TRNG AI HOC CONG NGHIEP THANH PHO HO CH MINH KHOA CONG NGHE HOA HOC

&

BAI GIANG

AN MON VA BAO VE KIM LOAI

Ngi soan : ang Kim Triet

TP. HCM, 01-2005

CHNG I

KHAI NIEM VE AN MON KIM LOAI

I. NH NGHA AN MON KIM LOAI VA Y NGHA CUA VIEC NGHIEN CU AN MON KIM LOAI : An mon kim loai la s pha huy kim loai do tng tac hoa hoc hoac ien hoa cua kim loai vi moi trng xung quanh. S gay, t, s xam thc, mai mon, trng n cao phan t khong goi la an mon. S bien dang cua cau truc khi thay oi nhiet o khong goi la an mon. Nghien cu ve an mon la nghien cu xac nh nhng qui luat chung ve s pha huy kim loai do tac dung hoa ly cua moi trng ben ngoai. a so cac kim loai ky thuat khong on nh ve mat nhiet ong. Chung co xu hng b oxy hoa. Xu hng nay c the hien qua nang lng t do khi tien hanh cac phan ng. Nghien cu ve qua trnh nhiet ong cho phep ta ket luan co hoac khong co kha nang qua trnh an mon kim loai. Tuy nhien muon biet c toc o an mon ta phai nghien cu an mon kim loai ngi ta rut ra c cac phng phap tao ra tren be mat kim loai mot ieu kien nao o e giam hay khong xay ra phan ng an mon kim loai ngi ta goi o la chong an mon kim loai. Khi anh gia nhng mat mat do an mon, ngi ta phai khao sat tat ca nhng hau qua do an mon gay ra. Nhng mat mat do an mon co the chia thanh mat mat trc tiep va mat mat gian tiep. An mon kim loai gay ra nhng thiet hai vo cung nghiem trong v the nghien cu ve an mon va chong an mon kim loai la cong viec het sc quan trong trong tat ca cac lnh vc khoa hoc ky thuat khac nhau. II. PHAN LOAI CAC QUA TRNH AN MON KIM LOAI : Co nhieu cach phan loai cac qua trnh an mon kim loai. Thong thng co 3 cach : 1. Phan loai theo c che cua qua trnh an mon : Theo c che cua qua trnh ngi ta chia ra lam hai loai an mon hoa hoc va an mon ien hoa : a. An mon hoa hoc : An mon hoa hoc la qua trnh an mon do tac dung hoa hoc gia kim loai vi moi trng. Th du : tng tac gia kim loai vi moi trng long khong dan ien, hay cac kh kho.

b. An mon ien hoa : An mon ien hoa la qua trnh an mon do tac dung ien hoa hoc gia kim loai vi moi trng phan ng ien hoa, no tuan theo qui luat ong hoc ien hoa. An mon ien hoa xay ra 2 qua trnh ong thi. - Qua trnh anot la qua trnh bien oi trc tiep kim loai thanh ion hydrat hoa trong dung dch. Me + xH2O Me (H2O) n+ + ne x Trong kim loai con mot lng tng ng cac electron d tha. - Qua trnh catot la qua trnh lam cho cac electron d qua trnh anot b ong hoa do mot vai chat nhan electron, c goi la chat kh phan cc. Nghien cu chi tiet c che qua trnh an mon hoa hoc va ien hoa hoc cho thay khong co ranh gii phan biet ro net gia chung. Trong nhieu trng hp, s bien oi cham t c che hoa hoc sang c che ien hoa co the xay ra va ngc lai. S an mon trong dung dch ien ly co the xay ra theo ca c che ien hoa lan c che hoa hoc. 2. Phan loai theo ieu kien cua qua trnh an mon : - An mon kh quyen la an mon kim loai trong kh quyen hay cac kh am t khac. - An mon trong chat ien ly (axt, baz, muoi) - An mon di at ngha la an mon cac cong trnh ngam di at. - An mon ien gay ra di tac dung cua dong ien ngoai hay cac dong lang thang. - An mon di tac dung cua ien the gay ra do tac dung ong thi cua moi trng xam thc va cua ien the tren kim loai. - An mon sinh vat hoc va an mon gay ra do cac vi sinh vat hay san pham chuyen hoa cua chung. c. Phan loai theo dang ac trng cua an mon : - An mon toan bo xay ra tren toan bo be mat kim loai, no co the eu an hoac khong eu. - An mon cuc bo tap trung cac khu rieng biet cua be mat v du : an mon hang hoc, an mon iem. - An mon gia cac tinh the la s pha huy kim loai doc theo ranh gii gia cac tinh the. - An mon xuyen tinh hnh thanh cac vet ran xuyen tinh dan en s pha huy toan bo kim loai.

III. CAC PHNG PHAP ANH GIA O AN MON : 1. anh gia o an mon theo thiet hai ve khoi lng : Ngi ta anh gia o an mon bang mat thng e xac nh s ong eu cua be mat, ac iem cac san pham an mon o bam dnh cua san pham an mon vi be mat kim loai kieu an mon. oi vi s an mon toan bo, eu hoa. Toc o an mon co the bieu dien bang s thiet hai khoi lng cua mot n v be mat trong mot n v thi gian c bieu th bang cong thc : Q= Trong o : Q - toc o an mon : g/m 2 . gi ; mg / cm2 . ngay m - thiet hai khoi lng g ; mg m = G1 Ngi G1 - Khoi lng trc khi th nghiem : g ; mg G2 - Khoi lng sau khi th nghiem : g ; mg StDien tch be mat : m 2 ; cm2 Thi gian th nghiem : gi ; ngay

m . g/m2 . gi ; mg / cm 2 ngay S. t

(1-1)

2. anh gia toc o an mon theo ch so o sau an mon : Ch so thiet hai ve khoi lng khong cho phep so sanh s an mon cua cac kim loai co khoi lng rieng khac nhau. Do o ngi ta a ra viec an gia toc o an mon theo ch so o sau c xac nh bang cong thc : P = 8,76

Q ; mm / nam (1 - 2) d

Trong o : P - ch so o sau an mon mm/nam Q - toc o an mon theo khoi lng g/m 2 . gi d - Khoi lng rieng cua kim loai g/m 2 8,76 - he so Th nguyen cua ch so o sau :

g / m 2 . gi g cm 3 1.000 mm 3 P= = 7,76 mm/nam = 2 = g / cm 2 m gi . g 10 6 mm 2 . 1nam / 8760

3. Thang on nh an mon : Nhom on nh Ben hoan toan o ben cao o ben trung bnh o ben yeu o ben rat yeu Khong ben Ch so o sau an mon P . mm/nam 0,001 0,001 0,005 0,005 0,01 0,01 0,05 0,05 0,1 0,1 0,5 0,5 1,0 1,0 5,0 5,0 10,0 > 10 Bac 1 2 3 4 5 6 7 8 9 10

oi vi an mon cuc bo, toc o an mon khong the tnh bang ch so an mon khoi lng hay ch so o sau, ma c xac nh bang ch so c kh, c tnh theo cong thc : K0 = Trong o :

0 1 . 100% 0

(1 3)

K - ch so c kh % 0 - o ben keo ban au, kg / cm 2 1 - o ben keo sau khi an mon, kg/cm 2

IV- KIM LOAI VA HP KIM : 1. Kim loai : Qua trnh an mon kim loai la qua trnh tng tac gia kim loai va moi trng. Co nhieu yeu to anh hng en qua trnh an mon. Mot trong nhng yeu to o la cau tao kim loai. Trong kim loai ton tai ca nguyen t va ion. Goi chung la ion nguyen t cung cac ien t t do. Cac ion nguyen t trong kim loai c sap xep theo qui luat nhat nh va dao ong quanh v tr can bang. Neu noi tam cua cac v tr cac ion nguyen t lai ta se c o mang khong gian goi la mang li tinh the. Tuy theo s sap xep trong khong gian cua cac ion nguyen t ma tao nen cac mang li tinh the hnh hoc khac nhau. Phan nho nhat cua cau tao hnh hoc trong mang li tinh the goi la o mang c s. Co 3 loai o mang c s thng gap : lap phng the tam, lap phng dien tam, luc giac xep chat.

a) Lap phng the tam : Trong mang li lap phng the tam cac ion nguyen t nam nh va gia khoi cua hnh lap phng. Trong mot o c ban co 8 ion nguyen t nh va mot ion nguyen t nam gia. Trong thc te cac ion nguyen t c xem nh qua cau xep chat. So ion nguyen t 1 o c ban la : n=
a a

O mang lap phng the tam

1 8 + 1 = 2 nguyen t 8

(8 ion nguyen t thuoc 8 o c ban bao quanh no la mot o thuoc ban than no). 3 khoi tru, 2 ion nguyen t nam trung tam 2 ay cua khoi tru. So lng ion nguyen t trong o c ban la : n=

1 1 12 + . 2 + 3 = 6 6 2

Mat o ion nguyen t tnh toan nh tren : M = 74% o ben an mon cua kim loai lien quan en cau truc mang tinh the cua kim loai. Kim loai nao co cau truc chat che o ben se cao hn. mot khoang nhiet o nao o, kim loai co nhieu kieu mang tinh the khac nhau. Tnh chat nay c goi la tnh thu hnh cua kim loai. V du : Sat la kim loai co tnh thu hnh. T 0 1392 C en 1539 0C sat co mang lap phng the tam.

O mang luc giac xep chat

3310C 13920C co mang lap phng dien tam. Cac dang thu hnh khac nhau cua cung mot nguyen to c ky hieu bang , , , v.v... V du : nhiet o thng, thiec Sn co mau sang, co tnh tot, co the han c. Song khi nung chay lam nguoi nhanh xuong di 30 0C Sn chuyen thanh Sn co dang bot mau xam. Khi thay oi tnh thu hnh cua kim loai, tnh chat ien hoa cua kim loai cung thay oi do o o ben an mon cung thay oi.

Mat o ion nguyen t M cua mang tinh the la phan the tch cua mang do cac ion nguyen t chiem cho tnh bang phan tram : M=

n.v 100% V

(1 - 4)

n - so nguyen t trong 1 o c ban v - the tch nguyen t V - the tch o c ban Neu xem nguyen t nh hnh cau ban knh r : V=

4 n r3 3

oi vi mang lap phng the tam cac nguyen t st nhau nen : r=

a 3 4

a - khoang cach hai ion nguyen t tren cung mot mat tinh the

4 a 3 2. n 3 4 100% = 68% Vay M = 3 a

b) Lap phng dien tam : Trong mang li tinh the lap phng dien tam ngoai cac ion nguyen t nam nh con co cac ion nguyen t nam mat ben cua hnh lap phng. So ion nguyen t nam trong mot o la : N=

1 1 8+ 6 =4 8 2

Mat o nguyen t c tnh la :

M=

4 a 2 4 . n 3 4 a3

= 74%

O mang lap phng dien tam

c) Luc giac xep chat : Trong mang li tinh the luc giac xep chat cac ion nguyen t nam nh luc giac 3 ion nguyen t nam trong tam.

2. Hp kim : Hp kim la vat the cha nhieu nguyen to mang tnh chat kim loai, nguyen t chu yeu trong hp kim la kim loai. Hp kim co cac ac tnh u viet hn kim loai co o ben nhiet, o ben an mon cao. Hp kim co cac dang cau tao : Hp kim co cau tao mot pha la dung dch ran. Hp kim co cau tao mot pha la hp chat hoa hoc. Hp kim co cau tao bi hai hay nhieu pha. Cung giong nh dung dch long, trong dung dch ran cung phan biet nguyen to dung moi va nguyen to hoa tan. Nguyen to nao cha lng nhieu hn goi la nguyen to dung moi. Con cac nguyen to khac la hoa tan. V. MOI TRNG AN MON : 1. Moi trng chat kh : Kim loai tiep xuc vi nhieu moi trng kh khac nhau, trong ieu kien nhiet o, ap suat khac nhau. C cau an mon cung hoan toan khac nhau.

CHNG II

AN MON HOA HOC

I. KHAI NIEM VE AN MON HOA HOC : An mon hoa hoc la qua trnh pha huy kim loai do tac dung hoa hoc cua no vi moi trng xung quanh. An mon hoa hoc tien hanh khi kim loai tac dung vi chat long khong phan ly hoac kh kho. ac iem cua an mon hoa hoc la qua trnh an mon khong sinh ra dong ien. San pham an mon tao thanh ngay cho kim loai tiep xuc vi moi trng. II. AN MON TRONG MOI TRNG KHONG PHAI LA CHAT IEN LY DANG LONG : Cac chat khong phai la chat ien ly la cac chat khong phan ly thanh cac ion t do trong dung dch hoac trong trang thai nong chay. V du : Brom long, lu huynh nong chay, nhieu dung moi hu c (Benzen, tetraclorua cacbon, clorofom ...) va cac nhien lieu long (dau hoa, xang, dau khoang ...) la cac chat khong ien ly. Cac chat long hu c phan ln khong an mon sat, hp kim cua sat. Nhng co mot so loai an mon kim loai mau. V du : Hp chat hydrocacbua dan xuat halogen, hp chat mecaptan va cac hp chat cha lu huynh. Cac san pham dau mo (xang, dau la, dau khoang ..) la san pham hu c khong ien ly, no gay an mon do lan tap chat, hoac trong thanh phan co cha hp chat hydrocacbua khong no, co kha nang b oxy hoa, cac san pham o se an mon kim loai. V du : Xang cracking trong thanh phan co cac andehyt axit, nha va cac san pham khac rat de b oxy hoa bi oxy trong khong kh. Chnh san pham nay gay an mon kim loai. III. AN MON KIM LOAI TRONG MOI TRNG KH : 1. Khai niem : Qua trnh an mon kim loai do tac dung hoa hoc cua cac chat kh vi kim loai goi la s an mon trong moi trng kh. Qua trnh an mon kh pho bien nhat la s oxi hoa kim loai trong moi trng khong kh nhiet o cao.

Toc o an mon kh phu thuoc vao tnh chat cua kim loai va hp kim, tnh chat cua moi trng, kh, nhiet o, tnh chat cua san pham an mon. 2. Kha nang oxy hoa kim loai va o ben cua mang oxyt : a) Kha nang oxy hoa kim loai : Muon biet qua trnh phan ng co xay ra hay khong, ta phai nghien cu s bien thien the nhiet ong cua no. Xet mot qua trnh an mon theo phan ng oxy hoa kim loai : m Me(p) +

m.n O2 (k) = Mem Om . n/2 (r) 4

(2-1)

Muon xet qua trnh an mon kim loai co xay ra hay khong ta phai xet bien thien the ang nhiet ang ap G khi tien hanh phan ng tren. Khi ap suat P va nhiet o T khong oi phng trnh ang nhiet c viet di dang : GT = RT 2,303 lg

1 (PO2 )
m .n 4

2,303 RT lg

1 (PO2 )
m .n 4

(2-2)

Trong o : R - hang so kh ly tng T - Nhiet o tuyet oi

8,31451 J/mol.k.

PO2 - Ap suat rieng phan cua Oxy ng vi trang thai ban au (PO2 ) cb - Ap suat rieng phan cua oxy ng vi trang thai can bang.
m - so nguyen t kim loai trong phan t oxyt n - hoa tr kim loai T phng trnh tren ta rut ra : GT = 2,303RT lg

PO2cb PO2

m.n

m.n

(2-3)

T phng trnh (2-3) ta thay : Qua trnh oxy hoa xay ra neu GT < 0 Tc la : (PO2 ) cb < PO2 Qua trnh oxy hoa khong xay ra neu GT > 0

(PO2 ) cb > PO2

Trong thc te e n gian ta phai so sanh ap suat phan huy cua oxyt va ap suat rieng phan cua oxy trong khong kh. Nh vay neu chiet ap suat phan huy ma oxyt, co the biet qua trnh oxy hoa co the xay ra hay khong. Ap suat rieng phan cua oxy trong khong kh : PO2 = 0,21 at. V du : Cho phan ng bac oxy hoa trong khong kh theo phan ng : 4Ag + O2 = 2Ag2O Tra bang 3000K ap suat phan huy cua 2Ag2O ta co (PO2 ) 400 cb
0

4Ag + O2

(PO2 ) 300 cb

= 0,69 at > 0,21 at

Nh vay 300 0K bac b oxy hoa tr thanh Ag 2O mau xam con 4000K
K

= 0,69 at > 0,21 at

b) Mang cua san pham an mon va o ben cua no : Cac san pham an mon kim loai do kim loai b oxi hoa eu dang mang bam tren be mat kim loai. o day cua mang phu thuoc ma /c cua kim loai va moi trng. Mang san pham an mon oi khi co kha nang bao ve kim loai khoi b an mon, lp mang co tnh chat bao ve can phai co tnh chat : - Mang st chat khong co lo xop, bao phu toan bo be mat kim loai. - Mang khong b pha huy trong moi trng an mon. - Mang bam chac len be mat kim loai. - He so dan n nhiet cua mang xop x he so dan n nhiet cua kim loai. ieu kien e lp mang bao phu kn be mat kim loai la the tch oxyt kim loai tao thanh do mot nguyen t gam kim loai b oxy hoa phai ln hn the tch nguyen t gam cua kimloai o. The tch nguyen t gam cua kim loai la : VKL = Trong o :

A d

(2-4)

A - nguyen t gam cua kim loai (g) d - Khoi lng rieng cua kim loai (g/cm 3)

The tch oxyt kim loai do 1 nguyen t gam kim loai b oxy hoa : VOX =

M n.D

(2-5)

Trong o :

M - phan t gam cua oxyt kim loai (g) n - so nguyen t kim loai trong phan t oxyt kim loai. D - Khoi lng riengn cua oxyt kim loai (g/dm 3)

ieu kien e lp oxit kim loai bao phu kn be mat kim loai la : VOX > VKL hay Ngc lai : ty so

VOX M.d = >1 VKL n . DA

(2-6)

VOX qua ln no se gay ng suat pha huy mang. VKL

V du : WO3 co

VOX < 1 mang oxit khong bao phu kn be mat kim loai neu VKL

VOX = 5,35 nen tnh bao ve mang WO3 kem. VKL

c) Qui luat phat trien cua mang : Qui luat phat trien mang phu hp vi qui luat khuyen tan ong hoc cua phan ng hoa hoc. + Qui luat phat trien mang xop : Qui luat phat trien mang xop bao gom may giai oan : * Chuyen chat oxy hoa (oxy) en be mat phan chia kim loai kh. * Chat phu chat oxy hoa len be mat kim loai. * Phan ng tao thanh oxyt. Me(r) +

mn mn 2 O2 = m Me +n + O = Mem Omn/2 (n) 2 2

V mang xop khong co tnh bao ve nen oxy i qua be day. Nen giai oan phan ng la giai oan cham cua qua trnh. Toc o phan ng khong phu thuoc vao chieu day cua lp mang. V mang xop oxy de dang lot qua lp mang vao be mat kim loai va c bieu th bang phng trnh : Y = kC t Trong o : y - chieu day mang t - thi gian oxi hoa kC - hang so toc o phan ng. C - nong o chat oxy hoa tren be mat (2-7)

Tuy nhien trong thc te s phat trien cua mang khong phai n thuoc la ng thang : Theo o th phat trien mang xop giai oan au s phat trien mang phu thuoc vao hang so toc o phan ng. Sau o tren be mat tao thanh lp oxit mong tiep tuc mang li tinh the cua kim loai. D C Nhng at ti gia tr ti han nao o A mang sinh ra ng suat noi va gay ra O mang xop. Nh vay mang oket chia lam hai lp : lp sat be mat mong va lam Toc o phat trien mang xop cham s khuech tan. Lp tiep theo day hn cha nc lo xop. Khong gay tr ngai cho s khuech tan. * Qui luat phat trien mang st : oi vi kim loai khi b oxi hoa tao thanh lp mang st co tnh chat bao ve kim loai toc o phat trien mang cham dan theo thi gian, mang cay day toc o khuech tan chat oxy hoa qua mang en be mat kim loai se cang kho khan. S phat trien cua mang oxit co cau tao st chat gom nhng giai oan sau : a- Kim loai phan ly thanh ion kim loai va ien t : Me Me+n + ne b- Ion kim loai chuyen vao lp oxit : Me mO
y

mn 2

c- Oxy trong moi trng chuyen en be mat tiep xuc giac mang oxit kim loai va moi trng kh : d- Oxy hap thu tren be mat mang oxit. MemO

mn mn + O2 = MemO + 2 Ohp 2 2

e- Cac ien t mang ion hoa oxi hap phu : Ohp + 2e = O2 f- Chuyen ion O 2 vao lp oxit Me mO

mn 2

g- Phan ng carbon kim loai vi ion oxi. mM+n +

mn 2 mn O = MemO 2 2

Trong cac giai oan tren giai oan b va f la giai oan di chuyen cua cac ion Me+n, O2 va ien t qua mang. Khi toc o cua 2 qua trnh nay quyet nh toc o chung cua qua trnh oxy hoa kim loai th mang cang day, toc o phat trien cua mang cang cham. S phat trien cua mang khong tuan theo qui luat ng thang ma thng tuan theo qui luat phc tap nh qui luat Parabon hay qui luat Logarit. d) C cau ln len cua mang va khuech tan qua mang bao ve : Khi a hnh thanh mang oxit, mang oxit se tiep tuc ln len. Vung ln len cua mang la vung gap nhau cua 2 luong khuech tan. Khuech tan ion kim loai va ien t qua mang oxyt ra pha ngoai moi trng va oxy cung khuech tan vao be mat kim loai. Co the chia lam 3 trng hp : - Vung ln len cua mang la vung gom mat ngoai cua mang, nh vay s khuech tan qua mang chu yeu do ion kim loai va ien t. - Vung ln len cua mang la vung ben trong tiep giap vi be mat kim loai khuech tan qua mang do amin oxy. - Vung ln len cua mang la vung gia mang. S o vung ln len cua mang

Me

Me+n ne

O2

Ohp

S khuech tan qua mang chu yeu la do 2 luong khuech tan. a so cac trng hp xay ra phu hp vi trng hp 1. V ng knh ion kim loai va ien t nho hn ng knh ion oxy, nen khuech tan qua mang chu yeu la do ion kim loai va ien t. 3. Cac nhan to anh hng en toc o an mon kh : Toc o an mon kh phu thuoc vao nhieu yeu to khac nhau nhng co hai nhan to chnh : nhan to ben trong va nhan to ben ngoai. a) Nhan to ben trong : - Anh hng cua thanh phan hp kim. Trong hp kim co nhng thanh phan chong an mon tao thanh mang oxit co tnh chat bao ve cao cho nen nhng cau t nay co the cho them vao thanh phan hp kim e tao ra hp kim ben nhiet.

- Anh hng cua cau truc kim loai. Kim loai nao cau tru cang st chat th cang ben. - Anh hng bien dang kim loai ch anh hng eu giai oan au cua an mon, sau o an mon phat trien qua mang oxit nen the hien khong ro. - Anh hng cua giai cong be mat cang ch anh hng giai oan au giai oan sau the hien khong ro ret. b) Nhan to ben ngoai : - Anh hng cua nhiet o : Nhiet o cao toc o an mon ln. - Anh hng thanh phan cua moi trng khi tang ham lng oxy trong khong kh. Toc o oxy hoa tang theo nhng khong phai theo qui luat tuyen tnh. - Anh hng cua toc o khong kh. Trong giai oan au tang ro ret, nhng sau th khong ro ret. 4. S kh cacbon cua thep, gang va s dan hydro : a) S kh cacbon cua thep : Khi ot chay be mat cua thep, mot thi gian se gay ra s kh cacbon cua thep. Nguyen nhan tren gii han phan chia gia oxy va kim loai se gay ra phan ng oxi hoa, cacbon tao thanh dang kh. Cacbon se khuech tan ra vung phan ng va lam ngheo cacbon trong thep, gang lam thay oi c tnh cua thep gang. Phan ng kh cacbon cua thep xay ra theo 4 phan ng sau : Fe3C +

1 O2 = 3Fe + CO 2

Fe3C + CO2 = 3Fe + 2CO Fe3C + H2O = 3Fe + CO + H2 Fe3C + H2 = Fe + CH4 b) S don hydro cua thep : Hydro trong kh quyen khi nhiet o 250 3000C va ap suat cao lam giam o ben cua thep 0 khong thay xay ra hien tng an mon ben ngoai ta goi o la an mon hydro hay s don hydro cua thep. Nguyen nhan la do : - Hydro hoa tan trong thep tao thanh dung dch ran don hn va kem ben hn. - S thoat hydro phan t tao thanh t hydro nguyen t theo gii han hat cua thep tao thanh khuyet tat ben trong.

- Lam ngheo cacbon trong thep theo phan ng : Fe3C + H2 = 3Fe + CH4 - Qua trnh kh oxy theo gii han hat va tao thanh hi nc pha huy mang tinh the cua kim loai : FeO + H2 = Fe + H2O II. CAC PHNG PHAP BAO VE AN MON KH : 1. Phng phap bao ve an mon kh bang cach tao hp kim ben nhiet : Ngi ta a vao thanh phan hp kim cac nguyen to co kha nang tao nen hp kim co tnh chu nhiet cao. Hp kim o phai co tnh chat : Tnh chu nong o la kha nang chu an mon hoa hoc cua moi trng kh nhiet o cao. o bc nhiet : kha nang bao toan cac tnh chat c ly nhiet o cao. Ngoai ra phai co tnh chat cong nghe thoa man cac yeu cau s dung nh tnh linh ong khi nong chay (khi uc), o cng (khi gia cong c). Co ba thuyet e giai thch c cau tao nen hp kim ben nhiet. a) Thuyet th nhat : Khi cho mot lng nho nguyen to hp kim vao kim loai. Trc het nguyen t cua nguyen to hp kim b oxi hoa tr thanh cacbon kim loai co hoa tr nhat nh. Cac cacbon nay hoa tan vao mang li tinh the cua oxi kim loai goc lam giam tr so khuyet trong mang li tinh the cua oxit kim loai goc. giam. Han che s khuech tan ion kim loai qua mang toc o oxi hoa

Tuy theo cac kim loai khac nhau ma ta a cac lng nho cac nguyen to hp kim vao kim loai co the lam giam toc o an mon cung nh co the lam tang toc o an mon. e tao hp kim chu nhiet, nguyen to hp kim phai co tnh chat : * Ai lc cua nguyen to hp kim oi vi oxi phai ln hn ai lc cua kim loai goc vi oxi va c bieu dien bang bat ang thc : (ZT) MemOmn/2 < (ZT) Me*mOmn/2 * Oxyt cua nguyen to hp kim phai hoa tan vi oxyt kim loai goc.

* Khi tao hp kim cho kim loai goc ma oxit cua no d kim loai th hoa tr cua nguyen to hp kim phai ln hn hoa tr cua nguyen to kim loai goc. Ly thuyet nay ch phu hp vi ieu kien toc o oxi hoa phu thuoc vao qua trnh khuech tan cation. b) Thuyet th hai : Theo thuyet nay khi a nguyen to hp kim vao kim loai goc e tao thanh hp kim chu nhiet. Trong qua trnh oxy hoa hp kim, mang oxit cua nguyen to hp kim c tao thanh tren be mat cua hp kim phai co tnh bao ve cao. No ngan can ca qua trnh khuech tan va qua trnh oxi hoa. V vay yeu cau cua nguyen to hp kim phai co tnh chat : + Oxit cua nguyen to hp kim phai co cau tao st ac ngha la thoa man ieu kien :

VMe* O Vme*
m

>1

+ Cau tao hp kim phai co ai lc vi oxi manh hn kim loai goc. Ngha la thoa man ieu kien nhiet ong : (ZT) MemOmn/2 < (ZT) Me*mOmn/2 + Kch thc ion cau t hp kim phai nho hn kch thc ion kim loai goc : ri* < ri ieu nay lam cho cau t hp kim de khuech tan ra be mat hp kim tao thanh oxit cho thong so li nho. Toc o khuech tan kim loai qua mang se thap do o tnh bao ve cang cao. + Cau t hp kim phai tao thanh oxit co ien t cao ngan chan chuyen ong cua ion va ien t qua mang. + Oxyt cua cau t hp kim phai co nhiet o nong chay va thang hoa cao. Khong ket hp vi oxyt kim loai goc tao thanh oxit cung tnh de nong chay. + Cau t hp kim va kim loai goc phai tao thanh dung dch ran vi ty le hp kim nhat nh e tao thanh mang oxyt cua cau t hp kim phan bo eu va bao phu toan bo be mat hp kim. Ly thuyet nay phu hp vi hp kim khi b oxy hoa tao thanh oxit cua cau t hp kim co tnh bao ve cao.

Al2O3.

V du : Hp kim goc Fe cha 8 10% Al khi oxi hoa tao mang bao ve Hp kim goc ong cha 20% kem Zn, tao thanh ZnO. Hp kim goc ong cha > 3% Al Al2O3.

Da tren ly thuyet nay, can c vao tnh chat cua nguyen to va oxit cua no, ta d oan tnh chat nh tnh viec tao hp kim nang cao tnh chu nhiet cua no. c) Thuyet th 3 : Thuyet nay cho rang neu cau t hp kim khi cung vi kim loai goc khi b oxi hoa tao thanh oxit kep co cau tao dang Spenen. V du : Me Me2O4 th oxit kep nay co tnh bao ve caohn so vi oxit cua cau t hp kim. Theo thuyet nay nguyen to tao hp kim tot nhat la tao hp kim goc sat la giam c kha nang tao thanh FeO khi b oxi hoa. Bi v nhiet o cao. FeO trong r co tnh bao ve kem hn ca. Cac nguyen to hp kim nh : Cr, Ni, Al ... trong hp kim goc sat c giai thch la do s tao thanh cac oxit kep khi b oxi hoa cau tuc cua no co dang Spinen nh : FeCr2O4 ; FeAl2O4 ; NiFe2O4 ; NiCr2O4 ... co thong so li nho, tnh bao ve cao. Cau t chu yeu e tao hp kim chu nong la Crom. V du: Thep thng, gang xam s dung nhiet o khong qua 550 0C. Thep cha 18% Cr s dung en 1.000 0C Thep cha 25% Cr s dung en 1.100 0C Thep cha 30% Cr s dung en 1.200 0C Neu cho them Cr, Si va nhom vao hp kim tnh chu nong con cao hn na. V du hp kim sicromal (6% r, 1-2 Si, 0,5 - 1% Al) la hp kim chu nong tot. Ham lng Si chu nong khong qua 3,5% ln hn se ran kho gia cong. Trong hp kim ham lng Cr cao, neu ta them mot lng nhom khac nhau, se tao hp kim chu nong tot. V du : Hp kim Fecral (12 - 14% Cr, 4 -5% Al) Hp kim Cantan (30% Cr, 5% Al, 3% Co) ... chu nhiet 1.300 0C Silic va nhom tang tnh chu nhiet nhng giam o ben nhiet nen thng pha Silic va thep Crom hoac thep Crom - Niken.

Ngoai ra, ngi ta con a vao mot lng nho Molipden (2%) va Vonfram (4 6%) cung tang c tnh chu nhiet cua hp kim. S dung hp kim chu nhiet trong cong nghiep san xuat can lu y en tnh chat cua moi trng. V du : moi trng kh Oxi, Clo, Brom ... co tnh oxi hoa. Moi trng H 2S, SO2, H2 va hi lu huynh lai co tnh kh. Mot hp kim ben trong moi trng oxi hoa nhng lai khong ben trong moi trng kh. e chong an mon kh trong cong nghiep san xuat hoa chat ngi ta s dung hp kim tuy theo tnh chat cua moi trng. V du : Chong an mon hydro nhiet o cao ! 6000C va ap suat 300at ngi ta dung hp kim sat cha 6% Cr. Crom co kha nang ngan can qua trnh khuech tan cua hydro. Thep cacbon cha 0,5% Mo va lng nho Vanadi dung e che tao thiet b tong hp amoniac. Trong moi trng H 2S dung hp kim cha Silic ; Thep fenet cha 25 30% Cr them 3 5% Si chu c nhiet o 1.000 0C. 2. Phng phap bao ve an mon kh bang lp phu bao ve : e tao thanh lp bao phu kim loai ngi ta co the bao phu bang kim loai hoac phi kim bang nhieu phng phap : khuech tan nhiet, han ap, boc kim loai, phun kim loai, ma, trang men chu nhiet, phu hp chat kho nong chay, phu bang kim loai, gom. a. Phng phap khuech tan nhiet (tham nhiet) Di tac dung cua nhiet o cao, dao ong nhiet cua cac nguyen t kim loai goc, co the chuyen di khoi v tr cua no trong mang li tinh the va tao nen nhng v tr khuyet. ieu kien o cung do dao ong nhiet ma cac nguyen to cua nguyen to hp kim t be mat kim loai goc khuech tan ma chiem cac v tr khuyet ma tao cac hp kim tng ng. Muon tao lp phu bao ve ngi ta s dung kim loai khuech tan dang bot, dang nong chay hoac dang hi. n gian nhat la dung dang bot. T c cau khuech tan ta thay : muon co kha nang xam nhap vao mang li kim loai goc : kch thc nguyen t kim loai khuech tan khong c ln hn kch thc cua nguyen t kim loai goc qua 10 15%. Tuy theo kim loai khuech tan ma ngi ta goi qua trnh o la tham nhiet nhan, tham nhiet Crom hay tham Silic.

+ Tham nhiet nhom : Ngi ta thng bao phu lp khuech tan nhiet nhom cho cac chi tiet bang thep, gang e bao ve cac chi tiet o trong cac moi trng kh nhiet o cao. Qua trnh tham nhiet nhom cho cac chi tiet bang thep, gang tien hanh nh sau : - Lam sach r va chat ban bang phng phap phun cat hoac phng phap hoa hoc. - at chi tiet trong lo phan ng co cha hon hp bao gom : 40 50% hp kim sat nhom (FeAl) dang bot. 49 - 53% bot nhom oxit Al 2O3 la bot tr tranh thien ket. 2 - 5% amon clorua NH 4Cl - Lo phan ng c em vao nung nhiet o 900 - 1.000 0C trong khoang thi gian xac nh (4 - 24 gi). Khi nung Amon Clorua b phan huy NH4Cl NH3 + HCl Khi o : 2Al + 6 HCl = 3 H 2 + 2AlCl 3 nhiet o cao AlCl 3 d5ng hi va xay ra phan ng : AlCl3 + Fe= FeCl3 + Al Nhan thoat ra se khuech tan vao thep va tao nen hp kim co thanh phan thay oi. Chieu day lp khuech tan phu thuoc vao thi gian nung va nhiet o nung. Sau khi nung thng phai u 900 0C trong khoang 3 gi e tranh don be mat do co hp chat hoa hoc FeCl3 con d. o ben chi tiet co lp phu nhiet nhom tang len 20 lan khi lam viec thng xuyen nhiet o 800 0C, tang 10 lan neu lam viec 950 0C va 7 lan khi lam viec 1.0000C trong moi trng khong kh. Trong qua trnh lam viec nhiet o cao, ham lng Al tren be mat chi tiet tham nhiet nhom gian dan v Al khuech tan nhiet cua no vao sau trong chi tiet do o o ben nhiet kem i.

Nhiet nhom ben trong moi trng SO 2, hi lu huynh nhiet o cao. Tnh chu nhiet cua lp nhiet nhom trong moi trng khong kh va oxi la do tnh bao ve cua Al 2O3 hoac oxt kep FeAl2O4. Ngi ta tham nhiet nhom e bao ve noi hi, lo phat sinh kh, cac chi tiet bang thep gang lam viec trong moi trng khong kh, oxi, SO 2 hoac lu huynh ... nhiet o cao. + Tham silic : Qua trnh tham silic c tien hanh nh sau : - Lam sach be mat chi tiet can tham. - at chi tiet trong lo mot au cha bot silic. - Xong kh Clo qua lp bot thng c ieu che bang cho axit HCl tac dung vi Ca(OCl) 2. 4HCl + Ca(OCl) 2 = CaCl2 + 2H2O+ 2Cl2 Kh Cl2 c lam kho bang axit H 2SO4 am ac. - Kh Cl 2 c tac dung vi bot Silic hoac Ferosilic theo phan ng : Si + 2Cl2 = SiCl4 Clorua Silic dang hi tiep xuc vi thep xay ra phan ng : 4Fe + 2SiCl 4 = 2Si + 4FeCl3 Si ket hp vi Fe tao hp kim Fe - Si co o ben nhiet va c hoc kha cao v tao oxit kep FeSiO4. b) Phng phap han ap : Phng phap han ap hp kim chu nong len be mat chi tiet hoac thiet b e tao nen lp bao phu day, lien ket tot vi be mat bao ve. Ngi ta thng dung phng phap han ap e bao ve an mon kh cho cac chi tiet chu nhiet o cao ong thi chu tac ong kh manh. V du : Han ap hp kim Sfelit (35 50 Co, 20 35% Cr, 9 - 15% W, 1 - 2C, va con lai la Fe) cho cac tua bin kh. Han ap hp kim Stelit hoac hon hp Ni - Cr len mat mu van trong ong c may bay. c) Phng phap boc kim loai :

ay la phng phap hoan hao nhat e bao ve kim loai co o ben thap hn so vi moi trng an mon. Phng phap nay la dung kim loai co o ben cao oi vi moi trng e boc be mat kim loai cot co o ben thap. Thng boc 1 mat goi la thep 2 lp. Boc 2 mat goi la thep 3 lp. Chu y khi s dung nhiet o cao phai dung kim loai co o dan n v nhiet gan giong nhau. d) Phng phap phun kim loai : Ban chat cua phng phap la dung kh nen, hay kh tr phun kim loai hay hp kim nong chay ben nhiet len be mat kim loai can bao ve. Chat lng lp kim loai phun phu thuoc vao rat nhieu yeu to : o xop lp phun, kch thc hat phun toc o chuyen ong cua hat en be mat lp phu, ap suat kh nen. Khoang cach gia voi phun va be mat chi tiet. Phng phap va chat lng chuan b be mat chi tiet, tnh chat ngon la, thanh phan kh phun v.v... ng dung lp phu bang phng phap phun e chu nhiet, phun kim loai con c dung e bao ve lam kim loai trong khong kh, trong kh quyen vung bien, nc song, cho ket cau lap san v.v... e) Cac phng phap khac : Ngoai cac phng phap a neu ngi ta con dung phng phap ma ien, trang men chu nhiet, phu bang cac hp chat khong nong chay, phu bang kim loai gom ... 3. Dung moi trng e bao ve : Phng phap la chon va s dung thanh phan moi trng kh thch hp e chong an mon khi kh gia cong nhiet cac kim loai. Ve nguyen tac th tao ieu kien e loai tr kha nang tien hanh qua trnh an mon, ngha la the ang nhiet, ang ap cua kim loai trong moi trng la dng ngha la : G > 0.

CHNG III

AN MON IEN HOA

I. KHAI NIEM VE AN MON IEN HOA: Nghien cu mot pin Cu - Zn trong dung dch ien ly ta thay kem b an mon do hien tng hoa tan. Phan ng xay ra tren axit. Zn 2e = Zn+2 Trong thc te qua trnh an mon xay ra tren cung mot kim loai, ngha la tren cung mot kim loai co ca qua trnh anot va catot va a en s pha huy kim loai. Nh vay tren be mat kim loai co rat nhieu catot, anot gan nhau tao thanh he thong vi pin nhieu cc ta goi la an mon ien hoa. An mon ien hoa la qua trnh an mon ma trong o phat sinh ra dong ien. V vay an mon ien hoa ch xay ra khi kim loai tiep xuc vi moi trng ien ly. II. IEN LY IEN CC VA C CAU AN MON IEN HOA : 1. ien the ien cc : Khi nhung 1 thanh kim loai vao dung dch ien ly, gia chung hnh thanh lai s phan bo ien tch. Tren be mat phan chia pha tao thanh lp ien tch kep. Trong ieu kien an mon thng gap th cation kim loai se chuyen t mang li tinh the vao dung dch e lai be mat kim loai ien t d e tao thanh ion hydrat hoa theo phan ng : Me + mH2O =Me+n . mH2O + ne Lng ien tch do cac cation kim loai chuyen vao dung dch trong mot n v thi gian chnh la toc o qua trnh thuan c the hien bang dong ien tng ng i1 . Ta goi o la qua trnh oxi hoa. Cac cation kim loai trong dung dch chuyen en be mat phan chia pha gia dung dch va kim loai nhan ien t e tr thanh nguyen t theo phan ng: Me+n.mH2O + ne = Me + mH 2O Qua trnh nay ngc vi qua trnh th nhat. Toc o cua qua trnh ngc nay la i 2. Ta goi o la qua trnh kh.

Khi toc o i1 > i2 ion kim loai se chuyen ra ngoai dung dch qua trnh luc o la qua trnh oxi hoa : ia = i 1 i 2 Trong trng hp ngc lai i 2 >i1 ion kim loai phong ien, qua trnh luc o la qua trnh kh : ik = i 2 i 1 Khi lp ien tch kep hnh thanh, en luc nao o thiet lap trang thai can bang ong. Qua trnh oxy hoa bang qua trnh kh. Khi o i = i 2 = i0. Ta goi i0 la dong ien trao oi. Lp ien tch kep c can bang giong nh mot tu ien 2 lp ien tch trai dau va xuat hien mot bc nhay ien the. o chenh lech ien the gia be mat kim loai va dung dch goi la ien the ien cc cua kim loai. Rat kho xac nh c ien the ien cc mot cach chnh xac. Ngi ta ch xac nh gia tr tng oi ien the ien cc bang cach so sanh vi ien cc tieu chuan hydro va qui c ien the ien cc tieu chuan cua hydro bang khong. ien cc tieu chuan hydro la mot tam bach kim (Pt) co phu bach kim en (bach kim dang hat nho, co kha nang hap phu hydro tot) nhung trong dung dch cha ion hydro co hoat ong a Ht = 1 (v du : nong o dung dch H2SO4 nong o 1,8N hoac dung dch HCl nong o 1,3N) dung dch c bao hoa kh hydro co ap suat bang 1 at. Muon xac nh ien the cua mot ien cc nao o ta thiet lap mot pin, trong o mot ien cc la ien cc chuan hidro, ien cc kia la thanh kim loai can nghien cu nhung vao dung dch ien ly. Tr so sc ien ong sinh ra gia ien cc kim loai va ien cc chuan hidro - chnh la tr so ien cc kim loai trong dung dch ien ly o. Khi xac nh ien the cc chuan cua kimloai nhung trong dung dch muoi cua no co hoat o cua ion kim loai a metan = 1. 2. ien the ien cc thuan nghch va khong thuan nghch : Khi nhung mot thanh kim loai vao chat ien ly co kha nang xuat hien ien the ien cc thuan nghch hoac khong thuan nghch tiep theo ban chat cua kim loai va dung dch ien ly. a) ien the ien cc thuan nghch : Khi nhung mot thanh kim loai vao dung dch muoi cua no. Neu qua trnh ch co cac cation kim loai tham gia phan ng ngoai ra khong con cac

cation nao tham gia vao qua trnh ien cc na. Khi thiet lap trang thai can bang ong, dong ien i 1 = i2 = i0 c viet bang phng trnh thuan nghch sau: Me + mH2O Nh vay so lng cation hoa tan vao dung dch bao nhieu cung bang so cation. Ket tua tren be mat kim loai. Ket qua ien cc kim loai khong b an mon. Me+n.mH2O + ne
Me Me+n.mH2O

i1 i2
S o thiet lap ien the ien cc kim loai thuan nghch

Kim loai

Me Me+n.mH2O

ien the ien cc c xac nh bang cong thc :

0 ( Me)tn = ( Me )tn +

RT lg nal Me+ n nF

(3-1)

0 ( Me )tn - ien the ien cc tieu chuan cua kim loai.

R - Hang so kh ly tng. T - Nhiet o tuyet oi 0K. n - Hoa tr ion kim loai. F - Hang so Faraday.

a Me+ n - Hoat o ion kim loai trong dung dch.

Ta goi o la ien the ien cc thuan nghch. b) ien the ien cc khong thuan nghch : ien the ien cc khong thuan nghch la ien the xac nh trong ieu kien, qua trnh trao oi ngoai ion kim loai con co cac loai ion khac cung tham gia qua trnh trao oi : V du : Me + mH2O H + H2O
+

Me Me+n.mH2O Me Me .mH2O
+n

i1 i2 i1 ' i2 '

H H+.H2O

Me+n . mH2O + ne H .H2O + e

H H+.H2O

Ta goi dong ien thuan nghch cua qua trnh oxi hoa - kh kim loai la I1 va I2. Con S o thiet lap ien the ien cc
kim loai khong thuan nghch

dong ien thuan nghch cua qua trnh oxi hoa kh hydro la I1 va I2. Khi dong ien on nh, tong cac dong ien thuan bang tong cac dong ien nghch. I1 + I1 = I2 + I2 Nhng v I1 > I2 ngha la so cation kim loai chuyen vao dung dch trong mot n v thi gian ln hn so lng cation kim loai t dung dch ket tua bam vao be mat kim loai. Ket qua kim loai b an mon. ien the ien cc khong thuan nghch ch co the xac nh bang phng phap o, khong the tnh toan theo phng trnh nhiet ong Nerst. ien the ien cc khong thuan nghch phu thuoc ma ban chat hoa hoc, trang thai be mat cua kim loai, s hap phu nguyen t, phan t tren be mat kim loai (ac biet la oxy va hydro). Ngoai ra no con phu thuoc vao ban chat hoa hoc, nong o, nhiet o cua dung dch. 3. C che an mon ien hoa : S hoa tan ien hoa hoc kim loai la mot qua trnh phc tap bao gom 3 qua trnh : a) Qua trnh anot : Qua trnh anot la qua trnh xay ra khu vc ma kim loai b ion hoa va chuyen vao dung dch, do o tren be mat kim loai d mot lng ien t tng ng. Qua trnh xay ra theo phng trnh :
2O ne Me + mH Me+n.mH2O

(3-3)

Qua trnh nay, kim loai mat ien t, no b oxi hoa. b) Qua trnh catot : Qua trnh catot la qua trnh xay ra khu vc ma o cac ion, nguyen t hoac phan t cua chat ien ly nhan ien t tren be mat kim loai. Ta goi cac ion, nguyen t, phan t o la chat kh cc. Chat kh cc a nhan ien t d tren be mat kim loai theo phng trnh : D + ne [D.ne] Cac ion, nguyen t, phan t nhan ien t no a b kh. c) Qua trnh chuyen ien t : Khi hai qua trnh ien cc xay ra ong thi co s chuyen ien t t vung anot sang vung catot. Trong dung dch ien ly cung co s chuyen cation va anion tng ng. (3-4)

Nh vay qua trnh an mon kim loai xay ra ong thi vi s xuat hien dong ien gia hai cc (hai vung) khac nhau cua kim loai. Vung kim loai b hoa tan ong vai tro cc dng (anot). Vung kia ong vai tro cc am (catot).
Vung anot ne Vung canot ne Me
+mH2O

Me+n.mH2O K+

[D.ne]

S o qua trnh an mon ien hoq

Mot he thong xay ra cac qua trnh nh tren goi la nguyen to Gunvame. Vay nguyen to ganvame la he thong trong o xay r s bien oi hoa chnh la qua trnh lam viec cua cac nguyen to ganvame. III. ONG HOC CAC QUA TRNH IEN CC : 1. Hien tng phan cc va kh phan cc : a) Phan cc : Khi nhung hai thanh kim loai khac nhau vao mot dung dch ien ly. 0 Chung tao thanh hai ien cc khac nhau. 0 va a . Khi noi hai ien cc vi k nhau bang mot day dan se co mot dong ien chay qua trong mach. ien the ien cc luc nay lech khoi v tr can bang. ien the ien cc anot dch chuyen ve pha lng. ien the catot dch chuyen ve pha am. S dch chuyen ien the ra khoi trang thai can bang ta goi la s phan cc. b) ng cong phan cc : e nghien cu qua trnh ien cc, ngi ta thiet lap quan he s phu thuoc gia ien the ien cc ( V) vi mat o dong ien (I mA/cm2). Bieu o thiet lap s phu thuoc cua tr so ien the ien cc vao mat o dong ien ta goi o la ng cong phan cc. Tren he toa o, truc tung cua toa o ghi tr so am cua ien the, truc hoanh ghi tr so mat o dong ien. o doc cua ng cong phan cc cang ln o phan cc cang kn, ngc lai o doc cua ng cong phan cc cang nho th o phan cc cang nho, ngha la qua trnh ien cc xay ra de dang hn.

ng cong phan cc co y ngha thc te e giai thch nhng nh luat c ban cua qua trnh an mon. Xay dng ng cong phan cc bang thc nghiem la mot trong nhng phng phap c ban e nghien cu c cau cua qua trnh an mon. c) Phan cc : Nhng qua trnh lam giam s phan cc anot, catot co ngha la lam cho qua trnh anot va catot tien hanh de dang hn goi la s kh phan cc anot, catot. 2. Phan cc anot :

0 A
Va VK
0 K

A K

o th ng cong phan cc

Qua trnh anot la qua trnh hoa tan kim loai ngha la ion kim loai t mang li tinh the kim loai chuyen vao dung dchva tao thanh ion hydrat hoa. Me+n . ne + mH Me+n.mH2O + ne 2O S phan cc anot ngan can qua trnh anot lam cho qua trnh anot tien hanh kho khan hn. ien the anot chuyen ve pha dng hn. Nguyen nhan cua s phan cc anot la a) Lam cham qua trnh phan ng anot an mon kim loai do phan cc ien hoa hoc (a) c goi la qua the ion hoa kim loai. Khi mat o dong nho (I < 10-2 A/m2) qua the ion hoa kim loai phu thuoc tuyen tnh vao mat o dong anot the hien bang phng trnh. a = k1 ia o. Khi i > 102 A/m2 s phu thuoc qua the vao mat o dong bang phng trnh : a = a1 + b1 lgia Trong o : a1 - hang so phu thuoc vao vat lieu, trang thai be mat anot va nhiet o. b1 - Hang so lien quan ti c che xuat hien qua the ion hoa kim loai. (3-6) (3-5)

Trong o : k - he so phu thuoc vao vat lieu, trang thai be mat va nhiet

b) Lam cham s khuech tan ion kim loai t be mat vao dung dch a en s phan cc nong o (a)n. S phan cc nong o co the xac nh theo phng trnh: (a)n =

a' RT 2.303 lg Me+ n a Me+ n nF

(3-7)

a 'Me+ n - hoat o ion kim loai lp sat be mat

aMe+n - hoat o ion kim loai trong dung dch. c) Tao thanh mang thu ong tren anot : Trong dung dch ien ly co chat oxi hoa, khong co cac anion hoat ong nen no co kha nang tao mang bao ve lam cho ien the anot chuyen ve pha dng hn. 3. Phan cc catot : Qua trnh catot la qua trnh kh ngha la qua trnh lay ien t d do cac chat kh nao o. Ky hieu la D. D + ne [Dne] V du : Do cac ion b kh : H+.H2O + e = (3-8)

1 H2 + H2O 2

Ag+.mH2O + e = Ag + mH2O Do cac phan t trung tnh : O2 + 4e + 2H2O = 4 OH Mang khong tan : CuO + 2e + H 2O = Cu + 2OH Cac hp chat hu c : RO + 2e + 4H + = RH2 + H2O R - goc cua phan t hu c. Nguyen nhan cua phan cc catot : - Lam cham qua trnh catot do phan cc ien hoa goi la qua the cua phan ng kh phan cc catot. Ky hieu (k)h

nhan.

- Lam cham qua trnh catot do phan cc nong o : (k)n do hai nguyen + Khuech tan chat kh phan cc t dung dch en be mat catot cham. + Khuech tan san pham catot t be mat pha kim loai - dung dch ra dung dch cham.

4. S kh phan cc hydro : a) An mon kim loai vi s kh phan cc hydro va kha nang nhiet ong cua no : Qua trnh an mon kim loai ma chat kh phan cc la ion H + san pham thoat ra catot la hydro theo phan ng : H+H2O + e = H + H2O =

1 H2 + H2O 2

Goi la an mon kim loai vi s kh phan cc hydro. ieu kien moi trng : thng tien hanh trong moi trng axit. ieu kien c ban e kim loai b an mon vi s kh phan cc hydro la : (Me)tn < ( H2 ) tn (3-9)

( Me ) tn - ien the ien cc cua kim loai ( H2 ) tn - ien the ien cc hydro thuan nghch.
0 ( H2 ) tn = (H2 )tn +

a RT 2,303 lg H+ 1 nF PH2
2

0 ( H2 )tn = 0 ien the /c tieu chuan cua ien cc hydro.

aH+ - hoat o cua ion H+

PH2 - ap suat rieng phan cua hydro.

b) Qua trnh ien cc : Qua trnh catot kh phan cc hydro chia lam 6 giai oan : a- Cac ion hydro b hidrat hoa tao thanh ion hydroxan (H +.H2O) sau o khuech tan en be mat ien cc catot. b- catot cac ion hydroxan b kh thanh nguyen t hydro co kha nang hap phu tren be mat kim loai goi la hydro hap phu :

H+.H2O + e = Hhp + H2O c- Mot phan nguyen t hydro khuech tan sau vao be mat kim loai : d- Phan ln nguyen t hydro hp thanh phan t hydro : Hhp + Hhp = H2 e- Cac phan t H 2 khuech tan vao dung dch qua mat thoang khuech tan vao khong kh. g- Cac phan t hydro tren be mat catot tap hp lai thanh bot kh thoat ra khoi be mat kim loai. Cac giai oan cua phan ng ien c bieu dien theo s o. Nguyen nhan cua s phan c do ca phan cc ien hoa va phan cc nong o. + Phan cc ien hoa : S lam cham qua trnh phan cc catot do phan cc ien hoa c coi la qua the Hydro ky hieu la K
0 K = (VK)dh = VK VK

e C Me a H+.H2O d b S o cac giai oan cua qua trnh catot kh phan cc Hydro

(3-10)

Trong o :

0 VK - ien the cc can bang

VK - ien the ien cc catot sau khi a phan cc Qua the Hydro phu thuoc vao mat o dong ien catot, vat lieu lam catot, trang thai be mat, nhiet o ... Khi mat o dong ien nho i K < 10-2 A/m2. Qua the Hydro phu thuoc tuyen tnh vao mat o dong ien. K = K 1 iK cc. (3-11)

K1 - hang so phu thuoc vao vat lieu trang thai be mat nhiet o cua ien

Khi mat o dong ien ln : i K > 102 A/m2. Qua the hydro c the hien theo phng trnh logarit. K = a1 + b lgiK (3-12)

a1 - hang so phu thuoc vao vat lieu, trang thai be mat va nhiet o cua ien cc a 1 = K khi iK = 1 A/m2

b- Hang so lien quan en c che xuat hien qua the. V VK G

0 VH2

ng cong phan cc catot khi an mon vi s kh phan cc Hydro + Phan cc nong o : S khuech tan ion hydro en be mat catot cham gay nen s phan cc nong o. S phan cc nong o the hien theo phng trnh : n = (VK)n = Trong o :

RT

a* + F 2,303 lg H a H+

(3-13)

a* + - Hoat o cua ion hydro tren be mat catot. H a H+ - Hoat o cua ion Hydro trong the tch dung dch.
5. S kh phan cc oxi : a) An mon kim loai vi s kh phan cc oxi va kha nang nhiet ong cua no. Qua trnh an mon kim loai ma chat kh phan cc la oxy hoa tan trong dung dch theo phan ng nh sau : O2 + 4e + H2O = 4 OHieu kien moi trng : Khi kim loai tiep xuc vi moi trng trung tnh nh an mon trong nc bien, trong at, trong kh quyen, axit yeu hay kiem. ieu kien c ban la :

( Me ) tn < ( O2 ) tn
0 ( O 2 ) = O

(3-14)

RT 4F

2,303 lg

PO 2 a OH

0 O2 - ien the ien cc tieu chuan cua ien cc oxy.

PO2 - Ap suat rieng phan cua oxy. a OH - Hoat o cua ion Hydroxyn.
b) Qua trnh an mon kh phan cc oxi : Qua trnh an mon kh phan cc oxi gom 6 giai oan chnh : 1. Oxi khuech tan vao dung dch ien ly qua mat thoang cua dung dch tiep xuc vi khong kh. 2. Oxi hoa tan vao dung dch ien ly nh oi lu t nhien hoac khuay tron cng bc dung dch ien ly. 3. Chuyen oxi qua lp Pran (lp chat ien giai gan be mat an mon kim loai co chieu day la P) toc o dong chat ien giai thay oi t V0 en O nh s chuyen ong cua chat ien ly oxi hoa tan trong. 4. Chuyen oxi qua lp khuech tan lp ien giai co chieu day o hay mang san pham an mon tren kim loai. 5. Ion hoa oxi trong moi trng kiem : O2 + 4e + 2H2O = 4OH Trong moi trng axit yeu : O2 + 4e + 4H+ = 2H2O 6. Khuech tan ion OH t be mat catot ra dung dch.
-

K.Kh

V0 1 6
O2+4e+H2O 4OH

O2

Kim loai

2 3

S o qua trnh catot kh phan cc oxi

Trong 6 giai oan the giai 4 0,5 la cham hn ca. Do o hai giai oan nay 1 khong che qua trnh an mon kh phan cc oxi. Khi chat ien ly khong chuyen ong lp khuech tan ln en 1mm, giai oan cham la giai oan khuech tan. Khi khuay tron manh lp khuech tan ch con 0,02 0,1mm toc o an mon tang len.

5 4 P

IV. CAC NHAN TO ANH HNG EN QUA TRNH AN MON IEN HOA : 1. Cac nhan to ben trong : a) o ben nhiet ong cua kim loai : Kim loai b an mon ien hoa khi no ong vai tro ien cc anot trong nguyen to Ganvame. Ve phng dien nhiet ong, qua trnh an mon co kha nang t xay ra khi bien thien nang lng t do cua no G < 0 hoac sc ien ong cua cap nguyen to an mon E > 0. ien the ien cc phu thuoc vao ban chat cua kim loai o. Kim loai b an mon trong moi trng ien ly con phu thuoc vao tnh chat cua san pham an mon hoac kha nang thu ong cua no trong moi trng o. b) o ben cua kim loai phu thuoc vao v tr cua no trong bang he thong tuan hoan. Trong mot phan nhom o ben tang t tren xuong di, tc tang khoi lng nguyen t. V du: IB Cu Ag Au IIB Zn Cd Hg VIV Fe Rn Oz

c) Cau tao va tnh chat cua hp kim Hp kim c dung nhieu trong ky thuat. o ben cua no phu thuoc vao thanh phan va cau truc cua no, co hai loai hp kim : Hp kim 1 pha va hp kim nhieu pha. Hp kim 1 pha la dung dch ran c s dung nhieu trong ky thuat an mon. Hp kim nhieu pha c tao thanh do cac kim loai cac trang thai ket tinh khac nhau. Quan iem ien hoa hp kim nhieu pha o ben an mon kem. e) Trang thai be mat kim loai : Be mat kim loai ong nhat, nhan bong kim loai ben hn. Be mat khong ong nhat de b an mon hn.

2. Cac nhan to ben ngoai : a) o pH cua dung dch : pH = lg a H+ pH < 7 pH = 7 pH > 7 Moi trng axit Trung tnh Kiem

+ Anh hng trc tiep trong trng hp ion H + hoac OH trc tiep tham gia phan ng ien cc lam thay oi ien the ien cc. + Anh hng gian tiep : tao mang san pham thu ong lam giam toc o an mon hoac hoa tan san pham an mon lam mat kha nang bao ve cua mang. b) Thanh phan va nong o chat ien ly : Toc o an mon ien hoa phu thuoc vao ban chat dung dch muoi hoa tan va nong o cua no trong dung dch. Cac muoi co tnh oxi hoa co tac dung tao mang thu ong khi tang nong o, toc o an mon se giam. Nhng neu cac muoi oxi hoa co tac dung kh phan cc toc o an mon tang khi tang nong o. Cac muoi thuy phan (Na 2CO3) tao moi trng kiem lam thay oi o pH va anh hng en toc o an mon. - Cac muoi hoa tan tac dung vi kim loai tao san pham an mon kho hoa tan. - Toc o an mon con phu thuoc vao ban chat cua cation va anion cua dung dch muon hoa tan. Neu s hap phu cua cation hoac anion lam thay oi c cau cua lp ien tch kep gan ien tch ien cc kim loai do o lam giam toc o an mon. Ngc lai pha huy mang thu ong no se lam tang toc o an mon. c) Nhiet o va ap suat moi trng : a so trng hp nhiet o gay anh hng en toc o an mon. Nhiet o cao toc o an mon ln. Tuy nhien co mot so trng hp khi tang toc o an mon en mot gia tr nao o toc o an mon lai b giam. Ap suat cung anh hng en toc o an mon. Thay oi ap suat lam thay oi o hoa tan kh trong dung dch, thay oi qua trnh thuy phan va lam tang ng suat noi trong thiet b dan en tang toc o an mon. d) Toc o di chuyen cua dung dch ien ly : Anh hng cua toc o di chuyen cua dung dch en toc o an mon rat phc tap. Co loai khi tang toc o cua dch toc o an mon tang nhng sau o

lai giam hoac ngc lai. oi vi moi trng co cac anion hoat ong pha huy mang thu ong khi tang toc o di chuyen cua dong chay toc o an mon tang len. g) Anh hng cua dong ien ro : Dong ien ro la dong ien t cac nguon khac nhau i vao long at. Qua trnh an mon chu yeu do dong 1 chieu sinh ra. Trong vung dong ien i qua chia lam 3 vung nho : Vung catot la vung dong ien tan i vao thiet b hoac dung ong. Vung nay khong b an mon. Vung trung hoa la vung khong co dong ien i vao kim loai khong b an mon. Vung anot : dong ien t thiet b i ra i vao at e tr ve nguon, vung nay kim loai b an mon. h) Anh hng cua cau tao thiet b : Cau tao thiet b khong hp ly co the gay ra vung ng suat nen gay an mon manh. Ket cau khong hp ly gay ong chat long an mon. Ket cau thiet b hp ly la mot trong nhng bien phap CAM hieu qua. V. XAC NH TOC O AN MON IEN HOA THEO IEU KIEN AN MON : Phng phap xac nh toc o an mon ien hoa theo bieu o con goi la phng phap ien hoa : Tr so khoi lng kim loai b an mon anot c xac nh theo nh luat Faraay. m = Trong o : m - khoi lng kim loai b an mon A - nguyen t gam cua kim loai q - ien lng chay t anot qua catot I - cng o dong ien an mon T - thi gian an mon (g) (g) (culong) (A) (s)

A A q= IT nF nF

(3-15)

n - hoa tr cua kim loai F - hang so Faraday (F = 96.500) Toc o an mon ien hoa tnh bang khoi lng kim loai b an mon tren n v dien tch trong mot n v thi gian, c xac nh theo cong thc : Km = Trong o : SA - dien tch ien cc anot (m 2, cm2) iA - mat o dung anot (A/m 2 ; A/cm2) km : toc o an mon kim loai (g/m 2.s ; g/cm2.s)

m A I A = = = iA SA T nF SA nF

(3-16)

CHNG IV

PHNG PHAP CHONG AN MON

I. PHNG PHAP HP KIM HOA : 1) a vao hp kim cac cau t co kha nang tao mang san pham. V du : Hp kim Cu - Al ; Cu - Zn ... 2) a vao kim loai cac cau t lam giam hoat tnh catot cua hp kim. V du : lam tang qua the Hydro an mon trong c Axt nh hp kim Manhe Mangan. 3) a vao kim loai cac cau t lam giam hoat tnh anot. V du : Cu - Au, N - Cu. 4) Tranh tao lien hat co hoat tnh anot. 5) San bang gia tr ien the cua hat va lien hat. II. PHNG PHAP X LY MOI TRNG : 1. Giam ham lng chat kh phan cc : V du : Kh phan cc H + ta trung hoa moi trng bang voi song. 2. Kh oxy hoac kh ngam kh trong nc bang : + Tach nhiet : t 0 cao oxy hoa tan giam. + Tron nc vi cac kh khong cha oxi. + Phng phap hoa hoc cho vao nc cha chat kh : Na2SO3 ; SO2 ; Na2S2O4 ................. Na2SO3 + O2 = 2Na2SO4 3. Dung chat lam cham an mon : Chat lam cham (hay chat c che) la cac chat khi cho lng nho chat lam cham an mon vao moi trng. Toc o an mon kim loai hoac hp kim giam i rat nhanh. Do c cau tac dung ngi ta chia ra : Chat lam cham anot Chat lam cham catot Chat tao mang Chat lam cham do tac dung ong thi cua cac loai tren. Mot so chat lam cham an mon chnh dung la : - Chat lam cham an mon trong axit. - Chat lam cham an mon trong nc va dung dch muoi. - Chat lam cham an mon trong khong kh.

III. PHNG PHAP BAO PHU BAO VE : 1. Bao phu kim loai : Bao phu e chong an mon cho kim loai neu chia lam 2 loai : a) Bao phu catot : ngan no khong cho kim loai nen tac dung vi moi trng. Kim loai phu co ien the dng hn so vi kim loai nen trong ieu kien moi trng can bao ve. b) Bao phu anot : Kim loai phu co ien the am hn kim loai nen, khi lp phu b pha hoai cuc bo kim loai nen van khong b an mon. e tao lp phu ta s dung cac phng phap : - Nhung trong kim loai nong chay. - Khuech tan nhiet. - Phng phap nhiet c. - Phng phap ma ien (1837) - Phng phap hoa hoc. - Phng phap tiep xuc . - Phng phap phun kim loai. 2. Bao phu bang hp chat hoa hoc : La phng phap tao lp be mat kim loai thanh hp chat hoa hoc co tnh bao ve cao nh dong ien hoac chat phan ng. a) Oxi hoa : Ngi ta tat oxi hoa be mat cac chi tiet bang thep nhom ... e bao ve an mon trong khong kh. Co the oxi hoa bang hoa hoc hoac oxi hoa bang ien e tao lp mang oxit co kha nang bao ve. b) Phot phat hoa : Phot phat hoa la tao nen be mat kim loai mot lp mang phot phat co kha nang bao ve. c) Sunfua hoa : Tao nen be mat chi tiet mot lp mang sunfua nhiet o cao e bao ve cac chi tiet bang thep gang. d) Nitrat hoa :
Tao nen be mat kim loai lp phu bao ve co chc ion NO 2 co tac dung

nh chat lam cham an mon.

e) Nit hoa (tham nit) Tham nit nhiet o 650 7500C trong be cha NH 3 ion Nit chiem cho d tha trong mang li tinh the co tnh chat bao ve an mon kim loai. 3. Bao phu bang vat lieu phi kim : a) Bao phu bang hp chat hu c : + Bao phu bang sn phu : la phng phap co ien dung e bao ve kim loai trong khong kh, nc song, nc bien v.v... + Bao phu bang va trat : Mot so va trat thng dung : Va trat epoxi : nha Epoxy, chat on, chat mau, chat hoa dung mi va chat ong ran. Va trat faolit : gom Rezolfenol fomaldehit, chat on (bot grapht, amian), dung moi (ru etylic) Lp cao su.

+ Bao phu bang vat lieu cuon. Dung lp phu dang cuon co the lam lp phu oc lap, ngi ta dan lp phu dang cuon len be mat kim loai can bao ve. + Bao phu lp poplymer dang tam. b) Bao phu bang hp chat vo c : + Bao phu bang betong chu axit. + Bao phu va trat chu axit. + Xay lot. + Bao phu bang lp men. IV. BAO VE KIM LOAI BANG PHNG PHAP IEN HOA : 1. Bao ve bang protect : Bao ve bang Protect la noi kim loai can bao ve vi kim loai co ien the am hn trong cung moi trng an mon. Kim loai co ien the am hn goi la protect. Trong qua trnh bao ve protect b an mon dan. e bao ve cac ket cau bang thep trong nc bien ngi ta dung protect la hp kim Al - Zn hoac hp kim Manhe. 2. Bao ve catot bang dong ien ben ngoai : La phng phap bao ve kim loai bang dong ien mot chieu thc hien bang cac moi kim loai can bao ve vi cc am cua nguon (ong vai tro catot)

con cc dng noi vi ien cc phu (ong vai tro anot) se b an mon. Ngi ta hay dung ng ong, ng ray hong e lam cc phu. 3. Bao ve anot bang dong ien ngoai : Neu qua trnh thu ong xay ra tren anot th toc o an mon giam i rat nhieu. Kim loai thu ong hoa ien the ien cc se chuyen ve pha dng hn. oi vi mot so kim loai de b thu ong trong dung dch co moi trng oxi hoa manh va khong co cac anion hoat ong kh thu ong ta co the bao ve anot bang dong ien ngoai bang phng phap cc hoa anot kim loai can bao ve. Ngha la noi kim loai vao cc dng cua nguon ien mot chieu ben ngoai lam cho anot b thu ong. V. BAO VE BANG CACH CAU TAO THIET B HP LY : ac iem cau tao cua thiet b anh hng ln en qua trnh an mon cau tao thiet b khong hp ly la nguyen nhan tao ra nhng vung hoat ong cua kim loai lam tang toc o an mon. V the cau tao thiet b hp ly c coi nh mot bien phap bao ve kim loai. V vay khi thiet ke can lu y. - Tranh tiep xuc trc tiep gia cac kim loai cung nam trong moi trng ien ly. - Loai bo ng suat, ac biet ng suat cuc bo khong can thiet. - Cau tao ong thoat khong ong moi trng an mon. - Tranh an mon cuc bo do chat long chay doc thanh thiet b. - Giam nho en mc toi thieu cac khe hep trong cac moi noi cac chi tiet nam trong dung dch chat ien ly. - Tranh cac goc chet gay nen tnh khong ong nhat chat ien ly. VI. TO HP CAC PHNG PHAP BAO VE : Trong thc te ngi ta thng dung to hp cac phng phap bao ve lam sao cho hp ly va kinh te nhat. Thong thng e bao ve ket cau kim loai trong nc bi n ngi ta thng ket hp gia phng phap sn phu bao ve vi bao ve bang protect hoac bao ve bang dong ien ngoai. Phng phap oxi hoa hoac photphat hoa thng s dung lam lp nen cho sn phu. Ngi ta con s dung phoi hp cac vat lieu trong ket cau bao ve e at c hieu qua s dung hp ly va kinh te nhat.

LCH THI
Lp TCHD32 Th 3 ngy 14 thng 3 phng V8.4 T 09gi00 - 10 gi00

THI LI
Th 5 ngy 23 thng 3 phng A 3.3 t 7gi 00- 8gi00