Welcome!

5/4/2011CAC NGUYEN TO PHAN NHOM VIIA5/4/2011CAC NHAN XET CHUNGTen goi chung: Halogen, gom F, Cl, Br, I va At.Cau truc lp e ngoai cung: ns2np5. Xu hng nhan them 1 e, the hien tnh oxy hoa ac trng, tnh phi kim ien hnh.Tr F, cac nguyen to khac co kha nang tao cac hp chat +1, +3, +5, +7 vi cac nguyen to am ien hn (khong ac trng).T Cl, cac AO d, f t do co kha nang tao lien ket.Tnh Oxy hoa giam dan t F en At (t I a the hien tnh kh).5/4/2011N CHATLy tnhXFClBrIAtTrang thai thngKh vang nhatKh vang lucLong o nauRantm enRanr (Ao)0.640.991.141.33F (EA, eV)3.53.63.53.32.8I1 (eV)17.4212.9711.8410.459.2DAT (o am ien)4.03.02.82.62.25/4/2011Ly tnhXFClBrIAttnc (oC)-219.6-100.1-7.2113.5299ts (oC)-187-34.1558.75184.5411dX-X (Ao)1.422.002.292.67Hpl (kJ/mol)159243199150.7117o (V)X2 + 2e=2X-2.871.361.070.54H% (qua at)2.8x10-22.6x10-28.5x10-54x10-6Vet5/4/20115/4/2011Giai thch cac tnh chatts, tnc thap va tang dan, do lc tng tac phan t X2 trang thai long va ran la lc Van der Waals yeu, tang dan t F en At. Co 2 yeu to anh hng: dX-X tang dan lam o phan cc tang, M[X2] cung tang dan, lc vdw tang.F pha huy nc (tnh oxy hoa rat manh), cac chat khac t tan trong nc (kem phan cc).o ben giam dan (do dX-X tang dan).Rieng F2 kem ben la do cac X2 sau o co s tham gia tao lien ket cua cac AO d, f.5/4/2011Hoa tnhNhn chung cac halogen co tnh oxy hoa manh, phi kim ien hnh, hoat tnh hoa hoc cao.FLa phi kim co tnh oxy hoa manh nhat, oxy hoa c ca kh tr (tr Ne, Ar, He).F2+H2: No manh (ca trong bong toi).Xe+2F2=XeF4, H0298 = -252 kJ/molS+3F2=SF6, H0298 = -1207 kJ/mol2P+5F2=2PF5, H0298 = -3186 kJ/mol5/4/2011Trong kh quyen F2, bong thuy tinh va nc boc chay:H2O+F2 = 2HF+O, san pham tao thanh la oxy nguyen t.SiO2+2F2 = SiF4+2O (cung oxy nguyen t).

Do F2 kem ben, de tao nguyen t hoat ong trong khi cac hp chat cua no rat ben.

Fluor an mon hau het cac vat lieu. Tuy nhien vi Ni va Pb th tao lp muoi ben NiF2, PbF2 bao ve, nen dung ton tr va chuyen ch F2.5/4/2011ClCl cung la phi kim co tnh oxy hoa manh va hoat tnh hoa hoc cao, kem F do phan t ben hn.Oxy hoa trc tiep cac kim loai va phi kim khac (tr O2, N2, kh tr). Tnh kh ch the hien oi vi F, tao ClF.P trang, As, Sbchay trong kh quyen Cl2 am2P+5Cl2 = 2PCl5 (r), H0298 = -463 kJ/molNa, Mg, Fe, Cuchay trong Cl2 khi ot nong2Fe+3Cl2 = 2FeCl3 (r), H0298 = -400 kJ/mol

5/4/2011Vi cac kim loai noi chung phan ng manh liet ieu kien am, vi Cl2 kho noi chung ben, co the bao quan trong bnh thep.Vi H2O tao nc Clo: Cl2 + H2O = HCl + HClODung Cl2 lam chat kh trung v tnh oxy hoa cao.Oxy hoa c nhieu hp chat khac.FeCl2+Cl2 FeCl3KBr+Cl2 KCl + Br2Phan huy, the hay cong vi cac hp chat hu c.Cl2+CH4 4HCl + C (t0)3Cl2+C6H6 C6H6Cl6 (h)5/4/2011Ai lc e cua Cl ln hn cua F nhng tnh Oxy hoa thap hn, do hieu ng nang lng chuyen cua 2 qua trnh.X2 (k) 2X (k)(1)X (k) + 1e X- (k)(2)H (1) + H (2) F = 79.5 332.7 = -253.2 kJ/mol Cl = 121.5- 248.7 = -227.2 kJ/molT o thay F co tnh oxy hoa manh hn, mac du (2) cua Cl thuan li hn, tc ai lc electron ln hn.5/4/2011Br va ICo tnh oxy hoa, nhng khong manh lam. ieu kien thng:Na + Br2 NaBr K + I2 KI Na2S2O3 + Br2+H2O Na2SO4 +HBr H2S + I2 HI + SNhng I a the hien tnh kh yeu: 3I2+HNO3 HIO3 +NO +H2OI2 a the hien tnh kim loai: Mau am, ran, anh kim, tnh kh, co the con ton tai dang I+, I3+ trong dung dch. At a the hien tnh kim loai ien hnh.5/4/2011Cac v du halogen co tnh oxy hoa t manh en yeuPhan ng vi hydro:H2 + F2 2HF G0298 = -273 kJ/molH2 + Cl2 2HCl G0298 = -95 kJ/mol (h)H2 + Br2 2HBr G0298 = -53 kJ/mol (to)H2 + I2 2HI G0298 = +1.8 kJ/mol (to)Phan ng ay:F2 + 2NaCl 2NaF + Cl2Cl2 + 2NaBr 2NaCl + Br2Br2 + 2NaI 2NaBr + I25/4/2011Cl2, Br2 oxy hoa S+2 thanh S+6, con I2 th ch en S+2.5Na2S2O3+4Cl2/Br2+5H2O2NaHSO4 +8HCl/Br 2Na2S2O3+I2 Na2S4O6+2NaITrong phan ng gia nc, Cl2 vi Br2 va I2 th Cl2 oxy hoa c 2 chat con lai: 5Cl2+X2 +6H2O 2HXO3 +10HClI2 phan ng manh hn Br2.Vi H2O, tr F2 phan huy nc, con lai:X2 + H2O HX + HXO H2O+F2 = 2HF+O5/4/2011Trang thai thien nhienF: Fluorit CaF2, Floapatit 3Ca3(PO4)2.CaF2, Cryolit Na3AlF6.

Cl: NaCl, xinvinhit NaCl.KCl, cacnalit KCl.MgCl2.6H2O.

Br, I: Kem theo Cl trong muoi bien, nc khoan gieng dau, rong bien5/4/2011ieu cheNguyen tac la oxy hoa cac halogenua.F: ien phan cac hp chat: K[HF2] nong chay, hon hp eutecti HF-KF, K[HF2] dung dch trong HF long, thu c F2 anod.Cl: Trong cong nghiep ien phan dung dchNaCl, hoac NaCl nong chay. Trong phong th nghiem dung cac chat oxy hoa manh MnO2, PbO2, KMnO4, KClO3e oxy hoa HCl ac, nong.KMnO4 +HCl KCl +MnCl2 +Cl2 +H2OKClO3 +HCl KCl +Cl2 +H2OMnO2 +HCl MnCl2 +Cl2 +H2O5/4/2011Br va I:

Trong cong nghiep dung Cl e oxy hoa Br- va I- trong ruong muoi, muoi mo, nc tro tao, nc khoan gieng dau.

Cl2 + 2X- = 2Cl- + X2Trong phong th nghiem: Dung chat oxy hoa manh.NaX + MnO2 +H2SO4 X2 +MnSO4 + Na2SO4 + H2O5/4/2011ng dungTac nhan lanh Freon CCl2F2 (hien a b cam).

Si teflon chu nhiet, hoa chat (-C2F4-)n.

Hoa chat: HCl, CCl4

Thuoc tr sau: C6H6Cl6 (666)

Thuoc tay, sat trung: javel, clorua voi5/4/2011 CAC HP CHATCAC HP CHAT X-1

Halogenua vi kim loai: NaCl, MgBr2Vi phi kim: PBr5, SF6, SiCl4ac trng lien ket:T ion (vi kim loai kiem, kiem tho) ion-CHT (trong AlCl3) chu yeu la CHT (trong cac lien ket vi phi kim).Cac halogenua cua cung mot nguyen to: o cong hoa tr tang khi so oxy hoa tang.VD: TiCl4 o cong hoa tr > TiCl2 (ion).5/4/2011Cac halogenua ion: Co tnh base va khong b thuy phan.Cac halogenua CHT: Co tnh acid va b thuy phan.PCl5 + H2O H3PO4 + HClCac halogenua base va acid phan ng vi nhau:KF + BeF2 K2[BeF4]KI + HgI2 K2[HgI4]Halogenua + halogen tao polyhalogenua.KI + I2 KI3

Cac hang so ly hoa cua HX.5/4/2011HXHFHClHBrHIH0tt(kJ/mol)-270.9-92.8-34.1+26.6G0298 (kJ/mol)-272.8-94.8-53.2+1.8dH-X (Ao)0.921.281.411.60EH-X (kJ/mol)565431364297tnc (0C)-83.4-114.2-86.9-50.8ts (0C)19.5-85.1-66.8-35.4S 100C, mol/litVHan141512dd HX 0.1 N0.090.9260.9350.9505/4/2011Cac tnh chat Lien ket H-X co tnh CHT co cc va o phan cc giam dan t HF en HI (do chenh lech o am ien giam). Lien ket H-X ben (nang lng ln), giam dan t HF en HI, nen HX ben nhiet nhng giam dan. Giai thch:0.92AO F1.60AO I5/4/2011Do cac orbital tham gia che phu cua X ngay cang ln, nen mat o e chung cach xa nhan.Hieu ng chan tang len.o lech cua am may e ve pha X giam do o am ien cua X giam. HX co tnc, ts thap, tang dan, HF cao bat thng do lien ket hydro tao s lien hp phan t.FHFH134o0.92Ao1.78Ao5/4/2011 HX kh khong the hien tnh acid, tan nhieu trong nc va the hien tnh acid.HX co tnh acid tang dan (dd), do o ben lien ket giam.HF co tnh acid yeu bat thng do:2HF H+ + HF2- , 2 HF mi tao 1 H+. Mat khac do lien ket hydro nen kho phan ly cho H+.

Cac HX co X-1 trang thai oxy hoa thap nhat, nen co tnh kh va tang dan (do ai lc e giam dan).(khong kh) HF HCl HBr HI (manh nhat)5/4/2011Minh hoa:HF va HCl khong phan ng vi H2SO4.HBr+ H2SO4 Br2 + SO2 + H2O (S+4)HI+ H2SO4 I2 + H2S + H2O (S-2)HCl ch b KMnO4, KClO3 oxy hoa, con HI phan ng vi ca FeCl3.FeCl3 + HI FeCl2 + I2 + HClRieng HF phan ng vi SiO2 (kh va dung dch eu c) khac kieng.HF + SiO2 SiF4 + H2OSiF4 + HF H2[SiF6]5/4/2011ieu che HXHF: Phng phap ay duy nhat.CaF2+ H2SO4 HF + H2SO4

HCl: Cong nghiep: H2 + Cl2 HCl Trong PTN: NaCl + H2SO4 Na2SO4 + HCl (to)

HBr: 2P + 3Br2 + 6 H2O 2H3PO3 + 6HBr

HI: I2 + H2S HI + S5/4/2011CAC HP CHAT HALOGEN CO SO OXY HOA DNG

Tao thanh vi cac nguyen to am ien hn (halogen, oxy, nit): +1 en +7.Ban chat lien ket trong cac hp chat nay la CHT co cc.Cac hp chat nay thng t ben. ay tap trung khao sat cac hp chat cua halogen (ac biet Cl) vi oxy.5/4/2011CAC HP CHAT X (+1)Cl2O, HClO, HBrO, HIO, ClO-, BrO-, IO-.

tnc = -1210C, ts = -3.80C, H0tt=76 kJ/mol.Cl2O la kh, khong ben va de phan huy no. No co tnh acid:Cl2O + H2O HClOCl2 + H2O HClO + HClClOCl110o1.7Ao5/4/2011HClO rat khong ben:(h) HClO HCl + O(CaCl2) HClO Cl2O + H2O(to) HClO HCl + HClO3HClO la chat oxy hoa rat manh, dung lam chat diet trung, tay trang:4HClO + PbS PbSO4 + HClHClO la acid yeu (k=4x10-8) yeu hn ca H2CO3Nc javel:Cl2 + NaOH NaCl + NaClO + H2O5/4/2011HBrO, HIO giong HClO, nhng tnh acid yeu hn (k=2.10-11 va k= 4.10-13).HIO a co tnh lng tnh:OH- + I+ HIO H+ + IO-Tom lai:HClO HBrO HIO

Tnh oxy hoa, acid va o ben giam.(V o am ien X giam, r X tang, nen s phan cc lien ket O-H giam, o dai lien ket O-X tang)0.961,71130OHCl5/4/2011CAC HP CHAT X (+3)ac trng la HClO2, va cac muoi clorite.HClO2 rat khong ben: Phan huy ngay trong dung dch, khong ieu che c dang t do.HClO2 la acid trung bnh (k=10-2). Tnh oxy hoa manh nhng kem HClO.

NaClO2NaCl+NaClO3 (to) NaClO2NaCl+O2 (to,xt)

OClO110.5o1.64Ao5/4/2011CAC HP CHAT X (+5)HClO3, HBrO3, HIO3, va cac muoi.

Ben hn HClO, nhng ch ton tai dang dung dch, nong o max 40%, de b phan huy theo phan ng:HClO3 ClO2 + H2O + O2 (oxy hoa rat manh).OClO106.7o1.57AoO5/4/2011Tnh oxy hoa: Mang nhng kem HClO.Tnh acid: Manh hn HClO, c HCl, HNO3.Muoi clorat co tnh oxy hoa manh, b nhiet phan giai phong oxy:2ClO3- 2Cl- + 3O2 (to, MnO2 xuc tac) ClO3- ClO4- + Cl- (to, khong xuc tac)Muoi Bectole: KClO3 (tinh the, t tan) dung lam diem, phao (muoi diem tieu).KClO3 + C KCl + CO2 (to)ieu che: ien phan dung dch KCl khong mang ngan 700CCl2 + KOH KClO3 + KCl + H2O5/4/2011HBrO3 thu c dang dung dch 50%, HIO3 tach ra c dang tinh the ran. ieu che: Cl2 + X2 +H2O HCl + HXO3 Tom lai:HClO3 HBrO3 HIO3

Tnh oxy hoa va acid. o ben .

5/4/2011CAC HP CHAT X (+7)Cl2O7, HClO4, ClO4-, BrO4-, H5IO6 (HIO4.2H2O), IO6-5.

Tao thanh t 2 nhom ClO4 (t dien), ay Cl: sp3 va O: sp2. Cl2O7 la chat long nh dau (tnc=-93.40C va ts= 830C).HClO4 long, khong mau tnc=-1020C va ts=1100C (co lien ket hydro gia cac phan t). Ben hn HClO3, tach c dangHClO4.H2O co tnc>500C Hoat tnh oxy hoa thap hn.OClO 115o1.42AoOOCl 97oOOO1.72Ao5/4/2011HClO4 la acid manh nhat trong cac acid c biet hien nay. ieu che:KClO4 + H2SO4 KHSO4 + HClO4 (700C, 70mmHg) 109o28OClOOO1.42Ao 100oOClOOO1.64AoH1.42Ao5/4/2011Muoi perchlorate ben hn acid nhieu v cac lien ket Cl-O eu c ben hoa nh cac lien ket di ong Ch the hien tnh oxy hoa trong acid manh hoac khi nong chay.

Vi I: H5IO6, IO6-5 ben hn cac hp chat tng ng cua I v at phoi tr cc ai vi oxy. Ion IO6-5 co dang bat dien (nguyen t I trung tam- lai hoa sp3d2).H5IO6 la acid trung bnh.5/4/2011Tom lai:HClO4 HBrO4 H5IO6Tnh oxy hoa va acid. o ben .

HClO HClO2 HClO3 HClO4 Tnh oxy hoa . Tnh acidva o ben . 109o28OClOOO1.42AoOClO106.7o1.57AoOOClO110.5o1.64AoClO1.7Aong thangDang gocDang thapDang t dien5/4/2011Giai thch:So e tham gia tao lien ket va ngay cang nhieu, trong o vai tro lien ket ngay cang tang, lam bac lien ket Cl-O tang (ClO-:1, ClO2-:1.5, ClO3- :1.67, ClO4-:1.75) tang o ben. Tnh oxy hoa giam dan do o ben tang dan.

Tnh acid: So O noi oi vi Cl trong phan t tang, hut e cua O-H ve pha Cl-O, lam tang o phan cc lien ket O-H, dan en de phan ly cho H+, nen tnh acid ngay cang tang.