhng phn ng amid ho vi nhng amin s cp v th cp. 6.4.2. Dung dch kim Cc dung dch kim thng c iu ch trong mi trng cn hay cn - benzen. a) Dung dch potat (b tt) trong methanol (KOH trong MeOH): Dung dch potat c th pha ch trong EtOH hoc MeOH, nhng MeOH thch hp hn v EtOH thng cha nhng aldehyd nn khi c mt mt base mnh s ho nha lm dung dch tng mu t vng C2H5OH2+ + NH3
11/25/2010
Page 135 of 239
n nu. Bt li ny khng xy ra khi s dng MeOH. chun ca nhng dung dch ny khng bn v cn xc nh li trc khi dng. Thun li: K2CO3 khng tan trong mi trng v t s t ng decarbonat ho. b) Dung dch natri methylat 0,1N (CH3ONa) trong mi trng cn - benzen. Dung dch ny dng nh lng nhng acid yu trong mi trng tuyt i khan nc. iu ch theo cch sau: Dehydrat ho trc MeOH bng cch un si hi lu vi s hin din ca Mg v chng ct hay tip xc trong 2 - 3 ngy vi m phn t tamis moleculaire. Thm mt lng natri kim loi (2,5g / 150 ml MeOH). Ho long vi benzen khan (qsp 1000 cm3). Trc khi s dng, dung dch pha ch s c chun bng acid benzoic trong pyridin hay butylamin. c) Dung dch tetrabutyl ammonium hydroxyd (C4 H9)4 N+OH Dung dch ny l 1 base mnh tan c nhiu trong mi trng benzen: MeOH 5% hoc benzen 95%. Hai dung dch rt kim ny rt ho anhydrid carbonic ca khng kh nn kh bo qun. 6.4.3. Pht hin im kt thc - Dng ch th (theo kinh nghim): tm tinh th, tm methyl, soudan III, tropeolin 00. - o th in cc. - Ch th trong mi trng khan. Acid acetic hoc acid formic l nhng dung mi c kh nng nhn proton yu hn nc nn nhng base rt yu trong nc cho vo dung mi ny li tr nn mnh hn. Nhng cht ch th chuyn mu trong nc mi trng rt acid li chuyn mu cc pH trung bnh ca mi trng khan v do vy hay c s dng. Trong nhng dung mi cho proton (acid). Ch th hay dng nht l tm tinh th, a - naphtol benzen, orange IV, paradimethylaminobenzen (PDAB = vng methyl), xanh oracet B. Cn trong nhng dung mi nhn proton (base), ngi ta hay dng ch th xanh thymol, paranitrophenylazo - 4 resorcinol, orthonitranilin. Cc ch th mu ny cng hay c s dng trong dung mi c proton hot ng (mi trng nc). Tht vy, cc ch th ny l nhng acid (hay base) yu hn nhng cht nh lng. C ch chuyn mu ging nh c s phn ly ca dung mi hay khng. 6.4.4. ng dng vic chun trong mi trng khan Phi kt hp dung mi, cht chun , im kt thc, xt tan, gi c thuc th, c, trang thit b,
B ng 7.14. Mt s iu cn ghi nh khi nh lng trong mi trng khan nh lng acid: benzen; toluen; dimethylformamid; aceton; ceton; acetonitril; cn tert-butyl.
11/25/2010
Page 136 of 239
Dung mi
nh lng base: acid acetic khan; hn hp acid acetic khan v anhydrid acetic c bc nhy ln hn acid acetic; cc anhydrid acetic tc ng vi amin bc 1 v bc 2 khi nng; acetonitril; benzen; toluen. nh lng acid: KOH/ EtOH; KOH/MeOH; CH3OMe/ Methylat alcalin; CH3OMe/ benzen-MeOH (95/5); dung dch ammonium bc 4 nh hydroxy tertbutyl; ammonium / benzen MeOH (95/5) nh lng base: acid percloric/ 1-4 dioxan; acid percloric/ acid acetic khan; HCl t dng.
Dung dch chun
nh lng acid: acid benzoic (C6H5 COOH); acid succinic; acid sulfanilic; phtalat Cc cht gc acid kali. nh lng base: phtalat acid kali. nh lng acid AH + C5H5N A C5H5NH+
AC H NH+ + KOH AK + C H H+OH 5 5 5 5 C ch nh lng base RNH + CH COOH 2 3 RNH3CH3COO
RNH3 CH3COO + HClO4 RNH3+ClO4 + CH3COOH RNH2 + HClO4 RNH3+ClO4 ng dng nh lng acid: nh lng cc barbituric nh lng base: nh lng cc base hu c
Trng hp c bit: Kh tan: un nng cn thn v c th acetyl ho nhng nhm amin. Thm lng t acid formic lm tng hng s in ly ca dung mi nhm d ho tan cht cn nh lng nhng lng acid formic a vo cng t cng tt v pKa ca acid formic (3,75) < pKa ca acid acetic (4,75) nhng i khi acid formic c th trung ho cc base yu. T KHA - Phng php acid base - Thuyt Bronsted - Henderson - Hasselbalch - Cht lng tnh - pH, pKa - Chun trung ho - ng cong chun - Dung dch m - Dung lng m - Chun trong mi trng khan
11/25/2010
Page 137 of 239
CU HI LNG GI
1. Trnh by thuyt Bronsted v Lewis v acid - base. Trong bi, acid - base c vit theo quan im no.
2. Trnh by cch xc nh pH, pKa. 3. Trnh by cc giai on khi tin hnh chun trung ho. pH thay i nh th no khi chun 100 ml HCl 0,1N bng NaOH 0,1N (khng tnh n s pha long)? 4. nh ngha dung dch m. Kh nng m? Dung lng m? Trnh by vic ng dng dung dch m trong ngnh Dc. 5. Nu nguyn tc v c ch phn ng khi nh lng acid - base trong mi trng khan? 6. nh ngha cc ch s acid, ch s ester, ch s acetyl v ngha xc nh trong thc t. 7. Nu mt s cht chun gc v trng hp s dng trong phng php acid - base. 8. Trnh by khong i mu ch th dng trong phng php chun acid - base. CU HI TRC NGHIM 1. Quan nim v acid base trong bi ging ny l theo thuyt ca a. Langmur b. Lewis c. Bronsted d. Faraday e. Henderson -Hasselbalch
2. Theo thuyt acid base nu trong bi, acid l nhng cht c kh nng proton. a. phn ly b. cho c. nhn. d. tham gia bt gi e. trao i
3. Mt base lin hp vi acid mnh c lc ...... a. trung bnh b. kh yu c. yu d. rt yu e. coi nh b qua
4. .................l dung dch khng li s thay i pH khi thm acid hay base mnh vo dung dch hoc l dung dch m khi pha long th pH ca dung dch thay i t. a. Dung dch km phn cc b. Dung dch phn cc c. Dung dch m d. Dung dch phn ly e. Tt c cc cu u ng
5. pH ca dung dch natri hydroxyd (.19.10-3 mol.dm-3) l: Xem NaOH nh phn ly hon ton a. 10,2 b. 7,3 c. 2,92 d. 12,6 e. 11,1
11/25/2010
Page 138 of 239
6. Mui no sau y khi ho tan vo nc s cho mt dung dch c pH gn bng 7? a. Kali carbonat b. Ammonium bromid c. Natri nitrat d. Natri cyanid e. Ammonium nitrat
7. Mt mu cha 15,0 cm3 HCl c chun bng dung dch NaOH 0,0830 mol.dm-3 . im kt thc t c sau khi thm 19,2 cm3 NaOH. Nng ca HCl l bao nhiu? a. 0,178 mol.dm-3 b. 0,0648 mol.dm-3 c. 0,130 mol.dm-3 d. 0,212 mol.dm-3 e. 0,106 mol.dm-3
8. Trong dung mi l acid, cc cht tan l s kh phn ly hn (v gim s cho proton) a. cht trao i ion b. base 9. 25oC th Knc = a. 14 b. 14 c. 7 d. 7 e. 0 c. cht lng tnh d. acid Knc gi l tch s ion ca nc. e. cht trao i in t
10. Dung dch chun hay c s dng nh lng base yu trong mi trng khan nc l dung dch a. acid percloric 0,1N / acid hydrocloric b. acid percloric 0,1N / acid acetic c. KOH/MeOH d KOH /EtOH. e. acid percloric 0,1N / acid acetic khan
Chng 8 PHNG PHP OXY HO KH

MC TIU - Trnh by c nh ngha phn ng oxy ho - kh, nh ngha th oxy ho - kh v th chun biu kin.
11/25/2010
Page 139 of 239
- Trnh by s nh hng ca pH, ca s to kt ta, ca s to phc trn h thng oxy ho kh. - Tnh hng s cn bng K, th oxy ho - kh ti im tng ng v cch d on chiu ca phn ng oxy ho - kh. - Chn c ch th oxy ho - kh theo th oxy ho - kh ca cht chun v cht cn chun . - Tnh th ti tng thi im chun oxy ho - kh v v th. - Trnh by cc phng php oxy ho hay c s dng trong ngnh Dc. NI DUNG 1. S OXY HO KH 1.1. nh ngha phn ng oxy ho kh Phn ng oxy ho - kh l phn ng trao i electron gia hai hp cht: mt hp cht nhng electron (cht kh) v mt kia nhn (cht oxy ho). Th d: Thm dung dch st(III) clorid vo thic(II) clorid th phn ng cn bng nh sau: 2FeCl3 + SnCl2 2FeCl2 + SnCl4 (8.1)
mi nguyn t gam st (III) (55,85 gam) b kh thnh st (II) phi s dng 96,493 ( 96500) Coulomb (1 Faraday) v cn s dng (2 96.500) Coulomb mi nguyn t gam thic (II) (118,70 gam) b oxy ho thnh thic (IV). Trong phn ng trn, in tch clorid khng thay i do khng tham d vo phn ng oxy ho - kh. Phn ng (8.1) c xem nh th d chung ca 2 phn ng cng mt lc:
Nh vy:
s oxy ho: s mt e s kh: s nhn e
Khi c s oxy ho xy ra l c s kh v mi e nhn c bi cht oxy ho l do cht kh b mt i. Cht kh v cht oxy ho c th l hai cht ho hc (phn ng ho hc) hoc l mt cht ho hc v
mt in cc m th c chn thch hp (phn ng in ho). Trong phn ng in ho, tu gi tr ca th in cc m in cc s nhng e v kh cht ho hc hoc l nhn e v oxy ho cht ho hc. Hnh 8.1 minh ho mt th nghim phn ng oxy ho kh: hai bnh cha dung dch ni nhau bng mt cu mui l ng dn thng c to bng dung dch KCl bo ho c gel ho (agar agar). Nhng vo mi bnh mt in cc Pt (in cc tr) v ni vi mt volt k. Khi xut hin th, ngha l dung dch thic (II) c khuynh hng cung cp nhng e cho dung dch
11/25/2010
Page 140 of 239
st (III). Dng in i qua cho n khi to s cn bng. Nh vy, cp oxy ho - kh kt hp dng oxy ho v dng kh s tng ng vi s trao i e. Ni chung, 1 phn ng oxy ho - kh c th trnh by nh sau:
1.2. Nhn xt Phn ng oxy ho - kh tc l qu trnh cho nhn electron c th thc hin trong cc dung dch ring r (hnh 8.1). Cn trong phn ng acid base th qu trnh chuyn H+ t acid sang base ch c thc hin trc tip trong mt dung dch (hnh 8. 2), H+ khng th chuyn t cht cho sang cht nhn thng qua mt dy dn in t nh trong phn ng oxy ho - kh. V tc phn ng: c nhiu phn ng oxy ho xy ra chm nn cc phng php chun da vo phn ng ny thng i hi tng nhit , thm xc tc. L do l phn ng xy ra qua nhiu giai on. Qu trnh chuyn electron l mt trong chui cc giai on (ph v lin kt, proton ho, sp xp li phn t...) V s c mt ca dung mi nc: trong phn ng oxy ho - kh nu phn t nc tham gia vo phn ng: 2H2O 2OH +2H+ 2H2O O2 + 4H+ + 4e Kh H2 v O2 c gii phng ra khi dung dch. Trong cc phn ng oxy ho kh ngi ta tm cch trnh qu trnh oxy ho hoc kh nc.
Hnh 8.1. Phn ng oxy ho kh xy ra trong hai dung dch
Hnh 8.2. Phn ng oxy ho kh xy ra trong mt dung dch
1.3. Th oxy ho kh
11/25/2010
Page 141 of 239
Khi 1 kim loi nhng vo dung dch mui ca kim loi ny s to mt bn pin. Th d: - Km nhng trong dung dch km sulfat to bn pin (bn pin oxy ho) - ng nhng trong dung dch ng sulfat cng to bn pin (bn pin kh). Pin in ho Galvanic c to thnh bi 2 bn pin, mi bn pin gm mt thanh kim loi nhng trong dung dch in ly (hnh 8. 3). Hai bn pin ni nhau bng mt cu mui v c hai bn pin cng c ni nhau bn ngoi bi mt dy dn (hnh 8. 4). Cu mui l mt hng ro c l xp ngn s trn ln ca dung dch nc trong cc bn pin nhng cho php cc ion di chuyn c hai chiu duy tr trung tnh in tch. Theo s sp xp ny th cc electron cung cp bi phn ng oxy ho s i ngang qua dng in bn ngoi n ni xy ra phn ng kh. Khi cc bn pin c ni nhau th phn ng t xy ra v kim volt k lch i ch r l c s khc nhau v th nng. Th nng ny l th oxy ho kh.
Hnh 8.3. Cc bn pin oxy ho - kh
Hnh 8.4. S cu to 1 pin in ho
Th d: hai bn pin l t cc kim loi: Km v ng Zn (rn) Zn2+ (dung dch) + 2 e Cu2+ (dung dch) + 2 e Cu (rn)
Zn l mt kim loi c kh nng cho nhng electron to thnh ion Zn2+ i vo dung dch (ngha l
11/25/2010
Page 142 of 239
cho cc e), do vy in cc km tch in m. Cn cc ion Cu2+ trong dung dch n tch in trn in cc lm in cc ng c in tch dng. Cng lc s c 2 phn ng ngc nhau v phn ng ny s mnh hn phn ng kia. Sau cng, phi c mt s cn bng c thit lp v in cc phi c th cn bng E dng hay m. Gi tr ca th oxy ho kh cn bng c cho bi phng trnh Nernst:
T: nhit tuyt i F: s Faraday (96500 Coulomb) n: lng e s dng E0: hng s ph thuc kim loi R: hng s kh l tng (8,314 J/ K. mol) aM: hot ca ion M+ trong dung dch - Nu dung dch c pha long y th hot aMn+ c th s dng ln vi nng kim loi [Mn+]. - Khi thay R = 8,314 J/ K. mol v F bng gi tr ca n ( 25oC th T = 273o + 25o = 298oK) v tip tc chuyn ln thnh lg (ln aMn+ = 2,303 lg amn+) th phng trnh Nernst tr thnh
Khi nng hay hot = 1 (n v) th th nhn c bi in cc bng E0. E0: th chun ca h thng oxy ho - kh to thnh bi kim loi v ion tng ng ca n Mn+ / M0. Nh vy s ion ho v s oxyd ho - kh c hiu theo ngha hp: Ion Mn+: dng oxy ho t nguyn t M0, nu xt phn ng: Mn+ + ne M0 Cng vy, i vi phi kim loi th dng ion ho l dng kh cn nguyn t l dng oxy ho: Cl2 + 2e 2Cl Khi nim tng qut ny cng p dng cho H+ (ch l dng oxy ho t nguyn t hydro). 2H+ + 2e H2 in cc hydro (hnh 8.5), to thnh bi mt in cc Pt bo ha kh hydro nhng chm trong mt dung dch H+ (v d: HCl 1M) c th E c cho bi biu thc tng qut: E = Eo + 0,0591 lg[H+]
11/25/2010
Page 143 of 239
Khi hot bng 1 ngha l [H+] = 1 th E = E0(2H+ / H2).
Hnh 8.5. in cc hydro
Theo quy c, th chun Eo ca hydro bng 0,00 volt v th oxy ho - kh ca nhng h thng khc c xc nh bng cch so snh vi th ca in cc ny. Nh vy, c th phn loi nhng h thng oxy ho - kh khc nhau c to thnh bi kim loi v ion tng ng theo th chun ca n (bng 8.1). Th cng thp, kim loi cng c khuynh hng cung cp ion i vo dung dch. Th d: Natri l cht kh phn ng kh mnh vi nc cho ion Na+. 1.4. H thng oxy ho - kh ha tan Mt kim loi khi ho tan vo dung dch c th cho nhng ion tng ng vi nhiu ho tr khc nhau.
B ng 8.1. Th chun (volt) ca mt vi cp oxy ho- kh Cht oxy ho Li+ K+ Na+ Zn2+ Fe2+ Cr3+ Sn2+ 2H+ Sn4+ Bi3+ + + + + + + + + + + S electron trao i e e e 2e 2e e 2e e e 3e Cht kh Li0 K0 Na0 Zn0 Fe0 Cr2+ Sn0 H2 Sn2+ Bi0 Th chun (V) 3,03 2,92 2,70 0,76 0,44 0,41 0,14 0,000 +0,14 +0,23 Cht oxy ho Cu2+ I2 Fe3+ Ag2+ Br2 Cl2 Cr2O72MnO4 Ce4+ S2O82 + + + + + + + + + + S electron trao i 2e 2e e e 2e 2e 6e 5e e 2e Cht kh Cu0 2I Fe2+ AgO 2Br 2Cl Cr3+ Mn2+ Ce3+ 2SO42 Th chun (V) +0,34 +0,5345 +0,77 +0,80 +1,08 +1,36 +1,36 +1,51 +1,60 +2,0
Th d: Nguyn t thic c nhng ion thic (II) v thic (IV). Sn4+ + 2e Sn2+.
11/25/2010
Page 144 of 239
Nguyn t st c nhng ion st (II) v st (III). Fe3+ + e Fe2+ Ion c in tch dng ln nht tng ng vi dng oxy ho v ion c in tch dng nh nht tng ng vi dng kh. Mt in cc tr (platine, vng....) c nhng vo hn hp s gi mt th xc nh. Th ny bin thin theo nng ca tng dng oxy ho v dng kh theo phng trnh
Nu cc nng dng oxy ho v dng kh bng nhau, th c gi trong in cc bng E0 v E0 c gi l th chun ca h thng. Do , c th thit lp mt bng sp xp nhng h thng oxy ho kh ha tan theo th chun ca mi th. Mt kim loi s dch chuyn ion kim loi tng ng vo mt h thng oxy ho kh c th cao hn. Th d: Lp mng st (c th chun -0,44 V) s b ng (c th chun +0,34 V) ph ln khi n c nhng chm trong dung dch ng. Cng cch ny, c th phn loi h thng oxy ho kh c thnh lp bi halogen v cc ion ca n: H thng oxy ho kh F2 + 2e 2F Cl2 + 2e 2Cl Br2 + 2e 2Br I2 + 2e 2I Th chun (volt) + 2,65 + 1,36 + 1,08 + 0,534
Nh vy clor oxy ho bromid v iodid phng thch ln lt brom v iod cn brom th oxy ho nhng iodid phng thch iod. 1.5. Th oxy ho kh biu kin Trong thc t, cht oxy ho v cht kh ca mt cp lin hp thng tham gia vo nhng phn ng khc nh phn ng acid base, phn ng to phc, phn ng kt ta. Do th oxy ho - kh nhn c gi l th oxy ho - kh biu kin cng b nh hng bi nhiu yu t khc do cc phn ng ny. 1.5.1. nh hng ca pH a) Th d 1: Th biu kin ca h thng Mn7+ / Mn2+ Trong mi trng acid: Mn7+ + 5e- Mn2+ Trong thc t, h thng oxy ho - kh ny to thnh cp MnO4 / Mn2+ tng ng vi cn bng: MnO4 + 8H+ + 5e Mn2+ + 4H2O
11/25/2010
Page 145 of 239
Th ca h thng ph thuc vo nng proton
(8.2) Khi nng dng oxy ho = dng kh, ngha l [ ] = [Mn2+]
l gi tr ca th chun biu kin v EO = EO 0,0944 pH pH cng cao th gi tr th chun biu kin cng thp. Ion permanganat l cht oxy ho cng mnh khi tnh acid ca mi trng cng mnh. Nng H+ ng mt vai tr trong s cn bng do vy m th biu kin ca h thng ph thuc vo pH. b) Th d 2: Th biu kin ca h thng As5+/ As3+ Trong php o oxy ho - kh, kh nng kh ca arsenic (III) c s dng rt rng ri, kh nng oxy ho ca arsenic (V) cng c th c li trong vi trng hp. H thng oxy ho - kh tng ng vi s cn bng: As3+ As5+ + 2e
Arsenic (V) tng ng vi acid arsenic H3AsO4. l nhng a acid (nhiu proton trong mt acid) m s ion ho thay i theo pH ca mi trng (lin quan n pKa ca nhng nc acid khc nhau).
11/25/2010
Page 146 of 239
Hnh 8.6. Th chun biu kin ca h As (V) / As (III)
- Dng oxy ho ca As(V) thng dng phn t v 3 dng ion ho: Vi nhng pKa tng ng: pK1 = 2,2; pK2 = 7,0; pK3 = 11,5. - Dng kh ca As(III) tng ng vi mt dng phn t v vi 3 dng ion ho
Vi nhng pKa tng ng: pK1 = 8,1; pK2 = 12,1; pK3 = 13,4 Do vy, nng ca nhng dng khc nhau s thay i theo pH v mt pH nht nh th s c vi h thng chim u th (hnh 8.4). Th d: - pH < 2, s cn bng nh sau: H3AsO4 + 2H+ + 2e H3AsO3 + H2O - pH = 2,2 tr i, tnh acid th nht b ion ho v H2AsO4 chnh l dng chim u th:
- pH =7- 8, dng H2AsO42- chim u th:
Th tng ng t ba cn bng trn c tnh ton theo cc biu thc sau:
11/25/2010
Page 147 of 239
Theo nh ngha, th chun c xc nh khi nng ca dng oxy ho bng nng ca dng kh: th chun biu kin ca 3 h thng tng ng vi 3 s cn bng c cho theo biu thc: E0 = E0 0,059pH, E0= E0 0,0885pH, E0= E0 0,118pH Th oxy ho - kh chun biu kin gim khi pH tng v nh vy nh hng ca pH trn h thng ( / H3AsO3) v hn h thng / H3AsO3) quan trng hn trn h thng ( (H3AsO4 /H3AsO3). dc ca tng on thng tng ng vi 3 phn cng ln khi s ion ho cng ln. Xt mt phn ng c in kh iod bng anhydrid arsen H2AsO3 + H2O I2 + 2e H2AsO3 + I2 + H2O 2I + 2I + 3H+ + 2e + 3H+
pH khng c nh hng no trn th chun ca h thng Io/ I = + 0,53 volt. Phn ng coi nh l hon ton khi hiu th gia hai h thng i khng trong khong 0,3 volt. Trong phn tch chun i vi iod, h thng As5+/As3+ ch c th c s dng nh l cht kh khi n c th < 0,53 0,3 = 0,23 volt, c ngha l theo l thuyt nu pH ca mi trng phn ng > 4 th trn thc t nu mun oxy ho mt dung dch arsen bng iod th ngi ta phi m dung dch ny bng natri hay kali hydrocarbonat. 1.5.2. nh hng ca s to phc Xt mt kim loi c kh nng cho hai ion c in tch khc nhau, ion M2+ tng ng vi dng oxy ho v ion M+ dng kh. E0 l th chun ca h thng: M2+ + e M+
Nhng ion kim loi ny c kh nng to phc vi thuc th X v nhng hng s phn ly ca mi phc cht nh sau: (8.3)
11/25/2010
Page 148 of 239
(8.4) E0 l th chun ca h thng M2+/M+. tng thi im th ny tun theo nh lut Nernst. (8.5) T (8.3) v (8.4), ta thu c:
Kox v KKh l nhng hng s nn 0,0591
cng l hng s.
Do , E0 l th chun biu kin ca h thng oxy ho - kh MX2+/MX+: MX2+ + e MX+ Kox / KKh bin thin theo bn vng ca mi phc v thng l cc hng s ny rt nh v trong trng hp ny bn vng ca phc ln nht khi ion lin hp tch in nhiu hn, h thng MX2+/MX+ c tnh kh mnh hn h thng M2+/M+. Trng hp c bit: Nu ch mi mt dng oxy ho t to phc th php tnh tng t s chng t l E0 cng nh th phc cng bn (Kox rt nh). Th cng yu th lng tha thuc th to phc X cng ln.
Th d: Xt h thng oxy ho kh Co3+ / Co2+ : Co3+ + 1e Co2+ (8.6) Thm ion cyanid (CN) vo dung dch cha Co3+ / Co2+ s lm mt i cc ion t do ny do to nn phc cyanid: Co(CN)63 v Co(CN)64 (8.7) (8.8)
11/25/2010
Page 149 of 239
Kox v KKh ln lt l nhng hng s phc ca Co3+ v ca Co2+. T cc phng trnh (8.7) v (8.8) ngi ta thu c:
Thay th [Co3+] v [Co2+] vo phng trnh (8.6)
th c th xc nh th chun mi E0 tng ng vi h thng mi E'0 = E0 + 0,059 lg
thay i theo bn vng ca tng phc
Ngi ta c th chng t rng phc
bn hn phc
, ngha l t s
rt
nh (khong 10-44). H thng mi ny c tnh kh rt mnh. 1.5.3. nh hng ca s to kt ta Tng t nh trng hp to phc, dng oxy ho Mox hoc dng kh Mkh to thnh hp cht t tan vi mt cht Y no . Kt qu l nng gim lm thay i th in cc ca cp. Gi s dng kh Mkh to kt ta vi Y: Mkh + mY Mkh Ym vi hng s TST = [Mkh][Y]m
(8.9)
11/25/2010
Page 150 of 239
Eo: th oxy ho kh chun biu kin. Nh vy, nu dng kh ca cp to hp cht t tan th khi kt ta c TST cng nh, nng thuc th Y cng ln th th oxy ho - kh cng tng. Nu kt ta xy ra vi dng oxy ho Mox th d dng suy ra th oxy ho ca cp s gim i. Th d: Tnh th chun biu kin ca cp Cu2+/Cu+ khi thm ion I- to kt ta CuI vi TST = 10-12. Bit v nng [I]=[1M] Hai bn phn ng: Cu2+ + e Cu+ + I Cu+ CuI CuI
Cu2+ + e + I
v E = E0 0,0591.lg(10 12/1) = 0,8792(V) S c mt ca I to kt ta CuI lm cho kh nng oxy ho ca Cu2+ tng ln nhiu. 1.6. S thay i th trong qu trnh phn ng - Hng s cn bng Xt hai qu trnh ha tan 1 v 2 ca 2 h thng c th oxy ho - kh khc nhau: Ox1 + qe Kh2 Kh1 pe + Ox2
Nu th chun ca h thng Ox1/Kh1 cao hn th chun ca h thng Ox2/Kh2. Khi p phn t ca Ox1 tc ng trn q phn t ca Kh2 th phn ng s cn bng v cn bng ny s bin thin theo th ca h thng oxy ho - kh.
T phn ng ny, hng s cn bng K c tnh theo biu thc:
Theo nh lut Nernst. Khi cc h thng ny cn bng th th E tng ng vi mi h thng bng nhau. Nu v ln lt l th chun ca tng h thng: (8.10)
11/25/2010
Page 151 of 239
(8.11) Trong trng hp phn ng ch s dng 1 electron [th d nh s oxy ho ca Fe(II) bng cesium (IV)], biu thc tr thnh:
1.7. Th im tng ng C th tnh th im tng ng i vi mt phn ng c s dng trong phn tch nh lng. Gi s mt thi im no dung dch Ox1 c thm vo dung dch Kh2. Theo (8.10)
Ti im tng ng, kt qu lun c xc thc: p[Ox1] = q[Kh2] v p[Kh1] = q[Ox2] v Ox2 v Kh1 ch c th c c t s kh Ox1bi Kh2. Phng trnh trn c n gin ho v biu thc ;
Trong trng hp c bit, cc phn ng ch s dng mt e .
c n =1, th E bng: (8.12)
p dng: C th tnh gi tr K v th im tng ng trong hai th d c s dng sau y. Th d 1: Tnh K Oxy ho Sn (II) bi Fe(III) Fe3+ + e Fe2+ ; Sn2+ Sn4+ + 2e ; = + 0,77 (volt) = + 0,14 (volt)
11/25/2010
Page 152 of 239
Oxy ho Fe (II) bi Ce(IV) Ce4+ + e Ce3+ ; Fe2+ Fe3+ + e ; = +1,60 volt = +0,77 volt
Th d 2: Tnh th im tng ng: Trong hai trng hp trn, phn ng c th c xem nh dch chuyn hon ton v pha phi. im tng ng, theo (8,12) c th l: nh lng Sn(II) bng Fe(III)
nh lng Fe(II) bng Ce(IV)
2. PHNG PHP CHUN OXY HO - KH 2.1. nh ngha Php chun oxy ho - kh l phng php phn tch th tch dng dung dch chun ca cht oxy ho chun cht kh nh st (II), mangan (II), iodid.... hoc dung dch chun ca cht kh chun cht oxy ho nh st (III), Mn (VII)... Ngoi ra, c nhng hp cht khng c tnh oxy ho - kh nhng phn ng hon ton vi cht oxy ho hay cht kh (to kt ta hoc phc cht) cng c th nh lng theo phng php ny. 2.2 Yu cu ca phn ng oxy ho - kh dng trong phn tch th tch phn ng xy ra theo chiu cn thit. phn ng phi hon ton. phn ng xy ra nhanh. Chiu ca mt phn ng c d bo da vo th oxy ho - kh chun. Trong phn hng s cn bng trnh by E0 ti thiu cho phn ng xy ra hon ton. Tuy nhin hiu E0 ch cho ta bit kh nng xy ra phn ng, cn thc t phn ng c xy ra khng, tc nhanh hay chm ph thuc c vo bn cht ho hc ca chng. Nh nu trn phn ng oxy ho - kh thng l qu trnh phc tp, xy ra qua nhiu giai on trung gian. Do vy tc phn ng thng l chm, nhiu khi khng p ng yu cu nh lng. 2.3. Cc bin php lm tng tc phn ng a) Tng nhit : Khi nhit tng thng th tc phn ng tng theo. i vi h ng th khi
11/25/2010
Page 153 of 239
nhit tng 10oC, tc phn ng tng ln khong 2-3 ln. Th d phn ng gia dung dch KMnO4 vi acid oxalic H2C2O4 xy ra chm nhit thng, khi un nng phn ng ny xy ra kh nhanh. Nhng c trng hp khng th dng nhit lm tng tc phn ng, v tng nhit s lm bay hi cht phn ng (nh iod), to phn ng oxy ho do oxy ca khng kh. b) Tng nng : Trong mt s trng hp ngi ta tng nng ca thuc th lm tng tc phn ng v hay s dng k thut chun ngc xc nh nng . c) Dng cht xc tc: Cc phn ng oxy ho - kh xy ra qua nhiu giai on trung gian. Cht xc tc thng lm tng tc ca cc giai on trung gian ny. V d: iodid (I) c dng xc tc cho phn ng oxy ho S2O32 bng H2O2. Mn2+ d) C nhng phn ng m sn phm to thnh ng vai tr xc tc cho chnh phn ng . Th d: trong chun bng thuc th KMnO4.
2.4. Kho st s bin thin ca th oxy ho - kh, ng cong chun oxy ho - kh Tng t nh trng hp chun acid-base. Trong qu trnh chun oxy ho - kh, nng thuc th v cht cn chun lun thay i. iu dn n s thay i th. C th biu din s bin i ca th theo th tch cht chun trn mt th nh biu din s bin i pH theo th tch cht chun (bi chun acid base). Bi ton: V ng cong chun khi nh lng 50,0ml dung dch Fe2+ 0,2M bng dung dch 0,1M mi trng l H2SO4 (duy tr nng 1M trong sut qu trnh chun v [H+] lun lun l 1M). Gii: Phng trnh phn ng xy ra nh sau:
5 mol st (II) + 1mol permanganat /mi trng acid cho 5 mol st (III) v 1 mol mangan Bn phn ng 1: 5Fe2+ + 5e 5Fe3+ ; Bn phn ng 2: + 8H+ + 5e Mn2+ + 4H2O; E0 = 0,68 volt / H2SO4 1M E0 = 1,51 volt
Hng s cn bng ca phn ng ny c tnh:
v th c th khng nh l cht phn tch v cht chun phn ng hon ton. - Sau khi thm 5ml KMnO4
11/25/2010
Page 154 of 239
Tng th tch hin c: 50 ml + 5ml = 55ml Th oxy ho - kh ca cp (Fe3+ / Fe2+) sau khi thm 5ml permanganat:
- Tnh th ti im tng ng
- Sau khi thm 25 ml KMnO4
Tng th tch hin c: 50 ml + 60ml = 110ml
11/25/2010
Page 155 of 239
Th oxy ho - kh ca cp (
/ Mn2+) s l:
B ng 8.2. S bin thin ca th E theo [
] c cho vo
thm vo (ml) 5
E (V)
thm vo (ml) 20
E (V)
0,65
1,37
10
0,68
25
1,50
15
0,71
30
1,51
Nhn xt ng biu din nh lng trong phng php oxy ho - kh c dng tng t nh trong phng php trung ha. gn im tng ng c bc nhy th t ngt. C th dng ch th pht hin im ny. ng biu din khng ph thuc vo pha long dung dch v trong phng trnh tnh th E cho thy t s nng cht oxy ho v cht kh khng thay i khi pha long. Tr s bc nhy ph thuc vo hiu s E0 = E01 E02. Hiu s E0 cng ln bc nhy th cng cao. Bin thin ca th E trong qu trnh chun . 2.5. Ch th s dng trong phn ng oxy ho kh 2.5.1. nh ngha Ch th oxy ho - kh l cc h thng oxy ho kh m dng oxy ho v dng kh c mu khc nhau xc nh im kt thc phn ng. 2.5.2. iu kin s dng Mt cht ch th oxy ho - kh phi p ng: - Thay i mu tc thi v c th cng thun nghch cng tt (iu kin ny kh thc hin c v t c phn ng oxy ho - kh no xy ra nhanh v thun nghch).
11/25/2010
Page 156 of 239
- nhy: c th s dng mt lng ch th nh m khng k n sai s do lng dung dch ch th oxy ho hay kh c tiu th xc nh s thay i ca mu sc. 2.5.3. C ch chuyn mu ca ch th oxy ho - kh - C vi ch th chuyn mu do cc dng oxy ho v dng kh ca ch th c mu sc khc nhau. Th d: Dung dch c mu tm m. Tuy nhin, trong dung dch acid th dng kh ca c s dng nh cht chun oxy ho th
permanganat l Mn2+ gn nh khng mu. Khi
dung dch s khng mu (do dung dch phn tch c tnh kh) cho n lc git tha u tin c thm vo th dung dch nhum mu hi tm xanh s cho bit im kt thc ca phn ng. - C vi cht ch th chuyn mu khi kt hp vi cc cht oxy ho kh c bit c trong dung dch chun . Th d: Tinh bt to phc xanh dng vi tha nn c th s dng pht hin s c mt ca lng
(chuyn mu t khng mu sang xanh dng) hay tinh bt pht hin im kt thc ca phn
ng m trong c tiu th ht (chuyn t mu xanh dng sang khng mu). Th d khc ca mt ch th loi ny l thiocyanat to vi Fe3+ phc Fe(SCN)2+ ho tan. - Tuy nhin, c loi ch th chuyn mu l do th in ho ca dung dch thay i. Loi ch th oxy ho kh rt quan trng ny l cc cht khng tham d vo chun oxy ho- kh nhng chuyn mu l do khi thm ch th loi ny vo dung dch phn tch th mu ch th s tu thuc vo th in ho ca dung dch. V s thay i mu p ng vi th in ho nn nhng hp cht ny gi chung l ch th oxy ho kh chuyn bit. 2.5.4. Phn loi ch th oxy ho kh Ch th oxy ho - kh: c 2 loi ch yu l ch th chung v ch th chuyn bit. Ch th chung: l nhng cht c mu thay i khi b oxy ho hay b kh. Ch th chuyn bit: s thay i mu ca ch th oxy - ha kh tht s c lp vi bn cht ho hc ca cht phn tch, cht chun v tu thuc vo s thay i th in cc ca h thng xy ra trong lc chun .
B ng 8.3. Mt s ch th oxy ho kh Tn ch th Indigo tetra sulfonat Xanh methylen Diphenylamin Diphenylbenzidin Diphenylamine sulfonic acid Tris (2,2- bipyridin) st Mu ca dng oxy ho xanh dng xanh dng tm tm tm xanh dng m Mu ca dng kh khng mu khng mu khng mu khng mu khng mu E0 (V) 0,36 0,53 +0,76 +0,76 0,85 1,12
11/25/2010
Page 157 of 239
Ferroin Tris (5- nitro- 1,10-phenanthrolin) iron Acid phenylantranilic
xanh dng nht xanh dng m tm
tm khng mu
+1,06 1,25 +1,08
chn cht ch th cho mt php chun ngi ta thng dng phng php v ng biu din s bin thin ca th theo th tch, ch th s chn thng c th chun gn vi th chun ti im tng ng ca phn ng oxy ho kh. Phn ng i mu khng lun lun nhanh ca ch th mang mu s dn n sai s h thng trong khi nh lng. Mt khc, vi mi trng phn ng c mu khng s dng c cht ch th. loi i cc bt li ny, ngi ta s dng php chun th. 2.5.5. Khong i mu ca ch th oxy ho kh Nu gi ch th mang mu dng oxy ho l Inox, dng kh l InKh, th: Inox + ne- InKh Nh vy, th oxy ho kh ca h thng c th vit l:
l th chun ca h thng Inox / InKh Khong i mu ca mt ch th oxy ho kh l khong bin i th khi t l chuyn t chuyn sang
Nh vy, khong i mu ca ch th nm trong gii hn:
Trong nhiu trng hp cc h thng oxy ho kh c s tham gia ca cc H+ th khong i mu ca ch th (ch yu ph thuc vo th chun biu kin E'o ca ch th) s bin thin theo pH v do vy khong i mu s ph thuc pH. 3. MT S PHP O OXY HO - KH S DNG TRONG NGNH DC 3.1. Php o Permanganat 3.1.1. Nguyn tc Phng php Permanganat vn dng kh nng oxy ho ca permanganat c thc hin trong mi trng acid v mui duy nht c s dng l mui kali. . Phn ng thng
11/25/2010
Page 158 of 239
Permanganat l cht oxy ho mnh i vi nhng h thng kh ( /Mn2+ = +1,51 volt pH = 0) dn n kt qu l tnh chn lc ca cht oxy ho ny rt yu v cc cht khc u ng vai tr l cht kh ca permanganat, do vy thng s dng nh lng cc cht kh. 3.1.2. Vai tr ca pH a) Trong mi trng acid: Mn7+ + 5e Mn2+. b) Trong mi trng trung tnh hay kim: - Trong mi trng trung tnh hay kim yu, kh nng oxy ho yu hn. Mn7+ + 3e Mn4+
(Mn4+ di dng MnO2 ta nn kh s dng) - Trong mi trng kim mnh, kh nng oxy ho cn yu hn na. Mn7+ + e Mn6+ - Trong mi trng trung tnh hay kim, phn ng km lp li hn trong mi trng acid, s oxy ho ngng nhng giai on khc nhau v sn phm c mu do cn s dng k thut chun tha tr khi mun thc hin trong mi trng ny. Thc t hay s dng mi trng acid chun bng phng php permanganat. 3.1.3. Acid c s dng trong php o permanganat a) HCl: khng th dng v c th oxy ho Cl gii phng Cl2.
2KMnO4 + 16 Cl + 16H+ 2K++ 2Mn2+ + 6 Cl + 8H2O + 5Cl2 Trong thc t, s oxy ho nhng ion Cl ch xut hin khi nng mui cao v khi nhit mi trng cao hn nhit ca phng th nghim. Do c th phng thch Cl2, phi trnh nh lng FeCl2 bi phng php permanganat trong mi trng HCl v ion Fe2+ li cng xc tc phn ng ny. Trong nhng trng hp c bit HCl cng c dng khi oxy ho trc tip anhydrid arsen (phng php Bright). b) HNO3: ion nitrat cha nhng ion nitr khng nh hng bt li nhng v HNO3 trong thng mi lun lun v anion ny kh permanganat nn acid HNO3 thng khng uc dng.
c) H2SO4 v H3PO4: thng s dng 2 acid ny lm mi trng 2KMnO4 + 3 H2SO4 hay K2SO4 + 2MnSO4 + 2H2O + Mn2+ + 4H2O O2
+ 8H + + 5e
11/25/2010
Page 159 of 239
3.1.4. Dung dch chun s dng trong php o permanganat - Dung dch chun KMnO4 0,1N: mui ny t kh d dng khi c mt nhng tp hu c, do khi cn trc tip ha tan th nng thng di mc mong mun. - iu ch: Ho tan khong 3,25 g KMnO4 ny trong 1 lt nc un si trc. Bo qun dung dch trong l sch v vi ngy trc khi thc hin chun li. Trong khong thi gian ny nhng cht hu c s b oxy ho v nng gim nh. Khi tt c nhng cht hu c b oxy ho th nng ca dung dch hu nh bn vng. Lc qua bng thu tinh hay phu thu tinh xp. Dch lc c cha trong nhng chai thu tinh mu v nh sng xc tc s phn hu permanganat. Khi s dng, xc nh li nng bng dung dch acid oxalic. - Bo qun: trnh nh sng hon ton v nh sng xc tc s phn hy permanganat. 3.1.5. ng dng nh lng bng php o permanganat 3.1.5.1 nh lng cc hp cht v c a) nh lng mui st II: (Fe2+ c tnh kh) trong thc t hay s dng mui Mohr Fe2+ Cl Fe3+ (mi trng H2SO4)
Nu mui st II dng clorid th s dng cromat acid kali hay cerium (IV) lm tc nhn oxy ho v s lm ri nh lng do to Cl2. b) nh lng mui st (III) (Fe3+ c tnh oxy ho)
Phi kh ion Ferric (Fe3+) trc vi mt lng tha thuc th Sn2+, amalgam km (Zn), anhydrid sulfur hay H2SO4. Ion st II (Fe2+) c to nn s uc chun bng dung dch permanganat. c) nh lng peroxyd Hydroperoxyd (nc oxy gi) (peroxyd hydro) va c tnh oxy ho, va c tnh kh. Khi tc dng vi cht kh mnh hn th th hin tnh oxy ho: (O2)2 + 2e + 4H+ 2H2O Khi tc dng vi cht oxy ho mnh hn th th hin tnh kh: (O2)2 2e O2 Trng hp hydroperoxyd l cht kh: s dng dung dch kali permanganat 0,1N nh lng nc oxy gi trong mi trng acid. C ch phn ng: KMnO4 phn hy hydroperoxyd phng thch oxy theo phng trnh: 2KMnO4 + 5H2O2 + 3H2SO4 K2SO4 + 2Mn SO4 + 5O2 + 8H2O
11/25/2010
Page 160 of 239
Hydroperoxyd l cht kh: H2O2 2e- + 2H+ + O2 tnh c cc loi nng ca dung dch hydroperoxyd phi tnh c ng lng gam, ng lng th tch ca hydroperoxyd: ng lng gam:
ng lng th tch ca hydroperoxyd l s lt oxy gii phng ra do 1 ng lng gam hydroperoxyd b phn hy hon ton.
Vy ng lng th tch ca hydroperoxyd l 5,6 lt ( iu kin tiu chun). T tnh c s lt oxy gii phng ra do 1 lt dung dch nc oxy gi c nng N b phn hy hon ton. = 5,6 N l th tch oxy gii phng ra do 1 lt dung dch hydroperoxyd b phn hy hon ton. N l nng ng lng ca dung dch hydroperoxyd. Ch : php nh lng ch cho kt qu chnh xc khi nng dung dch hydroperoxyd em chun xp x 1 th tch. Mt ng lng ca KMnO4 tng ng vi 17 gam hydroperoxyd hoc tng ng vi 16 gam oxy hay tng ng vi 11,2 lt kh O2 trong iu kin tiu chun v p sut v nhit . Ch : nhng cht bo qun (acid benzoic...) trong nc oxy gi c th dn n nhng sai s tha v nhng hp cht ny b dung dch permanganat oxy ho. d) nh lng nitrit Cc nitrit trong mi trng acid c oxy ho bng KMnO4. ng lng ca KMnO4 tng ng vi nitrit mol nitrit. Phn ng xy ra nhit gn 40oC. Ion
b phn hy d dng cho nn nitrit vo buret v cho t t vo dung dch chun c acid ho trc bng H2SO4 n khi mt mu dung dch.
11/25/2010
Page 161 of 239
3.1.5.2. nh lng cc hp cht hu c Vic s dng trc tip KMnO4 phn tch cc hp cht hu c hin nay t c s dng. 3.2 Php o iod 3.2.1. Nguyn tc Phng php iod bao gm vic nh lng s dng tnh cht oxy ho kh ca h thng iod/iodid (I2/2I) Iod (I2) l mt halogen c tnh oxy ho mnh thu 1 electron khi tc dng vi cht kh. I2 + 2e 2I Ngc li iodid (I) c tnh kh d nhng 1 electron khi tc dng vi cht oxy ho: 2I - 2e I2 Do vy dung dch I2 nh lng cht kh v dung dch iodid nh lng cht oxy ho: I2 + 2e 2I 3.2.2. Cc k thut chun trong php o iod Cc k thut chun c gii thiu trong bi phng php phn tch th tch, phn ny s nhc s b cch tin hnh trong php o iod. 3.2.2.1. Chun trc tip Tin hnh: chun cc dung dch c tnh kh bng dung dch chun iod. Th oxy - kh chun E0= + 0,535 V cho thy iod l mt tc nhn oxy ho yu ( v tr gia ca bng th oxy ho - kh chun). I2 + 2e 2I ; E0 = + 0,535 (V) Tuy vy, c vi cht c chun trc tip bng dung dch iod thch hp hn v tc ng oxy ho nh ca iod li c li trong khi s dng cht chun mnh hn c th gy ra s oxy ho khng t lng. 3.2.2.2. Chun tha tr (chun ngc) Tin hnh: thm mt lng tha dung dch KI vo mu cha cht oxy ho. Cht oxy ho ny b iodid kh, kt qu to thnh mt lng iod tng ng v c chun bng natri thiosulfat chun. Aox + I (lng tha) AKh + I2
11/25/2010
Page 162 of 239
Iod to thnh trong phn ng u tin tng ng vi lng tc nhn oxy ho Aox c trong mu. K iod to thnh c chun bng natri thiosulfat, cc ion iodid v tetrathionat l cc sn phm. 3.2.2.3. Chun th Tin hnh: cho mt th tch chnh xc dung dch cn nh lng tc dng vi mt lng d thuc th no , phn ng sinh ra mt lng cht mi tng ng ho hc vi lng cht cn xc nh. Dng dung dch chun nh lng cht mi sinh ra. Th d: nh lng K2Cr2O7 bng cch cho tc dng vi KI tha (mi trng acid) gii phng iod (lng tng ng). K2Cr2O7 + 6KI + 7H2SO4 3I2 + Cr2(SO4)3 + 4K2SO4 + 7H2O Thay v nh lng K2Cr2O7 th s nh lng I2 phng thch bng Na2S2O3. 2Na2S2O3 + I2 2NaI + Na2S4O6 3.2.3. iu kin tin hnh 3.2.3.1 Vai tr ca pH V h I2/2I trong thang th oxy ho kh v tr gia (th chun oxy ho kh = 0,54 volt pH = 9) nn tnh oxy ho hay tnh kh ca h ny thay i theo bn cht ca cp oxy ho - kh hin din v theo pH ca mi trng phn ng. - Trong mi trng acid: kh nng oxy ho ca iod th hin i vi cc h thng c th oxy ho kh thp hn h thng (I2/2I). Th d: iod c th oxy ho thic clorid (SnCl2), hydro sulfua (H2S), acid sulfur (SO2), natri thiosulfat (Na2S2O3). - Trong mi trng acid mnh: mt s h oxy ho - kh li c th tng ln v kh nng kh ca iodid li th hin. Do vy trong mi trng acid mnh, iodid kh acid nitr HNO2, cc arseniat .
- Trong mi trng trung tnh, th ca vi h thng oxy ho kh gim v nh vy c th b oxy ho bi iod. Th d: c th oxy ho nhng arsenit bi iod trong mi trng trung tnh.
Nh vy, mi trng acid yu hoc trung tnh hoc kim nh (pH = 5 - 8): thng c s dng chun trc tip iod trong php o iod. Trong vi trng hp chun trc tip iod, pH cn phi theo tht ng. Th d: trong dung dch trung tnh, vic chun arsenic (III) thnh arsenic (V) bng iod din ra tt theo phng trnh phn ng:
Tuy nhin, trong dung dch acid mnh th phn ng s chy theo chiu ngc li, arsenic (V) thnh arsenic (III): H3AsO4 + 2I + 2H+ H3AsO3 + I2 + H2O
- Trong mi trng kim pH 9 thng mc phi sai s do iod oxy ho thnh hypoiodid (IO-)
11/25/2010
Page 163 of 239
khng bn v phn hu thnh iodat (
), IO- c tnh oxy ho mnh hn iod, n chuyn c ion
thnh S4O6 dn n sai s do khng nn tin hnh php o iod trong mi trng kim. I2 + 2OH IO + I + H2O 3.2.3.2. Nhit Tin hnh nhit thng (trong phng) v tin hnh nhit cao th iod s b thng hoa v nhy ca ch th gim, dn n sai s kt qu nh lng. 3.2.3.3. Thi gian phn ng Khi nh lng bng k thut chun th, phn ng gia kali iodid v cht oxy ho cn tin hnh trong 10 n 15 pht phn ng xy ra hon ton, ng thi kali iodid khng b phn hy thnh iod, cn trnh nh sng do phn ng:
3.2.3.4. Ch th Ch th thng s dng h tinh bt. Trong chun trc tip, nu h tinh bt c thm vo sm qu th iod s hp th trn h tinh bt d dn n sai s khi pht hin im kt thc. Khi nh lng dung dch iod c nng thp th nn thm h tinh bt hay thioden v khi c mt iodid, cc cht ny s cho phc mu xanh dng. Khi c mt ca cc dung mi hu c khng c oxy (cloroform, carbon tetraclorid) th mt git tha s lm cho pha hu c ny c mu hng. 3.2.3.5. Sai s oxy Sai s oxy l vn khi chun tha tr bng iod. Trong dung dch acid, oxy t khng kh oxy ho iodid thnh iod. O2 + 4I + 4H+ 2I2 + 2H2O Phn ng ny gy ra sai s tha khi chun gin tip bng iod. Sai s gia tng theo tnh acid. Sai s oxy trnh c khi thc hin trong kh quyn tr hoc thm carbon dioxid rn hay natri bicarbonat vo dung dch acid to ra s bo v ca carbon dioxid hoc trnh tha acid. 3.2.4. Dung dch chun s dng trong php o iod 3.2.4.1. Dung dch oxy ho a) Dung dch iod: iod l mt cht rn tan c trong mt s dung mi hu c nhng li t tan trong nc v d bay hi. Nhng khi c mt ca iodid (nh NaI hay KI) th iod phn ng vi iodid to thnh phc anion triiodid c mu nu m c th tan c trong nc. I2 + I I3
11/25/2010
Page 164 of 239
Do vy, khc phc khuyt im khng tan trong nc ca iod, dung dch chun iod c th iu ch bng cch ho tan cn thn mt lng iod trong dung dch nc c iodid. Trong cch vit v cn bng phng trnh ho hc, ngi ta vit n gin dung dch iod ho tan trong iodid l I2. Cc dung dch iod c pha ch nh th phi c bo qun trnh nh sng trong nhng l mu, c nt kn trnh s oxy ho cc iodid do oxy ca khng kh v trnh mt iod do bay hi. Phi trnh mi vt ng v kim loi ny d dng oxy ho cc iodid do oxy ca khng kh. b) Dung dch kali iodat: KIO3 (M = 214,02): Khi c mt 1 lng tha iodid v H+, 1 ion iodat phng thch 3 phn t iod s dng 6e-
+ 5I + 6H+ 3I2 + 3H2O
Pha dung dch kali iodat 0,1N theo Dc in Vit nam III (trang PL 28). C th thm vo dung dch ny mt lng tha KI trong lc iu ch (15 g/lt) hay trong trng hp ngc li, cho I vo mu th nghim ca dung dch ny lc s dng. Hn hp c acid ho bng 1 th tch tha dung dch HCl hay H2SO4 long. Iod phng thch s c chun bng natri thiosulfat. c) Dung dch kali bromat: (KCrO3; M = 167,01) c lm kh trc t 120oC 150oC BrO3 + 6I + 6H+ 3I2 + Br + 3H2O Khi pha, thm dung dch I vo lc nh lng (ging trng hp ca kali iodat). - pha dung dch kali bromat 0,1N theo Dc in Vit nam III (PL 27). d) Dung dch kali dicromat: (K2Cr2O7; M = 294,21) ging trng hp trn, khi c mt lng tha KI trong mi trng acid th kali dicromat c th phng thch iod theo phn ng: + 14H+ +6I 3I2 + 2Cr3+ + 7H2O Phn ng thc hin vi s c mt ca 1 lng tha acid. Dung dch natri thiosulfat c cho vo buret. im tng ng c xc nh nh h tinh bt c thm vo cn im tng ng. Ion Cr3+ c mu xanh lc. S chuyn mu t xanh dng m n xanh lc. 3.2.4.2. Dung dch kh Dung dch natri thiosulfat (Na2S2O3) - Pha ch: thng thng, dung dch natri thiosulfat c pha ch nng 0,1N. Nc dng pha phi ui kh carbonic trc v acid i vo dung dch ny s lm c t t thiosulfat do to ta lu hunh: + 2H+ SO2 + S + H2O Phi bo qun trnh nh sng. Cn thm vo mt t cht bo qun nh natri borat (3%) hay cn
11/25/2010
Page 165 of 239
amylic (0,8%) trnh nhim vi sinh vt. Phn ng xy ra do iod oxy ho ion thiosulfat 2 + I2 thnh ion tetrathionat + 2I .
ng lng ca thiosulfat tng ng vi mt phn t gam (E = M = 248,2) Natri thiosulfat (Na2S2O3.5H2O) khng phi l cht gc v d ht nc. Do vy, mi ln nh lng phi chun li bng dung dch chun iod hoc dung dch chun permaganat (chun tha tr) hoc dung dch chun kali iodat (KIO3). 3.2.5. ng dng nh lng bng php o iod 3.2.5.1. Php o iod trong mi trng nc - Chun trc tip: Php o iod trong phn tch hp cht v c nh lng natri thiosulfat, cc sulfit, cc cyanid, cc mui kim loi. - Chun tha tr: (php o iodid) + Phn tch hp cht v c: nh lng halogen, cc hypohalogenid, cc iodat, cc arseniat, cc peroxyd: nc oxy gi, cc mui kim loi: mui ceric, mui ng, cc ferricyanid. + Phn tch hp cht hu c: Vi hp cht hu c c kh nng gn vo iod mt cch nh lng nhng mi trng thch hp v vi mt lng tha iod nn nh lng lun lun theo k thut chun tha tr. Song song thc hin mt mu trng. p dng k thut ny nh lng cc dn cht ca lu hunh hu c c cha nhm thiol, cc hydrazin v dn cht ca chng, nh lng gin tip cc formaldehyd, nh lng gin tip cc aldehyd + Xc nh ch s iod nh ngha: ch s iod l s gam iod c kh nng c nh trn ni i ca 100 g cht kho st. chnh l phn trm iod c gn bi mt cht. Trong nhng iu kin c bit, iod c th c kh nng c nh trn ni i (trong mi trng khan). Tht vy, mt mnh iod khng th t gn trc tip v phi dng 1 halogenid (iodid, clorid hay bromid) tc ng bng cch t phn cc ho thnh I+ X theo phn ng: R C = C R + R CX Cl R Thuc th phi c cho vo vi lng tha v sau mt thi gian tip xc xc nh s c nh lng. Mt lng tha dung dch nc KI c thm vo v nh vy s phng thch nh lng iod bng tc ng ca halogenid iod trn KI: XI + I I2 + X Iod c phng thch s c nh lng bng natri thiosulfat. Trong nhng iu kin ny, mt nguyn t halogen X tc ng nh mt nguyn t iod v t tnh ton kt qu. Thc hin song song mt mu trng. 3.2.5.2. Php o iod trong mi trng khan (chun Karl Fischer)
11/25/2010
Page 166 of 239
Vic xc nh hm lng nc trong nhng cht v c cng nh cht hu c thng rt quan trng. Cho n nay, c nhiu phng php vt l v ho hc nh lng nc, nhng k thut Karl Fischer m t nm 1935 c s dng nhiu do tnh chnh xc v chuyn bit cng nh do tnh ton kt qu tng i n gin. Nguyn tc nh lng nc theo Karl Fischer: khi c mt nc th iod tc ng trn anhydrid sulfur cho acid sulfuric (H2SO4) v acid iodhydric (HI). 2H2O + SO2 + I2 H2SO4 + 2HI
Phn ng ny li c Bunsen thc hin vi s c mt ca pyridin lm cho phn ng hon ton dch chuyn v pha phi bng cch kt hp base ny vi nhng acid to thnh theo phn ng l thuyt tng qut: 2H2O + SO2 + I2 + 4C6H5 N (C6H5NH+)2 SO4 + 2C6H5NH+I Trong nhng iu kin cho, lng iod c tiu th thay i theo lng nc c mt trong phn ng, 1 phn t iod tng ng vi 2 phn t nc. nhy ca phng php tng c th gp i nu phn ng xy ra vi s c mt ca MeOH, 1 phn t ca dung mi ny s thay th 1 phn t nc. Phn ng c th b phn hy thnh 2 giai on lin tip: - Iod v anhydrid sulfur kt hp trc vi pyridin. SO2 + I2 + 3C6H5 N C6H5 N + C6H5 NI2 + C6H5 NSO2 Sau phn ng ton phn ny, mt phn t nc tiu th 1 phn t iod, mt phn t anhydrid sulfur, 3 phn t pyridin v mt phn t methanol. H2O + C6H5 N + C6H5 NI2 + C6H5 NSO2 2C6H5 NH+I + C6H5 N+SO3 C6H5 N+SO3 + CH3OH C6H5 NH+CH3O SO3 3.3. Php o nitrit 3.3.1. Nguyn tc Trong mi trng acid, natri nitrit tc dng vi amin thm bc nht to mui diazo khng mu (phn ng diazo ho). NaNO2 + HCl HNO2 + NaCl ArNH2 + HNO2 + HCl [ArN+ N]Cl + 2H2O T th tch dung dch natri nitrit 0,1M phn ng, tnh nng hoc hm lng cht cn xc nh. 3.3.2. iu kin tin hnh - Mi trng phi acid v long. - Nhit thp (thm nc ). - Khuy u dung dch cn chun .
11/25/2010
Page 167 of 239
- Lc u nh dung dch chun khong 2ml /pht, n trc im tng ng khong 1ml th nh tng 0,1ml mt v yn t nht mt pht sau mi ln thm dung dch. (hin nay phng php nitrit c nu r cch tin hnh trong cc dc in v c th c kt qu do s thay i th oxy ho kh hoc chun ampe. Nu khng c my th s s dng ch th pht hin im kt thc). 3.3.3. Dung dch chun s dng trong php o nitrit Dung dch natri nitrit (NaNO2) nng 0,1M. Cc nitrit (NaNO2) bn hn l HNO2. Chng ho tan tt trong nc. Cht ha tan km nht l AgNO2 (bc nitrit) nhng tan tt nhit nng. Vi mui phc cha ion NO2 km tan, Th d: K3[CO (NO2)6], (NH4)3[CO(NO2)6],.... Khc vi acid nitric, acid nitr tng i yu (K= 4.10-4). l anion ca HNO2. Acid ny ch hin hu trng thi t do trong dung dch acid long nhit lnh v s b phn hy mt cch d dng thnh anhydrid nitr v nc: 2HNO N O + H O 2 2 3 2 Anhydrid nitr bn v ch c mt nhit thp. nhit trong phng, n t phn hy tc khc vi s to thnh oxyd v peroxyd nit. N2O3 NO + NO2 3.3.4. Ch th s dng trong php o nitrit Ti im tng ng, 1 git tha dung dch natri nitrit s phn ng vi ch th tropeolin 00 lm cho dung dch nh lng c mu vng. Cch dng ch th mu tropeolin 00: cho 4 git ch th mu vo bnh nh lng, nh dung dch natri nitrit 0,1M vi tc 2ml trong 1 pht. Khi mu chuyn sang mu nht ri mt mu th tc nh natri nitrit chm li (1 git trong 1 pht), n khi xut hin mu vng nht bn vng trong 2 - 3 pht th kt thc nh lng. C th dng hn hp tropeolin 00 (4 git) v xanh methylen (2 git) thay cho tropeolin 00, chuyn t mu tm thnh xanh da tri. 3.3.5. ng dng nh lng bng php o nitrit - Xc nh cc ch phm c cha nhm amin thm bc nht nh procain, cc sulfamid hoc nhng ch phm khc m qua bin i ho hc chuyn c thnh hp cht c nhm amin thm bc nht. 3.4. Php o crom 3.4.1. Nguyn tc Trong mi trng acid, cn bng oxy ho - kh c vit:
11/25/2010
Page 168 of 239
+ 14H+ + 6e- 2Cr3+ + 7H2O ng lng = E0 (Cr2O72- / 2Cr3+) = +1,35V pH=0
Kh nng oxy ho ca bicromat yu hn permanganat (E0 = +1,51V pH = 0). Bicromat l mt cht chun v c th pha ch dung dch c chun chnh xc bng cch cn n gin. Phn ng cng c th c thc hin trong mi trng HCl c pH 1-2 v cc ion Cl khng gy ri phn ng v cc cht hu c c trong nc khng kh bicromat. Dung dch chun c bo qun tt ngay c di nh sng. Ngc li, c mt khuyt im l kh ghi nhn c im tng ng do s thay i mu ca mui crom: c mu vng hi m 3+ trong dung dch long thnh Cr mu xanh lc. Ch th cn thit s dng l diphnylamin p-sulfonat (khng mu dng b kh v tm nht dng b oxy ho) hoc dimethyl furoine. 3.4.2. Dung dch chun s dng trong php o crom Kali bicromat (K2Cr2O7) phi c sy kh trc 120oC 130oC v nghin nh ri ho tan trong nc (c th dng nc m). Dung dch 0,1N ca cht ny rt bn v c th bo qun v hn. 3.4.3. ng dng nh lng bng php o crom 3.4.3.1. nh lng cc hp cht v c a) nh lng mui st (II) hay mui st (III) bng my chun th hay bng ch th mu sau khi kh trong mi trng acid phosphoric pha long. b) nh lng gin tip mui ch hay mui baryum Trong mi trng acid acetic, cc ion nh Pb2+ v Ba2+ ta hon ton vi s hin din ca mt lng tha ion bicromat. Vic nh lng c thc hin theo 2 k thut khc nhau: Hoc l sau khi tch ta, lng tha ion bicromat c nh lng bng php o iod. (Mt lng KI tha c thm vo v iod phng thch c chun bng thiosulfat natri). Hoc l thu li ta, em cn v ra bng acetat ammonium loi lng bicromat tha. K ta c ho tan li trong acid hydrocloric 5N v cc ion bicromat gn vi ch hay baryum c nh lng bng dung dch chun mui st II. 3.4.3.2. nh lng cc hp cht hu c nh lng cn EtOH: cn ethanol tinh khit c oxy ho bi bicromat trong mi trng acid thch hp n khi to thnh acid acetic: CH3 CH2OH + O2 CH3COOH S oxy ho c thc hin theo 2 k thut khc nhau: Phng php NICLOUX: Oxy ho cn trong mi trng sulfuric vi s hin din ca lng bicromat tha 45oC. K , lng tha bicromat c kh bng lng mui st (II) tha ri chun
11/25/2010
Page 169 of 239
mui st (II) tha bng permanganat. Song song thc hin mt mu trng. Phng php CORDEBARD: Oxy ho cn trong mi trng nitric mnh nhit lnh vi s hin din ca lng bicromat tha. Sau mt thi gian phn ng khong 30 pht, s oxy ho s hon ton v lng tha bicromat c nh lng bng php o iod vi s pha long kh ln ca dung dch. Song song thc hin mt mu trng. Phng php ny c dng nh lng cc acid c chc alcol nh l acid lactic. 3.5. Php o ceri 3.5.1. Nguyn tc Trong mi trng acid, cn bng oxy ho - kh c vit: Ce4+ + 14H+ + 1e Ce3+ ng lng = M, E0 = 1,33V pH= 0. Th chun biu kin ca h thng Ce4+/Ce3+ thay i theo bn cht ca acid c s dng acid ho mi trng v nng ca n. Th thp nht c quan st trong mi trng acid hydroclohydric v cao nht trong mi trng acid percloric. Trong mi trng nitric, gi tr ca th gim nh khi chun ca acid i t 1N n 8N. Ngc li, trong mi trng percloric th ny tng theo nng ca acid. Cc thay i ny c c do s to thnh phc trong mi trng kho st. - Tht vy, trong mi trng sulfuric th Ce4+ hon ton dng phc tetrasulfatoacetic [Ce(SO4)4] H4. Kt qu l khi tng nng acid sulfuric t nh hng n th oxy ho - kh v khng to phc khc vi phc trc. - Ngc li, trong mi trng percloric th to thnh phc [Ce(OH)2]2+,[Ce(OH)]3+, [OHCeO CeOH]4+, [CeOCeOH]5+ m nng tng ng lin quan vi nng ca acid percloric. Kt qu l th oxy ho - kh gia tng theo nng acid tng. - Trong mi trng acid yu hay trung tnh: Ce4+ ta khi to Ce(OH)4 v cc tnh cht oxy ho ca chng bin mt.
B ng 8.4. Th chun biu kin ca h thng Ce4+/Ce3+o c trong cc acid khc nhau Th chun biu kin (volt) acid percloric 1,70 1,71 1,75 acid nitric 1,61 1,62 1,61 acid sulfuric 1,44 1,44 1,43 acid hydrocloric 1,28 -
Nng acid (N) 1 2 4
11/25/2010
Page 170 of 239
6 8
1,82 1,87
1,56
1,42
3.5.2. Dung dch chun s dng trong php o ceri Cc dung dch mui ceri thng c s dng ca cc mui: Ceri sulfat khan Ce(SO4)2; Ceri ammoni sulfat (NH4)2Ce(SO4)4.2H2O; Ceri ammoni nitrat (NH4)2Ce(NO3)6. Thng thng, cc dung dch chun 0,1N c iu ch trong mi trng sulfuric (1-3M) hoc trong mi trng percloric. Dung dch sulfuric ca mui ceri c th c bo qun trong 1 nm. Cc dung dch percloric ca mui ceri ch c th gi trong mt gi. Cc dung dch dng chun li dung dch ceri hay c s dng: dung dch permanganat hay bicromat, mui st II, anhydric arsen. 3.5.3. ng dng nh lng bng php o ceri 3.5.3.1. nh lng cc hp cht v c: mui st (II), peroxyd, nitrit (nh php o permanganat). 3.5.3.2. nh lng cc hp cht hu c: cc acid nhit nng hoc lnh (acid lactic, acid pyruvic), alcol, aldehyd, polyalcol. V s oxy ho xy ra thng chm nn phi s dng phng thc chun ngc nh sau: cho mt lng tha ion ceric vo dung dch cn nh lng, sau mt thi gian phn ng thch hp th nh lng ion ceric tha bng mui st (II). T KHA Phn ng oxy ho kh H thng oxy ho - kh Th in cc H thng oxy ho kh Phng php oxy ho kh Th oxy ho kh Th oxy ho kh biu kin Hng s cn bng Php o permanganat Php o iod Karl Fischer Chun oxy ho kh Php o nitrit Php o cromat Th oxy ho kh Th chun Chun oxy ho - kh Php o permanganat Php o iod Php o nitrit
CU HI LNG GI 1. Phn ng oxy ho kh l g? S khc nhau gia phn ng oxy ho kh v phn ng acid base?
11/25/2010
Page 171 of 239
2. Th oxy ho kh? Th biu kin? Cc nh hng ca pH, s to phc, s to ta n th biu kin? 3. Cch tnh th im tng ng? 4. Phng php chun oxy ho kh? 5. ng dng phng php chun oxy ho kh trong ngnh Dc? CU HI TRC NGHIM 1. Phn ng oxy ho - kh l phn ng tng ng vi s trao i electron gia hai hp cht: mt cht cho electron - gi l cht...A.... v mt cht nhn electron -gi l cht....B..... a. (A) = kh v (B) = oxy ho b. (A) = acid v (B) = base c. (A) = acid lin hp v (B) = base lin hp 2. Cht kh v cht oxy ho c th l hai cht....(A).... [phn ng ho hc] hoc l mt cht....(B)... v mt....(C).... m th c chn thch hp [phn ng in ho]. a. (A) = trung tnh; (B) = acid; (C) = base b. (A) = ho hc; (B) = oxy ho; (C) = kh c. (A) = ho hc; (B) = ho hc; (C) = in cc d. (A) = lng tnh; (B) = ho hc; (C) = in cc e. (A) = ho hc; (B) = kh; (C) = in cc 3. Phn ng oxy ho - kh l phn ng trao i ....... t cht tham gia ny sang cht tham gia kia. a. H+ b. OHc. cation d. ion e. electron d. (A) = oxy ho v (B) = kh e. (A) = base v (B) = acid
4. Phn ng oxy ho kh tc l qu trnh cho nhn... (A)... thng xy ra...(B)...v i hi tng nhit , thm xc tc. a. (A) = electron v (B) = nhanh b. (A) = proton v (B) = chm c. (A) = electron v (B) = chm 5. Nu dung dch c pha long y th.......... v nng c th c dng ln ln. a. ng lng b. cht in ly c. dung dch m d. hot e. dung dch gc d. (A) = proton v (B) = nhanh e. (A) = ion v (B) = chm
6. Theo quy c, th Eo ca hydro bng...... volt v th ca nhng h thng khc c xc nh theo t l ca th ca in cc ny
11/25/2010
Page 172 of 239
a. 0,00 b. 1,00
c. 1,00 d. 10,0
e. khng cu no ng.
7. Mt kim loi c th cho nhng ion tng ng vi nhiu ho tr. Ion c in tch dng ln nht tng ng vi dng... (A)... Ion c in tch dng nh nht tng ng vi dng... (B) a.(A) = kh v (B) = oxy ho b. (A) = oxy ho v (B) = kh c. (A) = acid v (B) = base 8. Nu nhng nng dng oxy ho v dng kh bng nhau, th c gi trong in cc = Eo v Eo c gi l...(A)... ca h thng. a. th biu kin b. th cn bng c. th chun d. im tng ng e. im kt thc d. (A) = base v (B) = acid e. (A) = phn ly v (B) = khng phn ly
9. Th biu kin nh hng bi: a. pH b. s to phc c. s to thnh kt ta d. c ba cu tr li trn e. ch a v c ng
10. Thuc th KF ch yu gm thnh phn a. MeOH b. SO2 c. C6H5 N d. iod e. SO2 + I2 + C6H5 N
Chng 9 PHNG PHP KT TA

MC TIU - Gii thch c biu thc tch s tan, tan v ngha ca n trong phn tch. - Trnh by c cc yu t nh hng n tan cht in ly t tan v tnh c tan ca cht trong cc iu kin c th. - Trnh by c hin tng hp ph khi chun theo phng php bc. - Trnh by c nguyn tc, iu kin tin hnh v ng dng ca 3 phng php: Mohr, Fajans,
11/25/2010
Page 173 of 239
Volhard. - Nu c ng dng ca phn ng kt ta- ho tan trong phn tch. NI DUNG 1. L THUYT V S KT TA Phn ng kt ta l phn ng to thnh cht rn t cc cht tan trong dung dch. Trong qu trnh phn tch nh tnh, nh lng ta thng phi s dng n phn ng kt ta tch ring cc ion phn tch khi cc ion khc. 1.1. Tch s tan ngha trong phn tch 1.1.1. Biu thc tch s tan Khi ha tan mt cht no trong nc, th hai qu trnh ngc chiu nhau s xy ra cng mt lc. Khi dung dch ca cht no cha bo ha, th qu trnh ha tan nhng lng mi ca cht s ln hn qu trnh kt ta n t dung dch. Th d:
Khi dung dch qu bo ha, c hin tng ngc li qu trnh tch cht tan khi dung dch ln hn qu trnh ha tan n. Khi dung dch bo ha c kt ta cht tan lng xung di, trng thi cn bng ng c thit lp. Trong trng hp ny tc ha tan bng tc kt ta. Khi cn bng c thit lp, trong 1 n v thi gian c bao nhiu ion Ag+ v Cl chuyn thnh kt ta, cng c by nhiu ion chuyn t b mt kt ta vo dung dch. Theo nh lut tc dng khi lng khi cn bng c thit lp, trong dung dch nc bo ha ta c:
Trong cc h ng th, s va chm gia cc phn t c bn xy ra trong ton b vt th ca cht. Trong cc h d th, s va chm gia cc phn t c bn ca cht tan v cht rn ch xy ra trn b mt phn chia cc tng v khng ph thuc vo lng ca cht rn, nng ca n khng i v khng nh hng n tc ca phn ng. Do c th vit: [Ag+ ] [Cl] = KAgCl [AgCl] = hng s Tch s nng cc ion ca cht in ly t tan trong dung dch nc bo ho gi l tch s tan v c k hiu bng ch T cng vi cng thc ho hc ca cht in ly . Th d: [Ag+ ] [Cl ] = TAgCl
11/25/2010
Page 174 of 239
ngha trong phn tch Theo nh lut tc dng khi lng khi thit lp cn bng trong dung dch nc bo ha ca cht in ly t tan nhit v p sut nht nh, tch s nng ion (T) l i lng khng i v c biu din bng cng thc chung: TAmBn = hng s (const) = [A]m x [B ]n h s m, n ch s ion tng ng to thnh khi phn ly 1 phn t. - Nu tch s [A]m [B ]n > TAmBn th hp cht t tan tch ra dng kt ta (mun c kt ta). - Nu tch s [A]m [B ]n < TAmBn kt ta khng tch ra m b ha tan (mun kt ta tan c). Quy lut ny l c s l thuyt quan trng lm c s ca l thuyt to thnh kt ta. N c ngha trong phn tch l bit T ca 1 cht ta c th suy ra iu kin c kt ta hay ha tan ta. Thm bt k ion to thnh hp cht AmBn u lm gim tan, thm cc cht in ly khc khng c ion chung vi hp cht AmBn lm tng tan. 1.2. tan (S) 1.2.1. tan trong nc nguyn cht c trng cho tnh tan ca kt ta, ngoi T, ngi ta cn dng tan S. tan S v T lin quan mt thit vi nhau, bit T c th tnh c tan v ngc li. tan tnh theo mol/l, g/l. - i vi cht in ly t tan dng AB (cng ho tr), th d AgCl, BaSO4 AB A+ + B
Th d: Tnh tan ca BaSO4, bit
- i vi cht in ly t tan dng AmBn (khng cng ho tr), th d Ag2CrO4 AmBn mAn+ + nBm
11/25/2010
Page 175 of 239
Th d: Tnh tan ca Ca3(PO4)2 20 25oC trong nc nguyn cht, bit
Tnh tan ca Ag2CrO4, bit
1.2.2. tan cht in ly trong nc khi k ti h s hot i vi cht in ly dng AB
Th d: Tnh tan ca SrCrO4 bng g/l 25oC (tnh ti h s hot ).
i ra: 6.10-3 203,61 = 1,22 (g/l) Khi k ti h s hot
i ra: 1,05.10-2.203,61 = 2,14 (g/l) 1.2.3. tan ca hydroxyd kim loi trong nc Cch tnh theo phng php h thng. xc nh tan ca hydroxyd kim loi, ta xt hai cn bng ca phng trnh.
11/25/2010
Page 176 of 239
Th d, i vi hydroxyd kim loi ho tr 2 (M2+): M(OH)2 (rn) 2H2O H thng ny c th vit: [M2+] [ OH] 2 = T (9.1) (9.2) Ph hp vi iu kin ca cn bng trung ha in tch: 2[ M2+] + [ H3O+] = [ OH] Nu nh hydroxyd tan, nng ion H3O+ s nh v phng trnh c rt gn: 2[ M2+] [ OH] Thay vo phng trnh (9.1) v sau khi bin i s l: [M2+] = (T/4)1/3 = S (9.4) (9.3) M2+ + 2OH
H3O+ + OH
Mt khc, khi tan ca M(OH)2 qu thp, i lng 2[ M2+] tr nn nh hn [ H3O+] v phng trnh (9.3) lc l: [H3O+] [OH] = 1,00. 10-7 Th tr li vo phng trnh (9.1) v chuyn i cc thnh phn ca phng trnh: [M2+] = T/[ OH] 2 = T / (1,00.10-14) = S Th d: Tnh tan ca Fe(OH)3 trong nc: Bc 1: Vit cc phng trnh phn ng c trong h. Fe(OH)3 (rn) 2H2O Fe3+ + 3OH (9.5)
H3O+ +OH
Bc 2: Xc nh cc nng cn bng l n s S = [ Fe3+] Bc 3: Vit cc hng s cn bng cho phn ng bc 1 [ Fe3+] [ OH] 3 = T = 2. 10-39 [ H3O+] [ OH] = 1,00. 10-14 Bc 4 v 5: Vit phng trnh bo ton khi lng v phng trnh cn bng in tch [ OH] = 3[ Fe3+] + [ H3O+]
11/25/2010
Page 177 of 239
Bc 6: Xc nh n s v s phng trnh c lp c Bc 7: Tm cch gim n s a h v mt phng trnh n gin 3[ Fe3+] [ OH] Bc 8: Gii phng trnh bc 7 tm ra nng cn bng ca mt n s [ Fe3+] (3[ Fe3+] )3 = 2.10-39 [ Fe3+] = [ (2.10-39)/ 27] 1/4 = 9,27.10-11 S = [ Fe3+] = 9,27.10-11 (mol/l) Bc 9: Kim tra li p s tm, kim tra cc gi thuyt bc 7. Gi thit rng: [ OH] 3[ Fe3+] = 3 (9,27.10-11) = 3.10-10
Khng nn tnh rng [ H3O+] nh hn 3[ Fe3+] nhiu m trong trng hp ny ta theo di hin tng nguc li: 3[ Fe3+] << [ H3O+] [ H3O+] = [ OH] V phng trnh trung ha in tch c vit nh sau: [ H3O+] = [ OH] = 1,00. 10-7
3[ Fe3+] << [ OH] hoc 3 2. 10-18 << 10-17 S = 2. 10-18 (mol/l) Gi thuyt 3[ Fe3+] << [ H3O+] l ng. iu ny khng nh thm rng trong cch tnh u khi gi thit khng ng c sai s ln. Cc th d trn chng minh rng tan ca cc hydroxyd kim loi c tnh tng t nh tan ca cc hp cht mang tnh kim yu; cc tnh ton ny c th khng nh chn 1 trong 2 kt qu gn ng. Nh vy tn ti khong gi tr tch s tan nn khng ly mt kt qu ngay t cc gi tr gn ng m tip tc gii theo cc phng trnh (9.1), (9.2), (9.3) tng ng vi c ba trng hp thay i. 1.3. Cc yu t nh hng n tan cht in ly t tan 1.3.1. nh hng ca ion cng tn ln tan ca cht in ly t tan Khi thm d thuc th kt ta, tan ca kt ta gim xung v ph thuc vo lng d ca ion thm vo ng dng vi mt trong cc ion to thnh kt ta. Th d: - Tnh tan ca AgCl trong dung dch NaCl 0,1M. Bit TAgCl = 1,7.10-10
11/25/2010
Page 178 of 239
Trong nc nguyn cht
tan AgCl trong dung dch NaCl 0,1M so vi tan trong nc gim i
7647 ln.
Nh vy, thm ion cng tn gy nh hng ln n tan ca cht in ly t tan v c kh nng lm cho s kt ta tng rn hon ton hn. 1.3.2. nh hng ca ion l (ion khng cng tn) ln tan ca cht in ly t tan (hiu ng mui) Nu cho vo dung dch bo ha ca mt cht in ly t tan bt k mt mui no khng c ion chung vi n th lc tng tc gia cc ion tng ln, do h s hot gim xung dn n T ca cht t tan tng ln so vi i lng T ca cht in ly ny trong nc tinh khit. S tng T ca cht in ly trong dung dch mui bo ha ion l gy ra s tng tan ca cht in ly. Tng tan ca cht in ly t tan khi c cc mui tan khc (hiu ng mui) c gy ra do s gim h s hot gn lin vi s tng lc ion ca dung dch v thm cc cht in ly l vo. Ni cch khc, khng phi ch c cc cht in ly c ion chung mi nh hng n tan ca mui t tan. tan ca mt s mui t tan tng ln khi c cc mui tan khc khng c ion chung vi chng. Nng mui khng c ion chung vi cht in ly t tan c thm vo cng ln th tan ca n tng ln cng nhiu, v sc ion ca dung dch tng ln, do a cc ion khc vo, hin tng ny c gi l hiu ng mui. S thm cc cht in ly khc nhau gy nh hng khc nhau n tan ca cht in ly t tan v lc ion ca dung dch khng nhng ph thuc vo nng m cn vo ln in tch ca cc ion. Th d: tan ca PbSO4 tng ln khi c NaNO3, tan ca BaSO4, SrSO4, CaSO4 tng ln khi thm KCl, NaNO3, KNO3 v.v... vo dung dch. Tnh tan ca CaSO4 trong nc v trong dung dch NaCl 0,1M, bit tan trong nc: = 6,26.10-5
tan trong dung dch NaCl 0,1M (I = 0,1; f2 = 0,33)
11/25/2010
Page 179 of 239
Do tan ca CaSO4 trong dung dch NaCl 0,1M tng ln so vi tan trong nc gn 3 ln
1.3.3. nh hng ca nng ion hydro n tan ca hp cht t tan tan ca kt ta c ngha quan trng trong phn tch nh lng, n ph thuc vo nng ion hydro trong dung dch. C hai trng hp ch yu l anion ca kt ta l anion ca mt acid yu v cc hydroxyd ca cation kim loi. 1.3.3.1. pH mi trng l acid Ion hydro c nh hng ln n tan ca cc cht khc nhau. Trong mi trng acid, tan ca cht t tan cng ln nu T ca n cng ln v [H+] cng ln. Th d: so snh = 1,7 10-7 = 5,6 10-8 = 3,8 10-9 > > do trong mi trng acid, BaC2O4 tan tt hn, SrC2O4 tan km hn, CaC2O4 tan km hn c. tan ca cc mui ny trong acid HCl ln hn trong CH3COOH (phn ng tm Ca2+: CaC2O4/ CH3COOH trng khng tan). tan ca cht in ly cho trong nc cng ln v acid to thnh mui cng yu th tan ca cht in ly trong acid cng ln (hng s phn ly ca acid c tham gia vo thnh phn mui cho cng nh). Th d: trong CH3COOH, CaC2O4 khng tan (T = 3,8.10-9, 1,7.10-8; = 4,13.10-7) tan. = 5,9.10-2) cn CaCO3 (T =
1.3.3.2. tan ca kt ta khi anion l anion ca acid yu
- Trong dung dch nc AB

Kt ta
A+ + B
Dung dch
Nu thm acid mnh vo dung dch ny th anion B- s lin kt vi H+ to thnh acid yu HB. Khi cn bng s b ph hy v kt ta s b tan v [A+] [B] = TAB. Mi mt anion B c trong dung dch v lin kt thnh phn t HB tng ng vi cation A+, do :
11/25/2010
Page 180 of 239
[A+] = [HB] + [B] Thay gi tr [A+] t phng trnh biu din TAB ta c:
T nh lut tc dng khi lng rt ra
y [H+] = CHB [HB] ngha l nng ion H+ bng hiu s gia nng chung ca acid v phn khng phn ly ca n. Trong trng hp ring, khi [H+] = KHB
ngha ca phng trnh tan ca mui acid yu t tan (trong k c hydroxit v mui base) trong dung dch nc ca acid mnh to v p sut cho trc tng ln so vi tan ca n trong nc tinh khit. Hn na tan ny cng tng khi T ca cht in ly t tan, nng ion hydro cng cao v hng s phn ly ca acid yu to thnh mui ny cng nh. - Khi tnh tan ca mui t tan trong acid k ti h s hot ngi ta dng cng thc:
Th d: Tnh tan ca CaC2O4 trong dung dch c pH = 4. Bit T ca CaC2O4 = 1,8 10-9; H2C2O4 c K1 = 6,5 10-2 v K2 = 6 10-5. Phng trnh ca phn ng:
11/25/2010
Page 181 of 239
Ta tnh:
trc
y pH = 4 [H+] = 10-4 Thay vo phng trnh ta c:
tan tng nhng khng ng k so vi tan trong nc nguyn cht
Khi [H+] = 0,1 M th kt ta CaC2O4 s tan kh nhiu. Tht vy, lc :
So vi tan trong nc nguyn cht, tan tng
ln.
1.3.4. nh hng ca s to phc tan ca ta c th thay i khi c mt cc cht to thnh phc vi anion hay cation ca ta. Nh vy s to phc nh hng n tan ca ta. Nu nh bit hng s bn ca phc c th tnh c tan ca ta khi c tc nhn to phc. 1.3.4.1. Cht to phc l cht l Th d: Tnh tan ca AgBr trong dung dch NH3 0,1M: Bc 1: Vit phng trnh cn bng AgBr(rn) Ag+ + Br
11/25/2010
Page 182 of 239
Ag+ + NH3 + NH3 NH3 + H2O + OH
Bc 2: Xc nh cc nng cn bng l n s
Bc 3: Thay cc hng s cn bng [ Ag +] [ Br ] = T = 5,2. 10-13 (9.6) (9.7)
(9.8)
(9.9) Bc 4: Vit phng trnh cn bng in tch (9.10) Bc 5: Thay nng NH3 = 0,1M, c th vit: (9.11) Ngoi ra, trong tc dng ca amoniac vi nc trn mi mt ion nh vy: [ OH] [ Bc 6: Cn bng in tch [ ] + [ Ag +] + [ ]+[ ] = [ Br ] + [ OH ] (9.13) ] s c to mt ion OH, (9.12)
Bc 7: Loi bt n s; gi thit: -[ ] nh hn nhiu cc s hng khc trong phng trnh (9.11). iu ny thy r t phng trnh phn ly Kb. - Trong dung dch NH3 0,1M nng ln hn nhiu [ Ag +] nn [ Ag +] .T cc gi thit trn c: v
11/25/2010
Page 183 of 239
[ Br ] [ [ NH3 ] 0,10 - 2[
] ]
(9.14) (9.15)
Bc 8: Tm cc gi tr gn ng ca n s [ NH3 ] = 0,10 - 2[ Br ] (9.16)
(9.17)
t vo phng trnh cui (9.16) v (9.14) c: Thay [ Ag+] t phng trnh (9.6)
Gii phng trnh bc hai [ Br ] 2 + 2,88. 10-6[ Br ] 7,2.10-6 = 0 T y c: [ Br ] = 2,7. 10-4 (mol/l) S = 2,7. 10-4 AgBr (mol/l) Bc 9: Kim tra li thy rng cc gi thuyt trn l ng. So vi tan trong nc nguyn cht, tan tng 375 ln. 1.3.4.2. Cht to phc l ion cng tn Nhiu ta c th tc dng vi nhng ion c kh nng to phc tan. Th d: AgCl to phc clorid c thnh phn AgCl (rn) Ag+ + Cl AgCl + Cl Ag+ AgCl + , Cl v
11/25/2010
Page 184 of 239
+ Cl + Cl Khi nng cc ion cng tn tng trong nhng phn ng ny lm tng tan ca ta. Trn hnh 9.1 kho st s ph thuc tan tm thy qua thc nghim ca AgCl theo logarit nng KCl trong dung dch. Khi nng Cl nh hn 10-3M gi tr tan tm thy qua thc nghim hu nh khng khc so vi tnh ton theo tch s tan ca AgCl. Khi nng Cl tng cao, tan tnh c tin ti gn bng 0, trong lc ny cc i lng o c tng ln t ngt. Khi nng KCl gn bng 0,3M, tan ca AgCl ging nh trong nc nguyn cht, nu trong dung dch 1M, tan AgCl gn nh gp 8 ln ln hn i lng ny.
Hnh 9.1. tan ca AgCl trong dung dch KCl 1. ng cong tnh theo tch s tan; 2. ng cong qua thc nghim nhn c.
Khng t trng hp s tng tan khi cho lng tha ion cng tn, c bit l trng hp cc hydroxyd lng tnh nh Al(OH)3 v Zn(OH)2. Cc cht ny c to thnh dng ta t tan khi cho kim tc dng vi cc ion tan trong dung dch. Cc hydroxyd ny tan trong lng tha ion OH to thnh phc hydroxo nhm - km. i vi nhm phng trnh c th vit nh sau: Al3+ + 3OH + OH Al(OH)3 rn Al(OH)4
Al(OH)3 rn
Ging nh trng hp ca AgCl, tan ca Al(OH)3 v Zn(OH)2 sau khi t ti thiu, s tng t ngt khi nng ca ion cng tn tng. Nng ion OH- tng quan vi tan ti thiu, c th tnh ton khi bit hng s cn bng ca phn ng. Th d: Vi nng no ca OH th tan ca Zn(OH)2 t ti thiu? Hy tnh tan ti thiu? Phng trnh cn bng: Zn(OH)2 rn Zn2+ + 2OH
11/25/2010
Page 185 of 239
Zn(OH)2 rn + 2OH Biu th tan ca Zn(OH)2 l S, khi : S = [Zn2+] + [ Hng s cn bng: T = [Zn2+] [OH]2 = 1,2. 10-17 (9.19) (9.20) Thay phng trnh (9.19) v (9.20) vo phng trnh (9.18) (9.21) c tan ti thiu, ta ly vi phn phng trnh (9.21) v cn bng o hm theo [OH] tin ti 0 ] (9.18)
Nu
Th
tan ti thiu S tnh c khi thay nng OH vo phng trnh (9.21)
1.3.5. nh hng ca nhit n tan
11/25/2010
Page 186 of 239
Tch s tan ch l hng s mt nhit nht nh. Nhit thay i th tan cng thay i. S thay i ca tan theo nhit c lin quan ti hiu ng nhit khi ha tan. i vi cht thu nhit, khi ha tan, tc l nhit gim khi tan, th tan s tng cng vi nhit . V d: PbI2 tan rt nhiu khi un nng, khi lm ngui dung dch mi un nng th PbI2 kt tinh li, vy nh vng sng rt c trng. tan AgCl 100oC ln gp 25 ln tan ca n 10oC. i vi cht ta nhit khi ha tan th tan s gim khi nhit tng. V d: CaSO4.2H2O c tan thay i rt t khi nhit bin thin 0oC 60oC. 60oC phn t CaSO4.2H2O mt bt nc kt tinh thnh CaSO4.0,5H2O, CaSO4 c tan gim r rt khi tng nhit . tan ca n 60oC ln gp 3 ln tan 100oC. 1.4. ng dng trong phn tch Cn bng kt ta ha tan c ng dng nhiu trong phn tch nh tnh v nh lng. 1.4.1. Ha tan kt ta Cht kt ta Am Bn trong dung dch: AmBn mA + nB
ha tan kt ta ny cn gim nng ca A hoc B hoc c hai ion cn bng chuyn dch sang phi. C nhiu cch lm gim nng A hoc B: - Dng phn ng ho hc to cht t phn ly hoc cht bay hi. - Nu kt ta c tch s tan qu nh c th dng phn ng oxy ho - kh lm gim nhiu nng ion A hoc B. - C th ha tan bng cch chuyn ta kh tan thnh ta d tan. V d chuyn ta CaSO4 thnh CaCO3. 1.4.2. Kt ta hon ton Mun kt ta hon ton mt cht t dung dch cc kt ta tch ra phi c tan nh. V vy, cn phi to mi iu kin gim tan ca kt ta nh: - Cho thuc th d lm gim tan nhng lu khng cho d qu nhiu v xem c s to phc vi ion cng tn khng. - Chn pH thch hp. - Trnh cc phn ng ph ca ion kt ta trong dung dch (phn ng to phc, phn ng oxy ho, ...). 1.4.3. Kt ta phn on Trong dung dch nu c nhiu cht (nng gn bng nhau) cng to kt ta khi ta thm dn mt thuc th vo. Cht no c T nh s kt ta trc, cht c T ln hn s kt ta sau. l hin tng kt ta phn on.
11/25/2010
Page 187 of 239
Th d: Trong dung dch c ion Cl v I vi nng 10-2 mol/l. Thm dn dung dch AgNO3 vo. V TAgI = 10-16 nh hn TAgCl = 1,8 10-10, nn tch s ion Ag+ v I- vt TAgI nn ta c ta AgI trc. Khi kt ta AgI tip tc to thnh th [I] s gim dn, cn [Ag+] tng dn v ta AgCl bt u xut hin lc [Ag+][Cl] > TAgCl. Vy dung dch bo ha cha c ta AgCl khi [Ag+] = TAgCl/[Cl] = 1,8 10-8. thi im nng [I] trong dung dch: [I] = TAgI/[Ag+] = 1 10-16/1,8 10-8 = 0,55 10-8 Nh vy, cho AgNO3 vo dung dch ny kt ta c hon ton I di dng AgI, ion Cl vn cn ha tan. tch c ion I khi hn hp. Nguyn tc kt ta phn on l dng mt lng thuc th thch hp va kt ta ion c T nh hn nhng cha kt ta ion c T ln hn. Trong thc hnh phn tch, mt s trng hp tch cc ion di dng kt ta, ngoi yu t khc nhau v tan ln, ngi ta cn vn dng thm cc yu t khc nh pH, s to phc... qu trnh tch c hon ton. 2. NH LNG BNG PHNG PHP KT TA 2.1. Nguyn tc chung L phng php nh lng da trn vic dng phn ng kt ta (to thnh hp cht t tan) gia thuc th v cht cn nh lng. Phng php kt ta cho php ta nh lng cc anion nh Cl, Br, CN, SCN, v.v... v ngc li nh lng cc cation to thnh ta vi cc anion trn. Th d: Ag+ + Cl AgCl . 2.2. Phn loi Ngi ta phn loi phng php kt ta nh sau - Phng php bc: da trn vic dng dung dch chun l AgNO3, da trn kh nng to thnh mui bc. - Phng php thu ngn I: da trn vic dng dung dch chun mui thu ngn (I), to thnh hp cht thu ngn I khng tan nh Hg2Cl2, Hg2Br2, Hg2I2 . - Phng php thu ngn II: da trn vic dng dung dch chun mui thu ngn (II) to thnh hp cht thu ngn II km phn ly: HgCl2, Hg(CN)2, Hg(SCN)2... Tuy nhin cc phng php thu ngn (I), (II) c nhc im l mui thu ngn rt c nn t s dng. 2.3. Yu cu i vi phn ng trong phng php kt ta , ,
11/25/2010
Page 188 of 239
Khng phi tt c cc phn ng kt ta u c th dng xc nh nh lng. Cc yu cu c bn i vi cc phn ng c dng trong phng php kt ta l: - Phn ng gia cht cn xc nh (A) v dung dch chun ca thuc th B cn phi xy ra vi iu kin to thnh kt ta c tan ti thiu, v trong mi trng hp khng c vt qu tan -5 cho php 10 mol/l. Phc to thnh phi c hng s khng bn nh nht, hng s ny biu th mc bn ca phc. - V thm cc cht in ly khng c ion chung i vi kt ta AmBn lm tng tan ca n nn phn ng cn tin hnh iu kin khi cht l c mt trong dung dch phn tch khng cn tr s chun cht cn xc nh, phn ng kt ta kt thc nhanh v thc t n tn cng. 2.4. Phng php bc 2.4.1. c im ca phng php Phn tch chun da trn vic dng cht kt ta l dung dch chun Ag+ (AgNO3). Ag+ + An AgAn Phng php bc dng ch yu xc nh ion halogenid v Ag+. 2.4.2. ng biu din nh lng Th d: nh lng dung dch NaCl 0,1 N bng AgNO3 0,1N. Trc khi thm AgNO3 vo dung dch NaCl 0,1N phn ly hon ton thnh ion, nng ca Cltrong dung dch bng nng chung ca NaCl. [Cl] = C (nng NaCl) 0,1N = 10-1 pCl = -lg[Cl] = -lg10-1 = 1 pKa = -lgK pH = -lg[H+] pCl: ch s nng ging nh ch s phn ly acid. - Khi thm 90% AgNO3 0,1N th cn 10% Cl khng kt ta
- Khi thm 99% AgNO3 0,1N tng t nh vy ta c:
11/25/2010
Page 189 of 239
- Khi thm 99,9% AgNO3 tng t nh vy ta c:
B ng 9.1. Chun 100 ml dung dch NaCl 0,1N bng dung dch AgNO3 0,1 (khng k s pha long) Dung dch AgNO3 thm vo (%) 0 50 90 99 99,9 100*
NaCl cn li (%) 100 50 10 1 0,1 0 0,1 10-1
[Cl]
pCl 1 1,3 2 3 4 4,885 -
[Ag+] -
pAg
5. 10-2 10-2 10-3 10-4 1,303. 10-5 1,7. 10-6
3,4. 10-8 1,7. 10-8 1,7. 10-7 1,7. 10-6 1,303. 10-5 10-4
8,47 7,77 6,77 5,77 4,885
100,1
AgNO3(d) 1
5,77
101
AgNO3(d) 10
1,7. 10-7
6,77
10-3
110
AgNO3(d)
1,7. 10-8
7,77
10-2
* im tng ng
do :
Khi thm 100% AgNO3 0,1N, im tng ng ta c dung dch bo ha AgCl, [Cl] = [Ag+ ],
11/25/2010
Page 190 of 239
[Cl-] = [Ag+ ] = pCl = pAg =5-lg1,3= 4,885 Khi cho tha 0,1% AgNO3 0,1N [Ag+ ]= 10-4 pAg = 4, [Cl]= 1,7. 10-6 (mol/l), pCl = 5,77
- Khi tha 1% AgNO3 0,1N [Ag+ ] = 10-3 pAg = 3 [Cl] =1,7. 10-7 pCl = 6,77 ng biu din
Hnh 9.2. ng cong chun dung dch NaCl 0,1N bng dung dch AgCl 0,1N
Nhn xt ng biu din c dng chung ging cc ng biu din nh lng khc, gn im tng ng c bc nhy pCl = 4-5,77, pAg = 5,77-4. Tr s bc nhy ph thuc vo nng dung dch cn chun v dung dch chun. Nng cng ln th bc nhy cng di (Nu nng 1N bc nhy bt u pCl = 3 v kt thc pCl =6,77 di hn bc nhy nng 0,1N). Bc nhy cn ph thuc vo tch s tan ca ta. Tch s tan cng nh bc nhy cng di v ngc li. Trong phng php kt ta dng nhng phn ng kt ta T 10-10. Cch chn ch th mu tng t cc phng php trn ch th c s bin i mu trong bc nhy. 2.4.3. Cc yu t nh hng n ng cong chun - nh hng ca nng dung dch cn chun v dung dch chun
11/25/2010
Page 191 of 239
so snh, trong bng 9.2 trnh by cc s liu th hin s thay i ca pCl khi chun 100 ml dung dch NaCl vi nng 1N, 0,1N, 0,01N bng cc dung dch AgNO3 vi nng tng t. Cc d liu ny c biu din bng th trn hnh 9.3.
B ng 9.2. nh hng ca nng dung dch cn chun v dung dch chun n s thay i ca pCl khi chun 100 ml dung dch NaCl bng dung dch AgNO3 Dung dch AgNO thm vo 3 (ml) Nng NaCl hay AgNO (%) 3 pCl 1N 0,1N 0,01N
Trc im tng ng 0 50 90 99 99,9 100 50 10 1 0,1 0 0,3 1 2 3 Ti im tng ng 100 0 4,885 Sau im tng ng 100,1 0,1 AgNO (d) 3 1 AgNO (d) 3 10 AgNO (d) 3 6,77 5,77 5,04 4,885 4,885 10 1,3 2 3 4 2 2,3 3 4 4,73
101
7,77
6,77
5,77
110
8,77
7,77
6,77
11/25/2010
Page 192 of 239
Hnh 9.3. nh hng nng ca dung dch chun (NaCl) v dung dch chun (AgNO ) i vi s thay i pCl
3
Phn tch ng cong chun v cc s liu bng 9.2 c th kt lun rng nng dung dch cn chun v dung dch chun cng ln th bc nhy chun cng ln. nng 1N, bc nhy t 3 6,77, vi nng 0,1N bc nhy ngn hn t 4 5,77 trong khi vi nng long 0,01N, bc nhy khng c s cch bit 4,73 5,04. Tuy nhin cn ch rng, khi chun dung dch 0,1N bc nhy ln, v vy khng nn chun cc dung dch vi nng ln hn 0,1N. Sai s chun do vic o khng chnh xc khi dng cc dung dch c nng ln c bit tng ln rt nhiu so vi khi chun cc dung dch c nng nh. - nh hng ca tan cht kt ta Cc hp cht to thnh trong qu trnh chun theo phng php kt ta l cc cht t tan. Tuy nhin sai s gy ra do tan ca chng c th lm sai lch kt qu phn tch, v vy khng th b qua tan c. nh hng ca tan cht kt ta tch ra n bc nhy chun c a ra bng 9.3. Trn c s cc s liu ca bng 9.3 ngi ta xy dng ng cong chun .
B ng 9.3. nh hng ca tan cht kt ta tch ra n bc nhy chun khi chun 100ml dung dch 0,1 N bng AgNO3 pHal Dung dch AgNO3thm vo (ml) Nng NaHal hay AgNO3 (%) khi chun NaCl (TAgCl = 1,7. 10-10) NaBr (TAgBr= 3,3. 10-13) NaI (TAgI = 8,5. 10-17)
Trc im tng ng 0 50 90 99 99,9 100 50 10 1 0,1 1 1,3 2 3 4 Ti im tng ng 100 0 4,885 Sau im tng ng 100,1 101 110 0,1 AgNO3 (d) 1 AgNO3 (d) 10 AgNO3 (d) 5,77 6,77 7,77 8,42 9,42 10,42 12,07 13,07 14,07 6,211 8,035 1 1,3 2 3 4 1 1,3 2 3 4
11/25/2010
Page 193 of 239
Hnh 9.4. nh hng gi tr tan ca cht kt ta tch ra n bc nhy chun
Phn tch ng cong chun v cc s liu bng 9.3, c th kt lun rng tan ca hp cht kt ta cng nh th bc nhy chun cng ln. Khi chun dung dch NaHal 0,1N bc nhy chun l: NaCl bc nhy (45,77 ), NaBr (48,42); NaI (412,07 ). Bc nhy chun trong tt c cc trng hp ny l ln. 2.4.4. Hin tng hp ph khi chun theo phng php bc - Keo v tnh cht hp ph ca dung dch keo Keo l nhng tiu phn c kch thc khong 10-7 10-4 cm, nm trung gian gia ion v kt ta. Dung dch keo l trng thi trung gian gia dung dch tht v hn dch. Trong nhng iu kin nht nh mt dung dch c th chuyn t trng thi ny sang trng thi khc. Trong thc t khng c ranh gii cht ch gia ba trng thi ny. Dung dch keo c tnh cht: - N l mt h khng ng nht (khc vi dung dch tht l mt h ng nht). Dung dch keo c tnh cht in ly do s xut hin in tch trn b mt phn chia - s to thnh lp in kp ca ion v gn lin vi chng l tnh cht hp ph. - Cc ht ca dung dch keo mang in tch dng hoc m. S tch in ca cc ht keo do hp ph cc anion (tch in m) hay cation (tch in dng) trn b mt ca n. Th d: cc halogenid bc hp ph Ag+ hay ion Hal nh khi cho AgNO3 vo dung dch NaCl, kt ta AgCl to thnh trong mi trng d NaCl nn ta ny s hp ph u tin ion Cl trong dung dch. Kt ta to ra cc ht mang in tch m. Nh vy in tch ca ht keo c xc nh bng in tch ca cc ion b hp ph trn b mt ca n v ph thuc vo iu kin to thnh keo. Cc ht keo bao gm cc phn t v ion lin kt vi chng v cc ion tri du trong dung dch to thnh mixen. Mixen to thnh t cc nhn khng tan trong mi trng v bao bc bng lp in kp cc ion. Mt lp ion c gi l lp hp ph nm trn b mt ca nhn lm cho n tch in. Trong thnh phn lp hp ph c mt phn ion tri du m phn chnh ca n to thnh lp th hai. Mixen trung ha in (tng in tch bng khng).
11/25/2010
Page 194 of 239
- S ng t keo Cc ht keo tch in c th bin thnh cc ht ln bng cch c bit. Qu trnh kt hp cc ht keo thnh cc ht ln hn gi l s ng t keo. S ng t keo c th xy ra bng s tng nhit , tc dng ca nh sng, dng in cao tn, siu m, lc, trn, khuy dung dch... - S pepti ho Pepti ho l qu trnh chuyn dung dch keo ng t tr v trng thi phn tn ban u, ngc vi s ng t, ngha l lc kt ta chuyn thnh keo. Hin tng ny thng xy ra khi ngi ta ra ta keo ng t bng nc. Do gim nng cht lm ng t, ra kt ta khng ch loi cht bn m cn loi c cht in ly to nn s ng t keo. Cc ht keo tr li tch in, y nhau phn tn trong dung dch, chuyn n thnh h keo. Nh vy ra ta lm gim tp cht, nhng ng thi c th mt mt phn kt ta. ngn nga hin tng ny ngi ta khng ra kt ta bng nc m thng ra ta bng dung dch cc cht in ly bay hi, cc cht ny c th c loi khi kt ta bng sy kh. Th d ra ta AgCl bng dung dch HNO3 long, khi sy kh 110oC acid ny bay hi ht. - S hnh thnh dung dch keo ca bc halogenid Kho st trng hp to dung dch keo AgCl. Khi ta cho tng git AgNO3 vo dung dch NaCl, cc ht keo u tin xut hin, l cc vi tinh th (AgCl)m, bc halogenid rt d to dung dch keo, nu lng AgNO3 cho vo tng ng vi lng NaCl trong dung dch ta s c ta tinh th. Khi trong dung dch c d ion Cl, ngha l trc im tng ng khi chun halogenid bng bc, hoc khi d ion Ag+ ngha l trc im tng ng khi chun ion bc bng halogenid th cc vi tinh th ban u s hp ph u tin chng to ra lp ion hp ph mang in tch (in tch m trong trng hp d Cl, hoc mang in tch dng trong trng hp d ion bc), cn gi l lp s cp. Lp ny s ht cc ion tri du trong dung dch to ra lp ion i hp ph, cn gi lp th cp, lp th cp kt hp vi nhn mixen (tc vi tinh th u tin) lng lo hn nhiu so vi lp s cp. Hai lp ny to ra lp in kp bao quanh nhn mixen hnh thnh tiu phn keo. Cc tiu phn keo, v vy mang in tch cng du nn y nhau, ngn cn s kt hp ca cc tiu phn keo thnh ht ln. Mun cc tiu phn keo ng t cn lm mt in tch ca lp s cp. S tiu phn keo cho 2 trng hp: - Khi c d ion Cl [ (AgCl)m nhn (mixen) nCl lp s cp (n-x)Na+]x .xNa+ lp th cp
- Khi c d ion Ag+
11/25/2010
Page 195 of 239
Hnh 9.6. Cu to ht keo AgCl trong dung dch AgNO3
Trn b mt ca cc ht keo mang in tch hp ph cc ion to kt ta t tan nht vi cc ion trong thnh phn cc ht . Ngoi ra, chng hp ph cc ion c nng cao. Th d: Khi kt ta AgI c th xy ra cng kt Br, Cl, SCN v cc ion khc. Khi chun halogenid khng c tp cht l, kt ta hp ph cc ion Hal- c trong dung dch, cc ht AgHal- tch in m. Trong trng hp no th kt ta chun cng sai lch. V vy cn phi tun theo ng iu kin kt ta trong cc phng php xc nh cc cht. 2.4.5. Cc cch xc nh im kt thc trong phng php bc Cht ch th c dng trong phng php bc cn khng i mu cho n khi ton b ion cn xc nh chuyn thnh kt ta (chuyn thnh kt ta ca dung dch cn xc nh vi dung dch chun trc), cht ch th to vi ion ca dung dch cn chun kt ta mang mu, c tan ln hn tan cht kt ta chnh, cht ch th cn nhy i vi lng d nh AgNO3. Ngi ta dng cht ch th cng nh khng dng cht ch th (so snh c v.v...) Ta ch nghin cu cc phng php dng ch th. C 3 phng php: 2.4.5.1. Phng php Mohr - dng K2CrO4 lm ch th - Nguyn tc Phng php ny da trn phn ng gia Ag+ v Cl vi ch th K2CrO4, im tng ng K2CrO4 tc dng vi lng Ag + d to ta gch.
11/25/2010
Page 196 of 239
Ch th dng l ion cromat
n to ta gch Ag2CrO4 c tan ln hn AgHal.
= 7,9. 10 5 M, S AgCl =1,3. 10 5 M, SAgBr =5,7. 10 7 M Khi cha ti im tng ng Ag2CrO4 cha to thnh khi cha c lng d ion halogenid nn iu kin cn thit ca php nh lng ny l Ag+ phi kt ta hon ton vi Cl di dng AgCl trc khi ta Ag2CrO4 c to thnh. Do nng ca ch th phi bng bao nhiu sai s ch th khng qu 0,1% (im kt thc nm trong phm vi bc nhy). Trong khong sai s chun 0,1% nng c th thay i t 0,35 M 1,1.10-4M.(Khi = 0,1 M). sai s chun 0,1 % [ Cl]= 1,0.10-4 M, suy ra [ Ag +] = T AgCl / [ Cl]= 1,7. 10-6 t y c: [ ]= /[Ag+]2 = 0,35 M ] = 1,1.10 4 M
sai s chun + 0,1%[Ag+] = 1,0.10-4 M, suy ra [ Thc t nng bng 0,01 0,005 M.
Theo l thuyt, Ag2CrO4 ch to thnh im tng ng khi ch th c nng t 0,35 M 1,1.10-4M. Thc t ta thng dng ch th vi nng t 0,01 0,005 M v nu c hn th dung dch c mu vng m ca ch th, kh nhn thy s chuyn mu, nu long hn th khi lng ca ta Ag2CrO4 to thnh qu t mt ta t nhn thy. - iu kin ca phng php + Phng php ny dng trong mi trng pH = 6,510 (khng nh hn 6,5 v khng qu 10), khi c mt ca mui amoni pH = 6,5 7,2. + Phng php ny khng dng trong mi trng acid v trong mi trng kim, v nu dng trong mi trng acid to vi Ag+ kt ta tan trong acid:
+ Trong dung dch kim mnh to thnh oxyt v hydroxyd bc. Ag+ + OH 2 AgOH AgOH Ag2O + H2O
+ Phng php ny ch c dng xc nh cc Cl- v Br- m khng c dng xc nh I v SCN v kh nhn xt lc kt thc phn ng do hin tng hp ph v to thnh cc h keo. + Khng th chun dung dch c mu theo phng php Mohr v mu ca dung dch che mu ca Ag2CrO4 im tng ng.
11/25/2010
Page 197 of 239
2.4.5.2. Phng php Volhard - Phng php dng phn st amoni lm ch th nh lng Br, Cl theo phng php Volhard da vo k thut chun ngc. Nguyn tc: Dng mt lng d AgNO3 mi trng acid nitric kt ta hon ton bc halogenid. nh lng Ag+ (d) bng dung dch chun NH4SCN. Th d: Ag+(d) + Br AgBr Ag+ + SCN AgSCN 3SCN + Fe3+ Fe(SCN)3 ( thm)
Phn st amoni: Fe2(SO4)3.(NH4)2SO4.24H2O Dng dung dch chun: NH4SCN xc nh Ag+. AgNO3, NH4SCN xc nh cc halogenid v cc ion khc. Cn c vo cc tr s pSCN ti u v cui cc bc nhy ca ng biu din nh lng ta c th tnh c khong nng Fe3+ cn thit mu xut hin ng im tng ng v sai s ch th khng qu 0,1%. TAgSCN = 1,1.10-12 im tng ng [SCN] = 10-6 Theo l thuyt ngi ta cho rng mu ca Fe(SCN)2+ to thnh nng 6,4.10-6 M. Hy tnh nng Fe 3+ l bao nhiu phc mu to thnh. sai s chun bng khng, mu ca Fe(SCN)2+ cn xut hin khi nng Ag+ cn li trong dung dch bng tng nng SCN [Ag+ ] = [SCN] + [Fe(SCN)2+]= [SCN] + 6,4. 10-6 hay TAgSCN / [SCN] = 1,1. 10-12 / [SCN] = [SCN] + 6,4. 10-6 Sau khi bin i [SCN]2 + 6,4. 10-6 [SCN] + 1,1. 10-12 = 0 [SCN] = 1,7. 10-7 Hng s bn Fe(SCN)2+ bng:
Thay vo biu thc i vi hng s bn nng [SCN- ] to lng Fe(SCN)2+ m bng mt thng c th pht hin c.
[Fe3+] = 0,27 M
11/25/2010
Page 198 of 239
Chun theo phng php Volhar nng ny khng bt buc. Nng Fe3+ c th dao ng trong khong 0,002 1,6 M, sai s l thuyt khng hn 0,1 %. Trong thc t nng [Fe3+] trn 0,2M th mu vng ca n lm ta kh nhn s i mu ca dung dch chun . V vy ngi ta dng nng Fe3+ khong 0,01 M. - iu kin ca phng php + Mi trng phi acid mnh (dng HNO3 m c) trnh s thu phn ca Fe3+, trnh ta Ag2O v lm gim hin tng hp ph. + C th nh lng cc halogenid trong mi trng acid mnh v khng th chun cc halogenid trong mi trng trn bng phng php Mohr hay phng php dng ch th hp ph. + Ngi ta dng phng php ny nh lng Cl, I, Br, SCN v Ag+. Nhng nu nh lng Cl theo Volhard, mt kh khn thng xy ra khi nh lng bc cn li. Theo phng trnh phn ng Ag+(d) + Cl AgCl Ag+ + SCN AgSCN thi im khi lng d Ag+ c chun li bng SCN-, cc ion SCN d s phn ng vi AgCl AgCl + SCN AgSCN + Cl (9.24)
V AgSCN (TAgSCN = 10-12) t tan hn AgCl (TAgCl = 1,7 x 10-10) nn cn bng chuyn dch t tri sang phi. Phn ng t ti cn bng khi t s
Ngha l cn bng c thit lp khi [SCN-] < [Cl] 170 ln. Ni mt cch khc, mt lng tha SCN tham gia phn ng trao i vi AgCl. V vy rt kh nhn ra im cui chun , v mu hng xut hin do to thnh Fe(SCN)3 nhanh chng mt i do phn ng trao i Fe(SCN)3 + 3AgCl Fe3+ + 3Cl + 3AgSCN
Mun c mu bn ca phc sunfocyanid vi Fe3+ ta cn phi tip tc cho SCN na v s mc sai s. trnh hin tng ny ngi ta dng nhiu bin php khc nhau nh: thm mt lp ete, benzen hay bt k dung mi hu c khc vo hn hp dung dch nc AgCl, AgCl ng vn li mt phn cch ca nc v dung mi hu c v khng tc dng vi SCN. Hoc ng dung dch Cl trong bnh ng nc thm mt lng tha AgNO3 chnh xc, thm HNO3 m c, thm nc ct ti vch chun. Lc dung dch v ly mt phn dung dch nh lng bng SCN, nh vy AgCl b loi khi dung dch khng tr ngi cho qu trnh nh lng. 2.4.5.3. Phng php Fajans - Phng php dng ch th hp ph
11/25/2010
Page 199 of 239
Phng php ny da trn tnh cht ca cht kt ta hp ph mt s cht mu v lm cho cc cht mu ny thay i mu. y l phng php trc tip, c th nh lng Cl, Br, hay I bng dung dch AgNO3 v dng cht mu eosin hoc fluorescein lm ch th. C ch nh sau: Eosin l mt acid hu c yu, phn ly trong dung dch KI lm cho dung dch c mu hng. Eosin l Tetrabromfluorescein:
Eosin (mui dinatri mu ) Fluorescein
Mui dinatri mu HE H+ + E
Khi cha t n im tng ng cc tiu phn keo ca ta AgI to thnh trong phn ng s hp ph cc ion I c tha trong dung dch, cc tiu phn u mang in tch m nn khng hp ph cc ion Eosinat (E).
Vng nht mAgI + nI [AgI]m nI Khi t n im tng ng, khi d mt lng rt nh AgNO3, kt ta AgI hp ph cc ion Ag+ d v mang in tch dng do hp ph mnh cc anion E mang mu. Khi kt ta chuyn mu t hng sang tm:
11/25/2010
Page 200 of 239
tm mAgI + nAg+ [AgI]mnAg+ Nhng ch th ny khng lm i mu ca dung dch m ch i mu trn b mt keo mang in tch dng. - iu kin ca phng php: pH ca dung dch nh hng n chun bi v ch th hp ph l cc acid yu. Dng hot ng ca ch th l ion lin hp ca cht mu. V vy pH chun c lin quan n hng s phn ly ca ch th. iu kin cn thit s dng ch th hp ph l kh nng ca n nh ion tri du nhng khng th vo ion hp ph u tin ca ta. Anion in tch 1 cn tr nhau trn trn b mt AgHal theo th t, tng quan vi s phn cc hay vi kh nng i nhn ca cc anion. pH = 7 th t thay th: I > CN > SCN >Br > anion Eosin > Cl > anion diclofluorescein > CH3COO > anion fluorescein >
. ,
Nh vy pH = 7 anion s l ch th, nu nh n ng trong dy ny bn phi ca ion chun . Trong khi chun ch trnh nng ln cht in ly, n c th tng tc vi cht mu. nh lng Br, I vi ch th eosin mi trng acid pH 2. Ta khng nh lng Cl vi ch th eosin v anion eosinat b ta AgI hp ph rt sm, ta b trc im tng ng. Trong trng hp ny dng ch th l Fluorescein mu bin i t vng xanh sang mi trng pH = 7 -10. 2.5. Sai s ch th Nh bt k chun no, c th c sai s ngu nhin v sai s h thng. Sai s ngu nhin c lin quan n dc ca ng cong chun . lch chun ca gi tr th tch im tng ng cng nh, dc cng ln. Nh vy lch chun ca gi tr th tch cng nh bao nhiu, nng ca ion chun cng ln v tan ca ta to thnh cng nh. Sai s h thng lin quan ti s khng trng nhau ca im tng ng v im kt thc. Nu nh to thnh hn hp t tan loi AB th ti thi im cha t ti im tng ng f<1 gy sai s m, khi qua im tng ng f>1 gy ra sai s dng. im kt thc, nng ca ion (nh halogenid) [Hal]KT bng tng nng ion cha chun (hoc chun ) ngha l Co (1 f) hay Co (f 1) v nng ca cc ion tham gia vo s tnh tan ca ta AgHal m bng [Ag+]KT hay [Hal]KT. [Hal]KT = Co (1 f) + [Ag+]KT
11/25/2010
Page 201 of 239
[Ag+]KT = Co (f 1) + [Hal]KT M Suy ra Co = CoHal- = CoAg+
D dng thy rng sai s h thng cng nh bao nhiu, nng ca cht cn chun v cht chun cng ln v im kt thc cng gn im tng ng. tnh sai s chun , ngi ta lm th nghim kim tra cho dung dch AgNO3 vo dch nh tng CaCO3 vi ch th cromat cho n khi xut hin mu . Th tch tm c dng tnh kt qu. 2.6. Cc dung dch chun dng trong phng php bc Trong phng php bc ch yu dng dung dch chun l AgNO3, dung dch chun NH4SCN c chun li bng dung dch AgNO3. 2.6.1. Cch pha dung dch chun AgNO3 0,1N - C th pha dung dch AgNO3 0,1N bng cch ha tan mt lng tnh trc tinh th AgNO3 tinh khit ho hc trong mt th tch nc xc nh. - Hoc pha AgNO3 t ho cht khng c tinh khit lm, c nng xp x ri c xc nh theo NaCl tinh khit ho hc. Dung dch AgNO3 b thay i khi lu. Di nh hng ca nh sng, s phn hy c tng ln, v vy ngi ta dung dch trong chai thu tinh mu nu. 2.6.2. Cch pha dung dch amoni sunfoxianid 0,1N Khng th pha dung dch NH4SCN c nng chnh xc theo lng cn ca cht, v NH4SCN ht m. V vy ngi ta pha dung dch c nng gn ng vi yu cu, sau xc nh nng ca dung dch NH4SCN xp x 0,1N bng dung dch chun AgNO30,1n. 2.7. ng dng phng php bc
11/25/2010
Page 202 of 239
2.7.1. nh lng Cl trong NaCl k thut bng phng php Mohr Ngui ta xc nh ion clorid trong cc clorid tan da trn s chun trc tip lng cht cn phn tch hay dung dch ca n bng dung dch chun AgNO3, vi ch th kali cromat. Nu xut pht t sn phm tinh th th tnh hm lng phn trm ca NaCl hay Cl trong mu. Nu phn tch dung dch NaCl th tnh hm lng ion Cl hay NaCl trong dung dch thnh gam. 2.7.2. nh lng Cl theo phng php Fajans nh lng trc tip ion clorid bng dung dch chun AgNO3 vi ch th fluoressein c tin hnh trong mi trng trung tnh, mu trn b mt ca ta chuyn t vng sang hng. 2.7.3. nh lng KI theo phng php Fajans nh lng trc tip KI bng dung dch chun AgNO3, vi ch th eosin c tin hnh trong mi trng acid, mu trn b mt ca ta chuyn t hng sang tm. 2.7.4. nh lng Cl theo phng php Volhard nh lng clorid theo phng php Volhard bng cch chun ngc. Cho mt lng d chnh xc vo dung dch NaCl cn nh lng, to ta trng ca AgCl, lc b ta AgCl (hoc cho dung mi hu c nh benzen vo dung dch phn tch). nh lng Ag+ d bng dung dch chun NH4SCN vi ch th phn st amoni. T KHA - Tch s tan - Kt ta ha tan - Keo pepti ho - tan - Phng php bc - Hp ph
CU HI LNG GI 1. Vit biu thc tch s tan, tan; Cc cng thc tnh tan trong nc nguyn cht, khi k ti h s hot . 2. Nu cc yu t nh hng n tan v cch tnh tan trong tng iu kin c th. 3. Nu tnh cht ca dung dch keo, gii thch hin tng ng t v pepti ho. 4. Nu ngha ca phn ng kt ta ha tan trong phn tch. 5. Kho st ng biu din nh lng v nu cc yu t nh hng n ng cong chun kt ta. 6. Nu s hnh thnh dung dch keo ca bc halogenid. 7. Nu nguyn tc, iu kin tin hnh v ng dng ca phng php Mohr, Fajans, Volhard.
11/25/2010
Page 203 of 239
8. Nu ng dng ca phng php o bc trong phn tch. 9. Cho bit tch s tan ca cc mui iodid nh sau: iodid AgI PbI2 BiI3 T 8,50. 10-17 7,10. 10-9 8,10. 10-19
Hy xp cc mui trn theo th t gim dn tan trong: a) nc. b) 0,100 M dung dch NaI. c) 0,100 M dung dch cation tng ng. 10. Hy tnh tan ca BaSO4 trong a) dung dch trung tnh b) dung dch HCl 0,100M (HSO4- + H2O H3O+ + SO42-;
K2 = 1,20. 10-2) S: a) 1,10.10-5 M; b) 3,50. 10-5 M 11. Hy tnh tan AgCl trong dung dch NaCl c nhng nng sau: a) 2,00 M b) 0,50 M e) 1,20. 10-4 M h) 1,50. 10-5 M CU HI TRC NGHIM 1. Mun c kt ta: a. [A]m.[B]n < TAmBn b. [A]m.[B]n = TAmBn 2. Mun c kt ta tan c: a. [A]m.[B]n < TAmBn b. [A]m.[B]n = TAmBn c. [A]m.[B]n > TAmBn d. [A]m < TAmBn e. [B]n < TAmBn c. [A]m.[B]n > TAmBn d. [A]m < TAmBn e. [B]n < TAmBn c) 5,00. 10-2 M d) 5,00. 10-4 M g) 1,10. 10-6+ M i) 3,70. 10-7 M Bit K1 = 2,00.10-5, K2 = 1
11/25/2010
Page 204 of 239
3. Cng thc tnh tan trong nc nguyn cht ca cht in ly t tan dng AB (cng ho tr):
4. Khi thm d thuc th kt ta, tan ca kt ta: a. tng ln b. tng ln nhiu c. gim xung d. gim xung nhiu e. khng thay i
5. Trong mi trng acid tan ca cht in ly t tan ph thuc vo: a. tch s tan ca mui v nng H+ b. tch s tan ca mui c. nng H+ 6. Phng php Mohr thc hin mi trng: a. acid mnh b. kim mnh c. acid yu 7. Phng php Volhard thc hin mi trng: a. acid mnh b. kim mnh c. acid yu d. kim yu e. trung tnh, kim yu pH= 6,5-10 d. kim yu e. trung tnh, kim yu pH= 6,5-10 d. hng s phn ly ca acid trong mi trng e. nng ca mui
8. Phng php Fajans nh lng Br, I vi ch th eosin thc hin mi trng: a. acid mnh b. kim mnh c. acid yu d. kim yu e. trung tnh, kim yu pH= 6,5-10
9. Phng php Volhard dng k thut chun : a. trc tip b. th c. ngc d. gin tip e. gin tip - tha tr
10.Ch th dng trong phng php Mohr: a. Phn st amoni (Fe3+) b. K2CrO4 c. K2Cr2O7 d. eosin e. fluorescein
11/25/2010
Page 205 of 239
Chng 10 PHNG PHP TO PHC

MC TIU
Trnh by c nh ngha phc cht v phn bit c phc cht cng, phc cht ni, mui
kp.
Gii thch c ngha ca hng s to phc, hng s bn iu kin. Trnh by c nguyn tc v cch chn ch th trong phng php chun bng complexon
III.
Trnh by c cc k thut chun bng complexon III.

NI DUNG 1. L THUYT V PHC CHT 1.1. nh ngha phc cht Phc cht l nhng hp cht phn t c to thnh do mt kim loi (nguyn t trung tm) nh Ag, Cu, Ni, Co, Fe, Hg... ni vi cc phi t c th l ion m hay phn t (NH3, H2O, Cl, F, CN,...). Nguyn t trung tm v phi t to thnh cu ni phc v c vit trong du [ ], cc ion tri du vi cu ni phc gi l cu ngoi phc vit ngoi du [ ]. V d: [Ag(NH3)2]Cl Cu ni phc / cu ngoi phc Ch : Nhng cht nh FeSO4(NH4)2SO4.6H2O hoc KAl(SO4)2.12H2O l mui kp, tuy dng rn c thnh phn ging nh phc cht, nhng trong dung dch nc phn ly hon ton thnh nhng ion n gin; KAl(SO4)2.12H2O K+ + Al3+ + 2SO42 + 12H2O Nn khng phi l phc cht m l nhng mui kp. 1.2. Phn loi Phc cht thng chia lm 2 loi: phc cht cng v ni phc. Phc cht cng (lin kt phi tr). Phc cht cng gm mt nguyn t trung tm lin kt phi tr vi nhng tiu phn phn cc.
11/25/2010
Page 206 of 239
V d: Zn2+ c th phi tr vi 4 phn t NH3 to thnh ion phc [Zn(NH3)4]2+ m cng thc khai trin l
Phn t NH3 lng cc, cc m quay v pha ion kim loi v to thnh lin kt phi tr bng 2 electron t do lp ngoi cng ca nit. Ngi ta thy rng s ti a nhng tiu phn c th gn vi nguyn t trung tm gi l s phi tr cc i, s phi tr cc i thng l 2, 4, 6 hoc 8. in tch ca ion phc bng tng i s cc in tch (dng v m) ca ion trung tm v phi t. - Nhng phc cht ch c mt ion trung tm nh: [Ag(NH3)]+, [FeF6 ]3 c gi phc n nhn. Phc c nhiu ion trung tm cng loi nh [Fe2(OH)2]4+, [Cu3(OH)4]2+ gi l phc a nhn. 1.2.2. Ni phc Trong ni phc, kim loi to thnh vi phi t (thng l phn t hu c) va bng lin kt phi tr va bng lin kt chnh. Th d: dimetylglioxin to phc vi niken
11/25/2010
Page 207 of 239
T cc cng thc cu to trn cho thy cc hp cht ni phc c c trng bng s tn ti cc cm vng ch yu l cc vng 5 hoc 6 cnh. Nhng phc cht m phi t cha nhiu nguyn t lin kt vi ion trung tm gi l phc a cng. Cc ion trung tm (ion kim loi) b kp cht trong cc vng bi cc phi t nh trong gng km. Do phi t to vi ion trung tm mt vng kn gi l phc cng cua (Chelat). Nhng phc cht m phi t cha mt nguyn t lin kt vi ion trung tm c gi l phc n cng. Cc hp cht ni phc c nhiu tnh cht c trng, trong cc tnh cht quan trng nht l: bn cao, mu c trng tan nh trong nc, in ly yu, tan ln trong mt s dung mi hu c (thuc th Garola vi K+). 1.3. Danh php Khi gi tn mt phc cht, u tin gi tn phi t sau gi tn ion trung tm. 1.3.1. Phc l ion dng Gi tn phi t vi ui O v cc tip u ng ch s phi t nh sau: 1. Mono 2. Di 3. Tri 4. Tetra 5. Penta 6. Hexa 7. Hepta 8. Octa 9. Nona 10. Deca 11. Nodeca 12. Dodeca
Sau gi tn cc nguyn t trung tm vi cc ui ho tr nh sau: Ho tr 1: a Ho tr 2: o Ho tr 3: I Ho tr 4: e Ho tr 5: an Ho tr 6: on Ho tr 7: in Ho tr 8: en
V d: [Ag(NH3)2]Cl: diaminoargenta, hoc diamino bc (I) clorua. (Ghi ch: cng c th gi tn nguyn t trung tm km ch s La m vit trong du ngoc ch ho tr ca n).
11/25/2010
Page 208 of 239
1.3.2. Phc l ion m Gi tn nh phc ion dng nhng thm ui at. V d: [Fe(CN)6]3: hexa cyanoferiat hoc hexa cyanato ferat (III) [Hg(CSN)4]2: tetrasulfo cyano mercuroat (Ghi ch: cng c th gi theo cch thm ui at vo tn nguyn t trung tm trc khi thm ch s La m ch ho tr). 1.4. Hng s bn ca phc cht Phc cht trong dung dch cng phn ly nh cc mui n gin, c phc cht phn ly hon ton, c phc cht phn ly khng hon ton, ngha l c phc cht bn v phc cht khng bn. biu th bn ca phc cht, ngi ta dng hng s bn . Xt th d cn bng gia kim loi (M) vi s phi tr bng 4 ca phi t (ligand) (L): M+L Hng s cn bng ca phn ng: ML
K l hng s bn. Tng t cn bng gia M v phi t c s phi tr l 2 M + 2L Phn ng ny c 2 phn ng trung gian: M+L ML + L Tng ng vi (10.1) v (10.2) ML ML2 (10.1) (10.2) ML2
Tch s ca K1 v K2 biu th hng s cn bng tng cng
Tng t nh vy phn ng gia M vi phi t A c th vit dng cn bng tng cng: M + 4A MA4
Da vo gi tr hng s bn ca phc cht c th bit c mc bn ca chng. Hng s bn cng ln phc cng bn.
11/25/2010
Page 209 of 239
Th d: Phc Zn(NH3)42+ c to thnh qua 4 nc nh sau: 1. Zn2+ + NH3 Zn(NH3) 2+
2. Zn (NH3) 2+ + NH3
3.
+ NH3
4.
+ NH3
Zn2+
2NH3
K1K2 = 2 2 c gi l hng s bn tng cng ca 2 phn ng u trong 4 phn ng trn. biu th bn ca phc cht ngi ta dng hng s khng bn, nghch o ca hng s bn 1/ c gi l hng s khng bn K hoc hng s phn ly ca phc cht, hng s ny cng nh phc cht cng bn. Ngi ta cn thng dng i lng lgK c k hiu pK. Da vo hng s bn ca phc cht c th bit c mc bn hoc khng bn ca chng. Hng s bn cng ln phc cng bn. Th d: Phc FeY c = 1025,1 (tc K = 10-25,1) bn hn phc NiY 2 c = 1018,62 (K = 1018,62). Nu bit hng s khng bn ca phc cht ngi ta c th kho st s cnh tranh to phc. 1.5. ngha
11/25/2010
Page 210 of 239
1.5.1. Tnh nng ca cht to phc v phi t trong cc dung dch Da vo hng s bn hoc hng s khng bn ca cc phc v nng ban u ca phi t v ion trung tm, ta c th tnh c nng ca cht to phc v phi t. Th d: Tnh nng ca cht to phc v phi t trong cc dung dch [Ag(NH3)2]+, [Cu(NH3)4]2+ 1M v so snh cc kt qu nhn c. Cho Gii a) i vi [Ag(NH3)2]+ Nu k hiu [Ag+] bng x, theo phng trnh: [ c th vit: ] Ag+ + 2NH3
Thay cc gi tr nng ca cht to phc [Ag+] v ca phi t [NH3] vo biu thc hng s khng bn:
V trong dung dch in ly yu, [Ag+] rt nh so vi nng ca ion phc, c th coi gi tr 1 x gn bng 1. Khi ta c: 4x3 = 5,89. 10-8
[NH3] = 2x = 4,8.103 (mol/lit) b) i vi
Do
11/25/2010
Page 211 of 239
Khi so snh cc kt qu thu c i vi phc cht trong c hai dung dch gn bng nhau: [Ag+] = 2,4. 10-3 (mol/l) [Cu2+] = 1,29. 10-3 (mol/l) 1.5.2. S cnh tranh to phc
, c th thy l nng ca
Xt th d: nu cho tc dng mui Zn vi Mg complexonat MgY2 + Zn2+ ZnY2 + Mg2+
Ta bit rng K khng bn cng nh phc cht cng bn vng, = 10-16,3, = 10-8,7, vy phc km complexonat bn hn Mg complexonat, nn trong dung dch tn ti phc Zn complexonat. 1.6. ng dng ca phn ng to phc trong phn tch 1.6.1. Dng cc hp cht phc to kt ta - C nhiu mui phc kh tan trong nc c to thnh bi cc cation kim loi nng v cc anion ca nhng acid phc. Th d: Ni2+ to mui t tan vi hexacyanocobaltat (III) Ni3[Co(CN)6]2 mu xanh l cy. - C nhiu ion phc c bn cao, c mu c trng dng trong phn tch nh tnh v nh lng. Th d: Ngi ta pht hin K+ bng cch cho tc dng vi Na3[Co(NO3)6] to ra phc dng ta mu vng K3[Co(NO3)6]. nh tnh Fe3+: Fe3+ phn ng vi K4[Fe(CN)6] to kt ta mu xanh ph Fe4[Fe(CN)6]3. nh lng Fe3+, ngi ta cho Fe3+ tc dng vi thuc th NH4SCN, phc to thnh c mu mu, o ph hp th trong vng kh kin. 1.6.2. Dng cc phn ng to phc che cc ion cn tr C nhiu trng hp ngi ta dng phn ng to phc che cc ion ngn cn qu trnh phn tch. Th d: Trong qu trnh phn tch, Fe3+ c th ngn cn s pht hin cc ion khc, ngi ta che Fe3+ bng cch thm H3PO4, NaF, Na2C2O4 hoc Na2C4H4O6 vo dung dch phn tch, ion Fe3+ s to vi cc cht thnh ion phc bn vng khng mu: [Fe(PO4)2]3, [FeF6]3, [Fe(C2O4)3]3, [Fe(C4H4O6) 3 3+ 3] . Khi cc anion phc c to thnh bn vng ngay c khi cho thuc th nhy i vi Fe nh
11/25/2010
Page 212 of 239
NH4SCN cng khng tc dng r rt vi Fe3+. 1.6.3. Dng phn ng to phc ha tan cc kt ta Ngi ta dng cc phn ng to phc ha tan nhng kt ta khng tan trong nc, trong acid v trong kim. Nh trng hp Ag+ tc dng vi nhm halogenid (Cl, Br, I) to thnh cc mui bc halogenid khng tan. tch AgCl ra khi cc cht khc, ngi ta cho vo ta mt lng tha NH3, AgCl to thnh phc [Ag(NH3)2]Cl tan. 1.6.4. Dng phn ng to phc thay i tnh acid base ca cc cht - Ngi ta dng phn ng ny khi mun lm thay i (tng hay gim) tnh acid, tnh base ca mt hp cht. Th d: tng tnh acid ca acid boric, ngi ta thm vo dung dch mt lng glycerin. Lc ny c s lin kt anion ca acid boric thnh phc glyceroborat km theo lm yu lin kt ca n vi hydro. Do acid yu tr thnh acid mnh. tng tnh base ca Al(OH)3, ngi ta thm fluorid vo dung dch Al(OH)3, Al3+ to phc bn [AlF6]3 v OH c gii phng ra, do vy lm tng tnh kim ca dung dch. Al(OH)3 + 6 F [AlF6]3 + 3 OH Dng phn ng to phc thay i tnh oxy ho kh ca cc cht C nhiu trng hp do c s to phc m nng ca cc cht oxy ho hoc ca cht kh tng hay gim. Th d: 2 Fe3+ + 2 I 2 Fe2+ + I2
Chiu phn ng t tri sang phi. Khi thm F- vo dung dch th Fe3+ mt kh nng oxy ho I do to thnh phc [FeF6]3 , do vy cn bng phn ng chuyn dch t phi sang tri. 2. PHNG PHP COMPLEXON 2.1. S lc v cc complexon Cc hp cht hu c l dn xut ca acid aminopolycarboxilic thng gi l cc complexon. - Complexon I (Trilon A), l acid nitril triacetic (NTA), vit tt l H3Y
- Complexon II (Trilon BS) l acid etylen diamin tetra acetic (EDTA), vit tt l H4Y. y l acid 4
11/25/2010
Page 213 of 239
nc. Trong dung dch ca EDTA c th tn ti cc dng: H4Y, H3Y, H2Y2, HY3, Y4 v tu thuc vo pH ca mi trng dng no s l ch yu. pK1 = 2,0, pK2 = 2,73, pK3 = 6,24, pK4 = 10,34.
EDTA l tinh th mu trng, tan t trong nc, nhit 20oC tan ca n ch l 28,3 mg trong 100 ml nc. tan H4Y ti thiu pH 1,6 1,8. Khi tng hay gim nng ion hydro tan thay i (hnh 10.1).
Hnh 10.1. S ph thuc ca tan EDTA (trong 100 ml nc) v pH 200C
tan cao ca H4Y trong acid v c c gii thch bng s to thnh cc dng trao i proton H5Y+ v H6Y2+. S trao i proton ca anion Y4 v s phn b cc dng trao i proton khc nhau ph thuc vo pH c biu th trong s (hnh 10.2) v biu phn b (hnh 10.3).
11/25/2010
Page 214 of 239
Hnh 10.2. S trao i proton ca anion Y4
Hng s phn ly acid ca ion H6Y2+ bng: pKa,1 = 0,9; pKa,2 = 1,6; pKa,3 =2,0; pKa,4 = 2,67; pKa,5 =6,16 v pKa,6 = 10,26.
Hnh 10.3. Biu vng to thnh nhng dng khc nhau ca EDTA
- Complexon III (Trilon B) l mui dinatri ca EDTA. Vit tt l Na2H2Y
11/25/2010
Page 215 of 239
Dihydrat Na2H2Y.2H2O tan tng i tt trong nc: 108 g/l 22oC. Trong nc, Na2H2Y phn ly thnh Na+ v H2Y2, thnh phn ca dung dch complexon III ph thuc vo pH cng ging nh thnh phn ca dung dch EDTA. V vy, ngoi phn t lng ra tt c cc tnh cht i vi complexon II u ng vi complexon III v ngc li. Nhng v complexon III d iu ch c di dng tinh khit nn hay dng hn c. 2.2. Nguyn tc chung Phng php complexon l phng php nh lng da vo phn ng to phc ca cc complexon vi ion kim loi to thnh cc mui ni phc v cng bn t phn ly, tan trong nc. Khi chun , cc ion kim loi to phc vi EDTA xy ra cc phn ng trong dung dch acid: Na2H2Y 2Na+ + H2Y2 MY2 + 2H+ MY + 2H+ MY+ 2H+
M2+(Ca2+)+ H2Y2 M3+(Al3+) + H2Y2 M4+(Th4+) + H2Y2
Theo cc phng trnh trn mt ion kim loi bt k ho tr u phn ng vi mt phn t EDTA, t l (1:1) nn trong phng php complexon nng ng lng bng nng mol, E = M. 1 mol cation phn ng vi EDTA khng ph thuc vo ho tr ca n lin kt vi 1 mol Na-EDTA. T hnh 3 thy rng phn ng xy ra mi trng kim yu v trung tnh c th vit di dng: Mn+ + HY3 2.3. Tnh to phc ca EDTA 2.3.1. C ch phn ng Trong cc nhm complexon tng tc vi ion kim loi to phc do ho tr chnh l nhm cacboxyl (COOH), cn ion lin kt ph l nhm amino bc ba ( N). Mui ni phc vi EDTA to thnh, mt mt, do s th cc nguyn t hydro hot ng ca nhm cacboxyl bng ion kim loi to phc, y EDTA kt hp vi ion kim loi to phc bng ho tr chnh, mt khc do s tng tc vi nguyn t nit c kh nng to lin kt ph (phi tr) vi ion kim loi to phc. MY(n4)+ + H+
11/25/2010
Page 216 of 239
Hnh 10.4. Cu trc ca phc kim loi vi EDTA
Phn ng to phc gia EDTA vi ion kim loi c th biu din bng phng trnh chung: Mn+ + H2Y2 Mn+ + HY3 MY(n4)+ + 2H+ pH = 4 6 MY(n4)+ + H+ pH = 7 10
Ta thy trong cc phn ng lun gii phng ra H+ m mi trng acid mnh pH < 3, EDTA to thnh cc phc kim loi km bn. Do trung ha n ngi ta thng cho dung dch m (NH4OH/NH4Cl) pH = 8 9. Ni chung phn ng to phc cng thun li khi mi trng cng kim. Nhng c khi ngi ta duy tr mi trng acid i vi Fe3+, Bi3+, trnh thu phn, ion tr ngi. 2.3.2. bn vng ca cc complexonat Trong trng hp khng b nh hng bi cc qu trnh khc, phn ng to phc c vit gn li: Mn+ + Y4 MY(n4)+
Trong bng (10.1) tr s KMY vi mt s ion kim loi nh sau: lgKMY Ba2+ = 7,76, Ta c nhn xt sau: Cc complexonat ca mt s kim loi bn vng n mc c th dng complexon ha tan cc ta kh tan nh: BaSO4, PbSO4, CaC2O4,... Hng s to phc cng ln phc cng bn vng, do c th xy ra phn ng cnh tranh to phc. V d thm Mg- complexonat vo dung dch Ca2+ th: Ca2+ + MgY2 CaY2 + Mg2+ lgKMY Pb2+ = 18,04, lgKMY Ca2+ = 10,70, lgKMY Mg2+ = 8,70
V lgKMY Ca2+ = 10,7 > lgKMY Mg2+ = 8,7 Hoc nu thm complexon vo dung dch cha Ca2+ v Mg2+ th Ca2+ s to phc trc.
11/25/2010
Page 217 of 239
B ng 10.1. Hng s bn ca phc kim loi vi EDTA (gi tr hng s ny nhit 20 C v lc ion 0,1) Cation Ag+ Mg2+ Ca2+ Sr2+ Ba2+ Mn2+ Fe3+ Co2+ Ni2+ KMY 2,1. 107 4,9. 103 5,0. 1010 4,3. 103 5,8. 107 6,2. 1013 2,1. 1014 2,0. 1016 4,2. 1018 lgKMY 7,32 8,69 10,70 8,63 7,76 13,79 14,33 16,31 18,62 Cation Cu2+ Zn2+ Cd2+ Hg2+ Pb2+ Al3+ Fe3+ V3+ Th4+ KMY 6,3. 1018 3,2. 1016 2,9. 1016 6,3. 1021 1,1. 1018 1,3. 1016 1,3. 1025 7,9. 1025 1,6. 1023 lgKMY 18,80 16,50 16,46 21,80 18,04 16,13 25,10 25,90 23,20
Hng s bn ca cc complexonat ca cc ion kim loi khc nhau, nhiu khi s khc nhau rt ln. iu ny cho php c th chun mt s ion kim loi trong cng mt dung dch bng phng php complexon. Trn hnh 10.8 cho thy rng gi tr pH ti thiu c th c nh c im kt thc chun ca cc cation khc nhau, cc kim loi nng ho tr 2 c th chun mi trng acid yu cn ion Fe3+ mi trng acid mnh. 2.4. nh hng ca pH n cn bng to phc. Hng s cn bng iu kin (biu kin) Ngi ta kho st cn bng to phc ca ion kim loi (Mn+) vi EDTA thy rng mc to phc ph thuc vo pH ca dung dch. Khi chun cation to phc km bn (th d Ca2+ v Mg2+), yu cu mi trng kim. Ngc li, chun cation to phc bn hn (km hay niken) c th tin hnh trong mi trng acid. Ngi ta thy rng s ph thuc vo pH khi chun bng dung dch EDTA thng tin hnh trong dung dch m c pH c nh. S c nh pH cho php tnh c cc s c ngha. xy dng ng cong chun ca ion kim loi vi EDTA trong dung dch m, ngi ta dng k hiu 4 (10.3) C: nng chung khng to phc ca EDTA, bng tng nng cn bng ca tt c cc dng EDTA. C = [Y4] + [HY3] + [H2Y2] + [H3Y] + [H4Y] 4: k hiu phn ca cc tc nhn khng to phc tn ti dng Y4(tr MYn4). Ngi ta cn thy rng 4 ch ph thuc vo pH v hng s phn ly ca EDTA K1, K2, K3, K4. t 4, C vo ch Y4 phng trnh (10.3) vo biu thc ca hng s bn
11/25/2010
Page 218 of 239
(10.4)
biu thc mi s l:
l hng s bn iu kin (hay biu kin) biu th cn bng ch trong gi tr pH tnh c gi tr 4

B ng 10.2. Cc gi tr 4 i vi EDTA trong dung dch cc pH khc nhau pH 2,0 3,0 4,0 5,0 6,0 4 3,7. 10-14 2,5. 10-11 3,6. 10-9 3,5. 10-7 2,2. 10-3 pH 7,0 8,0 9,0 10,0 11,0 12,0 4 4,8. 10-4 5,4. 10-3 5,2. 10-2 3, 5. 10-1 8,5. 10-1 9,8. 10-1
Hng s bn iu kin cho php tnh ton d dng nng cn bng ca ion kim loi v phc trong bt k im no ca ng cong chun , ngi ta thy rng biu thc cho hng s bn iu kin khc biu thc cho hng s bn c s dng sm ch khi no nng cn bng phn ly hon ton ca anion [Y4] thay th vo gi tr C (nng chung ca EDTA). y l iu rt quan trng v C xc nh t php t lng ca phn ng d dng hn l [Y4]. Trn hnh (10.5) biu th s ph thuc logarit ca hng s bn iu kin ca phc i vi mt s kim loi vo pH ca dung dch, nh hng ca pH ln i lng 4 (nhnh bn tri ca ng cong), s to thnh hydroxocomplexonat v phc complexon vi NH3 ngha l do s tng 4 (nhnh bn phi ca ng cong).
11/25/2010
Page 219 of 239
Hnh 10.5. S ph thuc hng s bn iu kin ca mt s phc vo pH (tng nng [NH3] + [NH4+] = 1,0M)
2.5. ng biu din chun Xy dng ng cong chun 50,0ml dung dch Ca2+ 0,0100M bng dung dch EDTA 0,0100M trong dung dch m pH 10,00. 1. Tnh hng s bn iu kin: cc gi tr 4. KCaY ly t bng (10.1) cho kt qu nh sau: KCaY = 4. KCaY = 0,35 5. 1010 = 1,75. 1010 2. Tnh pCa trc im tng ng: Trc im tng ng nng chung ca Ca2+ bng tng nng tha cha chun ca ion Ca2+ v ion Ca2+ to ra bi s phn ly ca phc. Nng phc s bng nng chung ca EDTA c ngha l C. C th cho rng gi tr C nh hn so vi nng ion Ca2+ khng to phc. V vy, th d sau khi cho 25,00ml (50%) dung dch chun .
- Khi thm 45 ml (90%) dung dch chun :
11/25/2010
Page 220 of 239
- Khi thm 49,5 ml (99%) dung dch chun :
3.Tnh pCa im tng ng: thi im ny nng CaY2 trong dung dch bng 0,0050M v s phn ly ca phc ny l ngun duy nht sinh ra ion Ca2+. Nng ion Ca2+ s bng nng chung khng to phc EDTA: [Ca2+] = CEDTA [CaY2-] = 0,0050M [ Ca2+] 0,0050M Gi tr hng s bn iu kin to thnh CaY2- pH 10,00:
Sau khi thay s ta c:
4. Tnh pCa sau im tng ng: Sau im tng ng, nng chung CaY2- v EDTA d dng tnh. Th d: - Sau khi cho d 1% dung dch chun (51 ml):
Ly gi tr gn ng, c th vit: [CaY2] = 4,95. 10-3 [Ca2+] 4,95. 10-3 M CEDTA = 9,90. 10-5 + [Ca2+] 9,90. 10-5 M
11/25/2010
Page 221 of 239
- Sau khi cho d 10% dung dch chun (60,00 ml):
Ly gi tr gn ng, c th vit: [CaY2] = 4,55. 10-3 [Ca2+] 4,55. 10-3 M CEDTA = 9,10. 10-4 + [Ca2+] 9,10. 10-4 M
Trn hnh (10.6) m t ng cong chun ca ion Ca2+ trong dung dch m vi cc gi tr khc nhau ca pH. T y nhn xt rng pCa c s thay i r rng ch pH 8.
B ng 10.3. Chun 50 ml Ca2+ 0,0100 M bng dung dch EDTA 0,0100 M % EDTA thm vo 0 50 90 99 100 101 110 pCa 2,00 2,48 3,28 4,30 6,27 8,54 9,54 T Ghi ch
11/25/2010
Page 222 of 239
V ml EDTA Hnh 10.6. nh hng ca pH n chun ca dung dch Ca 2+ 0,0100 M bng dung dch EDTA 0,0100M
Th tch 0,0100 M EDTA, ml Hnh 10.7. ng cong chun 50,0 ml 0,0100 M cc dung dch cation pH 6,0
11/25/2010
Page 223 of 239
Trn hnh 10.7 cho thy rng khi chun cc cation to phc bn (c hng s to phc ln) im kt thc chun thy r ngay c dung dch acid. ng cong trn hnh 10.8 cho thy rng gi tr pH ti thiu no c th c nh im kt thc chun ca cc cation khc nhau khi khng c cht cnh tranh to phc. 2.6. Cc phng php pht hin im kt thc chun Trong chun to phc, im kt thc chun c th pht hin nh s nhn thy bng mt cng nh s dng cc phng php phn tch dng c. S la chn phng php ph thuc vo cc yu t, th d nh yu cu xc nh chnh xc v chn lc, chun dung dch c v c mu, chun trong mi trng hn hp phc tp. Trong phng php nhn bng mt, xc nh im kt thc bng cch s dng ch th kim loi. Ch th kim loi l ch th lm thay i mu ph thuc vo nng ion kim loi. Ch th kim loi thng l hp cht hu c, tc dng vi ion kim loi chun to mu ca phc. Ch th kim loi chia thnh hai nhm:
11/25/2010
Page 224 of 239
Nhm 1: Ch th t n khng c mu, nhng tc dng vi ion kim loi to mu ca phc c mu. Th d khi chun phc st III, ch th dng thng l acid salicylic hay sunfosalicylic. Phc ca st III vi acis salicylic (t l phn t 1:1) c mu . Cng mu ca phc thng khng cao, v vy nhn thy r mu ca phc, nng ch th cn ln hn gp 10 ln nng ion kim loi chun . Nhm 2: Trong loi ny, ch th kim loi l cc hp cht hu c, trong phn t c nhm mang mu (chromophor), tc dng vi ion kim loi to hp cht ni phc, c mu khc vi mu ca ch th lc ban u. Ch th ny gi l ch th kim loi chrom. Ngi ta chia ch th ny lm 3 nhm Ch th c nhm chc azo N = N. in hnh l en eriocrom T. Ch th xp trong nhm triphenylmetanic. Th d kxilen da cam Ch th bn vng. Trong nhm ny c murexit, dithizon, alizarin.... 2.6.1. Yu cu i vi ch th Ch th kim loi cn phi c khong pH la chn, tc dng vi ion kim loi to ra phc bn vi t l M: Ind = 1: 1. Hng s bn iu kin ca cht ch th phi nh hn hng s bn iu kin ca phc kim loi vi EDTA, ngha l 10 < KMY /KMInd 104. Trong trng hp mun t gi tr ln, hng s bn ca phc MInd cho php s dng t l khng ln ca nng ch th v kim loi
tng ng vi s gim sai s chun - Phc ca ion kim loi vi ch th cn khng bn v phn hy nhanh di tc dng ca EDTA. Ngi ta cho rng trong chun to phc c th dng ch th kim loi chu k na trao i phi t trong phc Mind bng 10 giy. - S thay i mu ca dung dch im kt thc chun cn phi tng phn vi mu ban u, ph hp vi thuyt v mu, gii hn mu, ngha l mu ban u (mu ca ch th vi ion kim loi MInd) v mu cui (mu ca ch th Ind) cn c kh nng b khuyt. B khuyt ln nhau cho n mu trng. Mu b khuyt th d nh: xanh l cy; cam xanh; vng xanh; vng tm,... Mu ca ch th thay i t mt mu b khuyt sang mu khc, im trung gian ny tr nn khng mu (hay sm mu) bi v lc ny nh ca mu b ht ln nhau (hp ph ln nhau). V vy thi im ny c bit d nhn thy. - a s trng hp ion kim loi v ch th to ch mt phc vi t l 1:1, khi hng s bn iu kin ca phc ny vi cch tnh cn bng ca ch th c th vit:
11/25/2010
Page 225 of 239
lc gii hn khong chuyn mu: pM = lg K'MInd 1 nh gi khong i mu ca ch th c th cho php mt ngi quan st s thay i mu trong nhng nng tng ng. Nh vy, khong thay i mu ca ch th trn thang pM c xc nh bng hng s bn iu kin ca phc MInd. Trong s thay i ca hng s ny khong chuyn rng ti 2 n v. pM di chuyn trn thang pM lc hng ny hay hng khc. Bi KMind ph thuc vo pH ca dung dch. S thay i pH gy ra s dch chuyn ca khong thay i. Ngoi ra, nu cc dng ch th HInd khc nhau theo mu, lc khong chuyn mu trn thang pM khng ch ph thuc vo pH m cn c c s i mu ca dung dch chun . Th d: en eriocrom T vi ion kim loi Mg2+, Ca2+, Zn2+ v mt s ion khc to phc mu hay mu tm. Kho st s ph thuc ca ch th i vi pH c th phn bit s thay i mu ca ch th. Th d ch th en eriocrom T i mu: phc ca kim loi vi ch th trong vng pH < 6 s i mu ca dung dch khi chun s kh nhn thy. Trong thi gian ny pH thay i t 7 11 s i mu t sang xanh, khi pH > 12 t sang cam.
Trng hp phc tp hn l s tc dng qua li ca murexit (H5Ind) vi ion kim loi. S ph thuc vo pH ca murexid vi ion kim loi c th to thnh phc trao i proton ca thnh phn MHiInd, vi I c th l 2,3 v 4. Th d: khi chun ion Ca2+ (hnh 10.9) dng ch th khng lin kt vi ion kim loi H4Ind (- tm pH < 9), H3Ind2 (tm, pH 9,2 11) v H2Ind3 (xanh - tm, pH >11), khi cn bng vi phc CaH4Ind+ (vng- cam, lg =2,6), CaH 3Ind ( - cam, lg = 3,6), v CaH2Ind (, lg = 5,0). Ph hp vi hnh 10.9 s thay i t ngt mu ca dung dch nhn thy pH > 10. Trong nhng trng hp ny khi pCa 3,5 mu chuyn t sang xanh tm.
11/25/2010
Page 226 of 239
Hnh 10.9. Gin phn b i vi dung dch murexid khi c ion calci 1- H 4Ind-, - tm; 4- CaH 4Ind +, vng cam; 2- H 3Ind 2, tm; 5- CaH 3Ind, cam; 3- H 2Ind 3, xanh tm; 6- CaH2Ind , .
2.6.2. Cc ch th kim loi 2.6.2.1. C ch Cc ch th kim loi l cc cht hu c c kh nng to phc mu vi ion kim loi. Cc phc ny km bn hn phc ca ion kim loi vi complexon. Mu ca ch th khi to phc vi ion kim loi khc vi mu ca ch th dng t do. Gn im tng ng complexon ly kim loi ch th gii phng ch th ra dng t do nn dung dch thay i mu, bo cho ta bit kt thc nh lng. Th d: nh lng Ca2+ vi ch th murexid, pH = 9 - 11 Ca2+ + H4I ( tm) Khi nh complexon xung: Ca2+ + HY3 CaH2I + HY3 CaY2 + H+ CaY2 + H3I2 Tm CaH2I + 2H+ ()
Gn im tng ng c s cnh tranh to phc
Cc iu kin i vi cht ch th kim loi Phn ng to phc vi ion kim loi l phn ng thun nghch v mu ca dng t do phi khc vi mu ca dng phc
11/25/2010
Page 227 of 239
Mn+ Khng mu Ca2+ Khng mu
Indm Mu 1 H3I2 tm MY(n4) +Indm
MInd(nm) Mu 2 CaH2I Hng + 2H+
Phc ca ch th vi kim loi phi km bn hn phc ca complexon vi kim loi. Mind (n-m) + Y4 2CaH2I + 2H2Y2 Hng
2CaY2 + 2H3I2 + 2H+ Tm, pH = 9 11
Thng cc ch th kim loi ng thi cng l acid a chc, nn mu ca ch th thay i theo pH ca dung dch, khi s dng ta phi c nh pH ca dung dch bng cc h m thch hp phn ng xy ra nhanh, hon ton v mu ca ch th t do khc vi mu ca phc. Hng s to phc ca cc ch th nh en eriocrom T, murexid vi mt s ion kim loi c trnh by bng 10.4; 10.5.
B ng 10.4. Hng s to phc (lg KMind) ca NET M2+ Ba2+ Ca2+ Mg2+ Mn2+ Zn2+ Hng s lg KMind BaL 3,0 CaL 5,4 MgL 7,0 MnL 9,6 MnL2 17,6 ZnL 12,9 ZnL2 20,0 lg KMY 7,76 10,7 8,70 13,79 16,5
B ng 10.5. Hng s to phc (lg KMind) ca Murexid M2+ Ca2+ Cu2+ Ni2+ Hng s lg KMind CaL 5,0; CaHL 14,5; CaH2L 22,7 CuH2L 25,1 NiH2L 24,1 lg KMY 10,7 18,80 18,62
Ngi ta c th tnh vng chuyn mu ca ch th da vo hng s to phc ca cc ch th vi ion kim loi. Th d: Tnh khong chuyn mu ca en eriocrom T pH = 10 khi chun Mg2+. Nu lgKMind = 7,0; ind = 3,1. 10-2. ind l hm to phc ph ca ch th.
11/25/2010
Page 228 of 239
Ta bit khong gii hn mu ca ch th l: pM = 1 lg K'MInd = lgKmind.ind = lg 107. 3,1. 10-2 = 5,5 Nh vy, pH = 10 khi chun Mg2+ mu ca ch th thay i trong khong: pMg = 5,5 1; tc l trong khong 4,5 6,5. Qua kho st ng cong chun ca Mg2+ bc nhy trn ng cong chun vi sai s 1% l 4 5,8, v vy c th dng ch th en eriocrom T trong chun ny. Vi cch tnh tng t khi chun Ca2+ vi ch th ny (KMind = 5,4) ta c pCa = 3,9 1; tc l khong chuyn mu ca en eriocrom T l 2,9 4,9, bc nhy trn ng cong chun kho st l 4,3 8,54 nn dng en eriocrom T cho chun Ca2+ s mc sai s ln. Ch th murexid thng dng cho chun Ca2+ pH > 10, tnh tng t nh ch th en eriocrom T, ta c khong chuyn mu pCa = 6,1 1; tc l khong chuyn mu ca murexid l 5,1 7,1, bc nhy trn ng cong chun kho st l 4,3 8,54 nn c th dng murexid cho chun Ca2+. Cc ch th thng dng en eriocrom T (NET) C20H13O7N3S. K hiu H3In
Ch th ny l mt acid ba nc, nc mt phn ly kh mnh (nhm HSO3). S phn ly nc hai v nc ba nh sau: H2In H+ Xanh + HIn2 2H+ + In3 Vng cam
pH = 7 10 ch th c mu xanh (HIn2) v to phc vi Ca2+, Mg2+, Ba2+,... c mu vang. Murexid (amoni purpurat) C8H8O6N6H2O. K hiu H4I
11/25/2010
Page 229 of 239
Murexid phn ly nh sau H4I tm H+ + H3I2 Tm 2H+ + H2I3 Xanh
pH = 9 11. Murexid c mu tm (H3I2) v to phc vi Ca2+ c mu (CaH2I). Murexid v en eriocrom T u km bn trong dung dch nn thng khng pha dung dch sn m dng dng rn (nghin trn vi NaCl). Kxilen da cam. Kxilen da cam l cht mu hu c dy triphenylmetanic. Cht ch th c mu vng. Trong mi trng acid pH nh hn 7, n to vi cc ion kim loi (Zn2+, Th(IV), Zr(IV) v.v.. phc cht mu . Cc cation c xc nh bng chun EDTA vi ch th kxilen da cam l Fe3+(pH = 11,5), Zr4+(pH = 1-2), Bi3+(pH = 2-3,5), Zn2+(pH =5-6)... Kxilen da cam l 3,3- bi [ di(cacboximetyl) aminometyl]- o-krenzolsunfophtalein:
Crom xanh en acid. Crom xanh en acid l cht mu azo hu c:
11/25/2010
Page 230 of 239
Cht ch th c mu xanh. Trong mi trng kim n to vi cc cation kim loi phc cht mu nho. Ngi ta dng n khi chun bng cc dung dch complexcon cc cation km, cadmi (pH = 910), mangan (pH= 10), magnesi (pH = 10-11), calci (pH > 12), ... PAN PAN l tn tt ca 1-(2-piridinazo) naphtol-2 c cng thc cu to l:
PAN c dng lm cht ch th chun trc tip nhiu ion. N to phc mu hng hoc tm, tm vi nhiu ion kim loi. Trong khong pH kh rng cht ch th t do c mu vng. -Vi Bi3+: dung dch HNO3 c pH =1-3 cht ch th i mu t hng sang vng lc. - Vi Cd2+: pH =5 - 6 dng m acetat, cht ch th i mu t hng sang vng. - Vi Cu2+: pH =3 - 5 dng m acetat, cn un ti 70- 80oC. Cht ch th i mu t tm sang vng. - Vi Zn2+: Dung dch c pH khong 4 - 6 dng m acetat, cht ch th i mu t sang vng. PAR PAR l tn tt ca 4- (2-piridinazo)- resorcin c cng thc cu to l:
Cht ch th ny to phc mu hoc nho vi nhiu ion kim loi trong khong pH rt rng t 111,5. Cht ch th t do c mu vng nn khi chun trc tip cc ion kim loi mu ca dung dch s chuyn t nho sang mu vng. Th d: Vi Bi3+: pH =1-3, dung dch HNO3. Cu2+: pH = 5, dung dch m acetat. pH = 6, dung dch m urotropin. pH = 11,5, dung dch m amoniac. Zn2+: pH = 5 11,5 dung dch m urotropin (pH = 5) hoc m amoniac (pH = 11,5).
11/25/2010
Page 231 of 239
2.7. Sai s chun Trong cc trng hp chung, sai s chun c th d dng tm nu bit nng chung ca ion kim loi hay EDTA im kt thc chun , lng ion chun f v hng s bn iu kin ca phc MY (n4)+. Nu im kt thc chun t sm hn im tng ng th nng chung ca ion kim loi sau khi loi b trong phc MY(n1)+ bng: CM = C O,M (1f) + CY Gi thit rng [MY] = CO,M , suy ra: Sau khi t gi tr CY v bin i ta c:
Sai s chun biu th bng phn trm %: % SS = (1 f) 100 Nu nh im kt thc chun n sau im tng ng CO,M = CO,Y, nng chung ca phn khng to phc EDTA tnh theo cng thc: CY = CO,M (f 1) + CM t gi tr CY vo biu thc ca hng s bn iu kin: CO,M, sau khi bin i c 2.8. Cc k thut chun bng dung dch EDTA Chun thng (chun trc tip) Phn ln cc ion kim loi (khong 30) c th chun thng bng dung dch EDTA vi s c mt ca ch th kim loi. Khi logarit ca hng s bn iu kin. lg K = lg lg khc nhau trong khong 4 n v, c th lin tip xc nh vi nguyn t trong dung dch. Trong trng hp ny cn thit s dng hai ch th kim loi cho mi mt ion ca mnh. Thc t y l iu kin kh thc hin v s khc nhau mt t hiu ng mu (hai ch th kim loi v hai phc vi chng), v vy tnh chn lc ca chun complexon tng bng cch tch ra hay che cc cht cn tr. Phng php n gin che l thc hin trong s thit lp tnh acid tng ng ca dung dch chun . Th d Fe3+, Th4+chun trong mi trng acid pH = 2, ion 2 in tch iu kin ny thc t khng cn tr. Trn hnh 10.8 chng minh rng trong gi tr pH ti thiu c th d dng chun cc ion kim loi. Phng php che bng cch to phc vi cc cht to phc l c s dng rng ri. Trong nhm ny th d nh cc ion florid, pirophotphat, citrat, triethanolamin... Phng php che c th thay i mc oxy ho ca nguyn t xc nh hay nguyn t cn tr. Mt s th d trnh by bng 10. 3. v tnh rng [MY] =
11/25/2010
Page 232 of 239
B ng 10.3. Phng php che nh cc cht to phc khi chun mt s ion kim loi bng dung dch EDTA Ion kim loi xc nh Zn (II) Cd(II) Pb (II) Ch th kim loi 1(2Piridinazo) naphtol2 4(2Piridinazo) resorcin 1(2 Piridinazo) naphtol2 Cht che Fluorid ion, pH 56 Triethanolamin, cyanid, tartrat ion, pH 10 Tartrat,fluorid ion, pH 4 5 Ion khng cn tr xc nh Ca(II), Mg(II), Mn(II), Fe(III), Sn(IV), Th IV) Cu(II), Ni(II), Co(II), Zn(II), Cd(II), Al (III), Fe(III), Bi(III), Sn(IV) Ti(IV), La(III), Ce(III), Th(IV), Al(III).
Mo (VI)
2.8.2. Chun ngc Da trn nguyn tc cho mt lng d EDTA v sau xc nh lng d, thc hin trong nhng trng hp khi phn ng to phc vi EDTA xy ra chm hay khng c ch th thch hp xc nh im kt thc. Th d phc ca Cr3+ ng hc tr, do phc vi EDTA c to thnh rt chm. Sau khi cho lng tha EDTA v un nng crom kt hp hon ton thnh complexonat. Tin hnh chun d EDTA gi tr ti thiu pH (pH: 1,5 2) bng dung dch chun Fe (III) m khng cn ch rng phc FeY bn hn phc CrY mt bc. Phn ng trao i CrY + Fe3+ FeY + Cr3+ xy ra sau thi gian, cn thit i vi chun , thc t khng xy ra. Phng php chun ngc tin li hn khi xc nh cc ion kim loi c mt cc anion m n to vi ion kim loi cn xc ng l hp cht t tan. Th d nh c th xc nh Pb2+ khi c s hin din ca ; xc nh Mg2+ khi c ion ... EDTA ngn cn s to ta. La chn ion kim loi i vi chun tha EDTA trong phng php chun ngc ch hai iu kin: hai ion ny cn to phc cht c mu vi ch th kim loi; hng s bn iu kin ca phc vi EDTA cn phi thp hn ca phc EDTA vi ion cn xc nh, nhng khng c thp hn K = 108 2.8.3. Chun gin tip Phng php ny dng xc nh cc nguyn t, anion khng to phc vi EDTA. Khi xc nh cc anion nh sunfit, sunfat, phosphat... To ta chng bng lng d dung dch chun ca mt ion kim loi no , ta c tch ra v trong dch lc chun bng dung dch EDTA, lng tha ca ion kim loi, khng to ta vi ion cn xc nh (anion). C th tin hnh s xc nh cc ion theo lng tha ca ion khc, m xc nh bng chun to phc sau khi ha tan ta vo nhng ion xc nh v chun vo thnh phn mt lng tnh thch hp. Th d: nh lng Ba2+ + BaSO4 , kt ta anion bng mt thuc th cha cation thch hp: cho d BaCl2
Sau nh lng cation cn li trong nc lc, nc ra, hoc lc ra ta ri ha tan ta trong EDTA d, nh lng EDTA cn li bng MgSO4 hoc ZnSO4. 2.8.4. Chun th
11/25/2010
Page 233 of 239
Da trn phn ng m trong ion cn xc nh ca kim loi M1 n+thay th ion ca kim loi M2n+ m n km bn hn phc vi EDTA M1n+ + M2Y(4m) M1Y(+n) + M2m+
Ion thay th ca kim loi M2m+ v lng tng ng (ng lng) vi M1 chun bng dung dch EDTA vi s c mt ca ch th kim loi thch hp. Th d: Da trn c s Mg2+ to phc vi complexon phc cht km bn (pK = 8,7) so vi a s cc cation khc (Ca2+, pK = 10,7). nh lng Ca2+, ta thm MgY2 vo dung dch ri chun Mg2+ b y ra bng dung dch chun EDTA. Ca2+ Mg2+ + + MgY2 HY3 CaY2 MgY2 Tha T Vcomplexon suy ra Ca2+ c trong mu. 2.9. Dung dch chun dng trong phng php complexon 2.9.1. Pha dung dch chun complexon III - Trng hp c complexon tinh khit ho hc: cn mt lng chnh xc complexon, pha trong nc vi th tch xc nh. - Trng hp khng c complexon tinh khit, pha dung dch c nng xp x, sau xc nh li nng . 2.9.2. Xc nh nng complexon III xc nh nng complexon ngi ta dng calci cacbonat tinh khit ho hc, ZnO tinh khit ho hc hay MgO tinh khit ho hc. Ho tan mt lng cn chnh xc tnh trc ca cc cht trong mt t acid (nu l CaCO3, MgO ha trong HCl tinh khit, nu l ZnO ha trong H2SO4 tinh khit), sau cho nc n th tch xc nh. Chun dung dch complexon bng cc dung dch va pha nh CaCl2, MgCl2, ZnSO4 vi cc ch th thch hp. 2.10. ng dng ca phng php complexon 2.10.1. nh lng Ca2+ Phng php complexon xc nh calci da trn phng php chun trc tip cc ion ca n bng dung dch chn EDTA vi cht ch th murexit hay crom xanh en acid. Cht ch th to vi ion calci phc cht mu . Khi chun bng EDTA, im tng ng mu chuyn sang mu c trng ca cht ch th t do. Khi chun mui calci bng EDTA, xy ra s to phc CaY2 v acid: Ca2+ + H2Y2 CaY2 + 2H+ + + Mg2+ H+
11/25/2010
Page 234 of 239
Phc to thnh CaY2 tng i khng bn:
nh lng calci tin hnh mi trng kim mnh pH 11 2.10.2. Xc nh cng ca nc cng ca nc c biu th bng s mili ng lng gam canxi v magne trong 1 lt nc. cng ton phn ca nc l tng mui calci v magnesi tan trong nc. C th xc nh cng ton phn bng complexon III vi ch th en eriocrom T. Ly mu nc cn nh lng, cho thm ch th en eriocrom T pH = 10, ch th s to phc mu vang vi mt phn Mg2+ trong mu. Khi nh EDTA vo, EDTA s phn ng vi Ca2+ t do, sau vi Mg2+ t do (v phc CaY2 bn hn phc MgY2), n im tng ng EDTA s ph phc ca ch th vi Mg2+, gii phng ra ch th t do c mu xanh. 2.10.3. nh lng Fe3+ Trong mi trng acid (pH: 2 3), EDTA tc dng vi Fe3+ to phc c mu vng nht FeY. Nu dng ch th l acid salicylic hay acid sulfosalicylic pH n tc dng vi Fe3+ to thnh phc c mu tm . Trong iu kin ny Al3+, Ca2+, v Mg2+ khng cn tr vic xc nh Fe3+. Ti im tng ng mt mu tm v dung dch c mu vng nht. 2.10.4. nh lng Ba2+: (theo phng php chun ngc) Cho Ba2+ cn nh lng tc dng vi mt lng d chnh xc EDTA. nh lng EDTA d bng dung dch Mg2+. 2.10.5. nh lng : (phng php gin tip)
Cho BaCl2 d kt ta hon ton Ba2+ + BaSO4
nh lng Ba2+ cn li bng complexon III. quan st d dng s chuyn mu ca ch th, thm vo dung dch mt lng Mg2+ nht nh v qu trnh nh lng c tin hnh hon ton tng t nh nh lng cng ton phn ca nc. 2.10.6. Dng trong phn tch dng c Php so mu, o quang. T KHA
11/25/2010
Page 235 of 239
- Phc cht - Phc cht cng - Phc cht ni - Hng s khng bn CU HI LNG GI
- Hng s to phc - Hng s bn iu kin - Complexon - Ch th kim loi
1. Nu nh ngha phc cht, phc cht cng, ni phc, cho th d minh ha. 2. Phn tch ngha ca hng s to phc, hng s khng bn ca phc, hng s bn iu kin. 3. Trnh by phn loi ca ch th dng trong phng php to phc. 4. Nu cc yu cu ca ch th kim loi. 5. Trnh by ngha ca hng s bn iu kin. 6. Hy phn tch nh hng ca pH n cn bng to phc. 7. Lm th no tng tnh chn lc ca chun to phc? 8. Trnh by ng dng ca phn ng to phc trong phn tch. 9. Nu nguyn tc ca phng php complexon, gii thch ng lng ca ion kim loi trong phng php complexon? 10. nh ngha complexon. Nu tnh to phc ca complexon III. 11. Trnh by cc phng php pht hin im kt thc chun . 12. Nu c ch chuyn mu ca ch th kim loi; Tn cc ch th thng dng trong phng php complexon. 13. Trnh by cc k thut chun bng complexon. - Chun thng. - Chun gin tip. - Chun th. - Chun ngc.
14. Nu ng dng ca chun complexon trong phn tch. CU HI TRC NGHIM 1. Phc cht l nhng hp cht phn t c to thnh do........... ni vi cc phi t a. mt ion b. mt cation c. mt kim loi d. mt vi ion kim loi e.mt nguyn t 2. Tnh cht c trng ca ni phc l a. mu c trng
11/25/2010
Page 236 of 239
b. bn cao c. tan trong dung mi hu c ln d. tt c cc cu trn ng e. khng cu no ng 3. Complexon III l a. dn xut ca acid aminopolycarboxilic b. acid nitril triacetic c. acid etylen diamin tetraacetic d. mui dinatri ca etylen diamin tetraacetic e. cc hp cht hu c 4. pH 4 -6 EDTA phn ly dng: a. H5Y+ b. H3Y c. H2Y2 d. HY3 e. Y4
5. Ch th kim loi l ch th lm thay i mu ph thuc vo a. hng s bn ca complexonat b. hng s bn iu kin ca ch th c. dng phn ly ca EDTA 6. nh lung Fe3+ bng phng php comlexon dng ch th a. en eriocrom T b. murexit c. kxilen dacam d. crom xanh en acid e. acid salicylic d. nng ca EDTA e. nng ca ion kim loi
7. nh lng Ca2+ vi ch th murexit thc hin mi trng a. pH > 12 b. pH = 7-8 c. pH = 9-11 d. pH < 3 e. pH = 7
8. Ch th en eriocrom T pH = 6,3 -11,2 c mu a. xanh b. 9. Ch th dng dng rn a. en eriocrom T b. murexit c. acid salicylic d. cu a,b e. cu a,b,c c. vng cam d. tm e. cam
11/25/2010
Page 237 of 239
10. nh lng Ba2+ bng phng php complexon dng k thut chun a. trc tip b. th c. ngc d. gin tip e. gin tip tha tr
P N CU HI TRC NGHIM
Chng 1 2 3 4 5 6 7 8 9 10 Cu 1 b d d c d b c a c c 2 c a c e e d b c a d 3 e e c a b a e e b d 4 d d c a a e c c b c e d a e c a e e e b a c d c a a a d c d e e b c 5 d a d c e b a b e a e c c b 6 7 8 9 10
TI LIU THAM KHO

Ting Vit 1. A.P. Kreskov. C s ha hc phn tch. Tp 1. Nh xut bn i hc v Trung hc chuyn nghip, H Ni, 1989. 2. A.P. Kreskov. C s ha hc phn tch. Tp 2. Nh xut bn i hc v Trung hc chuyn nghip H Ni, 1989. 3. A.T. Pilipenko, V.la. Pochinoc, i.p. xereda, ph. D. Sepchenko. L Ch Kin dch. S tay ha hc s cp. NXB Gio Dc, 1998. 4. Hong Minh Chu, T Vn Mc, T Vng Nghi, C s ho hc phn tch, Nh xut bn Khoa hc v K thut, 2002. 5. Kiu Dinh, Ho i cng, Nh xut bn i hc v Trung hc chuyn nghip, H Ni, 1969.
11/25/2010
Page 238 of 239
6. Phm Gia Hu, Trn T An, Trn Tch Ha phn tch I B mn Ha Phn tch, Trng i hc Dc H Ni, H Ni, 1998. Ting nc ngoi 7. D. Pradeau. LAnalyse pratique du mdicament, 1992, Tec et doc Lavoisier, 1992. 8. Daniel C. Harris. Quantitative chemical analysis 4th ed, 1995 9. David Harvay, Modern analytical chemistry, Depauw university, 2000, www.mhhe.com 10. Douglas A. Skoog, Donald M. West, F. James Holler Fundamentals of Analytical chemistry Saunders College Publishing, 1990. 11. IU. A.Zalatova, Osnovy Analitrica chimi. Tom 2. Moskva Vyshara Shkola, 2002. 12. James S. Fritz, George H. Schenk. Quantitative analytical chemistry, fifth edition, 1987. 13. M. Guernet, E. Guernet, E. Herrenknecht Trottmann. Td Chimie analytique, quilibres en solution Dunod Paris, 2000. 14. M. Guernet, M. Hamon. Abrg de chimie analytique. Tome 1. Chimie des solutions 2e ed. Masson 1990. 15. Raymond Chang, Luc Papillon, Chimie fondamentale, Chenelire / Mc GrawHill,1998. 16. Thuong C. Trieu, S. Troupel, G. Mahuzier. Travaux pratiques de chimie analytique. Facult des sciences pharmaceutiques et biologiques de Paris, 1975. Ti liu trn mng 17. Martindale's the "virtual" ~ chemistry center. Analytical chemistry http://www.martindalecenter.com/gradchemistry_4_a.html 18. A Redox titration. HTTP://WWW.NVCC.EDU/ALEXANDRIA/SCIENCE/REDOX2.HTM 19. HTTP://WWW.MARTINDALECENTER.COM/GRADCHEMISTRY_4_A.HTML - Martindale's the "virtual" ~ chemistry center . 20. Analytical chemistry. http://www.shodor.org/UNChem/basic/ab/ 21. Acid base chemistry. http://www.usoe.k12.ut.us/CURR/Science/sciber00/8th/matter/sciber/chemtype.htm 22. Four basic types of chemical reactions HTTP://WWW.CHEM.VT.EDU/RVGS/ACT/NOTES/TYPES_OF_EQUATIONS.HTML 23. http://www.stetson.edu/~wgrubbs/datadriven/activitieswtg/activitieshydrogenwtg.html 24. wgrubbs@stetson.edu - Activities of hydrogen ion from pH measurements 25. http://www.science.uwaterloo.ca/~cchieh/cact/applychem/reactivity.html
11/25/2010
Page 239 of 239
Chu trch nhim xut bn: Ch tch HQT kim Tng Gim c NG TRN I Ph Tng Gim c kim Tng bin tp NGUYN QU THAO Chu trch nhim ni dung: Ch tch HQT kim Gim c Cng ty CP sch i hc - Dy ngh TRN NHT TN Bin tp v sa bn in: VNG MINH CHU Trnh by ba: BI QUANG TUN Ch bn: THI SN
HO PHN TCH TP 1
M s: 7K725M7 DAI
In 1.000 bn, (Q: 96), kh 19x27 cm, ti Cng ty CP In Anh Vit. a ch: S 74, ng 310 ng Nghi Tm, Ty H, H Ni S KKH xut bn: 874-2007/CXB/5-1918/GD In xong v np lu chiu thng 1 nm 2008
11/25/2010

Hoa Phan Tich Bo Y Te VinaEbookChemistryHere PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Hoa Phan Tich Bo Y Te VinaEbookChemistryHere PDF

Uploaded by

Copyright:

Available Formats

Bo Y te - Hoa phan tich

NH XUT BN GIO DC H NI 2007

Ch o bin son : V KHOA HC V O TO B Y T Ch bin :

Bo Y te - Hoa phan tich

Bn quyn thuc B Y t (V Khoa hc v o to)

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Chng 1 I CNG HO PHN TCH

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

5. C my bc ch yu ca mt quy trnh phn tch a. 3 b. 4 c. 5 d. 6 e. 7

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

K hiu (k = th kh = gaz); (l = th lng = liquid); (r = th rn = solid); (nc = dung mi, nc = aqueous)

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Mt th d in hnh ca cn bng ho hc l phn ng: (2.1)

Hnh 2.1. Chuyn 2NO2 (k)

N2O4 (k), h thng cn bng cc 4, 5 v 6

Nu bt u vi N2O4, cng nhit c th minh ha cn bng t n l

Hnh 2.2. Chuyn N2O4 (k)

2NO2 (k), h thng cn bng cc 10, 11 v 12

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

vi a: hot ; (hoc f): h s hot ; C: nng mol;

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Ch : theo phng trnh: aA (k) Theo phn ng N2 (k) + 3H2(k)

Gi tr ca K = 4,3.10-4 375 C. Hy tnh K . p c

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Phn ng ho hc Cn bng ho hc Hng s cn bng Hot CU HI LNG GI

Nng H s hot Hng s phn ly Hng s bn

Bo Y te - Hoa phan tich

Chng 3 S DNG THNG K TRONG PHN TCH S LIU

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Bo Y te - Hoa phan tich

Qlt c tra t bng (3.2) vi s ln o n v xc sut bt gp P thng thng l 95%.

Bo Y te - Hoa phan tich

Tlt 1,412 1,689 1,869 1,996 2,093 2,172 2,237 2,294

Tlt 2,343 2,387 2,426 2,462 2,493 2,523 2,551 2,623

tlt = 2,45 tnh e = 0,047.