Hoa phan tch

CHNG 1. AI CNG VE HOA PHAN TCH

I. NOI DUNG VA YEU CAU CUA HOA PHAN TCH Hoa hoc phan tch, hieu theo ngha rong, khong nhng ch la khoa hoc ve cac phng phap phan tch nh tnh va nh lng cac chat ma con la khoa hoc ve cac phng phap kiem tra nhng qua trnh hoa ly va ky thuat hoa hoc. Phan tch nh tnh (PTT) nham xac nh s hien dien cua cac cau t (ion, nguyen to hay nhom nguyen to) trong mau phan tch va ong thi anh gia s bo ham lng cua chung: a lng, vi lng, vet, PTT phan ln da vao s chuyen chat phan tch thanh mot chat mi nao o co nhng tnh chat ac trng nh co mau, co cau truc tinh the hoac vo nh hnh, co trang thai vat ly nhat nh Phan tch nh lng (PTL) co nhiem vu xac nh chnh xac ham lng cua nhng cau t trong mau. Phng phap PTL da tren phep o cac thuoc tnh hoa hoc, vat ly hoac hoa ly cua cac chat hoac cua cac phan ng hoa hoc. Cac phng phap PTL bao gom PPHH, PPVL, PPHL. Vai tro chu yeu cua hoa phan tch la PTL. Tuy nhien trong thc te muon xac nh ham lng mot mau cha biet thanh phan rat phc tap, v s co mat cua ion hay nguyen to nay thng can tr viec xac nh cau t khac. Do o, du co yeu cau hay khong, vi mot mau cha biet thanh phan phai tien hanh phan tch nh tnh trc e co the chon c phng phap PTL thch hp va cho ket qua chnh xac. Cac phng phap phan tch nh tnh va nh lng cho phep xac nh ham lng cac nguyen to rieng re trong cac chat phan tch c goi la phng phap phan tch nguyen to, e xac nh cac nhom chc c goi la phan tch nhom chc. Da vao cac PPPT, ngi ta a tm ra nhng nh luat hoa hoc quan trong nh nh luat thanh phan khong oi, nh luat t le boi, nh luat tac dung ng lng, xac nh cac nguyen t khoi cua mot so nguyen to, thanh lap c cong thc hoa hoc cua rat nhieu hp chat . Hoa hoc phan tch tao ieu kien thuan li cho viec phat trien cac mon khoa hoc t nhien nh a hoa hoc, a chat hoc, khoang vat hoc, vat ly hoc, sinh vat hoc, y hoc, hoa ky thuat, cong nghiep luyen kim, va hoa hoc phan tch con la c s cho viec kiem nghiem hoa hoc trong nghien cu, san xuat (kiem tra nguyen lieu, ban thanh pham, thanh pham), xay dng cac phng phap kiem tra t ong cac qua trnh ky thuat. Vai tro cua hoa phan tch ngay cang cao cung co ngha la cac yeu cau oi vi nganh va ngi lam cong tac phan tch ngay cang khat khe hn. Vi nganh phan tch, phai luon luon phat trien hau theo kp a phat trien cua cac nganh khac. Vi ngi phan tch, do co s tng quan gia cac nganh khoa hoc t nhien nen ngi phan tch phai co kien thc ve cac mon toan, ly, hoa ai cng, hoa vo c, hoa ly va tin hoc e co the nam vng nguyen tac cua cac

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phng phap va co the i sau vao cac phng phap mi da tren cac can ban san co. Ngoai ra, trong phan thc nghiem, ngi phan tch can co nhng ao c nh can than, kien nhan, chnh xac, sach se, trung thc va co kha nang phan oan ket qua phan tch. II. PHAN LOAI CAC PHNG PHAP PHAN TCH (PPPT) Co nhieu cach phan loai cac phng phap phan tch, trong o pho bien nhat la cach phan loai da vao ban chat (hay ac iem) cua phng phap hoac da vao ham lng cua cau t trong mau phan tch. II.1. Phan loai theo ban chat cua phng phap Khi phan loai theo ban chat cua phng phap, hoa phan tch bao gom cac phng phap sau: Phng phap hoa hoc (PPHH) Dung phan ng hoa hoc e chuyen cau t khao sat thanh hp chat mi ma vi tnh chat ac trng nao o cua hp chat mi, ta co the xac nh c s hien dien va ham lng cua cau t khao sat. V du: trong moi trng ammoniac, vi ham lng thch hp Ni2+ tham gia phan ng hoa hoc vi dimetyl glyoxim (DMG) cho xuat hien ket tua mau o son. Nh vay, khi cho dung dch DMG tac dung vi dung dch phan tch: - Neu dung dch (DD) co xuat hien tua o son, ket luan co Ni2+ trong DD phan tch (nh tnh). - Tach va can tua ta xac nh c ham lng Ni2+ trong mau (nh lng). Phng phap vat ly (PPVL) Phng phap vat ly la cac PPPT dung e phat hien hoac xac nh thanh phan cua chat can nghien cu ma khong can phai s dung cac phan ng hoa hoc. Cac phng phap nay co the la cac phng phap da tren viec nghien cu cac tnh chat quang, ien, t, nhiet hoac cac tnh chat vat ly khac. PPVL co 1 so u iem so vi cac PPHH nh co the tach c cac nguyen to kho b tach bi PPHH, de ap dung cho cac qua trnh t ong hoa. Phng phap hoa ly (PPHL) Phng phap hoa ly la PPPT d tren s ket hp gia PPVL va PPHH: sau khi thc hien phan ng hoa hoc gia cau t khao sat va thuoc th, da vao viec khao sat ly tnh cua hp chat thu c hay DD tao ra e nh tnh hoac nh lng mau. Mac du xuat hien kha lau sau PPPT hoa hoc, cac phng phap hoa ly lai c phat trien va hien ai hoa vi toc o rat nhanh, c s dung ngay cang rong rai trong cac phong th nghiem nghien cu khoa hoc va trong ca phong th nghiem nha may, x nghiep. Nguyen tac chung cua phng phap la dung bien phap thch hp tac ong len oi tng nghien cu va ghi nhan s thay oi cac tham so hoa ly cua oi tng nghien cu sau khi tac ong. e quan sat va ghi nhan cac tham so hoa ly oi hoi phai s dung cac dung cu va

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thiet b kha tinh vi, phc tap. V ly do nay, cac PPPT vat ly va hoa ly thng c goi la PPPT dung cu hoac goi theo thoi quen la PPPT hoa ly. Cac PPPT dung cu thng c chia thanh cac nhom sau ay: (1) PPPT pho nghiem; (2) PPPT ien hoa; (3) PPPT sac ky va (4) la cac PPPT khac. Cac phng phap pho nghiem (PPPN) Cac PPPN la cac PPPT ma ket qua khao sat co the bieu dien di dang pho. Thuoc nhom phng phap nay gom co cac phng phap quang pho (quang hoc) da tren s nghien cu cua cac pho phat xa, hap thu va tan xa anh sang. Phng phap nay con bao gom phng phap khoi pho (phng phap nghien cu cac chat bang cach o chnh xac khoi lng phan t cua chat o) va phng phap pho cong hng t da tren s tng tac cua nguyen t, phan t chat khao sat vi t trng. Ngoai cac phng phap tren, nhom cac phng phap phan tch pho con bao gom PPPT da tren viec o chiet suat khuc xa cua vat chat; PPPT ham lng cac chat da tren s o lng anh sang va phng phap hap uc la phng phap da tren s o lng anh sang do mot huyen phu khong mau hap thu. Cac phng phap ien hoa (PPH) Ngay nay a co ti khoang ba mi PPPT ien hoa khac nhau ma c s cua phng phap da tren cac quy luat, hien tng co lien quan en phan ng ien hoa xay ra tren ranh gii tiep xuc gia cac cc va DD phan tch, hoac da vao tnh chat ien hoa cua DD tao nen moi trng gia cac ien cc, hoac da tren cac ng dung cua phan ng ien hoa. Nhieu tac gia e ngh chia cac PPPT ien hoa thanh 2 nhom ln: (1) nhom cac phng phap da tren cac qua trnh ien cc va (2) nhom cac phng phap khong dung cac phan ng ien cc. Cac phng phap thuoc nhom mot c chia thanh hai phan nhom: Phan nhom gom cac phng phap trong o cac phan ng ien cc trang thai can bang bao gom phng phap o the va chuan o ien the vi dong bang khong. Phan nhom da tren s ien phan (dong khac khong), bao gom phng phap volt amper, chuan o ien the vi dong khong oi, phng ien khoi lng dong khong oi hoac the khong oi, phng phap cc pho co ien, cc pho dong xoay chieu, phng phap ien hoa hoa tan. Cac phng phap khong dung phan ng ien cc bao gom cac phng phap ien dan va chuan o ien dan, phng phap xac nh hang so ien moi tng oi, phng phap ien dan cao tan va chuan o ien dan cao tan Cac phng phap sac ky (PPSK) Sac ky la qua trnh tach da tren s chuyen dch cua hon hp phan tch qua lp chat bat ong trang thai ran hoac trang thai long tam tren chat mang ran (c goi la pha tnh) va s chuyen dch o c thc hien bang mot chat

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long hoac chat kh co kha nang di chuyen (goi la pha ong). Cac PPPT sac ky cu the bao gom nhom sac ky hap phu (ran-kh, ran-long); nhom sac ky phan bo (long - long; long - kh), sac ky trao oi ion va sac ky ray phan t. Qua trnh tach sac ky co the xay ra tren cot hoac tren mat phang nh giay, ban mong. Phng phap sac ky c s dung rong rai e tach nhng chat vo c va hu c giong nhau ve thanh phan va tnh chat, ac biet la co the tach c cac nguyen to at hiem va nhng nguyen to phong xa vi hieu qua kha cao. Ngoai kha nang tach, PPSK con c dung e nh tnh va nh lng rat nhieu loai mau thuoc lnh vc khoa hoc va lnh vc cong nghiep khac. Cac PPPT hoa ly khac Ngoai cac nhom phng phap tren, thuoc nhom PPPT dung cu con co PPPT phong xa da tren s o bc xa cua cac nguyen to co hoat tnh phong xa, cac PPPT nhiet, PPPT nhiet ien, PP o o dan nhiet, PP chuan o nhiet lng va mot so PPPT khac. u iem cua cac PPPT dung cu la o nhay cao, toc o phan tch nhanh, lng mau phan tch be khi so sanh no vi PPPT hoa hoc: Ch tieu so sanh Lng mau Tnh chon loc Thi gian o chnh xac Dung cu Ngi phan tch
(*)

Phng phap hoa hoc Ln (kem nhay) Khong cao Cham Chnh xac (*) n gian, re tien

Phng phap dung cu Nho (nhay) Cao Nhanh Chnh xac (*) Toi tan, at tien Trnh o ky thuat cao

Neu ham lng cau t trong mau khao sat khong qua be, o chnh xac cua bat ky PPPT nao cung khong the vt qua o chnh xac cua PPPT hoa hoc.

Phng phap vi sinh Dung e nh lng vet cau t da tren hieu ng cua chung vi toc o phat trien cua vi sinh vat. Phng phap phan tch ong hoc Phng phap nh tnh va nh lng cac nguyen to da vao viec s dung cac phan ng xuc tac. V toc o cua cac phan ng hoa hoc phu thuoc vao nong o cua cac chat phan ng nen o toc o phan ng co the xac nh nong o cua chat phan ng. PPPT ong hoc co o nhay ac biet cao, gap nhieu lan o nhay so vi cac PPPT khac (10-5 10-6 g/ml). Cac phng phap khac Ngoai cac phng phap ke tren con mot so phng phap khac chu yeu dung cho PPL.

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Mau phan tch va thuoc th ran c nghien trong coi s, nguyen to can tm c phat hien da vao s tao thanh cac hp chat ac trng co mau sac hay co mui khac nhau. V du, nghien mau ban au vi KSCN, neu thay xuat hien mau o mau tc mau cha cac hp chat cua Fe3+. PPPT da tren s mao dan va hap phu. Cac phan ng c thc hien tren cac tam s, thuy tinh hoac giay loc. Khi s dung giay loc, chat long tham vao giay con hp chat mau c tao thanh b hap phu mot phan nho cua giay loc lam tang o nhay cua phan ng. V du, e xac nh ion Mn2+, ngi ta cham 1 giot DD phan tch len t giay loc va cho vet am bao hoa vi hi ammoniac. Them 1 giot DD benzidine trong acid acetic. Mn(OH)2 tao thanh c oxy hoa thanh Mn(OH)3 va Mn(OH)4 nh oxy cua khong kh. pH = 5, cac hp chat nay oxy hoa benzidine va tao thanh mau xanh cua xanh benzidine. Mot so kim loai phat ra t bc xa co mau ac trng khi c ot tren ngon la xanh cua en kh. V du: Na: la vang Ca: la o gach K: la o tm Ba: la o luc Dung knh hien vi co the phan biet c cac dang tinh the cua cac hp chat sau nh: Phan biet SrCrO4 vi BaCrO4 Phan biet CuSO4 vi BaSO4 nh tinh the cua chung co cau truc khac nhau ac trng. Mot so oxyt kim loai co the tao hp chat vi borax hay phosphate co mau ac trng di ngon la tnh oxy hoa/kh hay trang thai nong/nguoi. V du: Cu-Borax dang ngoc mau xanh am khi nguoi Mn-Borax mau tm ngon la oxy hoa II.2. Phan loai theo lng mau phan tch hay ky thuat phan tch Tuy ham lng cua cau t trong mau va PPPT, lng mau phan tch cung khac nhau. Ta phan biet: Phan tch tho Dung dung cu c 50-500ml va tach chat ran khoi chat long bang cach loc. Lng mau s dung t 1-10g hay 1-10ml. Phan tch ban vi lng Dung dung cu <1ml va thng tach chat ran khoi chat long bang ly tam. Lng mau s dung t 10-3-1g hay 10-1-1ml.

Phng phap nghien

Phng phap nho giot

Phng phap th nghiem ngon la

Phng phap soi tinh the di knh hien vi

Phng phap ieu che ngoc borax hay phosphate

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Phan tch sieu vi lng Phan tch di knh hien vi ien t va moi trng ac biet vi lng mau s dung <10-6g hay < 10-3ml. Phan tch ban vi lng ngay cang phat trien v dung t mau, ky thuat tng oi n gian, co the dung trong phong th nghiem hay ni san xuat. Phan tch vi lng oi hoi nhng ieu kien nghiem ngat hn. II.3. Phan loai theo ham lng chat khao sat Phan tch a lng Bao gom phan tch lng ln vi ham lng chat khao sat 0.1-100% va phan tch lng nho (ham lng chat khao sat 0.01 -0.1%). Phan tch vi lng Con goi la PPPT vet, khi ham lng chat khao sat < 0.01% Ngoai cac cach phan loai noi tren, ngi ta con phan loai cac PPPT theo trang thai chat khao sat. Theo cach phan loai nay, ta co phan tch loi t (mau phan tch dang DD) hoac phan tch loi kho (mau phan tch trang thai ran). III. CAC LOAI PHAN NG HOA HOC DUNG TRONG HOA PHAN TCH Nhng bien oi hoa hoc kem theo s thay oi thanh phan hoa hoc, cau tao cua cac chat va c dung trong hoa phan tch e PPT hoac PTL goi la nhng phan ng phan tch. Ngoai hai nhiem vu chnh noi tren, nhng phan ng phan tch con c s dung e hoa tan, chuyen dang oxy hoa hoac dang kh, tach cac nguyen to hoac hp chat cua chung, che cac nguyen to ngan can s xac nh va giai che cac nguyen to ang di dang b che. III.1. Cac loai phan ng dung trong hoa phan tch Cac loai phan ng dung trong hoa phan tch co the chia thanh hai nhom chnh: Phan ng oxy hoa kh Phan ng oxy hoa kh la phan ng trao oi ien t gia oi oxy hoa/kh, thng c dung trong hoa phan tch e: 1. nh tnh: 2 Fe3+ + 2 I- 2 Fe2+ + I2 I2 xuat hien lam xanh giay tam tinh bot 2. Hoa tan: 3 Cu + 8 HNO3 3 Cu(NO3)2 + 2 NO + 4 H2O NO + O2 NO2 khoi nau 3. nh lng: MnO4- + 5 Fe2+ + 8 H+ Mn2+ + 5 Fe3+ +4 H2O (s dung dung dch MnO4- co nong o biet trc e xac nh DD Fe2+ co nong o cha biet va ngc lai). Phan ng oxy trao oi tieu phan Phan ng oxy trao oi tieu phan la ten goi dung chung cho phan ng acid-baz, phan ng tao tua va phan ng tao phc.

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Phan ng acid-baz: Phan ng trao oi H+ gia oi acid/baz dung trong hoa phan tch e: 1. Xac nh tnh acid hay baz cua DD bang cach o pH 2. Hoa tan mau: CaCO3 + 2 HCl CaCl2 + CO2 + H2O 3. nh lng: HCl + NaOH NaCl + H2O Phan ng tao tua: Phan ng trao oi ion e tao thanh hp chat t tan, c s dung e: 1. nh tnh: Ag+ + I- AgI vang 2. Tach nhom: Ag+, Pb2+, Hg22+ + HCl AgCl , PbCl2 , Hg2Cl2 3. nh lng: SO42- + Ba2+ BaSO4 Phan ng tao phc: Phan ng ket hp ion e tao phc chat de tan, c s dung e: 1. nh tnh: Fe3+ + n SCN- [Fe(SCN)n](3-n)+ o mau 2. nh lng: Ca2+ + H2Y2- CaY2- + 2 H+ 3. Hoa tan: AgCl + 2 NH4OH [Ag(NH3)2]+ + Cl- + 2 H2O 4. Che cau t di dang phc ben: - Loai Ni2+: Ni2+ + 4 CN- [Ni(CN)4]2- e tranh tao tua CuS v: [Cu(NH3)2]2+ + H2S CuS 5. Giai che (tra cac ion b che ve trang thai t do): 2 Ag+ + [Ni(CN)4]2- 2 [Ag(CN)2]- + Ni2+ Ngoai cac acid va baz, DD cua nhieu muoi cung co tnh acid hoac kiem. Neu dung moi la nc, gia nhng ion cua muoi vi nhng ion cua nc se xay ra phan ng tng tac goi la thuy phan. Qua trnh thuy phan thng la qua trnh thuan nghch. V du: Ba(CH3COO)2 + 2 H2O CH3COOH + Ba2+ + 2 OHNH4Cl + H2O NH4OH + H+ + ClAl2S3 + 6 H2O 2 Al(OH)3 + 3 H2S Theo ngha rong, s thuy phan la phan ng tng tac gia nhng chat khac nhau (muoi, hydrua, hp chat cha oxy,...) vi nhng ion cua nc, kem theo s pha huy can bang ien ly cua nc va lam thay oi pH cua DD. Trong hoa phan tch, cac phan ng thuy phan c s dung e:

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1. Tao tua hidroxid: mot so thuoc th nh (NH4)2CO3, (NH4)2S, CH3COONa de b thuy phan tao thanh ion hidroxyl t do, tao cho DD co cac gia tr pH xac nh. Ngi ta s dung cac hidroxyl t do sinh ra e tao tua hidroxid nhieu cation bang DD nc cua cac muoi thuy phan ke tren. 2. Tach cac chat ra khoi nhau da vao mc o thuy phan khac nhau cua cac chat khac nhau. 3. Phat hien cac muoi anion b thuy phan tao thanh ammoniac t do. 4. Phat hien cac ion ma muoi cua chung khi thuy phan tao thanh cac hp chat khong tan. V du: BeCl2 khi thuy phan tao thanh BeO2Cl2 III.2. Yeu cau oi vi thuoc th dung trong hoa phan tch o tinh khiet o tinh khiet la khai niem dung bieu dien ham lng hp chat X trong thuoc th. Tuy vao ham lng nay, ngi ta phan biet: 1. Hoa chat ky thuat vi X 99.0% 2. Hoa chat tinh khiet (P) vi 99.0% X 99.9% 3. Hoa chat tinh khiet phan tch (PA) vi 99.90% X 99.99% 4. Hoa chat tinh khiet hoa hoc vi 99.990% X 99.999% 5. Hoa chat tinh khiet quang hoc hay ac biet vi 99.999% X 99.9999% Tnh chon loc Thuoc th phai co tnh chon loc (hay ac hieu) cao oi vi cau t khao sat X, ngha la thuoc th ch tac dung vi cau t X ma khong tac dung vi cac cau t khac ong hien dien trong mau. V du, ho tinh bot la thuoc th co tnh chon loc oi vi Iod. Tnh nhay Thuoc th phai nhay, ngha la co kha nang phat hien cau t khao sat X khi X hien dien trong mau vi ham lng thap. Tnh nhay cua thuoc th co the c bieu dien theo mot trong hai khai niem la gii han phat hien hoac o loang gii han. Gii han phat hien: la lng toi thieu cua X ( g/ml) ma thuoc th phat hien c. V du, gii han phat hien Cu2+ bang NH4OH la 4 g/ml, gii han phat hien Fe3+ bang SCN- la 0.25 g/ml, Gii han phat hien con co the c bieu dien bang nong o gii han hay nong o toi thieu. o loang gii han: la the tch dung moi toi a (ml) dung e hoa tan 1g cau t X ma co the phat hien c X. Ngoai cac ieu kien chung ke tren, thuoc th dung e pha DD co o ung cao (goi la DD chuan) con phai am bao them cac ieu kien sau: 1. Tr oi vi moi trng 2. dang vun, bot co the can c lng chnh xac en 1mg hay 0.1mg 3. Co phan t lng ln e giam sai so khi can.

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Cac hoa chat thoa man c ong thi cac ieu kien tren c goi la hoa chat chuan goc. Cac hoa chat chuan goc thong dung nh la: K2Cr2O7, (COOH)2.2H2O, AgNO3, Na2H2C10H12O8N2.2H2O (EDTA), Mac du co mot so han che, oi khi ngi ta cung dung Na2CO3 khan, NaCl, vi vai tro chat chuan goc. III.3. Yeu cau oi vi cac phan ng trong hoa phan tch Phan ng gia cau t X can xac nh vi DD thuoc th C phai hoi u cac ieu kien sau ay: 1. Xay ra tc thi; 2. Xay ra hoan toan theo chieu mong muon; 3. Co he so xac nh va cho san pham co thanh phan xac nh; 4. Co dau hieu ac trng e nhan biet luc phan ng cham dt. IV. CAC GIAI OAN CUA MOT PPPT Mot qua trnh phan tch thng bao gom cac giai oan sau ay: IV.1. Giai oan chon mau Mau phan tch co the la nguyen lieu, nhien lieu, ban thanh pham hoac thanh pham, co the ong goi hoac khong ong goi. dang nguyen lieu co quang mo, at a; nhien lieu co than, dau mo; ban thanh pham hay thanh phan rat a dang bao gom hoa chat (NaOH, Na2CO3, Na2SO4, NH4Cl,); san pham hoa hoc (xa phong, kem anh rang, DD xi ma,); thc pham (ru, bot ngot, ng, nc cham, dc pham, dc lieu (dch truyen, vitamin). Giai oan chon mau rat quan trong v t ket qua phan tch mot lng mau gii han, ta phai ket luan ve chat lng cua lo mau ln. Do o, lng mau phan tch phai c chon ung cach mi am bao tnh ai dien cua lo hang. Neu khong, viec phan tch ch gay hao ton vo ch, oi khi vi ket luan sai lech dan en nhng nguy hai tram trong. Mau phan tch c chon t lo ong goi hay khong ong goi theo trnh t sau: 1. Chon mau rieng: mau rieng c chon ngau nhien mot so n v bao goi (neu lo ong goi) hay t mot so v tr khac nhau trong lo khong ong goi (a c tron kha ong nhat). 2. Chon mau ban au: la mau ai dien c chon t cac n v ong goi hay cac v tr khac nhau cua mau rieng (khong ong goi). Tong lng mau ban au c goi la mau chung. 3. Chon mau trung bnh th nghiem: mau chung c nghien nho, ray vi c hat phu hp vi PPPT va tron eu. Mau trung bnh th nghiem c chia lam ba phan bang nhau: ni giao hang gi 1 phan, ni nhan hang gi mot phan va phan con lai ni phan tch gi. Moi phan u tien hanh tat ca cac th nghiem can thiet vi moi th nghiem lam ba lan.

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IV.2. Giai oan chuyen mau thanh DD Dang mau thch hp cho a so PPPT la dang DD. Co hai cach chuyen mau hoan toan thanh dang DD phan tch. Phng phap t Mau c hoa tan trong dung moi thch hp. Dung moi co the la nc cat, DD acid hay baz vi nong o thch hp: Nc cat hoa tan cac muoi NaCl, KNO3, DD HCl: c s dung hoa tan mau CO32-, PO43-, SO32-, S2-, DD HNO3: hoa tan PbS, CuS, As2S3, Hg2SO4, cac loai hp kim DD H2SO4 2000C co the hoa tan c thep khong g. DD HF: hoa tan SiO32-, SiO2, H2SiO3. Phng phap kho Nhieu hp chat cua Al2O3, Fe2O3, TiO2, Cr2O3, ZrO2 kho tan trong cac dung moi tren. Ta co the chuyen chung sang dang DD bang cach nung kho chung vi hoa chat ran nh: NaOH, Na2CO3, K2S2O7, Na2O2, Na4B4O7 500 10000C trong lo nung. Mau va chat nung c cha trong chen bang Pt hay Ni. Cau t c chuyen thanh muoi de tan, sau o c hoa tan bang dung moi thch hp. Du chuyen mau thanh DD theo phng phap nao cung phai am bao cac yeu cau nh khong c lam mat mau trong qua trnh hoa tan; khong lam ban mau (a them cau t la) khi hoa tan. IV.3. Chon phng phap thch hp va thc hien phan ng Phng phap thch hp la phng phap co o nhay, o chon loc, toc o phan tch cao va cho ket qua gan vi ket qua thc. Sau khi chon c phng phap thch hp, thc hien phan ng gia DD mau phan tch va thuoc th theo nhng ieu kien xac nh. Quan sat cac dau hieu ac trng xuat hien khi phan ng xay ra (nh tnh) hoac o the tch hoac can khoi lng hp chat tao ra (nh lng). IV.4. Kiem chng ket qua va x ly ket qua phan tch oi vi PPT, ngi ta co the kiem chng lai ket qua bang nhng phan ng ac hieu khac. Neu la PTL, ngi ta tnh ket qua phan tch da vao cac d kien ghi nhan c va bieu dien ket qua phan tch theo cac yeu cau cua phng phap thong ke.
B

Neu mau chung khong u ln e tao mau trung bnh th tang o ln cua mau ban au hoac tang so mau rieng. Neu mau chung qua ln co the giam mau i bang cach loai bt nhieu lan, moi lan giam phan na theo nguyen tac xen ke (trai mau chung len khay tron hoac vuong thanh lp mong, chia lam 4, 8 hoac 16 phan. Lay cac phan trong cac o co cung so chan hoac cung so le, chuyen sang khay khac va tiep tuc thc hien viec loai bt mau chung bang phng phap tren).

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CHNG 2. KHAI NIEM VA NH LUAT C BAN DUNG TRONG HOA PHAN TCH
I. DUNG DCH NONG O DUNG DCH I.1. Dung dch: la he ong the do s phan tan cua phan t hay ion, bao gom hai hay nhieu chat ma thanh phan cua chung co the thay oi trong mot gii han rong. He gom chat phan tan (chat tan) dang ran, long, kh (R, L, K) va moi trng phan tan (dung moi) cung co the dang R, L, K. Tuy trang thai tap hp cua chat tan va dung moi, ta co cac loai DD R/R nh hp kim, DD R/L nh ng trong nc, DD L/L nh ru trong nc, DD R/K nh bui trong khong kh va DD L/K nh sng mu Trong hoa phan tch, hai loai DD thng gap pho bien nhat la R/L hoac L/L. I.2. Nong o cua DD Cach bieu dien nong o cua DD Nong o DD phu thuoc vao chat tan co trong mot lng dung moi xac nh. Ngi ta phan biet: - DD loang: lng chat tan chiem t le nho - DD am ac: lng chat tan chiem t le ln - DD bao hoa: DD cha chat tan toi a ( t0C, P xac nh) - DD qua bao hoa: c tao thanh khi un nong DD bao hoa trong s hien dien cua chat tan va lam nguoi t t DD thu c. Trang thai bao hoa la trang thai kem ben, ch can lac, khuay hay them mot t tinh the chat tan, lng chat tan d trong DD se lap tc tach ra tra ve trang thai bao hoa ben vng. Nong o cua DD thng c bieu dien thong qua cac ai lng: m(g): khoi lng chat tan (co phan t khoi M) q (g): khoi lng dung moi Vx (ml): the tch chat tan V (ml): the tch DD nhan c khi hoa tan m(g) chat tan hay Vx (ml) chat tan vao q (g) dung moi d (g/ml): khoi lng rieng cua DD tao bi m (g) chat tan va q (g) dung moi. Cac loai nong o c s dung trong hoa phan tch thng la cac nong o sau ay: o tan la lng chat tan trong DD bao hoa t0C va ap suat nhat nh, thng bieu dien bang so gam chat tan /100g dung moi: S=
m x100 q

Nong o khoi lng hay nong o g/l: bieu dien so gam chat tan co trong 1 lt DD

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Hoa phan tch

Cg/l =

m x1000 V

o chuan: Khi nong o khoi lng dung bieu dien so gam hay miligam chat tan trong 1 ml DD, ngi ta goi o la nong o chun, ky hieu bang ch T: Tg/ml = Hay
m V m Tmg/ml = x1000 V

Nong o phan tram: co ba cach bieu dien nong o phan tram: % (khoi lng/khoi lng): bieu dien so gam chat tan/100g DD: C% (KL/KL) =
m x100 m+q m x100 V Vx x100 V

% (khoi lng/the tch): bieu dien so gam chat tan/100ml DD: C% (KL/TT) = C% (TT/TT) = % (the tch/the tch): bieu dien so mililit chat tan/100 ml DD: Nong o phan trieu ppm (part per million): bieu dien khoi lng chat tan cha trong 106 lan khoi lng mau co cung n v: 1 ppm = 1g chat tan/106g hay 1000kg mau = 1mg chat tan/106mg hay 1kg mau C(ppm) =
m x106 m+q

Neu mau dang long va co nong o chat tan be (DD loang) va neu dung moi co d0 1 tc d 1, 1 ppm = 1mg chat tan/1kg hay 1 lt DD. Nong o phan trieu bay gi tr thanh mot loai nong o khoi lng (mg/l). Ngoai ppm, e bieu dien nong o cac DD loang hn, ngi ta con s dung ppb (nong o phan t); ppt (phan ngan t). Nong o mol: la mot nong o c s dung kha pho bien, ky hieu CM, bieu dien so mol chat tan /1 lt DD: CM = Cm =
m 1000 x M V m 1000 x M q

Nong o molan: bieu dien so mol chat tan/1000g dung moi:

Nong o phan mol: ty so gia so mol cua cau t i (ni) tren tong so mol N cua cac chat tao thanh DD c goi la nong o phan mol Ni: Ni =
ni N

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Hoa phan tch

Nong o ng lng: e bieu dien so ng lng chat tan trong 1 lt DD, ngi ta s dung nong o ng lng CN. ay la nong o c s dung nhieu nhat trong hoa phan tch e tnh toan vi : CN =(mx1000)/(xV) Vi la ng lng gam cua chat tan. ng lng: ng lng cua mot nguyen to hay mot hp chat la so phan khoi lng cua nguyen to hay hp chat ket hp hay thay the va u vi mot n v ng lng (co gia tr bang 1.008 phan khoi lng cua H2 hay 8 phan khoi lng cua O2), hoac mot ng lng cua mot nguyen to hay hp chat khac. ng lng cua mot nguyen to: Nguyen to X (nguyen t khoi MX) trong cac hp chat se co ng lng gam X = MX/n; vi n la so hoa tr cua X trong hp chat. V du: nguyen to N co ng lng N bang 14/1 trong N2O, bang 14/2 trong NO, bang 14/3 trong N2O3, bang 14/4 trong NO2 va bang 14/5 trong N2O5. ng lng cua mot hp chat: Hp chat AB (phan t kho MAB) co ng lng gam AB = MAB/n vi n la so n v ng lng tham gia phan ng, thay oi theo tng phan ng ma AB tham gia. 1. AB la chat oxy hoa hay chat kh: ng lng cua AB la lng AB co kha nang cho hay nhan 1 mol ien t. Do vay, n la so ien t trao oi ng vi 1 mol. V du: 2 KMnO4 + 10 FeSO4 + 8 H2SO4 2 MnSO4+ K2SO4 + 5 Fe2(SO4)3 + 8 H2O KMnO4 = MKMnO4/5 2. AB la acid hay baz: ng lng cua AB co kha nang cho 1 mol H+ hay 1 mol OH-. Nh vay, n la so ion H+ hay OH- co trong 1 mol chat (thc s tham gia phan ng). Vi cac phan ng trung hoa hoan toan: HCl = M/1; H2SO4 = M/2; H3PO4 = M/3 NaOH = M/1; Ca(OH)2 = M/2; NH3 = M/1 3. AB la hp chat ion hay muoi: ng lng cua AB la lng AB co kha nang trao oi vi mot mol ion mang ien tch 1+ hay 1-: BaCl2 = M/2; NaCl = M/1; FeSO4 = M/2; Fe2(SO4)3_= M/6 4. AB la phc chat: Neu AB la phc chat [MLX]n+ tao thanh bi ion kim loai Mn+ (thng la nguyen to kim loai chuyen tiep, tc co phu tang d cha lap ay ien t) vi cac ligand L (nguyen to hoac nhom nguyen to co cac electron t do) theo phan ng: Mn+ + x L [MLX]n+ ng lng cua phc hoac cac thanh phan cua phc c xac nh giong ng lng cua muoi hoac hp chat ion. V du: Cu2+ + 4 NH3 [Cu(NH3)4]2+ Cu2+ = M/2; [Cu(NH3)4]2+ = M/2

13

Hoa phan tch

Nong o cua DD sau khi pha tron Tron DD a% vi DD b% (cua cung mot chat) se c DD c% vi a>c>b neu a>b. Ty le pha tron c xac nh bang quy tac ng cheo: a (c-b) = ma c b (a-c) = mb tc ma/mb =
cb ac

Lien he gia cac nong o thong dung T CM =

m 1000 x ; M V

CN =(mx1000)/(xV) ;

C% =

m x100 , ta co: q+m

Cg/l = CM*M = CN* Cac nong o con lai da tren nh ngha, co the chuyen oi rat de dang t nong o nay sang nong o kia va ngc lai: CM =
C % x10d ; M

CN = (C%*10d)/

CN = n*CM M=
C M xMxV C %(q + m) = (CN**V)/1000 = 1000 100

II. NH LUAT TAC DUNG KHOI LNG Khi cho cac chat tac dung vi nhau, co nhng phan ng hoa hoc xay ra hoan toan, ngha la toan bo cac tac chat phan ng het vi nhau e tao thanh san pham. V du: 2 H2 + O2 2 H2O Trong thc te, a so cac phan ng thng gap lai la thuan nghch, ngha la cac phan ng dien ra khong en cung ma ch dien ra en trang thai can bang, trong o co s ton tai song song gia san pham va tac chat. V du: H2 + I2 2 HI Theo nh luat tac dung khoi lng, ty so gia tch hoat o san pham tren tch hoat o tac chat la mot hang so, c goi la hang so can bang K. nh luat tac dung khoi lng ap dung cho phan ng thuan nghch tong quat: aA + bB K= cC + dD

(C ) c x( D) d ( A) a x( B) b
[C ]c x[ D]d [ A]a x[ B]b

Neu DD loang: K=

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Hoa phan tch

Hang so can bang K cho biet phan ng a chon dien ra vi mc o nao: K cang ln, phan ng thuan (1) cang chiem u the va ngc lai K cang nho, phan ng nghch (2) cang chiem u the. Tuy nhien, can bang at c la can bang ong nen khi co s thay oi mot trong cac yeu to nh: nong o, ap suat, nhiet o th can bang se thay oi goi la s dch chuyen can bang. S dch chuyen nay c xac nh theo nguyen ly Le chatelier (khi cac yeu to ben ngoai nh nhiet o, ap suat, tac ong len he, can bang se dch chuyen theo chieu hng chong lai s thay oi). Phng trnh K=
[C ]c x[ D]d ch hoan toan nghiem ung oi vi DD ly [ A]a x[ B]b

tng. Vi cac DD thc, phng trnh nay co the ap dung kha ung vi cac chat khong ien ly hoac cac chat ien ly yeu trong cac DD nc loang va hoan toan khong the ap dung oi vi chat ien ly manh (kiem, acid manh, muoi) hoac cac chat ien ly yeu trong cac DD am ac co dung moi la nc. III. NH LUAT TAC DUNG NG LNG nh luat tac dung ng lng c Daton phat bieu nh sau: Trong mot phan ng hoa hoc, so ng lng gam cua cac chat tham gia phan ng phai bang nhau. Noi cach khac, trong mot phan ng hoa hoc, mot ng lng gam cua chat nay ch thay the hay ket hp vi mot ng lng gam chat khac ma thoi. Xet phan ng: A + B C + D Goi mA, mB: khoi lng cua A,B nguyen chat tac dung va u vi nhau (g) A, B: ng lng gam cua A, B VA, VB: the tch cua A, B tac dung va u vi nhau (ml) CA, CB : nong o ng lng gam cua DD A, B Ap dung nh luat tac dung ng lng oi vi tac chat A, B (so ng lng cua A bang so ng lng cua B), ta co:
B B

va VAxCAx10-3 = VBxCBx10-3 hay VAxCA = VBxCB

B B

m A mB = D A DB

hay

mA DA = m B DB

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Hoa phan tch

CHNG 3. PHNG PHAP PHAN TCH KHOI LNG

Phng phap phan tch khoi lng la mot trong nhng phng phap nh lng co o chnh xac rat cao (co kha nang at ti 0.01%) nen thng c s dung lam phng phap trong tai. Tuy nhien, cac nhc iem cua phng phap (thao tac phc tap, ton nhieu thi gian,) a lam cho phng phap nay han che khi a vao s dung trong thc te, neu chon c phng phap khac thch hp hn. I. NGUYEN TAC: Phan tch khoi lng la phng phap nh lng cau t X da tren phep o khoi lng. Viec thc hien co the tien hanh theo nhieu phng phap khac nhau: Phng phap trc tiep X c tach di dang n chat hay hp chat ben, t tan khoi mau va em can: AX A + X V du 1: nh o tro cua mot chat: nung chat can xac nh o tro nhiet o thch hp cho en khi lng tro con lai at khoi lng khong oi. Can lng tro se xac nh c o tro. V du 2: nh lng vang trong mau hp kim: hoa tan hp kim co cha vang bang nc cng thuy, thu c DD cha ion vang va cac ion khac. Them H2O2 vao DD, ion vang c kh thanh vang nguyen to trong khi cac ion con lai khong b anh hng. Vang c tach khoi DD, ra sach va can. Phng phap gian tiep X c tach di dang hp chat de bay hi ra khoi mau, can mau trc va sau khi tach: AX A + X Phng phap nay dung e xac nh o am hoac nc ket tinh cua mau, hoac ham lng chat kh trong mau nao o (v du ham lng CO2 trong mau a voi). Phng phap gian tiep con co the la phng phap xac nh cac kh nh CO2, O2, CO, bang cach hap thu chat can xac nh vao mot hoa chat thch hp ; can chat nay trc va sau khi hap thu se suy ra lng chat can xac nh. Phng phap ket tua Hoa tan mau e chuyen X thanh ion trong DD; dung thuoc th C ket tua va tach X di dang hp chat t tan CX roi can CX: AX A+ + XX- + C+ CX V du: muon xac nh ham lng Ba2+ trong mau BaCl2.2H2O, hoa tan mau va dung DD H2SO4 ket tua thanh tinh the BaSO4, ra sach tua, say (nung) va can BaSO4. Trong cac phng phap phan tch khoi lng, PPPT ket tua ong vai tro quan trong va c ng dung rong rai nhat. Du bang phng phap nao trong cac

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Hoa phan tch

phng phap, t lng mau ban au xac nh va t khoi lng can c co the tnh ham lng cua X trong mau mot cach de dang. II. CAC GIAI OAN CUA PPPT KHOI LNG KET TUA Phng phap dung nhieu nhat la chuyen X thanh hp chat t tan. Ngoai cac giai oan bat buoc oi vi 1 qua trnh PPL bao gom viec chon mau ai dien, can lng mau thch hp va chuyen mau thanh DD phan tch, can phai tien hanh cac giai oan sau: - Ket tua cau t can xac nh di dang hp chat thch hp - Loc va ra tua - Chuyen dang tua sang dang can - Can Can phai lu y khong che lng mau ban au e nhan c lng can thch hp: - Tua tinh the 0.200 0.500g - Tua vo nh hnh 0.100 0.300g II.1. Tao tua: Chon dang tua va thuoc th thch hp Chon thuoc th C thch hp e tao tua vi X: C + X CX

Yeu cau oi vi dang tua va dang can

Dang tua va dang can phai ap ng cac yeu cau sau ay: 1. Ben, t tan e tao tua c hoan toan. Phan ng ket tua c xem la hoan toan neu sau khi ket thuc phan ng o tan cua tua trong DD xap x o chnh xac cua can. 2. Dang tua phai co tinh the ln e t tan, de loc va ra. 3. Tua co o tinh khiet cao, t hap phu hay nhiem ban. Thuan li nhat la nen chon ket tua tinh the cang to cang tot. 4. Tua co dang hp chat xac nh, co the chuyen hoan toan sang dang can mot cach de dang. 5. Dang can phai co s tng ng gia thanh phan va cong thc hoa hoc; phai ben vi moi trng (khong hap thu CO2, khong b oxy hoa bi O2 cua khong kh, khong b phan huy nhiet o cao).

Yeu cau oi vi thuoc th

Thuoc th c chon phai hoi u cac ieu kien sau: 1. Co tnh chon loc cao (ch tao tua vi cau t can xac nh). 2. e phan ng hoan toan, thuoc th c dung tha t 10 50% hoac 200 -300% neu thuoc th de bay hi. Can lu y khi s dung cac thuoc th ma lng tha co the lam tan tua. V du: Al3+ + 3 OH- Al(OH)3 + OH- AlO2- (tan) + H2O + 2 KI K2[HgI4] (tan) Hoac HgI2

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Hoa phan tch

3. Lng thuoc th dung tha phai c loai bo de dang trong qua trnh loc, ra, nung tua. 4. Thuoc th co kha nang tao thanh dang can co ham lng cua nguyen to can xac nh chiem ty le cang nho cang tot, bi ieu nay se giup giam sai so do can. Chon ieu kien tao tua thch hp ieu kien tao tua thch hp la ieu kien thc hien phan ng gia thuoc th C va cau t X sao cho viec tao tua hoan toan; tua thu c tinh khiet va de loc ra. Muon c vay, ngoai viec phai quan tam en dang tua thu c, cac nguyen nhan co the gay ban tua, con can phai quan tam en cac yeu to co kha nang anh hng en o ben cua tua nh pH cua moi trng, nhiet o cua DD, cac can bang phu co the lam tan tua Anh hng do dang tua Khi cho thuoc th vao DD cha ion cau t cho en khi DD qua bao hoa (tch nong o cac ion ln hn tch so tan cua tua) th bat au xay ra s ket tua. Giai oan au tien la mam ket tinh, c hnh thanh ch ch gom bon phan t nen kch thc rat be. Mam ket tinh ong vai tro trung tam tao ieu kien cho cac cation va anion trong DD tiep tuc ket tua tren be mat, lam cho mam ket tinh phat trien thanh hat ket tua co mang li tinh the ba chieu, co hnh dang xac nh, c goi la ket tua tinh the. Mam c sinh ra nhieu hay t va ket tua tao thanh co hat to hay nho phu thuoc vao o qua bao hoa cua DD: o qua bao hoa =
QS S

Trong o: Q: nong o cua cac thuoc th sau khi tron vao nhau, trcluc tao mam (mol/l) S: o hoa tan cua ket tua sau khi at can bang (mol/l) Nh vay, khi o qua bao hoa cang nho, toc o tao mam cang cham va do o, cac hat ket tua de phat trien thanh hat to thanh. Cac ion c sap xep tren mang li tinh the tao nen cac hat ket tua co hnh dang xac nh, goi la ket tua tinh the. Nhng ket tua co o hoa tan ln thng de tao tua tinh the. Ngc lai, o qua bao hoa cua DD cang cao th toc o tao mam cang ln. Neu o qua bao hoa ln, cac mam sinh ra mot cach o at, cha kp phat trien bao nhieu a lien ket vi nhau bang lc lien ket yeu, tap hp ngay thanh ket tua. Cho them thuoc th va DD, qua trnh lai tiep tuc nh tren. Cac ion c sap xep hon on, khong nh hng nen c goi la ket tua vo nh hnh. Loai tua nay thng c tao thanh khi ket tua co o tan qua nho (lam cho o bat bao hoa cua DD qua ln), v du nh cac ket tua sunfua va hidroxyt cua cac kim loai nang. Tham ch, o qua bao hoa cua DD qua cao con co kha nang tao thanh DD keo, cha cac hat rat be (la cac phan t khuyech tan bao gom 103 104 nguyen t co kch thc 10A0 1000A0) va mang ien tch cung dau. Cac hat nay khong b lang khi ly tam va b lot qua giay loc thng mot cach de dang. Neu them vao DD keo chat ien ly manh e trung hoa ien tch cua hat

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Hoa phan tch

keo, cac hat keo co ieu kien va cham vi nhau manh hn, nhieu hn se co nhieu kha nang ket hp vi nhau thanh cac hat ln hn. Cac hat nay lang xuong va tao thanh tua vo nh hnh. V vay ma co the noi rang tua vo nh hnh c tao thanh do s ong tu cua DD keo. Tuy nhien trong thc te, khong co ranh gii ro rang gia ket tua tinh the vi ket tua vo nh hnh. Ngoai yeu to phu thuoc vao ban chat cua ket tua, s tao thanh ket tua dang nay hay dang kia phu thuoc rat nhieu vao ieu kien tien hanh tua. V du, BaSO4 c tao thanh t dung moi nc de tao thanh ket tua tinh the nhng trong hon hp dung moi nc etanol (30-60% etanol) th lai de dang tao tua vo nh hnh. Trong PPPT khoi lng, neu tua thu c la tua tinh the cang to cang de loc, ra va giam nhiem ban, tao ieu kien cho qua trnh xac nh cang thuan li. e at c ieu nay, ngoai cac bien phap c s dung e lam tang S va giam Q nham muc ch lam giam o bat bao hoa cua DD trong ieu kien co the, mot so bien phap khac cung c s dung e co the nhan c tua tinh the co kch thc ln bao gom: 1. Tien hanh ket tua t DD loang, nong, rot them t t thuoc th vao DD, khuay eu e lam giam o bao hoa cuc bo cua DD. DD nong con giup giam hien tng hap phu cac ion la gay ban tua va giup cho tua khong b tao thanh trang thai keo. 2. Tien hanh ket tua pH thap ( ieu kien nay, ket tua se tan nhieu). Sau khi tao tua xong, a DD ve pH thch hp co o tan cua tua thap nhat. 3. Sau khi tao tua, e yen mot thi gian nham tao ieu kien cho tua ln len goi la lam muoi tua (20-30 phut hoac co the keo dai t 1-6 gi). Viec lam muoi tua thng c tien hanh nhiet o kha cao nhng tranh e DD soi bung. Trong thi gian nay, cac tinh the nho se tan ra, bam tr lai vao cac tinh the ln va lam tua ln len. Tuy nhien, can xem xet tng trng hp cu the e tranh cac sai so co the mac phai. V du, qua trnh hau tua co the xay ra khi keo dai thi gian lam muoi tua. 4. e tranh hien tng qua bao hoa, con co the dung phng phap ket tua ong the (hay con goi la ket tua trong moi trng ong tng) bang cach tao thuoc th t t trong DD phan tch qua mot hoa chat trung gian thay v cho thang thuoc th vao DD. V du, e ket tua cac hydroxyt kim loai, ngi ta s dung phan ng thuy phan ure (NH2)2CO khi un soi DD: (NH2)2CO + H2O 2 NH3 + CO2 NH3 sinh ra lam tang pH cua DD len t t tao tua hydroxyt kim loai khong tan . Qua trnh ket tua ong the tao cho DD co o qua bao hoa rat thap, giup thu c ket tua tinh the co kien truc tinh the hoan chnh, tham ch oi vi mot so ket tua von la ket tua vo nh hnh nh ket tua hydroxyt chang han.

19

Hoa phan tch

Neu trong ieu kien tao tua chac chan thu c tua vo nh hnh, e giam tap chat do tua vo nh hnh co dien tch be mat rat ln nen de hap phu chat ban, can tao tua trong ieu kien sau ay: 1. DD mau va thuoc th can nong va kha am ac e giam hap phu, tua t xop, de lang. 2. Thuoc th c them nhanh va khuay au e chat ban khong bam len tua. 3. Ngay sau khi tao tua, them ngay DD ien ly manh e pha lp ien tch kep tren be mat hat keo, lam tua de ong tu. 4. Them vao DD mot lng nc nong trc khi loc e tach tua ra khoi DD va lam giam nong o cau t la trong DD. 5. Tua c loc ngay e tranh phan ng phu. Neu tua de tan nhiet o cao th lam nguoi tua trc khi loc. S nhiem ban ket tua Trong thc te, ket tua luon luon co kha nang b nhiem ban do keo theo mot so chat co mat trong DD. Hien tng nay goi la s cong ket (ket tua theo). Cac loai cong ket gay tac dung nhiem ban co the ke nh sau: 1. Hap phu be mat: Hap phu la hien tng cac cau t la dang ion (do thuoc th dung tha hoac do s co mat cua mot so chat ien ly khac) bam vao cau t chnh, xay ra manh khi cau t chnh dang keo hay dang tinh the mn. Neu hap phu cac anion, ket tua se mang ien tch am va co kha nang hap phu tiep cac cation khac lam cho ket tua b nhiem ban bi cac tua khac. Qua trnh hap phu be mat co tnh chon loc (u tien hap phu cac ion co trong thanh phan ket tua hoac nhng ion co cung ban knh ion vi ket tua). V du, trong DD co cac ion I-, Cl-, K+, NO3-, ket tua AgI se hap phu I- trc, sau o ti Cl- va hau nh khong hap phu NO3-. Co the lam giam hien tng hap phu be mat bang cac bien phap: a) Tao tua tinh the to hay giam dien tch be mat cua tua b) Tao tua nhiet o cao (v hap phu la qua trnh toa nhiet). c) Pha loang DD mau va thuoc th e lam giam nong o tap chat. d) Ra ket tua sau khi loc bang DD thch hp. Trong DD ra co mat mot so chat ien ly co the hap phu canh tranh vi cac ion gay nhiem ban, va cac ion canh tranh nay se c tach ra khoi ket tua mot cach de dang trong qua trnh x ly tiep theo. Cac chat ien ly con co tac dung chong hien tng peptit hoa (tua vo nh hnh tr lai trang thai keo). 2. Noi cong ket: la hien gay nhiem ban ben trong hat ket tua, do mot so tua phu tua theo cung vi tua chnh. Hien tng noi cong ket bao gom ba loai chnh.

20

Hoa phan tch

a) Cong ket ong hnh: Cac v tr cua ion la thanh phan cua ket tua trong mang li tinh the b thay the bi ion khac, thng xay ra vi cac ion co ien tch va ban knh giong nhau hoac gan giong nhau. V du, khi tao tua BaSO4 co mat Pb2+, mot so ion Ba2+ trong mang li tinh the cua BaSO4 b thay the bi mot so ion Pb2+ theo can bang: Ba2+ (dd) + Pb2+ (dd) Ba2+(tt) + Pb2+ Ch co the khac phuc hien tng cong ket ong hnh bang viec tien hanh ket tua lai. b) Cong ket do s tao tua phu t mam tinh the cua tua chnh: Mot so hp chat khong tua trong ieu kien rieng le nhng lai tua khi cung hien dien vi mot chat khac. V du: Fe2(SO4)3 tan nhng khi them thuoc th SO42- vao DD Ba2+ co lan Fe3+, ta co hai phan ng tao tua: Ba2+ + SO42- BaSO4 2 Fe3+ + 3SO42- Fe2(SO4)3 Giam hien tng nay bang bien phap chuyen ion anh hng sang dang khac, v du: Fe3+ Fe2+ (cong ket) (khong cong ket) Cung co the che Fe3+ di dang phc ben, v du nh [FeF6]3+ c) Cong ket do tao thanh hp chat hoa hoc: Trong DD co Fe2(SO4)3, khi thc hien phan ng tao tua Ba2+ bang SO42-, ngoai phan ng tao tua: Ba2+ + SO42- BaSO4 Fe3+ co the tao phc vi SO42- thanh [Fe(SO4)2]-. Ion phc nay tac dung vi Ba2+ tao thanh hp chat ben: Ba2+ + 2 [Fe(SO4)2]- Ba[Fe(SO4)2]2 3. Cong ket do s hap lu: la hien tng ban b gi lai trong tua trong qua trnh ln len cua tinh the ket tua. Tap chat b cong ket vao ket tua phan bo khong ong eu ma tap trung chu yeu nhng cho khuyet tat cua tinh the ket tua. V du khi cho DD BaCl2 vao DD H2SO4, ket tua BaSO4 tao thanh hap phu ion SO42- len be mat cua no tao thanh lp hap phu. Do lp hap phu mang ien tch am, cac ion dng (ion oi) lai b hap phu tiep theo. Khi cho tiep thuoc th Ba2+ vao, cac ion Ba2+ se ay cac ion oi ra va tiep tuc tao thanh ket tua mi. Tuy nhien, neu cho nhanh BaCl2 vao th ket tua mi c tao thanh nhng cac ion oi lai cha b ay ra het, ket qua la con mot so ion oi nam xen ke gia cac o mang tinh the cua ket tua. Bien phap giam hien tng hap lu la tao tua t DD loang, rot them t t thuoc th, khuay eu hoac ket tua t moi trng ong the.

21

Hoa phan tch

4. Cong ket hau tua: la hien tng cau t phu tua theo cau t chnh neu tua chnh e lau trong DD. V du ZnS tua theo CuS , HgS neu trong DD co Zn2+. Giam hien tng nay bang cach loc, ra tua ngay. Cac anh hng khac Khi ket tua trong DD co mat nhieu ion khac, o tan cua ket tua b tang len do cac nguyen nhan: 1. Cac ion H+, OH- hoac ion khac) tham gia can bang phu vi cac ion thanh phan cua ket tua. 2. Ngay ca khi khong tham gia can bang phu vi cac ion thanh phan cua ket tua, o tan cua tua van co the tang len khi ket tua trong DD co mat nhieu ion khac, do s hien dien cua nhieu ion lam tang lc ion trong DD, lam cho he so hoat o cua cac ion giam xuong va v vay lam tang o hoa tan cua ket tua: AB An+ + BnS S n+ nTAB = [A ][B ].fAfB = S2 S = TAB /( f A xf B ) 3. Theo bieu thc tch so tan, khi tang nong o cua thuoc th trong DD se lam cho nong o cua ion trong ket tua giam xuong, tc la lam cho o tan cua tua giam xuong. Tuy nhien, tang lng thuoc th cung ong thi tang nong o cac ion trong DD va t o lai lam tang o hoa tan cua ket tua. Trong nhieu trng hp, lng thuoc th dung tha lai con co kha nang tao thanh phc vi ion ket tua va cang lam cho o tan cua tua b tang len. Do o, lng thuoc th s dung phai c khong che sao cho viec tao tua c thc hien hoan toan nhat. 4. Cac ket tua vo c (thng la hp chat ion) de tan trong dung moi phan cc, con cac chat khong phan cc se de tan trong dung moi khong phan cc. e lam giam o hoa tan cua cac ket tua trong nc (CaSO4, PbSO4), ngi ta thng them ru etylic vao nc. 5. o hoa tan cua ket tua ty le nghch vi ban knh cua hat ket tua, ac biet oi vi cac hat ket tua co sc cang be mat ln. 6. o tan cua ket tua phu thuoc kha ln vao nhiet o. a so qua trnh hoa tan chat ran vao nc la qua trnh thu nhiet, do o, khi tang nhiet o se lam cho ket tua tan nhieu hn. II.2. Loc va ra tua Loc la bien phap nham tach tua ra khoi DD. Chon dung cu loc phu hp lng tua va cach chuyen t dang tua sang dang can: 1. Neu tua c nung nhiet o cao: dung phieu thuy tinh va giay loc hau nh khong tro (lng tro sau khi nung t 3x10-5 5x10-5g). Giay loc co kch thc lo xop thay oi, thng gom 3 loai: lo xop mn, lo xop trung bnh va lo xop kha ln, vo hop co mau khac nhau c qui c tuy theo nha san xuat va c la chon sao cho tua khong chui c qua giay loc

22

Hoa phan tch

ma thi gian loc khong qua cham. V du: c, giay loc bang xanh c s dung cho cac ket tua hat mn, giay loc bang vang dung cho ket tua hat trung bnh va giay loc bang o dung cho ket tua hat ln hoac ket tua vo nh hnh. 2. oi vi ket tua de b kh trong qua trnh ot chay giay loc hoac nung (do carbon cua giay) hoac neu tua c say di 2500C dung phieu thuy tinh ca hoac hay chung loc gut. Mang loc la lp thuy tinh ca nho hay lp bot amiang. o mn cua mang loc cung c la chon phu thuoc vao kch thc tua. Ra tua: la dung DD ra e lam sach tua. DD ra thng co cac ac iem: 1. Nong (e tang qua trnh giai hap) 2. Cha ion chung so vi tua chnh (e lam giam o tan tua) 3. Co the cha lng nho acid hay baz e lam giam s thuy phan 4. Can them chat ien ly thch hp e giam hien tng peptit hoa (tua vo nh hnh sau khi ong tu tr lai dang keo). Thng dung NH4NO3 hay cac acid de bay hi khi chuyen sang dang can. Thc ra, qua trnh loc va ra tua thng c tien hanh song song. Viec ra tua c thc hien nhieu lan bang cach loc gan tua vi cac lng nho DD ra sao cho lng DD ra dung va u e lam sach tua nhng khong lam tan tua va ton thi gian. Sau khi c tao tua va lam muoi trong coc, ket tua se lang xuong ay coc. au tien, gan phan DD trong cho chay theo ua thuy tinh vao phieu loc. Khi phan ln chat long a c loc qua phieu, lai ra tiep ket tua bang phng phap gan (rot mot t nc ra vao coc, khuay hon hp bang ua thuy tinh, e ket tua lang xuong ay coc, gan phan nc trong vao phieu). Khi tua tng oi sach, tron tua vi nc ra va chuyen huyen phu vao phieu loc. Dung bnh tia nc cat xt that manh e keo phan tua a bam tren thanh vao coc. Neu cn, lau mat trong cua coc bang cac mau giay loc khong tro. Tiep tuc ra tua tren giay loc bang bnh tia. Nhap cac mau giay lau vao giay loc cha tua. Xep va chuyen toan bo giay loc vao vat cha tua (chen s, niken, thach anh hoac platin) em chuyen sang dang can. II.3. Chuyen sang dang can Dang can la dang trc tiep c can, viec chuyen dang tua sang dang can c thc hien bang cach say hay nung, vi muc ch loai het nc hap phu hoac nc ket tinh, hoac e chuyen hoan toan hon hp thanh hp chat xac nh: 1. Say nhiet o di 2500C (neu ch can loai nc hap phu hay ket tinh). AgCl: say 100 1300C 2. Nung nhiet o 600 12000C tuy theo dang tua: BaSO4 BaSO4 : 700 8000C (u chay giay loc) Fe(OH)3 Fe2O3 : 9000C

23

Hoa phan tch

Al(OH)3 Al2O3 : 1000 11000C CaC2O4 CaCO3 : (6000C) CaO (1000 12000C) Thi gian say hay nung c la chon sao cho khi can, tua co khoi lng khong thay oi. Sau khi say hay nung, e nguoi vat cha tua trong bnh hut am roi mi can. II.4. Can Can dung e xac nh khoi lng dang can thu c la can phan tch (chnh xac 0.0001g hay hn na). Luon luon phai s dung phep can lap e xac nh khoi lng cua tua: b (vat cha tua) c say hay nung trc cung nhiet o se say va nung tua. e nguoi trong bnh hut am va can, c khoi lng m0 (g). B cung tua c say (nung) e nguoi va can, co khoi lng m1 (g); m 1 = m0 + m Suy ra m = m1 m0 II.5. Tnh ket qua Mau dang ran 1. Can a(g) mau, bang PPPT khoi lng thu c m(g) cau t di dang n chat hoac hp chat: a) Neu dang can cung la dang can tnh ham lng: X% =
m x100 ag

V du 1: T 0.3200g at, bang PPPT khoi lng th c 0.1200 g SiO2: % SiO2 =

0.1200 x100 = 37.50% 0.3200

b) Neu dang can khac dang can tinh ham lng, s dung he so chuyen F e chuyen t khoi lng dang can sang khoi lng dang can tnh.: F=
M dangtinh M dangcan x he so thch hp

V du 2: nh ham lng Si trong mau at v du 1 vi dang can SiO2 la 0.1200g. Ta co: mSi =
M Si xmSiO 2 M SiO 2 28.08 x0.1200 = 0.0561 g = 60.08 0.1200 28.08 x x100 = 17.53% Hay % Si = 0.3200 60.08

2. Can a (g) mau, hoa tan thanh V(ml) DD. T VX (ml) DD mau bang PPPT khoi lng thu c m(g) cau t di dang n chat hoac hp chat: %X=
m V x100 x xF ag Vx

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Hoa phan tch

Mau dang DD 1. T Vx (ml) mau, bang PPPT khoi lng, thu c m(g) dang can: Cx(g/l) = m x F x
1000 Vx

2. Lay V(ml) DD mau empha loang thanh V1(ml) DD (loang), lay Vx (ml) DD loang em phan tch khoi lng, thu c m(g) dang can: Cx (g/l) = m x F x
V1 1000 x V Vx

III. NG DUNG III.1. nh o am nc ket tinh chat de bay hi o tro va mat khi nung Xac nh o am hoac nc ket tinh Nguyen tac xac nh o am hoac nc ket tinh la say mau nhiet o thch hp (100 1100C e xac nh o am; 120 2000C neu muon xac nh nc ket tinh) e uoi nc ra khoi mau cho en khi phan con lai cua mau co khoi lng khong oi. Cach thc hien nh sau: 1. Say chen nhiet o thch hp en khoi lng khong oi, can c trong lng m0(g) 2. Cho mau vao chen vi lng mau t 1 - 10g, can c khoi lng m1(g) m1 = m0 + mmau 3. Say chen va mau en khoi lng khong oi, can c khoi lng m2(g) m2 = m0 + m (m: khoi lng mau kho, g) % am =
(mmau m' ) m m2 x100 = 1 x100 mmau m1 m0

Xac nh chat bay hi Thc hien tng t nh cach xac nh o am nhng nhiet o cao. V du e xac nh ham lng CO2 trong mau a voi, nung mau 500 6000C e uoi CO2 en khoi lng khong oi: Khoi lng b: m0(g) Khoi lng b + mau: m1(g) = m0 + mmau Sau khi uoi CO2, can lai : m2 (g) = m0 + m % CO2 =
(mmau m' ) m m2 x100 = 1 x100 mmau m1 m0

nh o tro hay chat mat khi nung Thc hien tng t nh cach xac nh chat bay hi nhng nhiet o 600 8000C va o tro va chat mat khi nung c tnh tren mau a say kho: % o tro =(m2-m0)x100/(m1-m0) % chat mat khi nung =(m1-m2)x100/m1-m0 (m1 = m0 + mmau vi m mau a say kho) III.2. nh lng bang cach tao tua Ngi ta co the s dung thuoc th vo c, hu c hoac dung phng phap tao anion trong moi trng ong tng e ket tua cac cau t can xac nh.

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Hoa phan tch

Thuoc th vo c: Mot so thuoc th vo c thong dung dung e xac nh cac ion Ag+, halogenur, kim loai kiem tho,nh sau: Ion xac nh Ag+ Thuoc th Cl , Br-, I-

Cl-, Br-, IAg+ Fe3+ NH4OH Ket tua vo nh hnh, de nhiem ban 2+ 2+ 2Sr , Ba SO4 De b hien tng noi cong ket 2+ 2Ca C2O4 Thuoc th hu c Thuoc th hu c co the c dung trong PPPT khoi lng e nh lng cac ion kim loai bang cach tao tua thong thng, v du ket tua oxalat hoac ket tua natri tetraphenylboron nhng pho bien nhat la tao cac hp chat noi phc vi cac ion kim loai. Nhn chung, thuoc th hu c co kha nang tao vi ion can xac nh cac hp chat co khoi lng phan t ln, lam tang o nhay cua phep xac nh. Mot so thuoc th hu c thong dung nh sau: Thuoc th Ni Dimetyl glyoxim 3+ 3+ 2+ 2+ Al , Bi , Cu , Mg 8-hydroxyquinonlin 2+ 2+ 2+ 2+ 2+ 2+ 2+ Hg , Mn , Cu , Co , Cd , Ni , Pb , Anthranilic acid Zn2+ Ag+, Au3+, Bi3+, Cd2+, Cu2+, Pb2+, Ti3+ Mercaptobenzothiazole
2+

Ghi chu Thuoc th d co the tao phc (nh AgCl2-,) lam tan tua

Ion xac nh

Tao anion trong moi trng ong tng Phng phap phan tch khoi lng s dung moi trng ong tng c s dung ngay cang rong rai. Mot so hoa chat thong dung s dung cho phng phap nay nh sau: Ion xac nh Ion can Hoa chat s dung Phan ng tao anion dung 3+ 3+ Al , Fe , OHUrea (NH2)2CO + 3 H2O 4+ 3+ CO2 + 2 NH4+ + 2 OH Zr , Ga Zr4+, Hf2+ PO43Trietylphosphate (C2H5O)3PO + H2O 3 C2H5OH + H3PO4 2+ 2+ 2Mg , Zn , C2O4 Etyloxalat (C2H5O)2C2O2 + 2 H2O 2+ 2 C2H5OH + H2C2O4 Ca 2+ 2+ 2Sr , Ba , SO4 Dimetylsulfat (CH3O)2SO2 + H2O 2+ 2 CH3OH + SO42- + 2H+ Ca

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Hoa phan tch

CHNG 4. AI CNG VE PHNG PHAP PHAN TCH

I. CAC KHAI NIEM LIEN QUAN EN PHNG PHAP PHAN TCH Phan tch the tch la phng phap nh lng cau t X da tren phep o the tch. Khi thc hien phan ng gia cau t X va DD chuan C, C thng c cha trong buret va c nho t t vao DD cha chat can xac nh X (X thng c lay chnh xac bang pipet va cha trong erlen). Qua trnh tren c goi la s nh phan hay phep chuan o. S chuan o se cham dt khi co tn hieu cho biet phan ng a ket thuc. T the tch thuoc th C ghi nhan c se giup xac nh nong o cua cau t X trong DD em chuan o. - Phan ng C + X A + B goi la phan ng chuan o - Thi iem C tac dung va het vi X goi la iem tng ng - e xac nh thi iem ket thuc chuan o, thng s dung mot hoa chat co the tao nen s thay oi ghi nhan c tng ng vi thi iem o: DD oi mau, xuat hien tua Thi iem ngng chuan o theo cac dau hieu ke tren c goi la iem cuoi. Hoa chat giup xac nh iem cuoi goi la chat ch th. Trong thc te, iem cuoi co the ung hoac khong ung vi iem tng ng. S chech lech gia iem cuoi va iem tng ng nhieu hay t tao sai so chuan o ln hay nho phu thuoc vao ch th a chon. Trong PPPT the tch co the xac nh iem tng ng thong qua phep o mot so ai lng hoa ly nh ien the, o dan ien, mat o dong Cac phng phap nay c xep vao nhom PPPT dung cu. Tuy ieu kien chuan o ma DD X co the c cha trong buret va thuoc th C c cha trong erlen. II. IEU KIEN CHUAN O Trong qua trnh chuan o phai tuan thu nghiem ngat nhng ieu kien e am bao cho viec phan tch c nhanh chong va at c o chnh xac cua phep nh lng (ngha la e thu c ket qua phan tch nh y muon). Di ay la mot vai ieu kien c ban nhat cua viec chuan o: 1. Ni chuan o phai c chuan b can than va co u anh sang ban ngay hay anh sang ien. 2. Cac dung cu em dung va cac may moc o phai ra sach va hieu chnh chnh xac trc khi chuan o. 3. Cac thuoc th em dung, cac chat phu a vao trong phan tch chuan o, hon hp, nc cat hay nc trao oi ion phai khong co chat la, lam sai lech ket qua phan tch. 4. Trng hp oxy hay cacbon dioxyt co anh hng en qua trnh chuan o th tien hanh chuan o trong moi trng kh tr (thng la trong kh nit) e tranh nhng phan ng phu ma ta khong mong muon. 5. Phai lac can than va lien tuc cac chat phan ng trong qua trnh chuan o (lac bang tay hoac bang may khuay c hay t).

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Hoa phan tch

6. S chuan o phai hoan thanh trong khoang 5 10 phut va dien ra trong ieu kien a c kiem tra nghiem ngat ve nhiet o, pH cua DD, s co hay khong co cua chat ch th, v.v... can thiet theo phng phap xac nh. 7. e xac nh iem cuoi cua qua trnh chuan o, chat ch th hay phng phap cong cu nao o c chon phai am bao xac nh ro rang va chnh xac iem cuoi va co kha nang trung vi iem tng ng. 8. Khi chuan o can am bao moi trng phan ng acid hay kiem bang cach them vao hon hp chuan o cac chat ien ly, cac dung moi hu c hay cac tac nhan chiet, hon hp em, cac chat tao phc, cac chat xuc tac, cac chat cam ng, cac chat ch th, v.v... can thiet theo phng phap xac nh. 9. o chuan cua cac DD chuan em dung trc khi chuan o phai c xac nh va kiem tra can than theo cac chat tinh khiet hoa hoc xac nh. 10. Tat ca nhng phep chuan o song song can lam trong cung mot ngay. Viec di cac phep xac nh song song sang ngay khac ch c phep trong trng hp hoan toan toan tin tng vao o hang nh cua DD chuan dung e chuan o. Neu o chuan cua DD chuan khong hang nh th ngay hom sau lai phai kiem tra o chuan cua DD chuan. Y ngha cua phng phap phan tch chuan o Chuan o la mot phng phap phan tch nh lng rat quan trong, no c s dung rat rong rai trong thc te cac phong th nghiem cac nha may, trng hoc va cav vien nghien cu khoa hoc e xac nh thanh phan cua cac hp chat vo c, hu c va c nguyen to. Ngoai ra cac d kien nh lng thu c bang nhng phng phap chuan o con c dung e xac nh cau tao chat nghien cu, nghien cu ong hoc cua cac qua trnh hoa hoc, xac nh hang so phan ly cua acid va baz, lc tng oi cua cac chat ien ly, o dai va v tr cua thang hang so t prton hoa cua cac dung moi khac nhau, e nghien cu s bien dang va s cng hoa cua cac phng phap tong hp ieu che cac nguyen to va cac hp chat ac biet tinh khiet, am bao o toi u cua cac qua trnh cong nghe hoa hoc, v.v... Phan loai cac phng phap phan tch chuan o Tuy thuoc vao loai phan ng chnh c dung, ngi ta chia cac phng phap chuan o phan tch thanh cac nhom sau: - Phng phap trung hoa hay phng phap chuan o acid baz da ren phan ng trung hoa cac acid, baz, muoi cua cac acid yeu hay baz yeu b thuy phan manh trong dung dch nc, cac hp chat vo c hay hu c trong DD khong nc co tnh acid hay kiem, v.v... - Phng phap oxy hoa - kh da tren phan ng oxy hoa kh cua cac nguyen to co kha nang chuyen t mc oxy hoa thap len cao va ngc lai, cung

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Hoa phan tch

nh cac ion va phan t phan ng c vi cac chat oxy hoa hoac kh ma khong b oxy hoa hay kh trc tiep . - Phng phap ket tua da vao viec dung cac phan ng ket tua. - Phan ng tao phc da vao viec s dung phan ng tao phc, trong so cac phan ng o, phan ng gia cac ion kim loai vi complexon c s dung rong rai nhat. III. CACH TNH KET QUA TRONG PHNG PHAP PHAN TCH THE TCH III.1. Nguyen tac chung: da vao nh luat ng lng. Vi phan ng chuan o: C + X A + B Tai iem tng ng so ng lng cua C bang so ng lng cua X, tc: CCVC = CXVX Vi: CC, CX: nong o ng lng cua thuoc th C va cau t X VC, VX: the tch cua hai DD C, X (ml) III.2. Cac bieu thc tnh Mau long: Khi mau dang DD, cac trng hp pho bien nhat co the gap nh sau: 1. Lay VX (ml) mau, chuan o bang VC (ml) DD chuan co nong o ng lng CC: CN (X) = CC x VC/VX; CM (X) = CN (X)/n C(g/l) = CN x X = CN x MX/n 2. Lay V(ml) mau am ac pha loang thanh V1 (ml) DD loang; Dung VX (ml) DD loang chuan o bang VC (ml) DD nong o CC CN (dd) = CCx
VC V1 x C(g/l) = CN (dd) x X VX V

Cung co the tnh trc tiep theo so ng lng DD chuan o: C(g/l) = CC x 10-3 x VC x 1000 x V1 x X/(VX x V) Mau ran: Khi mau dang ran, chung ta co the gap cac trng hp sau: 1. Can a(g) mau, hoa tan va chuan o bang VC(ml) DD chuan CC: % X = CC x 10-3 x VC x 100 x X /a 2. Can a(g) mau, hoa tan va nh mc thanh V1(ml) DD loang; lay VX (ml) DD loang em chuan o bang VC(ml) DD chuan nong o CC: % X = CC x 10-3xVC x
V1 100 x x X VX a

Cac bieu thc tnh ket qua tren ch ap dung cho phng phap chuan o trc tiep va chuan o the. Vi cach chuan o ngc, bieu thc tnh nh sau: CCxVC = CX x VX + VC1xVC2 CX =
CC xVC CC1 xVC1 VX

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Hoa phan tch

Ngoai ra, con co the ap dung nh luat ng lng e tnh toan khi pha loang DD, da tren nguyen tac so ng lng trong hai DD am ac va loang bang nhau: Cx V = C1xV1 V = V1xC1/C (Co the ap dung cho ca hai DD tnh theo nong o mol) Trong mot so trng hp ac biet, viec tnh ket qua khong c tien hanh bang cach s dung cac bieu thc noi tren ma lai c tien hanh thong qua o chuan: 1. o chuan cua mot chat TX: So gam hay miligam chat X trong 1ml DD: TX (g/ml) = m/V hay T (mg/ml) = mx1000/V 2. o chuan theo chat xac nh TC/X: so gam hay miligam chat X tac dung va u vi 1 mililt DD chuan nong o CC: TC/X = CC x X/1000 CC = (1000 x TC/X)/ X V du: TC/X = THCl/NaOH = 0.00401g ngha la 0.00401 g NaOH se c tac dung va u vi 1 ml DD HCl 0.1N.

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Hoa phan tch

CHNG 5. PHNG PHAP CHUAN O ACID BAZ

I. ACID - BAZ I.1. nh ngha theo Arrhenius Acid la nhng chat khi hoa tan trong nc, phan ly cho ra H+ con baz la nhng chat phan ly cho ra ion OH.

V du:
HCl H+ + Cl NaOH Na+ + OH nh ngha Arrhenius n gian nhng co mot so mat han che nh sau: - Khong ap dung cho mot so chat khi hoa tan trong nc cho ra H+ hoac OHmac du cong thc chat nay khong co cha H+ hoac OH-.

V du: Dung dch cac muoi Al2(SO4)3 co tnh acid ro ret, con dung dch muoi
Na2CO3 co tnh baz ro ret. - Khong cho thay anh hng cua dung moi tren s ion hoa cac acid, baz. Khi dung mot dung moi khac e hoa tan cac acid, baz, cng o cac acid, baz co the thay oi han.

V du: HCl trong nc la mot acid manh nhng khi hoa tan trong aceton th

HCl la mot acid yeu. nh ngha Arrhenius khong giai thch c vai tro cua dung moi trong s tao thanh H+ t cac acid. Acid la cac chat khi tac dung vi dung moi tao ra H+ solvat hoa (H3O+). Baz la cac chat co the nhan H+.

I.2. nh ngha theo BRONSTED

nh ngha Bronsted giai thch c tai sao muoi Al2(SO4)3 co tnh acid va muoi Na2CO3 co tnh baz. Al3+ + 2H2O AlOH2+ + H3O+ CO32 + H+ HCO3 Con co the viet la (CO32 lay H+ t nc ong thi cho ra OH ) CO32- + H2O HCO3 + OH Mot acid Bronsted sau khi cho proton tr thanh mot baz goi la baz lien hp cua acid, va ngc lai mot baz Bronsted sau khi nhan proton cho ra acid lien hp.

V du:
HCl co baz lien hp la Cl CO32- co acid lien hp la HCO3 Mot cap acid baz lien hp co the bieu dien bang he thc: Acid baz + H+

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Hoa phan tch

u iem cua nh ngha Bronsted Cho thay ro anh hng cua dung moi tren s tao thanh H+ hoac OH nh o giai thch c anh hng cua dung moi tren cng o cac acid va baz. Theo Bronsted Lowry, o manh cua mot acid the hien kha nang cho proton, con o manh cua mot baz the hien kha nang nhan proton. Phan ng HCl + H2O H3O- + Cl- xay ra hoan toan: HCl la acid manh hn H3O+ va H2O la baz manh hn Cl-. Noi chung acid cang manh bao nhieu, baz lien hp vi no cang yeu bay nhieu. Ngi ta thng chon H2O lam dung moi e nh lc acid hay baz. Acid: A + H2O B + H3O+.
K = aB aH
3O +

a A a H 2O

Vi dung dch loang

[B] [H 3 O + ] K= [A] [H 2 O] [B][H 3 O + ] K [H 2 O] = [A]

Ta co:
ay la mot hang so can bang cua phan ng phan ly ion H+ con goi la
[ B ][ H 3 O + ] Ka = [ A]

hang so acid, ky hieu la Ka. Hang so acid Ka cang ln (tc la ch so acid pKa cang nho) th lc acid cang manh. Vi cac acid a chc yeu, s ien ly xay ra qua nhieu giai oan.

V du:
H3PO4 + H2O = H2PO4- + H3O+ K1 = 7,51 x 10-2 H2PO4 + H2O = HPO4 HPO42+ H2O = PO4
32-

pK1 = 1,12 pK2 = 7,21 pK3 = 12,66

+ H3O

+ +

K2 = 6,23 x 10

-8 -13

+ H3O

K3 = 2,20 x 10

Baz: B + H2O

A + OH[A][OH ] [B]

K b = K [H 2 O] = pK b = lgK b

V du: Amoniac co:

K NH = 1,79x10 5 , pK NH = 4,75
3 3

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Hoa phan tch

Anilin co: Hang so baz Kb cang ln ( tc ch so baz pKb cang nho) th lc baz
K C H NH = 4x10 10 ,
6 5 2

pK C H NH = 9,40
6 5 2

cang manh AB A + B Vi A va B co the la ion hay phan t. Theo nh ngha, hang so phan ly cua AB la: K =

[A][B] [AB]
pK = lgK

Hang so phan ly cang ln, hp chat AB cang b phan ly manh, cang t ben, do o K con c goi la hang so khong ben. Neu K kha nho, ngi ta thng dung ai lng pK vi: pK cang ln, K cang nho, AB cang t b phan ly. Vi mot acid yeu HA, ta co: HA H+ + AKa = [H + ][A ] va pK a = lgK a [HA]

Acid cang b phan ly (acid cang manh) khi Ka cang ln, pKa cang nho. HF manh hn CH3COOH.

V du: HF co pKa = 3,2 nho hn pKa cua CH3COOH (pKa = 4,75), nen

Xet baz cho phan ng can bang cang chuyen theo chieu thuan (cho cang nhieu OH). e nh cng o cua baz ta dung hang so baz Kb vi: Kb = [HA].[OH]
[A]

He thc gia Ka va Kb: Ka.Kb = 1014 Hay pKa + pKb = 14 T he thc tren cho ta thay Ka cang ln (acid cang manh) Kb cang nho (baz lien hp cang yeu).

V du:
HF HCN NH3 co pKa = 3,2 , co pKa = 9,4 , co pKa = 9,25 , pKb =14 3,2 = 10,8 pKb =14 9,4 = 4,6 pKb =14 4,75 = 9,25 pKb =14 9,25 = 4,75

CH3COOH co pKa = 4,75 ,

Vi cac acid that manh nh HCl th baz lien hp Cl la baz vo cung yeu. Vi cac baz that manh nh NaOH th axt lien hp Na+ la acid vo cung yeu.

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Hoa phan tch

I.3. Dung dch em Dung dch em la dung dch tao thanh khi tron lan mot acid yeu (hoac mot baz yeu) vi baz lien hp cua no ( hoac acid lien hp cua no). NH4+ la hai hon hp em. Noi chung: HA + A- hay B + BH+

V du: hon hp gom CH3COOH + CH3COO- hay hon hp gom: NH3 + Tnh chat:
HA + H2O H3O+ + A-

Khi them mot lng axit (H3O+), anion A- ket hp vi no cho acid yeu HA. Trai lai, khi them OH-, acid HA ien ly cho H3O+ trung hoa OH- cho baz yeu H2O. Ket luan: pH dung dch em thay oi rat t khi them mot lng axit hoac baz. II. Cach tnh pH cua cac dung dch acid, baz, muoi, dung dch em Thang pH Vi nhng dung dch acid hay baz loang, nong o H+ hoac OH hoac OH rat nho, e co nhng con so de s dung hn, ngi ta thng dung cac ai lng pH va pOH c nh ngha nh sau: pH = - lgC H+ va pOH = - lgCOH pH + pOH = 14 Khi tnh acid cua dung dch giam dan [H+] giam, [OH] tang, pH tang dan. Ta co mot dai gia tr cua pH goi la thang pH c gii han t pH = 0 en pH = 14. Trong nc nguyen chat [H+] = [OH] = 107 pH = 7 Trong dung dch axt [H+] > [OH] [H+] > 107 pH < 7 Trong dung dch baz [H+] < [OH] [H+] < 107 pH > 7 Vay pH = 7 la ranh gii gia cac dung dch acid va dung dch baz.
Dung dch acid 0 7 Dung dch baz 14

Cong Thc Tnh pH cua dung dch: (dung moi nc) - Nc nguyen chat pH = lg [H3O+] hay pH = lg [H+] = 7 - Dung dch acid manh: Vi Ca 106 M [H+] = Ca pH = lgCa

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Hoa phan tch

- Dung dch baz manh: Vi Cb 106 M [OH] = Cb pOH = lgCb pH = 14 pOH = 14 + lg Cb - Dung dch acid yeu: Vi Ka kha nho (acid kha yeu) Ca kha ln. pH =
1 (pKa lgCa) 2

- Dung dch baz yeu: Vi Kb kha nho (baz kha yeu) Cb kha ln. pH = 14 - Dung dch muoi + Muoi phat xuat t acid manh va baz manh o la trng hp cac muoi loai NaCl, KNO3. pH cua dung dch muoi nay chnh la pH cua nc nguyen chat co pH = 7.
1 (pKb lgCb) 2

+ Muoi phat xuat t acid manh va baz yeu V du: Tnh pH dung dch NH4Cl 0.1M co Kb =10 4,75
Muoi nay gom cation NH4+ co tnh acid yeu va Cl co tnh baz vo cung yeu vay dung dch muoi NH4Cl co the xem nh ch cha acid yeu NH4+ va ta co the tnh pH dung dch muoi NH4Cl nh trng hp dung dch mot acid yeu thong thng. Ta co: pH =
1 1 (pKa lgCa) = ( 9,25 + 1) = 5,12 2 2 1 1 Hoac: pH = (pKH2O pKb lgCM) = ( 14 4,75 + 1) = 5,12 2 2

+ Muoi phat xuat t acid yeu va baz manh V du: Tnh pH dung dch CH3COONa 0,05M co Ka = 10 4,75
Muoi nay gom cation Na+ co tnh acid vo cung yeu (Ka = 0) v la acid lien hp cua NaOH baz that manh va anion CH3COO co tnh baz yeu vay co the xem dung dch nay nh ch cha baz yeu vay co the xem dung dch baz yeu thong thng. Ta co: pOH =
1 1 (pKH2O pKa lgCM) = ( 14 4,75 + 1,3) = 5,275 2 2 1 1 Hoac: pH = 14 (pKb lgCb) = 14 (9,25 + 1,3) = 8,725 2 2

- Dung dch em

+ Dung dch co moi trng acid

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Hoa phan tch

[H+] = K a

Ca Cb Ca Cb

Vi Ca: nong o acid Cb: nong o baz

pH = pK a lg

Ka: hang so can bang acid

+ Dung dch co moi trng baz .

[OH] = K b
Cb Ca
C
a

b pH =14 p[OH] = 14 pK b lg C

III. Noi dung phng phap chuan o acid baz Phng phap chuan o acid baz la phng phap nh lng cau t X dang M(OH) bang thuoc th C dang HA hoac ngc lai: HA + M(OH) MA + H2O Tai iem tng ng, pH cua DD do muoi sinh ra quyet nh. Bc nhay cua ng chuan o co o dai phu thuoc o manh, yeu va nong o cua acid baz s dung. iem cuoi c xac nh bang ch th mau acid baz (hay con goi la ch th pH). IV. Cac phng phap chuan o acid baz thong dung IV.1. Chuan o acid manh bang baz manh V du: Chuan o HCl bang NaOH - Phan ng chuan o: H+ + OH- H2O - Tai iem tng ng: [OH-] = [H+] pHt = 7 - Bc nhay cua ng chuan o kha dai: vi CHCl, CNaOH ~ 0.1N, bc nhay t pH = 4 en 10 co the chon cac chat ch th pH co s chuyen mau trong khoang pH nay. Mot so ch th acid baz thong dung thng dung nh sau: Ten ch th Phenolphtaleion Bromothymol xanh Bromocresol luc Metyl da cam Metyl o Khoang mau chuyen Mau dang HIn Khong mau Vang Vang Hong cam o Mau dang In Tm Xanh Xanh Vang Vang

8.2 -10 6.0 7.6 3.8 5.4 3.1 4.4 4.2 6.2

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Hoa phan tch

Hnh 5.1: ng chuan o acid manh bang baz manh IV.2. Chuan o acid yeu bang baz manh Khi chuan o acid yeu HA bang baz manh V du chuan o CH3COOH bang NaOH - Phan ng chuan o: HA + NaOH NaA + H2O - Tai iem tng ng: pH cua DD do NaA quyet nh la mot baz yeu co nong o CNaA nen pHt c tnh: pHtd = 7 + pKHA + lgCNaA CNaA la nong o NaA sinh ra, ve mat ly thuyet chnh la nong o acid ban au hoac nong o acid ban au hoac nong o baz a tac dung, nhng thc te b giam xuong do the tch DD tang len. Bc nhay cua ng chuan o nam trong vung baz nen chon ch th co pHch/m >7, thng dung phenolphtalein.

Hnh 5.2: ng chuan o acid yeu bang baz manh

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Hoa phan tch

IV.3. Chuan o baz yeu bang acid manh Chuan o baz yeu A- bang acid manh V du: chuan o NH4OH bang HCl - Phan ng chuan o: A- + HCl HA + Cl- Tai iem tng ng, pH cua DD c quyet nh bi HA la mot acid yeu nen pHt c tnh: pHt: pKHA - lg CHA - Bc nhay cua ng chuan o nam trong vung acid nen chon ch th co pHchuyen/mau < 7, thng dung metyl da cam, bromocresol luc, metyl o.

Hnh 5.3: ng chuan o baz yeu bang acid manh IV.4. Chuan o mot a acid (hoac nhieu n acid) bang baz manh Neu a acid co ka1, ka2,, kan khac kha xa nhau ( pK 4) va moi ka khong qua be (>10-10) th co the chuan o lien tiep tng chc vi ch th thch hp nh khi chuan o tng n acid. V du: chuan o H3PO4 bang NaOH: H3PO4 NaH2PO4 Na2HPO4 + NaOH NaH2PO4 + H2O + NaOH Na2HPO4 + H2O + NaOH Na3HPO4 + H2O Ka1 = 10-2.12 Ka2 = 10-7.21 Ka3 = 10-12.38

pH tng ng c tnh gan ung nh sau: pHt1 = (pKa1 + pKa2) = 4.66 pHt2 = (pKa2 + pKa3) = 9.8 Co the xac nh hai iem cuoi bang hai ch th:
-

Bromocresol luc Vt1 Phenolphtalein Vt2 Vt2 = 2 Vt1

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Hoa phan tch

Vt2 la the tch OH- dung e chuan o hai chc (khong chuan o c chc th ba do Na2HPO4 la acid qua yeu).

Hnh 5.4: ng chuan o H3PO4 bang NaOH IV.5. Chuan o mot a baz (hoac nhieu n baz) bang acid manh Cung nh a acid, neu a baz co kb1, kb2,, kbn khac kha xa nhau ( pK 4) Va moi kb khong qua be (>10-10) th co the chuan o lien tiep tng chc vi ch th thch hp nh khi chuan o tng n baz. V du: Chuan o DD Na2CO3 bang HCl CO32- la baz lien hp cua diacid H2CO3 (Ka1 = 10-6.35; Ka2 = 10-10.32) Na2CO3 NaHCO3 H2CO3 + HCl NaHCO3 + NaCl + HCl H2CO3 CO2 + H2O + NaCl

pHt1 = (pKa1 + pKa2) = 8.33 pHt2 ~ 4 (tuy thuoc vao nong o H2CO3 trong DD) Co the xac nh hai iem cuoi bang hai ch th: Phenolphtalein Vt1 Metyl da cam Vt2 Vt2 = 2 Vt1 ; Vt2 la the tch HCl dung e chuan o hai nac.

Hnh 5.5: ng chuan o Na2CO3 bang HCl

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CHNG 6. PHNG PHAP CHUAN O OXY HOA KH

Cac phng phap chuan o oxy hoa kh thng c goi ten theo chat oxy hoa dung lam chat chuan. Phng phap permanganat Phng phap permanganate (chuan o vi KMnO4) c s dung kha rong rai trong hoa phan tch. Phng phap chuan o nay co cac ac iem sau ay: 1. MnO4- la chat co tnh oxy hoa manh trong moi trng acid: MnO4- + 8 H+ + 5 e- Mn2+ + 4 H2O E0 = 1.51V (a) + 0 MnO4 + 4 H + 3 e MnO2 + 2 H2O E = 1.69V (b) Phan ng (a) thng c dung nhieu hn phan ng (b) v tao thanh Mn2+ khong mau (de nhan iem cuoi). Mn2+ con co tac dung xuc tac giup cho phan ng xay ra nhanh hn. 2. MnO4- co mau hong ro trong DD nen con ong vai tro ch th giup nhan biet iem ket thuc phan ng. 3. Phng phap thng c dung e chuan o: - Trc tiep cac ion co tnh kh nh Fe2+, (COO)22-, H2O2 - Gian tiep cac ion co tnh oxy hoa nh Fe3+ (sau khi kh thanh Fe2+). - Chuan o ngc, v du hoa tan MnO2 bang lng (COO)22- tha va chuan o lng tha (COO)22- bang MnO4-. 4. Cac nguyen nhan co the gay sai so he thong cho phng phap permanganate: - DD MnO4- khong ben theo thi gian do 4 MnO4- + 2 H2O 4 MnO2 + 3 O2 + 4 OHnen can chuan o lai e xac nh nong o khi dung. - Khong dung HCl tao moi trng H+ v co phan ng 2 MnO4- + 10 Cl- + 16 H+ 5 Cl2 + 2 Mn2+ + 8 H2O - Nen dung H2SO4 loang tao moi trng - Phan ng cham nhiet o thng va khi cha co Mn2+ lam xuc tac. Do o, thng chuan o nhiet o t0 600C va chuan that cham luc au. Phng phap dichromat Phng phap dichromat (chuan o vi K2Cr2O7) cung c s dung kha rong rai trong hoa phan tch. Phng phap nay co cac ac iem sau: 1. Cr2O72- co tnh oxy hoa manh trong moi trng acid: Cr2O72- + 6 e + 14 H+ 2 Cr3+ + 7 H2O E0 (Cr2O72-/2Cr3+) = 1.33V Co the dung HCl, H2SO4 loang tao moi trng H+ 2. Chat ch th thng dung: Diphenylamin (E0i = 0.76V) hay diphenylamin sulfonat Ba (E0i = 0.85V)

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Hoa phan tch

Co mot vai trng hp ma E0i co the lech Et kha xa. Khi gap trng hp nay, co the dung hoa chat thch hp e keo dai bc nhay cua ng cong chuan o e E0i nam trong vung bc nhay. V du, dung Cr2O72- chuan o DD Fe2+ se co Et > E0i cua diphenylamine, do o, e keo dai bc nhay trc iem tng ng can lam giam Ecb bang cach giam [Fe3+], thng dung H3PO4 tao phc khong mau vi Fe3+. 3. Phng phap dichromat thng c dung e chuan o: - Trc tiep cac ion kh nh Fe2+ - Gian tiep cac ion co tnh kh (SO32- , S2O32-, ) qua trung gian I2. Phng phap iod Phng phap iod (chuan o vi I2) c s dung da tren cac ac iem: 1. I2 co tnh oxy hoa trong moi trng gan trung tnh hay acid nhe I2 + I- + 2e 3 I- (E0 = 0.545V) 2. Chat ch th la ho tinh bot tao hp chat mau xanh vi I2 khi ch th co nong o 2.10-5M (ch cho ch th ho tinh bot vao DD khi lng I2 con rat t trong DD, neu khong I2 se hap phu tren hat tinh bot gay sai so) 3. Phng phap thng dung chuan o: - Trc tiep cac DD S2O32-, Sn2+, SO32-, AsO33- Gian tiep cac DD co tnh oxy hoa nh Br2, Cl2, MnO4-, Cr2O72-, ClO3-, Cu2+, H2O2, Fe3+ bang cach cho DD muon chuan o tac dung vi lng tha I-. Phan ng tao I2, chuan o I2 bang DD chuan S2O32-. 4. Cac nguyen nhan co the gay sai so he thong cho phng phap iod: - I2 rat de thang hoa nen DD kem ben, can chuan o trong bnh co nap, pha loang DD va gi DD nhiet o thng (I2 ch tan trong nc dang phc I3- do o can pha I2 trong lng KI thch hp). - Khi chuan o moi trng qua acid se pha huy ho tinh bot va co the phan ng phu: S2O32- + 2 H+ H2SO3 + S - Neu moi trng qua baz co the tao phan ng phu: I2 + 2 OH- I- + IO- + H2O 3 IO- 2 I- + IO3Phng phap bromat Phng phap bromat (chuan o vi BrO3-) c s dung: 1. Da vao kha nang oxy hoa manh cua BrO3- trong moi trng acid hoac trung tnh 2. Chat ch th thng dung: metyl o (ch th bat thuan nghch) trong moi trng co [H+] = 2 N 3. Phng phap thng c dung e chuan o trc tiep cac ion kh nh As3+, Sb3+, Sn2+, 3 As3+ + BrO3- + 9 H2O 3 H3As O4 + Br- + 9 H+

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Hoa phan tch

Phng phap ceri Phng phap ceri (chuan o vi Ce4+) c s dung 1. Da vao kha nang oxy hoa manh cua Ce4+ Ce4+ + 1e- Ce3+ E0 (Ce4+/Ce3+) = 1.44V 2. Thng dung Ce4+ e chuan o NO23 Ce4+ + NO2- + H2O 2 Ce3+ + NO3- + 2 H+

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Hoa phan tch

CHNG 7. PHNG PHAP CHUAN O TAO TUA

Trong phng phap chuan o tao tua, cau t X c chuan o bang thuoc th C theo phan ng: C + X CX . Vi X la halogenur nh Br-, Cl-, I-, thuoc th c dung la Hg+ hay Ag+ (Hg+ qua oc nen thng dung Ag+) va ch th c s dung co the la ch th tao tua (thng dung K2CrO4), ch th hap phu (thng dung fluorescein) va con co the s dung ch th tao phc. ieu kien cua mot phan ng tao tua: - Van toc phan ng ln e tao tua nhanh - CX phai co Tst nho (< 10-7 10-8) Cac phng phap chuan o tao tua thong dung gom co: Phng phap Mohr Phng phap Mohr la phng phap chuan o trc tiep vi ch th tao tua K2CrO4: 1. Phan ng chuan o: Ag+ + X- AgX 2. Phan ng ch th: 2 Ag+ + CrO42- (vang) Ag2CrO4 (o nau) TAg2CrO4 = 10-12 Tai iem cuoi, DD chuyen t mau vang ti (CrO42-) sang hong ao. 3. ieu kien chuan o: - Chuan o trong moi trng co pH = 6.5 10 (neu trong DD khong co NH3) va pH = 6.5 - 8 (neu trong DD co NH3) v: Neu pH < 6.5 co phan ng: 2 HCrO4 2 Cr2O72- + H2O 2 CrO42- + 2 H+ Neu pH > 10 co phan ng: 2 Ag+ + 2 OH- 2 AgOH Ag2O + H2O Neu co NH3 co phan ng: AgX + 2 NH3 [Ag(NH3)2]+ + X- Chuan o nhiet o thng v Ag2CrO4 tan nhiet o cao - Lng K2CrO4 phai dung thch hp ([CrO42-] = 10-2M) e Ag2CrO4 xuat hien ngay sau iem tng ng ma mat co the nhan thay (luc o [X]- con lai khoang 10-5 10-6M). Phng phap Fajans Phng phap Fajans la phng phap chuan o trc tiep vi ch th hap phu fluorescein 1. Phan ng chuan o: Ag+ + X- AgX 2. Phan ng ch th: AgX X- AgX AgX Ag+Fl- (mau hong nhat) Mau DD tai iem cuoi: vang co anh huynh quang (fluorescein) tua trang pht hong.

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Hoa phan tch

3. ieu kien chuan o: - pH DD 6.5 10 v neu pH < 6.5: Fl- + H+ HFl - [X-]0 10-2M e lng AgX u nhieu cho phep nhan biet s chuyen mau cua tua. - e tua co be mat hap phu ln, can them vao DD chat bao ve keo AgX nh dextrin. Phng phap Volhard Phng phap Volhard la phng phap chuan o ngc vi chat ch th tao phc phen sat ba: 1. Cho lng tha Ag+ vao DD cha X: Ag+ + X- AgX 2. Lng Ag+ tha c chuan o bang SCN- vi ch th phen sat ba Fe3+: - Phan ng chuan o: Ag+ + SCN- AgSCN (trang uc) TAgSCN = 10-12 - Phan ng ch th: Fe3+ + SCN- Fe(SCN)2+ (o mau) Mau DD tai iem cuoi: DD cha tua trang uc xuat hien mau cam nhat. 3. ieu kien chuan o: - pH < 3 e tranh tua Fe(OH)3 (dung HNO3 tao moi trng) - Neu chuan o Cl- bang phng phap nay, do TAgSCN < TAgCl nen co kha nang xay ra can bang phu: AgCl + SCN- AgSCN lam tan tua AgCl. Co the han che can bang phu tren bang cach loc AgCl trc khi chuan o Ag+ tha, hoac un nong DD e AgCl ket von lai, hoac dung nitrobenzene e bao AgCl lai. Ngoai cac phng phap chuan o tao tua noi tren, ngi ta con co the dung DD SCN- e chuan o trc tiep Ag+; dung DD Na2SO4 hoac DD K2CrO4 chuan o trc tiep DD BaCl2; dung DD K2CrO4 chuan o trc tiep DD Pb2+, Cac phng phap chuan o trc tiep nay cung c xep vao nhom phng phap Mohr.

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Hoa phan tch

CHNG 8. PHNG PHAP CHUAN O PHC CHAT

Phc chat Phc chat la nhng hp chat c cau tao t s ket hp gia: Ion trung tam thng la ion kim loai ma phu tang d con trong (thng thuoc nhom kim koai chuyen tiep) Ligand hay phoi t la nhng phan t hay ion cua nguyen to hay nhom nguyen to vi nguyen to con ien t t do n. Ion trung tam va ligand noi nhau bang lien ket cong hoa tr hay lien ket phoi tr. Phc chat co the dang ion hay phan t. Moi hp chat phc co the gom 1 (goi la phc n nhan) hay nhieu ion kim loai trung tam (goi la phc a nhan) ket hp vi mot ligand (goi la phc n cang) hoac nhieu ligand (phc a cang). V du: Phc [Cu(NH3)42+ Phng phap chuan o tao phc Phng phap chuan o tao phc thng c s dung e chuan o DD ion kim loai vi DD chuan la DD ligand tao phc vi ion kim loai theo can bang C + M MC (phc tan). e can bang co tnh nh lng, C c chon e phc MC co hang so ben kha ln. Nhieu loai ligand a c dung trong phng phap nay nhng thong dung nhat la etylene diamine tetraacetic acid (EDTA) HOOCCH2 CH2COOH N-CH2-CH2 N HOOCCH2 CH2COOH EDTA dang acid khotan trong nc nen c dung dang muoi (2H+ c thay the bang 2Na+). Muoi nay co ten goi lacomplexon III hay trilon B ky hieu la Na2H2Y hay H2Y2- hay n gian hn Y4-. oi khi theo thoi quen ngi ta van goi muoi la EDTA. NaOOCCH2 CH2COONa N-CH2-CH2 N HOOCCH2 CH2COOH EDTA Tao phc vi kim loai theo can bang: H2Y2- + Mn+ MY n-4 + 2 H+ ac iem cua phan ng chuan o s dung EDTA: 1. EDTA va ion kim loai tao phc theo ty le mol 1:1 2. Can bang tao ra H+, do o [H+] se anh hng en o ben cua phc. e thc hien cac phan ng chuan o cu the thng s dung DD em pH tao moi trng chuan o trong o hang so ben ieu kien ' MY u ln cho yeu cau nh lng.

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Hoa phan tch

3. ieu kien cua phan ng chuan o: Phc MY phai kha ben ( ' MY 108) pH chuan o. Khi chon ch th cho phan ng chuan o, phc tao bi ch th vi kim loai cung ben nhng phai kem ben hn phc MY. Cac ion kim loai ton tai song song vi cau t chnh trong DD eu co kha nang tao phc ben vi EDTA gay anh hng tren ket qua xac nh. Co the loai bo cac anh hng nay bang cach tao dang tua ben va loc khoi DD, hoac oi pH cua DD e lam phc phu kem ben hoac dung hoa chat thch hp tao dang phc ben hn dang phc vi EDTA. Can bang tao phc thng cham, do o can chuan o cham hay un nhe DD trc khi chuan o.

Cac phng phap chuan o phc chat (dung EDTA) thong dung nh lng Ca2+, Mg2+ hay hon hp Ca2++ Mg2+ 1. Chuan o Mg2+: Mg2+thng c chuan o trc tiep pH = 10 vi ch th Erio-en-T: a) Phan ng chuan o: Mg2+ + Y4- MgY2b) Phan ng ch th: o Neu Mg2+ c cha erlen: MgIn + Y4- MgY2- + In (Hong, tm) o Neu Mg2+ c cha buret: In + Mg2+ MgIn (xanh) (Hong, tm) DD chuyen t mau xanh sang mau tm Khi chuan o Mg2+ trong DD khong c phep co mat Ca2+ v Ca2+ cung tao phc ben vi EDTA pH = 10 2. Chuan o Ca2+: a) Chuan o trc tiep pH = 12.5, ch th calcon, murexide hay Fluoresxon Murexide (CaIn: o; In: xanh) Fluoresxon (CaIn: vang luc huynh quang; In hong cam.) Khi chuan o Ca2+, Mg2+ khong gay anh hng v [Mg2+] con rat t do a tao tua Mg(OH)2, tuy nhien, lng Mg2+ ban au khong che v tua Mg(OH)2 tao thanh nhieu qua se hap phu Ca2+. (xanh) DD chuyen t mau tm sang mau xanh

46

Hoa phan tch

b) Chuan o pH =10, ch th Erio-en-T:

' MgY

Them vao DD mot lng MY2- trc khi them EDTA, do < ' CaY trong DD co can bang:

MgY2- + Ca2+ CaY2- + Mg2+ Lng Mg2+ sinh ra se tao phc vi ch th MgIn (hong, tm) Khi chuan o bang EDTA, Ca2+ con lai tac dung trc: Ca2+ + Y4- CaY2Khi het Ca2+ t do, co can bang: Mg2+ + Y4- MgY2Tai iem tng ng: MgIn + Y4- MgY2- + In Dung dch co mau xanh cua In pH = 10. 3. Chuan o hon hp Ca2+ + Mg2+: Chuan o Ca2+ pH = 12.5 dung V1(ml) EDTA. Chuan o tong Ca2+ + Mg2+ pH = 10, dung V2 (ml) EDTA DD EDTA dung chuan o Mg2+ co the tch V2 V1 (ml). nh lng DD ch cha hon hp Fe3+, Al3+ Da vao o ben khac nhau cua AlY- va FeY- moi trng pH khac nhau e chuan o lien tiep Al3+ va Fe3+ trong hon hp. 1. Chuan o Fe3+: Chuan o trc tiep pH = 2.5 vi ch th acid sulfosalicylic a) Phan ng chuan o: Fe3+ + Y4- FeYb) Phan ng ch th: FeIn + Y4- FeY+ In (tm) (vang nhat) (khong mau) Tai iem cuoi, DD chuyen t mau tm cua FeIn sang mau vang nhat cua FeY-. c) ieu kien cua phan ng chuan o: - pH nay, phc AlY- khong ben ( ' FeY =1012.7, ' AlY =104.2) nen Al3+ khong anh hng en phan ng chuan o. - Neu DD cha Fe2+, muon nh lng Fe tong, phai oxy hoa Fe2+ thanh Fe3+ (thng dung K2S2O8) roi mi chuan o v Fe2+ khong tao phc ben vi EDTA. 2. Chuan o Al3+: chuan o ngc pH = 5 a) Them vao DD (a chuan o Fe3+) lng tha xac nh DD Y4- pH =5. un soi DD ba phut tao ieu kien cho phan ng Al3+ + Y4- AlY- ( ' AlY =109.6) xay ra hoan toan. b) Chuan o lng Y4- tha bang DD kim loai M2+ (Cu2+, Zn2+, Pb2+) ch th thch hp:

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Hoa phan tch

P.A.N (CuIn: hong ; ZnIn: o; In: vang) Xylenol da cam (ZnIn: o; In: vang) Tai iem cuoi, DD chuyen t mau vang sang mau cam c) ac iem: Dung phep chuan o ngc do phc AlY- ch hoan toan 800C. - Neu khong chuan o Al3+ tren DD a chuan o Fe3+ ma chuan tren DD ban au, Fe3+ se anh hng v ' FeY =1014.2 (pH=5). - e de nhn mau tai iem cuoi, thng dung them chat ch th bromocresol luc co mau xanh pH 5). S cong mau se lam qua trnh chuyen mau t vang chanh sang tm de nhan biet hn la chuyen t mau vang sang vang cam (e tranh sai tha, phai dng chuan o khi DD va chuyen sang mau tm). nh lng SO42- theo phng phap chuan o ngc - Them vao DD lng tha xac nh Ba2+ co phan ng tao tua: Ba2+ + SO42- BaSO4 (trong moi trng ETOH e giam s tan tua) - nh lng Ba2+ tha bang cach chuan o trc tiep vi EDTA pH=10 ch th Erio en T hoac chuan o ngc bang lng tha xac nh EDTA sau o chuan EDTA tha bang Mg2+, ch th Erio en T.

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Hoa phan tch

CHNG 9. PHNG PHAP CHUAN O IEN THE

1. Nguyen tac: Phng phap chuan o ien the da tren viec o the cua ien cc c nhung vao dung dch. Ga tr cua the phu thuoc vao nong o cua cac ion tng ng trong DD. Th du, the ien cc bac nhung vao trong DD muoi bac bien oi cung vi s bien oi cua nong o ion Ag+ trong DD. Do o, bang cach o the cua ien cc nhung vao DD mot muoi a cho cha biet nong o, co the xac nh c ham lng cua ion tng ng trong DD. Cc da vao the cua no co the suy ra nong o cua ion can xac nh trong DD, goi la cc ch th. The cua cc ch th c xac nh bang cach so vi the cua mot cc khac goi la cc so sanh. Ngi ta dung cac cc nao ma the cua no khong thay oi khi thay oi nong o ion can xac nh lam cc so sanh. Ngi ta thng dung cc hidro tieu chuan lam cc so sanh. The cua cc hidro tieu chuan c quy c bang khong, do o sc ien ong (Ex) cua nguyen to ganvanic gom cc ch th va cc hidro tieu chuan bang the cua ien cc ch th: Ex = EInd - ESs Khi ESs = 0 th Ex = EInd Trong thc te, ngi ta thng khong dung cc hidro co the ien cc biet trc lam cc so sanh ma dung cc calomen. The cua cc calomen thc te khong thay oi trong thi gian lam viec. S phu thuoc cua the cc calomen (so vi the cc hidro tieu chuan) vao cac ieu kien phan tch c trnh bay trong bang sau: Khi muon o the cua ien cc (th du cc bac), ta noi no vi cc so sanh (cc calomen, cc hidro, v.v) va mac nguyen to o vao s o e o the (ien the ke, von ke ien t). Trong khi o the, cng o dong c gi u nho (t 10-6 en 10-14A). Khi cng o dong nho th nguyen to khong b thay oi. The cua ien cc la ham so cua hoat o chat. Th du: the cua cc bac trong DD cha ion bac c bieu th bang phng trnh: E = E0 + 0.059 lg aAg+ Bang the cua cc calomen (so vi the cc hidro tieu chuan) Nong o DD KCl Bao hoa 1N 0.1N The cua cc calomen, V 200C 250C 0.2458 0.2490 0.2819 0.2859 0.3369 0.3379

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Hoa phan tch

ay, E0 = 0.7795V the tieu chuan cua qua trnh c bieu th bang phng trnh: Ag+ + e- Ag V vay, hoat o cua ion bac (cung nh hoat o cua cac ion khac) co the c xac nh bang the E. e cac nh nong o cua ion bac (CAg+), can biet he so hoat o (fAg+): CAg+ = aAg+/ fAg+ 2. Cach xac nh iem tng ng Xac nh iem tng ng theo the cua cc ch th: S phu thuoc cua the cc ch th vao nong o DD co the c dung e xac nh iem tng ng khi chuan o. Tai iem tng ng, khi nong o cua ion can xac nh giam i manh va thc te tr thanh khong ang ke th s thay oi ot ngot the xay ra co the ghi c bang ien the ke nhay. Th du, neu nhung cc ch th bac va mot cc so sanh vao DD cha ion bac, th cc bac se tch ien dng. Khi chuan o DD cha ion Ag+ bang DD NaCl, nong o ion bac giam i, the cua cc ch th thay oi. The cua cc so sanh khong oi. Do o, trong qua trnh chuan o, cung vi s tng tac cua chat can xac nh (Ag+) vi DD chuan o c them vao (NaCl), ta thay c s bien oi t t va manh dan cua ien the cc ch th. Gan iem tng ng, nong o ion bac co s thay oi manh, kem theo bien oi ot ngot the cua cc ch th , o la dau hieu ket thuc chuan o. S chuan o, trong o iem tng c xac nh bang bc nhay the cua cc ch th nhung trong DD c goi la chuan o ien the. Chuan o ien the c s dung trong cac phng phap trung hoa, oxy hoa kh, ket tua va tao phc. ng cong chuan o ien the Tren hnh 9.1 la ng chuan o ien the ac trng, trong o truc tung at cac gia tr the cua cc ch th, con truc hoanh at cac gia tr the tch DD clorua c them vao.

Hnh 9.1: ng chuan o ien the AgNO3 bang NaCl

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Hoa phan tch

3. ng dung Phng phap chuan o ien the khong nhng ch ng dung rat tot oi vi s chuan o cac DD co the dung chat ch th ma con ca oi vi viec chuan o cac DD co mau, cac DD b uc khi khong the dung c cac phng phap chat ch th. Chuan o ien the c s dung rong rai e xac nh cac acid, baz yeu va rat yeu, cac hon hp acid hoac baz, cac hon hp chat oxy hoa hoac cac chat kh trong cac moi trng khong phai nc. Cuoi cung, phng phap o the c dung e xac nh pH cua ca DD can nghien cu. Neu truc tung khong ghi cac gia tr the ma ghi cac gia tr E / C , tc la ai lng bien thien cua the khi them 1ml DD clorua, th sr4 nhan c ng cong, tren o v tr cua iem tng ng con ro rang hn nhieu (hnh 9.2).

Hnh 9.2: ng vi phan chuan o ien the AgNO3 bang DD NaCl Xac nh pH: The cua cc ch th co moi lien he ham so vi nong o cua ion hidro. Cc hidro c chuan b bang cach nhung mot ban platin phu muoi platin vao DD acid bao hoa kh hidro, tham gia can bang vi ion hidro co: K = [H+]/[H] hoac K = aH+/aH Trong o: [H+] nong o ion hidro trong DD [H] nong o kh hidro trong platin khi ap suat khong oi. EH = E0 + V the cua cc hidro tieu chuan (E0) bang khong, nen the cua cc hidro c bieu th bang cong thc: EH = hoac EH = 0.059 lg [H+] hoac EH = 0.059 lg aH+ Khi dung cc calomen, the cua no a biet (Ecal), th gia tr Ex cua DD can nghien cu c tnh theo cong thc: Ex = Ecal - EH hoac - EH = Ex - Ecal V EH = 0.059 lg [H+] nen - lg [H+] = pH = (Ex - Ecal)/0.059 ay Ex: sc ien ong cua nguyen to can nghien cu.
RT ln [H+] nF RT ln [H+] nF

hoac EH = E0 +

RT ln aH+ nF

hoac EH =

RT ln aH+ nF

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CHNG 10. PHNG PHAP QUANG PHO HAP THU THAY C

1. ac iem cua phng phap phan tch o mau Trong so nhng phng phap phan tch quang pho th cac phng phap o mau la nhom c s dung rong rai nhat trong thc tien cua cac phong th nghiem phan tch. Cac phng phap o mau da tren s o cng o cua chum anh sang i qua DD mau. Phng phap phan tch o mau a c nha bac hoc Nga V. M. Xeverghin phat minh ra t nam 1795. Trong cac phng phap phan tch o mau, ngi ta s dung cac phan ng hoa hoc, trong o chat can xac nh c chuyen thanh mot hp chat co mau lam bien oi mau cua DD phan tch. Bang cach o s hap thu anh sang cua DD mau nay (phan tch o mau) hoac bang cach so sanh cng o mau thu c vi cng o cua DD a biet trc nong o (phng phap so mau), co the xac nh c ham lng cua chat mau trong DD th nghiem. Moi lien he phu thuoc gia cng o mau cua DD va ham lng cua chat mau trong DD o. S phu thuoc nay c goi la nh luat Buger Lambe Ber no c bieu dien bang phng trnh: I = I0 10 - Cl ay I: cng o chum anh sang i qua DD I0 : cng o chum anh sang ti DD : he so hap thu anh sang, la ai lng khong oi, ac trng cho moi chat mau, phu thuoc vao ban chat cua no; C: nong o chat mau trong DD l: chieu day cua lp DD hap thu anh sang (chieu day cuvet), cm Y nghia vat ly cua nh luat nay co the c the hien nh sau Cac DD cua cung mot chat mau khi co cung nong o cua chat mau o va cung chieu day cua lp DD, th hap thu mot lng nang lng anh sang nh nhau, tc la s hap thu cua nhng DD o nh nhau. Mot DD mau hap thu anh sang co bc song khac nhau nhng mc o khac nhau, do o e tang o chnh xac va o nhay, ngi ta s dung hap thu khong phai moi anh sang ma ch chon nhng tia b DD hap thu manh nhat. e nhan c cac ket qua chnh xac hn, t vung quang pho kha kien, ngi ta tach ra nhng tia co bc song ma DD hap thu cc ai, tc la s dung anh sang n sac. T anh sang trang, e tach nhng tia co chieu dai song cac nh, ngi ta dung cac knh loc. o la nhng vat the long hoac ran co tnh trong suot khac nhau oi vi phan pho khac nhau, chung hap thu tat ca cac tia ch tr chum hep cac tia thuoc mot vung pho xac nh. Viec chon ung knh loc la ieu rat quan trong e tien hanh phan tch. Vung pho hap thu cc tieu (hoac truyen qua cc ai) cua anh sang cua knh

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Hoa phan tch

loc a c chon ung trung vi vung hap thu cc ai cua DD mau nghien cu. e lam knh loc, ngi ta s dung cac loai thuy tinh mau va cac chat long mau. Trong cac may o mau, ngi ta thng dung cac knh mau. Co the chon nhanh nhat knh loc mau da vao mau cua DD phan tch (bang 1). Viec s dung cac knh loc mau gop phan nang cao o nhay va o chnh xac cua phng phap. Bang1: Chon knh loc mau theo mau cua DD phan tch Mau cua DD Mau cua phan tch knh loc tng ng La cay vang Tm Xanh bien Vang Cham Da cam Xanh luc o La cay o ta Vung bc song truyen qua 400-450 450-480 480-490 490-500 500-560 Mau cua DD phan tch Tm Xanh bien Cham Xanh luc Mau cua knh loc tng ng Vang luc Vang Da cam o Vung bc song truyen qua 560-575 575-590 590-625 625-750

oi vi DD mau c ng trong cuvet bang thuy tinh co cac thanh song song nhau, co the noi rang, cung vi s tang nong o va chieu day cua lp DD th mau cua no tang len, con cng o I cua anh sang truyen qua DD hap thu b giam i so vi cng o cua anh sang ti I0. Mat o quang cua DD: Neu lay logart phng trnh nh luat Ber va oi dau th phng trnh co dang: lg (I0/I) = Cl ai lng lg (I0/I) la ai lng ac trng rat quan trong cho mau cua DD, no c goi la mat o quang cua DD (*) va c ky hieu bang ch D: D = lg (I0/I) = Cl (*) e ac trng cng o hap thu anh sang, ngi ta dung thuat ng hap thu A; A =
I0 I x100 % I0

T phng trnh o chung ta rut ra c rang, mat o quang cua DD ty le thuan vi nong o cua chat mau va chieu day cua lp DD. Noi mot cach khac, vi cung mot chieu day cua lp DD cua mot chat cho trc, mat o quang cua DD o cang ln neu lng chat mau cha trong no cang ln. Hoac ngc lai, vi cung mot nong o cua chat mau cho trc, mat o quang cua DD ch phu thuoc vao chieu day cua lp DD o. T o co the rut ra ket luan sau: neu hai DD cua cung mot chat mau co nong o khac nhau, cac DD o se at c cac cng o bang nhau khi chieu day cua cac lp ty le nghch vi nong o cua DD o. Ket luan nay rat quan trong, v no la c s cua mot phng phap phan tch o mau.

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V vay, e xac nh nong o (C) cua DD mau, can phai o mat o quang (D) cua no. e o mat o quang can phai o cng o cua chum tia sang. 2. ac tnh cua cac phng phap phan tch o mau Co the o cng o mau cua cac DD bang cac phng phap khac nhau. Ngi ta phan biet cac phng phap chu quan (hoac cac phng phap nhn mat) va cac phng phap khach quan (hoac trac quang). Cac phng phap nhn mat: la nhng phng phap trong o ngi ta anh gia cng o mau cua DD th nghiem bang mat thng. Trong cac phng phap khach quan, e o cng o mau cua DD th, ngi ta khong quan sat trc tiep bang mat ma dung cac te bao quang ien. S xac nh trong trng hp nay c thc hien bang may mau (t o phng phap co ten la o mau). Hoac bang cac may phc tap hn, hien ai hn cac may pho quang. Cac phng phap nhn mat: gom co - Phng phap day tieu chuan; - Phng phap chuan o so mau; - Phng phap lam bang nhau. 2.1. Phng phap day tieu chuan: Khi tien hanh phan tch bang phng phap day tieu chuan, ngi ta so sanh cng o mau cua DD mau phan tch vi mau cua day DD chuan (co cuang chieu day) c chuan b trc. 2.2. Phng phap chuan o so mau: Phng phap nay da tren s so sanh mau cua DD phan tch vi mau cua DD khac DD kiem tra. e ieu che DD kiem tra, ngi ta chuan b DD cha tat ca cac hp phan cua DD nghien cu ch tr chat xac nh, cha tat ca cac thuoc th c dung khi che hoa mau , roi them DD chuan cha chat can xac nh t buret vao DD kiem tra o. DD chuan c them vao cho en khi cng o mau cua DD kiem tra va DD phan tch bang nhau, ngi ta tha nhan rang trong DD kiem tra cung cha bay nhieu chat can xac nh. 2.3. Phng phap lam bang nhau: Phng phap nay da tren s lam nh nhau mau cua DD phan tch va DD a biet nong o cua chat can xac nh DD chuan. Co hai phng an tien hanh xac nh so mau bang phng phap nay. - Theo phng an th nhat, s lam bang nhau mau cua hai DD co nong o chat mau khac nhau c tien hanh bang cach lam thay oi chieu day cua cac lp DD o trong ieu kien cng o cua chum anh sang i qua hai DD la nh nhau. Khi o mac du nong o cua DD phan tch va DD chuan khac nhau, cng o cua chum anh sang i qua hai lp DD o nh nhau. Ty so gia cac chieu day cua hai lp va ty so gia cac nong o cua chat mau trong cac DD tai thi iem can bang mau se c bieu th bang phng trnh:

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l1 C 2 = l 2 C1

trong o: l1: chieu day lp DD co nong o chat mau la C1 l2: chieu day lp DD co nong o chat mau la C2 tai thi iem can bang mau, ty so cac chieu day hai lp cua hai DD c so sanh ty le nghch vi ty so cac nong o cua chung. Da tren phng trnh o, sau khi o chieu day cua cac lp DD mau nh nhau va biet nong o mot trong hai DD o, de dang tnh c nong o cha biet cua DD kia. e o chieu day cua cac lp DD co mot chum sang c roi qua, co the dung cac ong knh hnh tru hoac cac ong nghiem va khi can xac nh chnh xac hn th dung cac may goi la cac sac ke. - Theo phng an th hai, e lam can bang mau cua hai DD co nong o chat mau khac nhau, qua hai lp DD co chieu day nh nhau, ngi ta cho hai chum sang co cng o khac nhau. Trong trng hp nay, hai DD co mau nh nhau khi ty so cac logarit cng o cua cac chum sang bang ty so cac nong o. Tai thi iem hai DD so sanh at c mau nh nhau khi chieu day cua chung bang nhau, nong o cua cac DD ty le thuan vi logarit cng o anhsang roi ti chung. Theo phng an th hai nay, ta ch can xac nh c bang cach dung sac ke. Cac phng phap o mau quang ien: tat ca cac phng phap o mau quang ien cung da tren mot nguyen tac chung. Chum sang c cho qua cuvet hoac ong nghiem ng ay chat mau nghien cu. Chum sang a i qua DD c thu nhan bi mot te bao quang ien, trong o quang nang c bien oi thanh ien nang. Dong ien c sinh ra khi o c o bang mot ien ke nhay. Nh A. G. Stoletop a chng minh, cng o cua dong ien c sinh ra

e xac nh nong o chat ngh ien cu bang phng phap nay, ngi ta o mat o quang cua DD th (Dx) va cua DD chuan a biet nong o (Dch). S tnh toan c thc hien bang cong thc: Cx =
Dx x Cch Dch

khi nang lng cua anh sang tac dung len te bao quang ien ty le thuan vi cng o chieu sang.

u iem chnh cua cac phng phap o mau quang ien la tnh chat nhanh chong, de xac nh va o chnh xac cao cua chung. Lap ng chuan: Khi phan tch hang loat bang phng phap o mau, e tien hanh xac nh nong o cua DD th, ngi ta khong so sanh s hap thu cua no vi s hap thu cua DD chuan trong moi lan phan tch ma lap trc mot ng

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Hoa phan tch

goi la ng chuan. Muon vay, ngi ta chuan b mot day cac DD chuan co nong o khac nhau. Khi a co c ng chuan, e xac nh nong o cua DD th, ch can o s hap thu cua no va da vao ng chaun e tm gia tr nong o tng ng vi o hap thu o c. e lap ng chuan, can phai chuan b mot day cac DD chuan cha nhng lng khac nhau chat can xac nh. au tien chuan b DD chuan goc cha mot lng xac nh chnh xac chat nghien cu. Dung buret lay vao nhng bnh nh mc dung tch 100ml nhng the tch chnh xac khac nhau cua DD chuan o va cac thuoc th tng ng tao nen mau cua DD phan tch. Sau o pha loang hon hp cha trong cac bnh bang nc cat e a the tch cua DD en vach mc. o mat o quang cua cac DD chuan a c chuan b tren may va ghi cac ket qua o c thanh mot bang. Th du nh sau: DD chuan 1 2 3 4 5 Ham lng nguyen to can xac nh, mg/100ml DD 1 4 6 8 10 Mat o quang 0.1 0.4 0.6 0.8 1.0 Tren c s cua cac ket qua thu c e dng ng bieu dien s phu thuoc mat o quang cua DD vao nong o cua no. ng o chnh la ng chuan (hnh10.1)

Mat o quang hoc D = lg I0/I

Nong o C Hnh 10.1: S phu thuoc cua mat o quang dung dch vao nong o (ng chuan) e ve ng chuan tren giay milimet, ngi ta at tren truc hoanh cac gia tr nong o cua DD chuan, tren truc tung cac gia tr mat o quang cua chung. Sau o, t cac iem tren hai truc, ke cac ng thang vuong goc vi tng truc roi noi cac giao iem cua chung lai vi nhau.

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