Sách “Hóa Đại cương - Vô cơ (Tập 2 - Sách đào tạo Dược sỹ đại học)” được biên soạn dựa vào chương trình giáo dục đại học của trường Đại học Y Dược Hà Nội trên cơ sở chương trình khung đã được phê duyệt. Sách được biên soạn theo phương châm: kiến thức cơ bản, hệ thống; nội dung chính xác, khoa học, cập nhật các tiến bộ khoa học, kỹ thuật hiện đại và thực tiễn Việt Nam. Nội dung tập 2 gồm có 2 phần, phần 1 sẽ cung cấp những kiến thức về cơ chế phản ứng và các trạng thái cân bằng. Mời các bạn cùng tham khảo.
BO YTE' H011 DAI MING - VO Ca TAR SACH DAO TAO DUQC ST DAI HOC Ma s6: D.20.X.05 ChU Wen: PGS.TSKH LE THANH PHUOC TAN TAO UNIVERSITY LIBRARY NHA XUAT BAN Y HOC 5- 40,1 HA NOI - 2009 CuuDuongThanCong.com https://fb.com/tailieudientucntt A 2011- 61)6q CHI DAO BIEN SOAN: Vu Khoa hoc va Da° tao, BO Y t6 CHO BIEN: PGS.TSKH Le Thanh Phutic NHONG NGUOI BIEN SOAN: PGS.TSKH Le Thanh Phu& TS Le Thi Kieu Nhi ThS Hoang Thi Tuyet Nhung TO CHUC BAN THAO ThS Phi Van Tham TS Nguyen Manh Pha © Ban quyin thuOc Bo Y to (Vu Khoa hoc va Dao tao) CuuDuongThanCong.com https://fb.com/tailieudientucntt LoI GIdI THIEU Thtfc hien mot s6 digu cUa Luat Gido duc, BO Gido due & Dao tao va BO Y t6 da ban hanh chtiong trinh khung ciao tao Dudc si Dai hoc BO Y to to chfic bien soan tai lieu day — hoc cac mon hoc chuyen mon, co ban chuyen nganh theo chuong trinh tren nham Bing budc xay dung bo tai lieu day — hoc chuan v6 chuyen mon de dam bao chat Wong ciao tao nhan luc y tg Stich "Hod Dai Wong - vo cd Tap 2" duoc hien soan dila tren chuong trinh gido duc dai hoc cUa trtiong Dai hoc Dude Ha NOi, Bo Y to vdi phudng cham: kign thitc co ban, he th6ng; not dung chinh xdc, khoa hoc, cap nhat cac tign bO khoa hoc, ky" thuat hien dai va thiic tin Viet Nam Stich "Hod Dai Wong - vo co Tap 2" db." duoc bien soan bdi cac nha gido giau kinh nghiem va tam huygt cua truong dai hoc DUoc Ha NOi Stich "Hod Dai Wong - vo cd Tap 2" da ducic Hoi dOng chuyen mon tham dinh sach va tai lieu day — hoc cila BO Y t6 th'am dinh vao nam 2008 BO Y t6 ban hanh la tai lieu slat chua'n chuyen mon dg sti dung cho nganh giai doan hien Trong 411a trinh sii dung sach phai duoc chinh 1Y, 136 sung va cap nhat Bo Y to xin than cam cac Nha giao, cac chuyen gia caa trucing Dai hoc Duoc Ha NOi da clanh nhigu ding sic hoan clan sach, cam on GS Dam Trung Bao va PGS.TS NO Si Luong da phan bien de cu6n sach sdm hoan kip thai phuc vu cho tong tac dao tao nhan 1iic y tg Vi Ian dau xuat ban, thong toi mong nhan &toe y kign dung gop cua dOng nghiep, cac ban sinh vien va cac dOc gia d6 Ian xuat ban sau chtoc hoan thien hon VU KHOA HOC VA DAO TAO BO Y TE CuuDuongThanCong.com https://fb.com/tailieudientucntt Tlap C1-6m phan: Ph'An I CO CHE PHAN (ING VA CAC TRANG THAI CAN BANG g6m chuong: T6c va cci the phan iing — Can bang hod hoc/Si hinh va cac tinh chat cila dung dich/Dung dich chat dien ly/Phan 1.tng oxy hod khii va dOng dien PhAn II HOA HOC VO CO gem 10 chtiong, trinh bay moi lien quan gifiia cau tao va di-1h chat cac nguyen to va cac hop chat vo co; vai tro va doc tinh cila cluing sinh quyen va nhung ling dung Y-Dtioc Tap nham ginp sinh vien thuc hien muc tieu va muc tieu CuOi Tap c6 kern theo cac phu luc de nguai doc tien tra ciiu nhieu hang s6, dai hiong hoac khdi niem thttong clang Hod hoc eu soan, van Chung t6i rat mong nhan duoc Sr kien dong k gop va phe binh cUa cac do'ng nghiep, sinh vien va ban doc de lan xuat ban sau tai lieu c6 chat liking cao hon Trong qua trinh Ha NIji, Thang nam 2008 Chez bier' PGS.TSKH LE THANH PHLIOC CuuDuongThanCong.com https://fb.com/tailieudientucntt Tlap C1-6m phan: Ph'An I CO CHE PHAN (ING VA CAC TRANG THAI CAN BANG g6m chuong: T6c va cci the phan iing — Can bang hod hoc/Si hinh va cac tinh chat cila dung dich/Dung dich chat dien ly/Phan 1.tng oxy hod khii va dOng dien PhAn II HOA HOC VO CO gem 10 chtiong, trinh bay moi lien quan gifiia cau tao va di-1h chat cac nguyen to va cac hop chat vo co; vai tro va doc tinh cila cluing sinh quyen va nhung ling dung Y-Dtioc Tap nham ginp sinh vien thuc hien muc tieu va muc tieu CuOi Tap c6 kern theo cac phu luc de nguai doc tien tra ciiu nhieu hang s6, dai hiong hoac khdi niem thttong clang Hod hoc eu soan, van Chung t6i rat mong nhan duoc Sr kien dong k gop va phe binh cUa cac do'ng nghiep, sinh vien va ban doc de lan xuat ban sau tai lieu c6 chat liking cao hon Trong qua trinh Ha NIji, Thang nam 2008 Chez bier' PGS.TSKH LE THANH PHLIOC CuuDuongThanCong.com https://fb.com/tailieudientucntt MUC LUC PHAN I CO CHE PHAN LING VA CAC TRANG THAI CAN BANG Chtecing TO'c dO va cd chg phan ling Can bAng hoa hoc 11 Le Thetnh Phu'dc - Le Kie'u Nhi T6c va co chO phan Ting 12 1.1 Dinh nghia va }Dieu din to-c phan fing 12 1.2 Anh huang dia n6ng den t6c phan iing 15 1.3 Anh Iniang cua thoi gian den nOng de chat phan ling PlutOng trinh 19 t6c tich phan 1.4 Anh huang cUa nhiet den -LOC phan ling 27 1.5 Giai thich cac anh Intang cUa neing va nhiet di) den to-c phan ling 29 1.6 Co the phan ling 34 1.7 Chat xtic tic tit& day to-c di) phan iing 38 Can bang hod hoc 42 2.1 Dai Wong 42 2.2 Phuong trinh ding nhiet Van't Hoff Hang s6 can bang 43 2.3 Hang s6 can bang K va bieu thfic tic dung kho-i Wong Q 47 2.4 Chieu hudng va gidi han cua phan iing 48 2.5 Cac dang cua bieu thlic tic dung khOi luong va hang so- can bang 53 2.6 Giai guy& nhiing van de Binh Wong lien quan den trang thai can bang 55 2.7 Su dich chuyen can bang Nguyen 1ST Le Chatelier 62 2.8 Can bang chuyen hod t6 bao 67 CuuDuongThanCong.com https://fb.com/tailieudientucntt Chito'ng Sy' hinh va cac tinh chat ciia dung dich 70 Le Thanh Phu'ac - Hoeing Thi Tuyet Nhung Nhfing van de chung ve ski hinh dung dich 70 1.1 Dinh nghia - Phan loai 70 1.2 Cac cach bigu thi n6ng.d6 • 72 1.3 Can bang pha 77 1.4 DO tan - Nhcing yeu to anh hang den dO tan dia cac chat 91 Cac tinh chat dia dung dich chfia chat tan khong din ly va khOng bay hcii 106 2.1 Do ap suat hcii cua dung dich DinhluSt Raoult 106 2.2 DO tang nhiOt dO soi dia dung dich Dinh lust Raoult 108 2.3 DO nhiOt dO dung dac dia dung dich Dinh lust Raoult 110 2.4 Ap su'at tham than Dinh it* Van't Hoff 113 Tinh chat caa dung dich cac chat din ly 119, Chafing 123 Dung dich chgt dien ly Le Thanh Phu'dc 1.Trang thai cila chat din ly dung dich 123 1.1 Dinh nghia - Phan loai chat din ly 123 1.2 DO diOn ly (a) 124 1.3 Hang so diOn ly (K) cua chat din ly yeu Dinh lust pha loang cua Ostwald 130 1.4 Hoat dO va hO s6 hoat dO 132 Thuye't acid — base 140 2.1 Thuye't Arrhenius (thuye't din ly H+, OH-) 140 2.2 Thuyk Bronsted - Lowry (thuyel proton) 141 2.3 Thuye't Lewis (thuy6t electron) 144 S4 din ly Thang pH dia Sorensen 146 3.1 Ski din ly caa ntioc 146 3.2 Thang pH 147 CuuDuongThanCong.com https://fb.com/tailieudientucntt Can bang acid — base 150 4.1 Su dien ly cua cac acid yeti 150 4.2 Su dien ly dia cac base yeu 151 4.3 Quan he gifia Ka va Kb clia mot cap acid - base lien hop 153 4.4 Su dien ly dia acid, base cia chiic Chat luring tinh 153 4.5 Cach tinh pH mot s6 dung dich 157 5: Dung dich dem Chat chi thi pH 165 5.1 Dung dich dem 165 5.2 Chat chi thi acid — base 175 Can bang dung dich dia chat dien ly it tan Tich so- tan 178 Phan ling dung dich dien ly 187 Chuang 10 Phan ifng oxy hoa khif va clong dien 191 Le Themh Phu'dc Phan iing oxy hoa khii Khai quat ve pin dien h6a 191 1.1 Khai niem chung 191 1.2 So- oxy hoa (S.0) 193 1.3 Can bang phan ling oxy hoa khii 194 1.4 Khai quat ve pin dien hoa 198 Pin Galvanic 199 2.1 Cau tao, hoat dOng va so d6 pin Galvanic 199 2.2 Dien the: san pha:m ciia pin Galvanic 202 Nang luong tu Gibbs va cong dien 211 3.1 Dien the pin chuan va hang so- can bang 211 3.2 Anh huang cua n6ng d6 den dien the dia pin Phtiong trinh Nernst 214 3.3 Dien the cilia pin va moi quan he gifia Q va K 219 3.4 Pin n6ng d6 va n6ng d6 220 Pin Galvanic va van dung thiic t6 223 4.1 Acquy 223 4.2 Su an mon kim loaf: van de moi truang cua dien hoa 226 CuuDuongThanCong.com https://fb.com/tailieudientucntt Nhung not dung cila chtiong se cho phep xac dinh hai thong tin tiep theo ToC DO VA CO CHg PHAN fiNG 1.1 Dinh nghia va bieu din Vic phan ling • Tdc dO phdn zing la sti bien doi niing cua chat dciu hay san phei'm mot don vi thdi gian: + C2 - C I t - t1 + AC — At (7-1) day, V IA tec dO trung binh khoang thai gian tit t1 den t2; AC IA su bien doi n6ng dO mol/L cna chat dau hay san phAm tit C1 den C2; vi tO-c dO IA dai lacing khong có gia tri am, nen dau + itng v6i viec xac dinh t6c theo sit Eden d6i n6ng san phAm, dau - itng voi chat dau Khi At —> 0, phtiong trinh (7-1) cho t6c dO titc thai: V = +dc dt (7-2) Doi voi mot phan ling bat kST, chang han: aA + bB —> eE + fF a, b, e, f IA cac he s6 tST Wong phuong trinh hoa hoc, thi tec dO phan ling dttoc xac dinh bang he thfic: V dc A adt dC B bdt dc E edt dc F fdt (7-3) Chu 51: Don vi thai gian tee dO phan ling the IA giay (s), phut (min), gia (h), (d) hoac thong, nAm Theo do, t6c dO co this nguyen IA mol/Lgiay (hoac mol.L-1.s4); mol/Lphnt (hoac Gia tri cua V phu thuOc vao viec quy ve chat nao (trong pinking trinh hod hoc) de tinh: chat có he s6 ty Wong Ion, gia tri bang s6 cila V cang 16n • Vi du ve' ccich xac dinh tdc de): phcin zing theo thai gian Xet phdn zing thuCin nghich d pha gia'a ethylen va ozon (kw khoi quang hoci, gay o nhijm tit giao thong a pho): C2H4 (k) + 03 (k) C2H4O (k) + 02 (k) Tit he s6 tY' Wong cho thay n6ng caa hai chat dau giam xueing voi t6c dO nhu nhau: 12 CuuDuongThanCong.com https://fb.com/tailieudientucntt Chu'cing 16 Nguyen to nhom IV 300 Pb 300 Nhom IVA: C - Si - Ge - Sn — Nhom IVB: Ti - Zr — Hf 322 Chu'cing 17 Nguyen to nhom V 325 Nhom VA: N - P - As - Sb - Bi 325 Nhom VB: V - Nb - Ta 345 Chu'cing 18 Nguyen to nhom VI 347 Nhom VI A: - S - Se - Te - Po 347 Nhom VIB: Cr - Mo - W 373 Chu'o'ng 19 Nguyen to nh6m VII 380 Nhom VIIA (cac halogen): F - Cl - Br - I — At 380 Nhom VIIB: Mn - Tc - Re 395 Chu'cing 20 Nguyen to nhom VIII 400 Nhom VIVA (cac hi6m): He - Ne - Ar - Kr - Xe - Rn 400 Nhom VIIIB: Fe - Co - Ni / Ru - Rh - Pd / Os - Ir — Pt 403 Teti lieu tharn kheto 421 10 CuuDuongThanCong.com https://fb.com/tailieudientucntt Ong dung quan hang Tau ciia pin n6ng de la de n6ng chiia biet, chang han tim [H+] (hoac pH) Gia sii ta tao pin neng di a tren niia phan ling H2 /H+, catod la dien ckic hydro chud.n va anod la niia pin Wong tki tri [H+] chiia biet dung dich Cac niia phan ling va phan ling tOng la: [anod] H2 (k; latm) > 2H+(aq, chiia biet) + 2e 2H+(aq, 1M) + 2e -> H2(k, latm) [catod] 2H+(aq, 1M) > 2H+(aq; chiia biet) E°01, = Epin= • Ap dung pinking trinh Nernst ta c6: E pn = E°.i n 0,0592 1g [H+ ]21nrabi6 ' -0 [H]2n.A.(=-1M) 0,0592 lg[H+ 12htabia = -0,05921g[H+1-chisabia Vi pH = -1g[H±], nen E pin = 0,0592pH Vay, Eon, tim dtioc pH Trong phep pH thong thang, -met pin n6ng dO gem dien clic hydro la qua tong kenh va kho bap quail tri Thay va.o d6, vie-d pH chicle thkic hien 136i may pH van hanh ttiong to nhii met may the Hai dien ckic may do.pH duoc nhung chim dung dich kiem nghiem Met dien clic vdi vai trO chi thi c6 ten la dien clic mang thiry tinh duoc sii dung reng rai nhat hien nay; no chiia ram phan Ting Ag/AgCl ngam dung dich HC1 en Binh (thang c6 n6ng 1,000M) va Wan kern mang m6ng bang thiry tinh dac biet c6 tra khang cao, nhay cam vdi ski c6 mat cila ion 11+(aq) Dien ckic 'al vdi vai tro dei chieu co ten la dien cue calomel g6m mot day Pt nIning chim Hg2C12 (calomel), Hg(1) va dung dich KC1 bao hOa Met pin v6i dien ckic nhu vay c6 the mo ta theo so de: Ag(r) I AgCl(r), HC1 (aq; 1,000M) I Mang thily tinh I Dung dich [W] = ? I I KC1 (bao Ilea) I Hg2C12 (r) I Hg(1) I Pt Dien cue mang thily tinh se chi thi [W] dung dich kiem nghiem lien he vdi [H4 ] co dinh ben (xem nini dien cuc hydro tao nen met dien the) va may se quy dei sii chenh lech v6 dien the giila dien cuc pin ve pH r6i chi gia tri cu the tren thang pH ciia may) 222 CuuDuongThanCong.com https://fb.com/tailieudientucntt [Dien cult thay tinh dung pH chi la mot dang cua dien clic ion dac hieu (hay ion chon loc) Khi sit dung cac loai thy tinh có phdn dac biet va cac vat lieu tao mang xac dinh, nguOi ta da tao nhiing dien cuc chon loc de ang dO mot ion cu the rat dac hieu Chang han, da có cac dien clic dac hieu cac ion: NH3/NH4+; CO2/HCO3-; F-; Br-; I-; NO3-; K+ Mat khac, de thuc hien cac sieu vi phan tich, nguai ta da the tao cac vi dien cult voi kith tint& het sic nhO (thiOng kinh tit 0,1 den 0,5um) có the choc qua mang mot to bao de dien the mang hoac nOng cac ion] * T6m tett muc 10.3: Hai tieu chi cila su tit phat AG < va Epin > có quan he AG = -nFEpin AG ciia phan lung pin dai dien cho tong dien lon nhat ma pin có the lam ditOc Bien thien nang Wong Gibbs chuan AG° có quan he voi E'pin va K nen có the dung E°pin de xac dinh K O dieu kien khong chuan, Epin phu thuOc vao Vpin va vao s6 hang chila Q Epin cao Q nhO ([CD] lon) va giam pin hoat Ong CS trang thai can bang, Q = K, vi the ca AG va Eon = Pin ang dO chi sii dung niia phan Ting xac dinh nhung dung dich a niia pin có ang dO khac Pin ang dO nguyen 151 hoat dOng dien cua to bao Dien clic ion dac hieu, nhu dien clic pH chang han, dung cu hohn hd.o de xac dinh cac eau tit PIN GALVANIC VA VAN DUNG THUG lig 4.1 Acquy - Acquy la mot tap hop pin Galvanic hoan chinh, theo day [(+)-(+)-(+)(+) ] Tuy nhien, thong thttang có the sii dung pin galvanic rieng le Acquy la mot sang the tai tinh: dung dich pin duoc thay bang chat ran nhao, ho bOt hay bun dac cua cac chat Do n"Ong cua chUng -Lacing dos'i on dinh gi6ng nint cac chat ran, nen dien the khong giarn nhanh pin hoat dOng ma tri thai gian kha dai Co vai loa.i acquy Acquy sd cap la loai khong the nap dien lai, no bi thai loai "chet" - lac cac chat phdn dat toi trang thai can bang v6 ang Acquy chuyin hoa loai có the nap them dien nang de dao ngucic phan Ting pin, tai tao lai cac chat ddu Noi cach khac, voi loai acquy nay, pin Galvanic có the chuyen pin dien phan Pin nhien lieu hay acquy king sit dung phan itng chay de sdn xuat d*/ nang, nhitng khong du till dlioc dien nang Sau day la chi vai vi du v6 cac loai acquy 223 CuuDuongThanCong.com https://fb.com/tailieudientucntt - Acquy sd cap: + Pin kit& goi la pin Leclanche Anod Zn có clang mat binh chaa hon hop Mn02 va chat muoi acid (g6m NH 4C1, ZnC12, H2O va tinh bat) Catod la thOi graphit dat vao han hop Cac phan itng pin: Anod (oxy boa): Zn(r) > Zn2 + (aq) + 2e Catod 2MnO2(r) + 2NH4+(aq) + 2e-*Mn203(r) + 2NH3(aq) + H20(1) Zn2+(aq) + 2NH3(aq) + 2C1-(aq) —> Zn(NH3)2C12(r) Phan ling tang: 2Mn02(r) + 2NH4C1(aq) + Zn(r)-+Zn(NH3)2C12(r) + Mn203(r) + H2O Epin=1,5V Pin kho la vat dung quen thuac dung cho dai, den pin, choi Thuan loi vi an toan, nhieu kich ca, re Bat loi tuai tho thap (vi Zn phan itng vdi NH4+), not tiep pin de sit dung clang dien cao thi NH3(k) tang len, lam giam dien + Pin ki6n, pin kilo difoc cai tien, "dung dich" dien phan la h6 KOH, khong có tao nen gift duoc then dp hang dinh Cac phan -tang pin: Anod (oxy hoa): Zn(r) + 2014-(aq) —> ZnO(r) + H20(1) + 2e Catod Mn02(r) + 2H2 0(1) + 2e > Mn(OH)2 (r) + 201-1-(aq) Phan iing tang: Zn(r) + Mn02 (r) + H2 0(1) —> ZnO(r) + Mn(OH)2(r) Epin=1,5V Nhuoc diem chinh cila pin la dat + Pin bac va pin thety ngan: pin giang pin kho - kiern, deu dung Zn lam anod; mat chlia HgO, that chlia Ag20 vat thing bang thep lam catod Chat phan ling ran ep vao KOH va giay am dtioc dung nhu cau muai Pin Hg dung van hanh clang h6, may tinh Pin Ag dung cho may trd tim, may quay, may thu phat tin hieu cap citu Ca có uu diem la nh6, nhieu dang hinh (m'Ong, trop, khuy ao ), dien the pin lon; pin Ag on dinh va khang dac hai nhiing dat Pin Hg sau sit dung có the giai phong Hg rat dac 224 CuuDuongThanCong.com https://fb.com/tailieudientucntt Cac phan ling pin nln.i sau: Anod (oxy boa): Zn(r) + 2011-(aq) > ZnO(r) + H2 0(1) + 2e Catod (Hg,khii): Hg0(r) + H2 0(1) + 2e > Hg(1) + 2011- (aq) Catod (Ag,khii): Ag20(r) + H20(1) + 2e -> 2Ag(r) + 2011-(aq) Phan ling tong trong: Pin (Hg): Zn(r) + Hg0(r) -> ZnO(r) + Hg(1) Epin=1,3V Pin (Ag): Zn(r) + Ag20(r) -+ ZnO(r) + 2Ag(r) Epin=1,6V - Acquy chuyen hoa + Acquy chi acid 12V g6m pin ket not day, m8i pin 2V M6i pin chila hioi chi boc voi vat lieu dien chic va nInIng dung dich dien ngan de ngat phan H2SO4 4,5M Cac mieng chat deo gifia cac mach gifia cac pin Pin phat dien nang voi vai trO pin Galvanic theo cac phan ling: Anod (Ox): Pb(r) + S042-(aq) -> PbSO4(r) + 2e Catod (Kh): Pb02(r) + 411+(aq) + S042-(aq) +2e > PbSO4(r) + 2H2 0(1) Phan ling tong: Pb(r) + Pb02(r) + 2H2SO4(aq) -p 2PbSO4(r) + 2H2 0(1) Epi„ = 2V Khi pin Wan het nang Wong tai Gibbs (het dien nang), no có the nhan nang hiOng dien tii ben ngoai (nap dien) de cac niia pin va phan ling pin dao ngtioc: 2PbSO4(r) + 2H20(1) —> Pb(r) + Pb02(r) + 2H2SO 4(aq) Acquy chi cung cap Wong dien ion d6n.g cac dOng cd (oto), on dinh, tu6i tho cao Tuy nhien, khong the nap dien lai (sac) dtioc nhieu lan (do PbSO bi giam) va có nguy cd ve sv an toan (khi sac dien^phai d6 them milk va ntioc de bi dien phan tao 02 va H2 Luc dung lai de Ong may moc, kill no va ban H2SO4 tung toe) Mat khac, acquy bi thai loci se thia vac) moi trithng mot luting lon chi gay d6c, neu khong có cong nghe thu h6i sach + Acquy Ni-Cd: dung dich dien phan la KOH hoac NaOH, ydi cac phan ling: Anod (Ox): Cd(r) + 2011-(aq) —> Cd(OH)2(r) + 2e Catod (Kh): 2NiO(OH) (r) + 2H2 0(1) + 2e -+ 2Ni(OH)2(r) + 2011-(aq) Phan ling tang pin: Cd(r) + 2NiO(OH) (r) + 2H2 0(1) —> 2Ni(OH)2 (r) + Cd(OH)2 (r) Eon = 1,4V 225 CuuDuongThanCong.com https://fb.com/tailieudientucntt Phan ling t6ng se d6i chieu nap dien Acquy Ni-Cd dinag cho den flash, may anh, cac may nhO cam tay Tien loi vi rat gon nhe, nhting Cd bi thai la rat dec hai - Acquy 16ng (pin nhien lieu) cang nhti nhang acquy khac, chat phan ling (nhien lieu) trai qua cac ban phan ling tach biet (nhting khong chay va electron dtioc chuyen qua mach ngoai Chang han, ngon met pin nhien lieu oxy hoa H2 c6 dien ctic bang carbon voi xuc tac kim loai va dung dich dien phan la Na2CO3: Anod (Ox): H2(k) + C032-(1) > H20(1) + CO2(k) + 2e Catod (Kh): 1/202(k) + CO2(k) + 2e > C032-(1) Phan ling t6ng pin: H2(k) + 1/202(k) —> H20(k) Bo, = 1,2V Pin hydro lOng diing cung cap dien va ntioc sach cac chuyen bay vu tru Pin nhien lieu sii dung cac phan ling khac, nhti: 2NH3(k) + 3/202(k) > N2(k) + 3H20(1) N2H4(k) + 1/2O2(k) —> N2(k) + 2H20(1) CH4(k) + 202(k) —> CO2(k) + 2H20(1) Pin nhien lieu /It hieu qua, no chuyen khoang 75% nang ltiOng li8n ket nhien lieu dien (met -Ong cd otos chi chuyen h6a dtioc khoang 25% nang Wong lien ket xang de lam xe chuyen deng): Mat khac, pin nhien lieu sach vi no thai cac chat khong dec NInioc diem dia pin la vat lieu lam dien ctic rat dat Ngoai ra, no khong the du trU nang Wong va chi van hanh vcii sti hiu thong lien tuc cira chat phan ling 4.2 Su an mon kim loai: van c16 m8i trtidng cua dilen hoa - Khong phai phan ling Ox-Kh tii phat Won c6 loi N6 la nguyen nhan cua sub an mon, hien cac kim loai oxyd va sulfid Ditoi day chi neu su an mon Fe, nhting nhi8u kim loai khac nhii Cu, Ag cling bi an mon Gi sat khong phai la san pham true tiep cua phan ling gifia Fe va 02, ma hinh qua met qua trinh dien hoa phuic tap Bang chi:mg la: Fe khong bi gi d nth khong kho (vay can c6 ntioc); Fe khong gi ntiac sach khong c6 khong hoa tan (v43T can co 02); Fe gi nhanh dung dich dien ly va nth c6 pH thap ([H+] cao); sti mat Fe Ira hinh gi thtiong xuat hien a nhting vi tri khac tren cling met vat; va Fe gi nhanh hon tiep xiic voi kim loai kern hoat &Ong hon (nhii Cu), gi cham hon tip xuc voi kim loai hoat deng hon Zn) Nhiing diet' visa ke ro rang lien quan den nhting dac diem dia 226 CuuDuongThanCong.com https://fb.com/tailieudientucntt pin Galvanic CO the viet cac phan iing tao gi sat nhti sau: not Fe tiep roc vOi giot nude, electron bi tach ra: (a) Fe(r) —> Fe"(aq) + 2e Ming anod / qua trinh Ox / Fe bi an mon] Electron di chuyen mieng sat toi gin be mat xung quanh giot nu& co dong dO 02 cao, xay phan (b) 02(k) + 4H+(aq) + 4e > 2H20(1) [virn.g catod-/ qua trinh Kh] Ion Fe" (a) giot nu& ciing tiep xtic voi 02 cho phan ifng: (c) 2Fe2+(aq) + 1/202(k) + (2+n)H20(1) —> Fe203.nH2 O (r) + 4H+(aq) Phan Ung tong: sau nhan vao (a) va lay (a) + (b) + (c) tao gi sit: (d) 2Fe(r) + 3/202(k) + nH20(1) + H+(aq) -*Fe203.nH2O (r) + 4H+(aq) Vdn viet H+ hai v6 phuon.g trinh r6i lai xoa di ngu ST H4 dung vai trO )(tic tac va giai thIch tai gi phat trier' nhanh hon moi trUang pH thap Dung dich dien ly (chang han flint rid& bier') ding tang cuing tao gi vi tang d6 din dien glib \Tung anod-catod a Trang hop c6 cac kim loai yeu-manh khac tiep xuc vOi Fe thi su an mon the gia tang hoac bi ngan than (hinh 10.4) 2Zn [anod] Fe [catod] A Hinh 10.4 Tac dung caa Cu va Zn den stf an man Fe A Sat tiep XCIC vai kim loaf kern hoat Ong hon (vi du nhti Cu), vai trO anod clia Fe du'dc tang curing (do tao pin Galvanic Fe-Cu), theo dO sat Pi an mon nhanh han B Sat tiep X(JC vai kim loaf haat ddng hon (vi du nhu' Zn), vai tit anod le cua Zn, theo dO Zn bi an mon; ngu'dc laf, sat nguyen yen (cludc Pao ye) Kh6ng am luon lam cho be mat cac vat the kim loai ton tai mit lop nu& mOng Lop milk hOa tan cac klif 0O2, C12, HC1, NO2, S02 có quyen va tra dung dich dien ly Be mat kh6i sat thtiOng chfia cac tap chat la nhiing kim loai kern hoat d6ng lion (Cu, Pb, Sn, ) va "ngam" dudi lop mOng dung dich dien ly se tao nen vo s6 cac vi pin Galvanic ma Fe la anod, 227 CuuDuongThanCong.com https://fb.com/tailieudientucntt d'an den an mon va pha hay kim loai (hinh 10.4A) De bao ve cac cgu true Fe, ngiidi ta boc, lot, ma hoac gan them vao chung nhcing kim loai hoat Tang hdn (Zn, Mg, Al) lam "vat by sinh" theo cd the a hinh 10.4B Mg va Al hay thicic dung vi cluing hinh mot 16p v`O oxyd lam ch'am qua trinh an mon chinh Con co cac bin phap khac de phong va - ch6rig an mon cac kim loai voi nguyen t ic chung la each ly chung khOi mai truing xung quanh (bed dau ma, scn, ma, trang men ) hoac tao cac hop kim ch6ng gi PINN PHAN: STY DUNG NANG LUNG DIEN DE DIEDKHIEN PHAN DUNG KHONG Tip PHAT 5.1 Nguyen 1ST va hoat dOng cua mot pin dien phan nhiing phLi tren chUng ta not ve pin Galvanic, phan Ting tti phat tao nang Wong dien Nguyen ly dia pin dien phan thi ngLioc lai: nang lddng dien tii mot ngu6n ben ngoai dieu khien mot phan -tang khong tti phat Hinh 10.5 minh hoa cu the boat do, ng dm loai pin qua cac nfia phan Sn va Cu Von ke 0.48 V Catod (+) A nod (-) Cau mue) i Sn Cu Sii! A Nit'a phdn zing Ox: Sn(r) Sn'(aq) + 2e Ntl'a phcin zing Kh: Cu'(aq) + 2e - Cu(r) Phdn zing tong:Sn(r) + Cu2+(aq) Sn2+(aq) + Cu(r) E°pi„ = 0,48V va LIG° = -93 kJ B Niect phdn zing Ox: Cu(r) Cu2+(aq) + 2e Nita phdn zing Kh: Sn+(aq) + 2e Sn(r) Phdn ang tong: Cu(r) + Sn2+(aq) -)Cu"(aq) + Sn(r) E° i„ - 0,48V va 4G° = +93 kJ Hinh 10.5 Phan zing Thie'c-D6ng dva tren cd sC) c5a pin Galvanic (A) Ira pin c1iOn phan (B) 228 CuuDuongThanCong.com https://fb.com/tailieudientucntt Chu ST rang, pin dien phan ciing nhti pin Galvanic, s1.1 oxy h6a van xay c3 cuc anod va ski WI d cue catod, nhting da./u cua cac dien cue ngtioc O pin Galvanic, cac electron "san c6" d anod Sn nen no am Tron * g pin dien phan, electron den tit nguen ngoAi nen Sn dong vai tro catod (nhan electron) va IA cue am Bang 10.3 tang ket.lai cac qua trinh \TA &Au hai loai pin dien boa Bing 10.3 So sanh pin Galvanic va pin diOn phan Loai pin AG Dien cktc Epin Ten Qua trinh Dau Galvanic 0 Anod Oxy hoa - Galvanic 0 Catod Kher + Dien phan >0 0 C12(k) + 2e -E° = -1,36V 231 CuuDuongThanCong.com https://fb.com/tailieudientucntt Do qua thg 0,6V nen the can thik de tao am hOn mot chit so vdi C12, vi vay C12 dude giai phong (chic khong phai 02) Cul tie-p tue each xem xet nhti tren, ngt.tai ta nit mot so ke't 1u4n hau ich dien phan cac muol dung dich 1/ Cation ciia kim loai kem boat &Ong bi khii kim loci, bao g6m Au, Ag, Cu, Pt va Cd 2/ Cation ciia cac kim loai rat hoat Ong khong bi khii, bao gom cac nguyen to IA, IIA va Al Thay vao do, nuoc bi khii H2 va OH- 3/ Cac anion bi oxy boa, qua the ma khong tao 2, bao g'6m cac halogenid ([Cl-] phai cao), trif F- 4/ Cac anion khong bi oxy boa Om F- va cac anion phlic tap S042-, C032-, NO3- va P043- vi cac oxoanion chfia phi kim d trang thai oxy hoa cao nhat Thay vao do, ntioc bi oxy hoa 02 va H 5.3 Quan he dinh hicing gifta dien tich va san ph'Arn Dinh lulat Faraday D*-1 tich quay \Tong binh dien phan tao san pham d cac dien Khi dien phan NaC1 nong chay, ngu6n dien cung cap electron cho catod de), Na+ nhan e va tra Na kim loci Cung inc do, e bi keo khOi Cl- va tra C12 Ro rang, cang nhieu e ma Na+ nhan va Cl cho thi kho'i Wong Na va C12 tao cang lon Quan he Ian dau tien di.toc Faraday xac dinh qua thtic nghiem va dtioc goi la dinh luat Faraday: Lacing chat xuat d moi dien cite ty le thutin vdi dieter, tich chg.), qua binh dien phan phan iing da can bang chi ro so mol cila chat phan iing, s6 mol electron va so mol cua san pham sti chuyen Ma., do no mang nhfing thong tin can thie't de gidi dap cac cau hoi "bao nhieu san pham vat chat ditoc tao vdi mOt tong then tich nhat dinh", hoac ngitoc lai "can bao nhieu dien tich san xu'at mot Wong vat chat an dinh tnioc" De ap dung dinh luat Faraday, ngliai ta tign hanh cac bride tinh toan: Tim s6 mol electron can cho moi mol san pham; diing s6 Faraday IF = 9,65.104C/mol e de tim dien tich -Wong ling (C) va khea Wong mol de tim dien tich oan cho mot kho'i Wong san pham cho truck Chting ta khong the dien Wong trvc tie'p ma coring dO dung dien: dien long (Wong dien tich chuyen qua don vi thai gian Don vi SI ciia Wang dO dung dien la Ampe (A) &toe dinh nghia la 1C chuyen qua tigt dien ls: lA =1— s Do do, curing dO dong nhan vdi thoi gian cho di.01 Wong: 232 CuuDuongThanCong.com https://fb.com/tailieudientucntt A.s =- —.s -= C Vay, mu6n biet dien Wong thi cuOng d6 dung cling vdi thai gian ma dung dien chay qua Ngu6c lai, dien l-ong lai lien quan den s6 mol va kh6i long san pham tao T6m lai, cac bai toan tren dinh luat Faraday thttong hdi each tinh cliang d6 dOng, khol luting vat chat hoac thoi gian Lai gidi railm d neta phcin ling VI du, can bao nhieu dien tich de tao 4,0g C12 (k) to phan Ting dien phan dung dich NaCl? Giai bang each viet nita phan Ung: 2C1-(aq) > C12(k) + 2e Mat 2mol e de tao mol C12 (k), nen dien tich can la: Dien tich (C) = 4,0gCI,x lmo/C/2 2mol e 9,65.104 C x =1,1.104 C 70,79gCl, lmoICI, lmole Xa hdn, c6 the hOi tiep: mat bao nhieu lau de tao Wong C12 neu ngu6n ngoai cung cap dong dien 12A Giai bang pile') tinh sau: Thai gian (s) = di e• ntich(C) is =1,1.10 Cx =9,2.102 s dong(AhayC/s) 12C 15 phut * Tom kit muc 10.5 Pin dien phan dung nang king dien de tien hanh cac phan -tang khong tai Oat Sti oxy hoa van xay rad anod va su khii van xay rad catod, nhung dien tich tren cac dien cue la trai dau vdi pin Galvanic Khi san pham c6 the tao m6i dien cue, chat nao de oxy hoa hdn se phan -Cing d anod va de Mail lion se phan ling catod-dieu c6 nghia la naa phan tiing nao c6 E° It am hdn (nhieu duong lion) se xay Su kfai hoac sill oxy hoa nu& xay rad dieu kien khong chuan Qua the gay dien the thuc to cao hdn mong mu6n va có the anh huOng toi san pham tao rad dien ctic Ltfong san pham tao phu thu6c vao luong dien tich chuyen qua binh dien phan, no lien quan den d6 lon cua atOng d6 dOng va thai gian chuyen Cac he th6ng Ox-Kh t6 bao sinh vat vdi su ket not gifia pin n6ng d6 Galvanic va pin dien phan c6 vai tro chuyen nang 'Along lien ket Ur& an dien nang va sau nang 'Along lien ket ATP (xem tiep muc sau) 233 CuuDuongThanCong.com https://fb.com/tailieudientucntt NANG LONG TRONG HOA SINH Trong hdu het cac to bao song, nhitng nguyen 1ST cila pin dien hoa duoc sit dung de san xuat nang luting Nang Wong lien ke't thiic an duoc dung de sinh the dien boa, sau d6 the lai ditoc dung de tao nang Wong lien ket- phan tit giau nang Wong ATP Cac phan tii OxKh hoan cac took tao nen chit& van chuyen electron (CVCE) nam tren mang cua ty the - mot cau true vi the san xugt nang Wong cho to bao CVCE mot chu8i cac phan tit lon (hau het la protein), in& Phan tit chila cap Ox-Kh, nhu Fe2+/Fe3+ chuyen electron theo Tai diem doe theo chuoi, sii chenh lech dien the duoc sit dung a bien de4 ADP ATP Nang Wong lien ket the dien hoa Cac to bao dung nang Wong thiic an bang each giai pilling no tit/1g buck duoc kiem soat chit khong phai tat ca ding mot Thay cho H2 khong ton tai co the, hydro chuyen 2H+ va 2e Wit tac nhan oxy h6a sinh hoc c6 ten la NAD+ (nicotinamid adenin dinucleotid) tiep nhan chUng qua trinh oxy h6a cac phan tii thiic an Nita phan "tang la: NAD+(aq) + 2H+(aq) + 2e NADH(aq) + 11+(aq) chuyen 2e toi cap Ox-Kh dau tien Tai mang ty the, NADH va cua CVCE va tach proton Tit day, cac electron duoc van chuyen theo chu6si cac cap Ox-Kh, cuo'i cung chUng khit toi H2O Toan IDO qua trinh vdi cac the dien Ctic chuan la: -E°' = 0,32V NADH(aq) + fr(aq) —> NAD+ (aq) + 2H+(aq) + 2e E' = 0,82V 1/202(aq) + 2e + 2H+(aq) > H20(1) Phan ling tang: NADH(aq) + H+(aq) + 1/20 (aq) -> NAD+(aq) + H2 0(1) E'toan bo = 1,14V la dung cho cac he thong sinh hoc vi cac trang thai chuan c6 (1ky hieu tinh den pH = 7, [W] = 1.10') Vi vdy, mol NADH di vao CVCE, nang Wong to Gibbs Wong ling vOi 1,14V c6 gia tri tinh theo phuong trinh (10-11) la: AG°' = -nFE" = -2mol e x 96,5 kJ/V.mol e x 1,14 V = -220 kJ/mol NADH 234 CuuDuongThanCong.com https://fb.com/tailieudientucntt Chitc nang cila qua trinh ttiOng to pin Galvanic Met phan iing to phat (khil 02 toi H2 O) duoc sit dung de sinh dien the Khac voi pin Galvanic phong thi nghiem, ca qua trinh chi xay buoc, qua trinh t6 bao xay nhigu buck nhO Hinh 10.6 la so d6 don gian cUa budc chi ch6t CVCE san sinh dien the cao cho san xuat ATP [trong to bao, moi bulk nhu d so d6 có vai chat vOi tang kho'i luong phan tit khoang 1,5.106 dv12 C] 'Tau het cac chat phdn CVCE protein chiia sat va phan iing Ox-Kh thuc su diAn nhO su chuyen doi gifia Fe' va Fe' Cac chat van chuyen electron CVCE trai qua su oxy hoa va su khii cluing chuyen electron doc theo chai Tai diem cho thay su chenh lech vg the 0' va AG' la dU lon dung cho san xuat ATP (Q = phan tit huu co 18n; Cyt = cytochrom, nhung protein chlia met cap Ox-Kh ion kim loci, nhu Fe'/Fe3+ de chuyen tai electron) • O Q bA bA z Deng electron ye.0 chuoi van chuydn electron (CVCE) - The dien hoa nang luring lien ke't Tai diem chi tren hinh 10.6, su chenh lech the dude sit dung de digu khien phan itng tao ATP khong to phat: AD133-(aq) + HP042-(aq) + H+(aq) —> ATP4-(aq) + H20(1) AG" = + 30,5 kJ/mol Chu Y rang, gia tri AG' a diem de san xuat ATP la vtfOt qua nang ltiOng Hinh 10.6 NhCing chat chO 235 CuuDuongThanCong.com https://fb.com/tailieudientucntt ttt can thiet Den day, cluing to da theo clOi qua trinh chuyen electron qua cac phan cua CVCE, nhting cac proton &toe giai phong di dau? Cau tra lOi se la diem mau ch6t cua viec dien nang chuyen nang hiong lien ket nInt the nao Khi e chay qua va cac cap Ox-Kh thay doi s6 oxy hoa, nang ltiOng tit giai phong blioc chi ch6t daoc clang de day cac ion FT+ yang mang gifta ty the, lam cho vi ng [H+] cao hon yang not ty the, theo pin niing hinh ben mang Khi su chenh lech [EP] dat khoang 2,5 lan, mang tit &Ong ma kenh cho cac ion H+ trail lai not 'ty the Nang Wong tki giai phong qua trinh tu phat se dieu khien sit tao ATP khong tit phat (nhtt phan ang da viet tren) Vay la, ty the da sit dung "laic chuyen- &Ong electron" caa cac cap Ox-Kh teen mang de tao "lilt chuyen Ong proton" qua mang, chuyen sti chenh lech dien the a pin n6ng nang Wong lien ket Qua trinh mo to teen chtoc minh hoa a hinh 10.7 a Ngoai ty the Mang ngodi Viing mang giCra ang [14-1 cao ++ + IT+ NADH NAD+ ADP + P ATP Nqi ty the [Hi thgp Hinh 10.7 Sy' ket not van chuygn electron Ira van chuydn proton de tong hop ATP Muc tieu cita CVCE la bien dOi nang Wong tit giai phong tit cac phan tit thitc an nang ltiOng tti tich trti ATP Dieu dtiOc hoan bang su van chuyen electron theo chuoi, cac proton clitOc born ngoai not ty the Qua trinh bom tao mot ski chenh lech [H+] va sinh mot dien the qua mang (pin n6ng do) Khi the dat dtioc gia tri kith &Ong, H+ chay ngtioc vao nOi ty the, va nang ltiong tit giai phong se dieu khien tao ATP 236 CuuDuongThanCong.com https://fb.com/tailieudientucntt ... T = 29 8K) T f (iii Ea = 50 kJ/mol) 50 1, 72. 1 0-9 25 °C (29 8 K) 1, 72. 1 0-9 75 7 ,13 .10 14 35°C (308K) 3, 31. 1 0-9 10 0 2, 96 .1 0 -1 8 45°C ( 318 K) 6, 12 . 1 0-9 Du lieu bang 7.4 cho thay, vii Ea = 50 kJ/mol - met... T = 29 8K) T f (iii Ea = 50 kJ/mol) 50 1, 72. 1 0-9 25 °C (29 8 K) 1, 72. 1 0-9 75 7 ,13 .10 14 35°C (308K) 3, 31. 1 0-9 10 0 2, 96 .1 0 -1 8 45°C ( 318 K) 6, 12 . 1 0-9 Du lieu bang 7.4 cho thay, vii Ea = 50 kJ/mol - met... dung phtiong trinh ( 7-3 4), to ( Ea k I -R In -k T2 T1 ( Lb -1 1 ? ?1. s ( 1 -9 L/mol.s 600 K 500 K 1, 10 .1 0-5 = - (8, 314 J/mol.K) in 9, 51. 10 1, 76 .10 5 J/mol = 1, 76 .1 02 kJ/mol 1. 5 Gfai thich cac anh