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    Li cm n !u tin em xin c by t lng bit n su sc nPGS.TS inh ThNg

    nhit tnh hng dn em hon thnh n ny.

    Em cng xin chn thnh cm n cc thy c gio B mn Hu c Ha du;cc thy c, cc cn b phng th nghim trc thuc cc khoa, b mn ca trng,Vin vt l k thut, Trung tm sc k kh to iu kin tt nht cho em trong

    sut thi gian lm n ca em.

    Em xin chn thnh cm n nhng thy c tn tnh dy d em trong sut thigian em hc ti trng.

    V cui cng em mun gi li cm n n gia nh v bn b ng vin, toiu kin thun li cho em hon thnh bn n ny.

    Em xin chn thnh cm n!

    H Ni, thng 6 nm 2007sinh vin

    Nguyn Trung Sn

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    MC LC

    M U

    Hn 10 nm tr li y, cng nghip dt c s tng trng ng k vthc s gi vai tr quan trng trong nn kinh t quc dn. Cc sn phm ca

    ngnh dt khng ch c tiu th th trng ni a m cn xut khu sangnhng th trng rt kh tnh v cc sn phm may mc nh M, Chu u. V vy,cnh tranh v thch thc ang l ng lc thc y mi doanh nghip dt may cn

    phi xc nh c cc yu t c nh hng trc tip ti kh nng nng cao u thsn phm. Trong , vn x l vi si trc khi nhum, in hoa l vn cpthit i vi ngnh cng nghip dt nc ta.

    Cc loi si thin nhin v si ho hc u cha mt lng tp cht nhtnh v sau khi dt si li cha thm h, du m t my dt. Hm lng tpcht v du m dnh trn vi si tuy nh nhng n nh hng trc tip n qutrnh nhum, in hoa v s dng vi. V vy, trc khi nhum v in hoa cc loi viu c lm sch ho hc hay thng gi l chun b, tin x l. Vi si sau x lkhng nhng d thm nc, c trng cao, mm mi m cn tng kh nng hp

    ph thuc nhum cao, lm cho nhum mu u v bn p hn.

    Trc y, trong cng nghip dt vic x l vi si ch yu l dng ccphng php c hc hoc cc loi ho cht c hi khng thn thin vi mi

    trng. Nhng ngy nay, vi nhng tin b ca khoa hc k thut, cc cht ty ratng hp lin tc c ci tin theo hng nng cao hiu qu v thn thin vi mitrng. Mt trong nhng khuynh hng c ng dng nhiu nht l s dng ccnguyn liu t du thc vt, bin tnh chng thnh cc sn phm c hot tnh b

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    mt cao. T tng hp cht ty ra c thnh phn ti u, ph hp vi mc chty ra nht nh.

    Vic nghin cu cht hot ng b mt thch hp ty sch du m bm

    trn vi si sau khi dt l nhu cu rt bc thit, khng ch ca ring cc cng ty dtm cn l nhu cu chung ca ton ngnh cng nghip dt may cng nh ca tonx hi.

    n ny nghin cu qu trnh tng hp cht hot ng b mt t du thngsulfat ho x l du m trn vi si.

    CHNG 1

    TNG QUAN L THUYT

    A. VI SI V NGUN NHIM BN VI SI [1,3,24,25]

    I. Gii thiu chung v vi si [3,24]

    Ngy nay mi ngi u nhn thy vi si s dng trong lnh vc may mcgm mt s si dt khc nhau m mi loi i hi s git i thch hp, tc ngmt cch khc nhau di cc tc dng ca nc, nhit , tc ng c gii camy v cht ty ra.

    Cc si dt c xp thnh ba nhm theo ngun gc ca chng :

    Si thin nhin :

    C th thuc tho mc (nh bng, si gai) hoc thuc ng vt (nh len,t).Trong bng c s dng trong cng nghip dt vi t l ln nht 5260%,cn len chim t 69%.

    Si nhn to :

    Dn xut t xenluloza (viscose, autate, rayonne) Si hn hp :

    Si hn hp gm nhng hn hp ca si thin nhin v si tng hp nhpolyester-bng si. Si hn hp phi hp u im ca tng loi si s dng.

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    Si tng hp :

    c to thnh t du ho : polyester, acrylic, polyamit

    Nhiu hng gm nhng hn hp ca nhiu loi si (nh polyeste-bng si),

    gip phi hp cc u im ca tng loi si s dng.Cc loi si dt khc nhau c tm tt bng 1.1

    Bng 1.1 : Cc loi si dt khc nhauLoi si c tnh Khuyn co x l

    Si thin nhin thcvt:BNG - SI GAI

    Dai, bn.Chu nhit cao, ch xtmnh v x l bngClo.

    Si thin nhin ngvt:LEN - T

    Mng manh, mt 40%sc bn dai ca chngnu b t.

    Phi x l vi mi thntrng, git v x nhit 20 n 30oC l tia.

    Si nhn to (viscose,axcetate)

    Dn xut ca si thinnhin thc vt.

    Khng dng Clo xl.

    Si hn hp (hn hpca si tng hp vthin nhin)

    Ngy nay c s dngnhiu, loi si tn tinny dung ho s thoimi ca si thin nhinvi li ch ca si tnghp.

    Nhit git gi cnchn tu theo loi simng manh nht.

    Si tng hp:

    NYLON - RILSAN

    C tnh bn chc. Chngkhng cho nc hoc

    cht bn thm su vo,ngoi tr mt s cht m.

    t chu c nhit cao. Do vic ty ra

    cn c xc nhn lthn trng.

    II. Cu trc v tnh cht ho l vi si. [1,3]

    II.1 Cu trc vi si. [1]

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    Vi c cu to t rt nhiu b si, b si gm nhiu si. Mi si vi lic to nn t rt nhiu x, cc x ny sp xp mt cch ngu nhin v to ramt h thng mao qun vi ng knh trung bnh l 50nm. Gia cc b si ckhong cch v cc b si ny li c xp chng ln nhau to ra dy ca

    vi. Chnh s sp xp nh vy to ra mt h thng cc l trng, gip cho chtbn d dng i su vo cu trc vi.

    II.2 Tnh cht ho l vi si. [3]

    Tt c cc loi x, si dt dng trong cng ngh dt u lcc hp cht cao phn t. Tt c cc hp cht cao phn t ukh ha tan, ch c mt s hp cht cao phn t c nhit nng chy c nh cn a s khi gia nhit s b phn hy trc

    khi chuyn sang trng thi mm hay chy lng, hoc b phnhy m khng chy lng.

    Cu trc l hc ca cc i phn t c chia thnh cc dngnh: dng thng, dng xon, dng cun, dng gp khc v cu trcdng mt li. Vic xc nh c mc nh hng v mc sp cc i phn t s cho ta bit trng thi l hc ca tng loisi. Cc si thin nhin nh bng, ay, lanh v t tm c nhhng cc i phn t kh cao. Cc cao phn t dng sn xut

    si ha hc l cc i phn t phi c cu trc mch thng dngth v khng c cu trc mt li.

    a. Si bng (si thin nhin):

    - Thnh phn ch yu cha trong x l xenlulo (C6H10O5)nchim ti 96%, cn li l cc thnh phn: keo pectin, nit, m, spv tro.

    - Khi lng ring vo loi trung bnh: 1,5 g/cm3.

    - Mm mi, bn c hc cao trong mi trng khng khv thp trong mi trng nc.

    - n nh ha hc tng i tt, kh nng nu, ty, l vgit thun tin.

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    - C kh nng ht m cao, thot nhanh m hi, m bo ctnh v sinh i vi mt hng may mc, hm m ca si kh caoW= 8-12%. Tuy nhin khi ngm trong nc vi ht nc nhanh, db co( co dc t 1,5-8%), d b nhu nt khi mc, dn nhit

    km, khi l kh gi np, nhit l thch hp t 140-150oC.

    b. Si polyamit (si tng hp):

    - Mch i phn t cha nhm metylen (-CH2-). Cc nhmny lin kt vi nhau bng mi lin kt peptit (-CO-NH-)

    - Nguyn liu ban u ca si ny l benzen v phenol.

    - bn ko t v bn mi mn cao (bn cao gp 10

    ln si bng, 20 ln len v 50 ln visco).- co dn n hi ca si tng i ln, bn vng khi mi

    mn, c kh nng nhum mu tt cho nn kh bt bi, khng bnhu nt.

    - ht m thp, kh bay hi thot kh. Hm m W= 4 -4,5% trong khng kh.

    - Kh nng tnh in ca si cao nn gy kh khn cho qu

    trnh gia cng.- Chu nhit km do l si nhit do, nhit 90 - 100oC

    si b km bn rt nhanh v chuyn thnh dng chy mm.

    - C bn tng i so vi kim nhng km bn vng khichu tc dng ca axit m c. D b lo ha di tc dng canh sng mt tri(hiu ng cng).

    c. Si polyeste:

    - Cc mt xch trong si polyeste c dng tng qut sau:-[CO - C6H4 - CO - O - (CH2)2 - O -]-

    - i phn t ca polyeste th hin tnh bt i rt caogia chiu dc v chiu ngang. Mt khc cc nhm (-CO-C6H4-

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    CO-) km linh ng, kh quay t do, cc nhn thm hu nh cphn b trong cng mt mt phng trong mch, lm cho cc iphn t ca polyeste km linh ng, d b cht vo nhau.

    - C nhm este do lin hp vi nhn thm nn c phncc ln.

    - Si polyeste l loi si tng hp c bn c, bnnhit cao.

    - Si polyeste tng i bn vi tc dng ca axit, vi cc chtoxi ho v cht kh v vi tc dng ca cc dung mi hu cthng thng. Nhng si polyeste km bn vi cc tc dng cakim

    - Si polyeste c khi lng ring bng 1,38g/cm3. Do chanhm t a nc, c cu trc cht ch nn si ny c hm m rtthp. V hm m thp nn si c kh nng cch in cao vng thi d tch in gy kh khn cho qu trnh dt.

    - L loi si rt kh nhum.

    B mt ca vi si polyeste l loi b mt khng cc, c sccng b mt yu, cho nn cc cht bo bm cht vo si

    polyeste rt d dng. Tri li, bng si l c cc, c sc cng bmt ln v v vy n b dy bn du kh khn hn

    III. Cc ngun nhim bn vi si. [3]

    III.1. Phn loi cht bn vi si theo ngun gc:

    Cc loi vt bn gp trong lnh vc git ty vi c th c nhng ngungc khc nhau. Chng c th c gy ra t:

    - Chnh thn th con ngi qua mt s ln vi si tip. Chng thng lcc nhm sau: cht nhn da (vt ng ca m v ca da, c bit l c o v ctay )

    - Mi trng (khng kh, m hng, bi, cy ci... ) hoc cc cht mu thinnhin (vt c...) hoc nhn to (kem dng da, mc, du khong cht...)

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    - Thc phm: nhm ny chim phn ln ca nhm. Tht vy, s lng vloi cc vt bn t thc n cc k quan trng, chng thuc cc vt bn rn(chocolat, tri cy...) hoc lng (ru, cafe...).

    - Ngh nghip: cc vt bn thng gp. Vt bn dnh trn qun o ca cngnhn trong cc nh my, trn gin khoan ...

    III.2. Phn loi cht bn theo quan im cht ty ra:

    Ngi ta thng chia cc vt bn thnh ba loi: vt bn bo, vt bn s si,vt bn c bit. Chng cu to bi nhng yu t: tan trong nc (mui, ng...)hoc khng tan trong nc (m, mnh nh...). Vic sp xp ny t nhiu mang tnhnhn to, v cc vt bn t nhin tm thy vi vc thng l nhng vt bn phihp. Chng hn nhng vt bn du m cng vi nhng vt bn c bit...

    Cc loi vt bn trn dnh vo vi si bng nhiu cch. C th do vic bmdnh bi cc lc vt l, do tnh cht l ho (nhng cht tit bo cun dnh bi), hocht

    Vic loi tr cc vt bn trong qu trnh ty ra c th c nng cao davo s thay i thi gian ty, tc ng c hc, nhit . Mc d vy trong mt scng ngh ty git th vic thc hin ty git li ph thuc vo s tc ng qua lic bit cn bn, cht hot ng b mt v cc thnh phn cht ty ra. Nhng

    iu ng quan tm nht l s tc ng gia cc loi cn bn khc nhau. Loi cnbn kh loi tr nht l i vi si vi l cht to mu nh mui than, cc oxit kimloi...Vic loi tr cn bn trn b mt vi si c th kt hp vi cc phn ng hohc hoc c th xy ra m khng c s thay i ho hc.

    III.3. Nguyn nhn gy bn du m trn vi si khi dt: [1]

    Vi c dt t si. Trc khi si qua my dt to thnh tm vi th ccsi ny c a qua nhng dung dch ho cht (c cha du) hoc sp. Mcch ca cng on ny l trnh cho si b x lng v cc si khng b dnh

    vo nhau trong qu trnh dt (do du hoc sp bao quanh mi si lm gim khnng tnh in ca si). Cc loi si dt bao gi cng cha mt lng tp cht nhtnh, sau khi dt si li cha thm du (bao gm du m t my dt v duc a vo bao quanh si nhm chng li s tnh in ca si). V nhng l m vi mc cha c cc tnh cht s dng, cha th em nhum v in hoa ngay

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    c v thuc nhum v ho cht s kh khuych tn vo vi lm cho mu khu, km bn mu. Bi vy, trc khi nhum v in hoa tt c cc loi vi u phic lm sch ho hc hay thng gi l chun b, tin x l. Vi qua chun bkhng nhng d thm nc, thm m hi, c trng cn thit, nhn mn, mm

    mi v p m cn c kh nng hp ph thuc nhum cao, lm cho mu d u vbn hn.

    phc v cho cng on tin x l trn vi si, chng ti nghin cu vtng hp ra cht hot ng b mt c hot tnh cao trong ty ra i t cc loi duthc vt sn c ti Vit Nam.

    IV. La chn du thc vt thch hp tng hp cht hot ng b mt. [3]

    Trong nhng nm tr li y, du thc vt c ng dng kh rng ri trong

    cng nghip bi cc cht thi c ngun gc thc vt c kh nng phn hu sinhhc cao, khng gy hi cho mi trng. Du thc vt c cu trc ho hc khc vicc loi du khong. Chng gm cc axit bo c ni vi nhau qua cu glyxerin(triglyxerit). Du thc vt thng cha hn 98% triglyxerit v khong 2% sterolcng cc hydrocacbon t hot ng khc.

    Du thc vt c ba im khc vi cc du gc khc :

    Thnh phn ho hc kh ng nht v c phn loi theo cc axit bocha nhiu nht trong du. Cc axit ny c chia thnh axit no (axit Stearic, axit

    Palmitic...), axit khng no mt ni i (axit Linoleic) cng cc thnh phn c bitkhc. c bit du c hm lng axit oleic hn 75% th c n nh oxy ho caohn hn du khng no c mt ni i.

    Phn t lng cao, thng t 850890 g/mol vi cc loi du oleic.

    Mc khng no ng k ca tri-glyxerit gip ci thin tnh cht nhit thp nhng li lm gim bn oxy ho.

    Du thc vt c s dng kh rng ri trong cng nghip, l nguyn liu

    ch yu ch to cht ty ra. C rt nhiu loi du thc vt c bin tnh tng hp cht ty ra tin vi si nh: du thng, du da, du s, du truTuynhin da trn tnh cht tng ng v cu to ca cc hp cht Tecpen trong duthng v cc cht bn bm trn vi si, ngi ta thy rng cht ty ra c ngungc t du thng c kh nng ty ra cao nht.

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    B. NGUYN LIU V CHT HOT NG B MTI. Nguyn liu.

    I.1 Du thng. [2,4,9,16,19]

    Nha thng Vit Nam c tch ra t 4 loi thng ly nha chnh:-Thng nha (pinus merkussi), phn b nhiu Qung Ninh v Ngh An.-Thng 3 l (pinus khasya), Lm ng .-Thng ui nga ( pinus massoniana), Lng Sn, Qung Ninh.-Thng Caribe (pinus caribasa), Vnh Ph, Yn Bi. Trong thng nha

    cho nng sut v cht lng nha thng cao nht. Du thng v tng hng(colophaly) l hai sn phm ca qu trnh ch bin nha thng.

    Sn phm nha thng, tng hng, du thng trong nhng nm gn yc thng k nh sau:

    Thnh phn trung bnh ca nha thng bao gm: 71- 79% cc axit nha, 14-20% du thng v tp cht. Do khi ch bin 1 tn du thng s thu c khong200kg du thng v 700kg tng hng.

    T nha thng c th sn xut ra cc sn phm sau: [19]- Du thng dng sn xut ha cht c bn bng chng ct phn on v

    bn tng hp ha hc: -pinen, -pinen, 3-caren, terpineol, camphen, camphor

    - Du thng sn xut ra sn, vecni, xi nh giy, nc hoa, thuc tr su,dung mi, dc phm, x phng, cht bin tnh, ph gia bi trn, nha cho cao su,giy

    - Colophan thng: sn xut sn, x phng, h giy, vecni, mc in, cao sucht do, luyn kim, pho hoa, hn thic, acquy, cht lm cng tc

    Cng ngh ch bin du thng gm ba cng on chnh: Lm sch nguynliu (nha thng), chng theo hi nc v tinh ch du thng.

    Du thng ng u danh sch cc tinh du trn th gii v mt s lng(khong 260.000tn/nm, bng 80% tng sn lng trn th gii). Du thng lcht lng khng mu, c mi c trng, v cay, khng tan trong nc, tan theo btk t l no trong benzen, ete, du bo.

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    Du thng l mt hn hp phc tp nhiu cu t, thnh phn ch yu l cctecpen hydrocacbonat, c cng thc chung l (C5H8)n (vi n=2, 3) v ccsetquitecpen. Du thng c s dng rng ri trong cng nghip, y t v i sngN c dng lm dung mi, lm nguyn liu iu ch camphora tng hp,

    tecpinhidrat, cc tecpineol, thuc tr su v cc cht thm

    Bng 1.2: Cc tnh cht ca cc cu t trong du thng [9]:

    STT Cu tCngthc

    phn t

    Phn tlng

    ToC si p sut

    nht(cp)

    Khilngring

    (kg/m3)

    20mmHg

    40mmHg

    70mmHg

    1 -pinen C10H16 136.23 51.8 66.8 155 1.7 857.82 -pinen C10H16 136.23 58.1 71.5 162 4.4 871.2

    3 3-caren C10H16 136.23 170 861.54 Dipenten C10H16 136.23 68.2 84.3 175 842.05 Limonen C10H16 136.23 175 842.26 Silrestren C10H16 136.23 176 848.07 -felandren C10H16 136.23 72.1 87.8 173 848.08 -terpinen C10H16 136.23 173 835.09 Terpinolen C10H16 136.23 184 862.3

    10 Sesquiterpen C15H24 204

    Thnh phn chnh ca mt s loi tinh du thm cy l nhn l cc hp cht ccu to mch thng v vng, m c th coi nh l cc dime, trime, v polymer caizopren.

    CH2C

    CH3

    CH

    CH2

    Izopren (2-metyl butadiene 1-3)

    l cc hp cht tecpen cha 10 nguyn t cacbon (dime ca izopren),setquitecpen cha 15 nguyn t cacbon (trime), ditecpen cha 20 nguyn tcacbon (tetrame), tritecpen, tetratecpen v.v..

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    Thng ngi ta phn bit cc loi tecpen sau: monotecpen; setquitecpen;ditecpen; tritecpen; tetratecpen

    Trong tng loi trn c cc hp cht cha mch thng, hp cht cha mt

    mch vng, cha hai mch vng.Pinen (c bit l -pinen) l cu t chnh v cng chnh l ch tiu nh gi

    cht lng du thng. Pinen l cht lng snh, khng mu, lu chuyn sang hivng, tan nhiu trong ru etylic, axit axetic, toluen, xylen.[11]

    HC

    H2C

    C

    CH

    CH2

    CH

    C

    CH3

    CH3

    CH3

    8

    2

    4

    3

    7

    1

    6

    5

    HC

    H2C

    C

    CH2

    CH2

    CH

    C

    CH3

    CH2

    CH3

    8

    1

    2

    3

    4

    5

    7

    6

    C10H16(-pinen) C10H16 (-pinen)

    Hai ng phn ch khc nhau v v tr ni i: Ni i 2-3 -pinen v ni

    i 2-8 -pinen.+ -pinen l ng phn pinen quan trng v ph bin nht. Hm lng ca

    -pinen trong du pinus palustris l 65%, trong du pinus pinaster thu c 70%,trong du pinus caribe thu c 70-80%. -pinen c th tri qua nhiu phn ng vc ng dng trong cng nghip cht thm. -pinen c th chuyn ha thnh

    pinane, l mt vt liu quan trng trong cng nghip cht thm. -pinen c thizome ha to thnh -pinen vi chn lc cao.

    + -pinen l thnh phn ca rt nhiu loi du thc vt, c phn ng tng

    t -pinen. Nhit phn chuyn ha thnh myrcen, l nguyn liu quan trng trongcc terpen vng, s dng trong cng nghip ty g cn. Phn ng cng hp viformandehyt to thnh nopyl, nopyl axetat c s dng nh l nguyn liu cacht thm.

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    Bng 1.3: Tnh cht vt l ca -pinen v -pinen [11]

    STTTn cu

    tTos(oC)

    Khilng ring

    20oC

    Ch s khcx 20oC

    Tonc(oC)

    1 -pinen 218.8219.4 0.953 1.4831 352 -pinen 209210 0.919 1.4747 3233

    I.2Tnh cht khng bn nhit ca du thng[19]

    Du thng l hp cht hu c thuc h khng bn nhit, nhiu cu t thnhphn d b phn hy, chuyn ha hay trng hp nhit si di p sut thng(p=760mmHg), nht l khi thi gian ko di.

    Di tc ng ca nhit, -pinen b chuyn ha dn thnh allocimen,

    dipenten, do cc phn ng vng ha v trng hp ca allocimen m chuyn hathnh , v - pinonen vi mt lng nh dime ca allocimen, cn -pinenchuyn ha dn thnh myrcen. Kh nng phn hy ca -pinen v -pinen phthuc vo nhit v thi gian gia nhit (thi gian lu ca vng nhit cao).

    Nhit cng tng hng s tc cng ln v thi gian phn ng cng gim.

    bn nhit ca 3- caren, camphen tricyclen v cc cu t khc trong duthng u cao hn ng k so vi , - pinen. Nhit chng ct ti a y thpc chn theo bn nhit ca , - pinen. S phn hy nhit cn xy ra trong

    thp do s qu nhit cc b. trnh s phn hy nhit, qu trnh chng ct chnkhng c chn tch -pinen t du thng.

    I.3 Nguyn liu du thng Ung B[19]

    i tng nghin cu l du thng Ung B, tch t du thng hai l (pinusmerlersi).

    Thnh phn ha hc ca du thng Ung B: trong du thng c tt c 22cu t, trong cc cu t chnh l , - pinen, 3- caren.

    Bng 1.4: thnh phn ha hc du thng Ung B[19]TT Cu t Cu to PT Phn t lng Nng 1 -pinen C10H16 136,24 78,02 - pinen C10H16 136,24 14,19

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    3 3- caren C10H16 136,24 1,8324 Cc tecpen khc 5,978

    II. Cht hot ng b mt [3,12,22,24].

    II.1. Cc nh ngha: hiu v tnh cht ha l ca cht hot ng b mt chng ta cn hiu mt

    s nh ngha sau:

    II.1.1. Nhng sc cng b mt /giao din. [3]

    a. Sc cng b mt

    Cc lc ht c gi l nhng lc Van Der Waals tc ng gia cc phnt.Trong mt cht lng cho sn, mt phn t ring bit c mi lc li vo v tr

    trung tm ca mt trng lc gia nhng lc hp dn ln nhau, mang dng hnhcu i xng,trng lc ny c to nn bi nhng phn t k cn. Hp lc caVan Der Waals ny bng khng.

    Nhng trn mt ca cht lng th mi s din ra khc hn: cc phn t li bt vo mt trng lc khng i xng. V pha pha kh, hp dn lc, do cc phnt b phn tn mng, th hu nh khng ng k. V pha cht lng, lc ht cto ra t cc phn t tng t, cng mnh m nh ngay gia lng cht lng .

    Do , cc phn t trn b mt cht lng chu tc dng bi mt hp lc ckhuynh hng y cc phn t ny v pha bn trong. Trn bnh din v m, hplc ny tc ng thu nh b mt trng tri tip gip vi khng kh. Chng hnlc ny s to dng hnh cu khi mt git nc ri t do trong chn khng. Trnglc khng cn i b mt cht lng c th tng trng bi mt lng nnglng t do b mt.

    Nng lng ny nh chng ta nhn thy, c khuynh hng lm mtphng co li. Ngc li, mt cng tng ng vi nng lng t do ny phi

    c cung cp nu ta mun tng phm vi b mt c biu hin bng Joule.

    Nng lng t do tnh trn mt n v din tch b mt c gi l sc cngb mt. Tht vy, theo quan im ton hc v th nguyn, nng lng t do cbiu din bng Joule trn mt vung tng ng vi mt sc cng c biu din

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    bng Newton trn mt (cng: F.d ; din tch = d2), do sc cng b mt l: F.d/d2

    = F/d ngha l N/m.

    Trong thc t ngi ta s dng N/m lm n v sc cng b mt.

    b. Sc cng giao dinBy gi chng ta hy xt cc trng hp cht lng khng th trn ln hay

    gia mt cht rn v mt cht lng. Ln ranh tch bit hai cht ny, c gi lgiao din, c cc im chung vi b mt phn chia gia mt cht lng v mt chtkh. C mi n v din tch, km theo mt nng lng t do. Nng t do ny c

    biu din bng Joule trn n v din tch c gi l sc cng giao din. Nnglng v sc cng giao din ny qu tht trn quan im ton hc, tng ngvi mt lc (sc cng) trn n v chiu di. Vy lc (hay sc cng) ny c biu

    din bng Newton / met. Cng phi lu rng sc cng b mt l mt trng hpc bit ca sc cng giao din.

    c.Mixen Nng mixen ti hn

    Cc cht hot ng b mt khc bit vi cc phn t ha tan khc bi nhngc tnh ring ca chng trong dung dch nc. Qu tht, qu mt nng no ca cht hot ng b mt, cc phn t hp li to nn cc mixen. Cc phn t canhng cht hot ng b mt, bao gm mt phn a nc v mt phn k nc,

    hp ph mnh m trn cc giao din, v d trn giao din du/nc. iu ny dinra l do giao din, phn k nc trong mt mi trng thun li hn trongdung dch ni n b bao quanh bi nhng phn t nc. Cng v l do , trongnc cc phn t ny hp li to nn cc mixen, v trong trng thi kt t, nhng

    phn k nc trong mt hon cnh thun li hn v mt nng lng v h thngn nh hn (lc ht hydrocacbon / nc < lc ht nc / nc v lc hthydrocacbon / hydrocacbon).

    S hnh thnh cc mixen lm pht sinh cc dng d thng trong c tnh

    vt l v in hc ca cc dung dch cht hot ng b mt.

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    Dung dch cht hot ng b mt S to thnh mixen

    Hnh 1.1: S hnh thnh cc mixen

    V th khi ngi ta tng nng cc cht hot ng b mt, mt vi c tnh sthay i t ngt. iu c th biu din s lc qua gin di y:

    Sc cng b mt dn in ring

    Log nng Nng

    Hnh 1.2: Xc nh nng ti hn

    Nhng s thay i ny l do cc mixen c hnh thnh bt ng. Nng ph hp vi vic hnh thnh cc mixen ny c gi l nng mixen ti hn(CMC).

    c bit ngi ta xc nh c nhng nng ny bng cch vch ra sbin i ca mt c tnh vt l theo nng ca cht hot ng b mt. Giao

    im ca hai ng thng ca ng biu din cho ta CMC.

    II.1.2. im kraft - im c

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    Mt trong nhng c tnh ca cc cht hot ng b mt anionic l kh nngho tan ca chng tng ln theo nhit . Kh nng ha tan ny tng trng tngt khi tc nhn b mt ho tan to mixen.

    Ngi ta gi im Kraft l nhit ha tan bng CMC (nng mixen ti hn) hay l nhit cc mixen ha tan c.

    im Kraft ny c th c tnh bng cch o nhit ngi ta cmt dung dch vi mt lng cht hot ng b mt no trong nc. iu nych l mt c tnh v nhit o c tu thuc phn no vo lng cht hotng b mt s dng.

    V nhng cht NI, chng ta thy rng ho tan l do mi lin h hydrotrong nc vi chui polyoxyetylen. Tuy nhin nng lng ca cu hydro kh ln

    n khi nng ln th din ra s mt nc, vi kt qu l gim ho tan. Ngita gi im c l nhit cht NI ang ni n tr nn khng ho tan c(im ny to mt dung dch c).

    II.1.3. Ch s cn bng - Tnh a nc - Tnh a du (HLB). [3]

    Mt vi c tnh l ho ca cc phn t hot ng b mt, c bit khnng nh ho ca chng, lin h mt thit vi tnh i cc ca chng. Vo nm1950, Griffin ngh rng c th xc nh tnh i cc ny bi v mt gi tr thc

    nghim m ng gi l HLB (Tnh a nc Tnh a du Cn bng). Mt hpcht t a nc (ngha l t ha tan trong nc) c mt HLB thp. Gi tr HLB giatng tng ng vi s tng trin c tnh a nc ni phn t. Vy HLB ch lmt n v o lng tnh i cc ca phn t.

    C nhiu phng trnh cho php tnh gi tr ca HLB.

    Di y cho thy mi lin h gia ho tan hot tnh phn tn ca cccht hot ng b mt v cc gi tr HLB.

    Gi tr HLB- Khng phn tn trong nc 1 4

    - t phn tn 3 6

    - Phn tn c nhng n nh 8 10

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    - Dung dch trong 13

    c bit vi nhng cht NI, ngi ta c th iu chnh gi tr HLB theo mun : ch cn bin i s mol oxit etylen. V nhng cht anionic, ngi ta b hn

    ch hn, v rng phn a nc (nhm ion) khng bin i ln lm.II.2 c tnh l ha ca nhng tc nhn b mt.[3,22,24]

    a. Nhng thay i cc sc cng b mt v giao din:

    Mt trong nhng c tnh quan trng ca cc tc nhn b mt l kh nnghp th ca chng ti cc giao din. Tc dng hp th ny lm thay i su sc ccsc cng b mt. Vic hp ph cc tc nhn hot ng b mt giao din nc /kh lm gim sc cng b mt ca nc. Cch s lc, cc phn t ca nhng tc

    nhn b mt tp hp cc phn a nc hng v pha nc giao din nc /kh.

    Hnh 1.3 : S hp ph ca cht hot ng b mt giao din kh nc.

    Ti giao din cht rn / lng hay lng / lng (chng hn trong trng hpsi / nc, vt bn dng ht / nc, du / nc), s hp ph ca nhng tc nhn bmt c tc dng lm gim sc cng giao din ca si hay ca vt bn dng ht sovi nc. Tri li, sc cng giao din si / vt bn dng ht li tng ln. S hp

    ph c th c biu din bi s sau (s tp hp cc phn a nc lun hngv pha nc):

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    Hnh 1.4: S hp ph ca cht hot ng b mt giao din cht rn / nc

    Mt c im cn phi lu l: nu s tp hp phn c in tch (trnghp cc cht anionic), th s hp ph cc giao din lng / rn cng thay i ctnh in ng ca chng, chng hn sc y tnh in ca chng.

    Tm li, s hp th cc tc nhn b mt giao din c tc dng:+ Gim sc cng giao din kh / nc c gi l sc cng b mt:

    A/E gim (A/E = kh / nc)

    + Gim sc cng giao din si / nc v vt bn / nc:H/E F/E P/E gim (H: du, P: ht, F:si)

    + Tng sc cng giao din si / vt bn:F/P F/H tng

    Vic gim cc sc cng giao din c th hin c th bi tnh lm t.Cho nn, nu ngi ta t nc tinh khit trn mt si no , nc ny c khuynhhng co li, bi v sc cng b mt ln. Nhng nu ngi ta thm mt cht hot

    ng b mt vo nc, ngi ta gim c sc cng b mt ca nc, lc ncc tri rng ra trn si. Ngi ta ni nc lm t si.

    b. S hnh thnh cc mixen:[24]

    Mt c tnh hp dn khc ca nhng dung dch hot ng b mt l khnng lm tng ho tan mt vi cht hu c thc t khng ho tan trong nc(nh cht hydrocacbon). Hin tng ny c gi l ho tan ho, din ra do vichi nhp cc cht hu c ny vo trong cc mixen theo ba cch khc nhau nh s hnh 1-5 cho thy:

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    Phn t khng cc Phn t bn cc Phn t c cc

    Hnh 1.5: S ho tan ho trong cc mixen.

    Cc phn t khng cc (nh heptan...) bn trong cc mixen, khng h tipxc vi nc. Cc phn t c cc (nh heptanol...), c a vo cc mixen cng

    mt cch thc nh cc phn t ca nhng tc nhn hot ng b mt. Cc phn tc cc li trn lp bn ngoi ca mixen.

    S hnh thnh cc mixen trong hn hp c th c xem nh l mt trnghp ring bit ca hin tng ho tan v c gi l Tnh hng nc; Hintng ny bao gm vic ho tan ca mt cht no (nh ABS) trong mt dungmi (nc) c gia tng mnh m bng cch thm vo nhng hp cht khc(chng hn Toluen Sulfonat Na). S ho tan ho khc hn vi tnh hng nc bivi mt lng cc tc nhn gy tan rt nh cng ho tan c cc cht hu c.

    S ho tan tu thuc vo s lng v kch c cc mixen. Cng c nhiumixen trong dung dch, s ho tan ho cng quan trng. Mt khc, ngi ta githit rng cc mixen c ln c kh nng ln hn ho tan cc cht hu c. Cngcn lu rng im c ca nhng NI c th c xem nh l s bo hiu hnhthnh cc mixen siu ln. iu ny c l gii thch c l do ti sao s ho tanho, (l mt trong nhng c ch ty ra, nh chng ta s thy v sau) l rt quantrng xung quanh im c i vi cc cht NI.[34]

    II.3 nh hng ca nhng nhn t khc nhau trn nhng c tnh l ho cacc cht hot ng b mt.[3,22]

    a. nh hng ca loi phn t:

    - n cc sc cng giao din hay b mt.

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    Nhiu cuc nghin cu c thc hin nhm lin h nhng c tnh vtl, c bit cc sc cng b mt v giao din vi s cu to ho hc ca nhng hpcht hot ng b mt.

    i vi nhng cht anion, Traube cho thy rng trong mt lot gingnhau, mi gc CH2 c thm vo mch cht bo th gim n 1/3 nng cnthit c c mt sc cng b mt no . Ni cch khc, vi nng no ,sc cng b mt gim i khi ngi ta gia tng di ca cc mch cacbon.

    Hartley nhn thy rng nu ngi ta ngn cn cc mixen thnh hnh, sccng b mt gim mt cch mnh m vi nng ln hn nng mixen ti hn(CMC) ban u. V ngi ta c th chng li s hnh thnh cc mixen bng cchlm gim i s i xng ca phn t. c th, ngi ta phi phn nhnh mch

    k nc hay l thay th hai mch ngn hn thnh mt mch di duy nht (chnghn di chuyn nhm c ion vo bn trong v xa phn gia ca mch cht bo).

    Nhng th nghim v kh nng lm t (lin h n sc cng b mt) sau xc nhn gi thit ca Hartley.[3]

    V nhng cht NI, i vi mt mch k nc cho, cc ln o lng ucho thy rng mc gim sc cng b mt tng ln vi mch bo C 12-C14 v etoxyl ho t n khong 3-5. Mt khc, vi mt mc etoxyl ho cho sn, vicmch cacbon gia tng cng c mt tc dng tng t.

    - n s hp ph cc giao din khc nhau.

    Ni chung, s hp ph tng ln theo di ca dy k nc. i vi cccht NI, s hp ph gim khi s oxyt etylen a nc tng thm.

    - n nng mixen ti hn (CMC).

    Trc ht, phi lu rng nng mixen ti hn ca cc NI yu hn nng ca cc cht anion (1/100). Mt khc, s lng mixen ca cc NI (s kt t)

    quan trng hn s lng mixen ca cht anion. i vi cht anion, nng mixenti hn (CMC):

    . Gia tng theo chiu di mch cacbon.

    . Bin i t theo bn cht ca nhm phn cc.

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    log CMC = A B. log C+

    Trong C+ l nng cc cht phn ion. Nu ngi ta thm mt lngquan trng cht hu c c cc (ure hay etanol chng hn) vo th c th ngn cn

    c vic hnh thnh cc mixen ca cht anionic. l nhng cht hng ncc s dng c bit trong cc cht ty dng nc. Mt khc, thm mt lngnh cht ny lm gim i CMC (nng mixen ti hn). i vi cc NI thm cccht in gii vo to nn tc dng mui, vy lm gim i CMC. Tuy nhin phighi nhn rng tc dng cc cht in gii trn vic hnh thnh mixen ch din ratht s vi cc cht NI, m s oxit etylen ca chng di 15.

    Tm li s ho tan ho lin h rt cht ch vi s lng mixen v kch cca chng: tt c nhng g c th lm gim nng mixen ti hn (mch k nc,

    cht in gii), u gia tng s lng v kch c cc mixen v cng v th gia tngs ho tan ho, s hp ph c tc dng lm thay i cc c tnh giao din, c

    bit lm gim sc cng b mt; iu ny c th hin qua vic gia tng kh nnglm t ca dung dch cht hot ng b mt.

    III. Nhng l thuyt ty ra khc nhau.[3,22]

    S ty ra c nh ngha l lm sch mt ca mt vt th rn, vi mt tcnhn ring bit, cht ty ra, theo mt tin trnh l ho khc hn vi mt vic ho

    tan n thun.Trong trng hp ca chng ta ty ra gm:

    . Ly i cc vt bn khi vt dng / vi vc

    . Gi cc vt bn ly i ang l lng trnh cho chng khi bm li trncc qun o hin din trong dung dch.

    Trn cc qun o gia dng ch yu ngi ta gp nhng vt bn c cht bo(m hoc du) v cc vt bn dng ht (cc ht mn). Cc vt bn cht bo v dng

    ht ny c th tn ti c lp hay ho ln vo nhau vi nhng t l rt khc nhau.Cc vt bn cht bo c th do t b nhn ni c th con ngi hay do tip

    xc vi cc cht bo mi trng (thc n, m phm, du my.) hay do cn cnb x bng bm li trn khn tm.

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    Cc vt bn dng ht gm oxit kim loi, t st hay cc hp cht cacbon haynh ni.

    Cc tc nhn b mt ch ch yu lin h n vt bn c cht bo v dng ht.

    C ch hot ng ca chng rt phc tp nu ngi ta bn chung n cc loi vtbn ny. Nhng gii thch qu trnh ty ra d dng hn nu ngi ta xt hai loivt bn ny c lp vi nhau. n gin ha chng ta s bn lun n vic ly icc vt bn c cht bo ri n cc cht dng ht tch bit hn nhau.

    III.1 Ty cc vt bn c cht bo.[3]

    a. Thuyt nhit ng phng thc lanza

    Chng ta hy xt n mt cht bo H (du) v mt b mt rn F (si). Vic

    vy bn F do H c th c biu din qua s sau:

    I II

    Hnh 1.6: S vy bn do mt cht bo.

    Khi git du H (th I) tip xc vi si F (th II), th git du tri ra cho nkhi t mt th cn bng vi mt gc tip gip, c xc nh bi b mt ca siv ng tip tuyn ca giao din du / kh. Nng lng t do ca th II c thc vit theo phng trnh sau y:

    EFA = EFH + EHA.cos (1)Trong : EFA: nng lng t do si / kh.

    EFH: nng lng t do si / du.EFH: nng lng t do du / kh.

    Nh chng ta thy trc y, nng lng t do tnh trn mt n v dintch th bng sc cng giao din hay b mt. Phng trnh (1) tr thnh:

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    FA = FH + HA. Cos (2)

    Mt khc, cng gn cht cht lng H vo cht nn F c biu din bngphng trnh Dupr

    WFH = FA + HA - FH (3)

    Theo phng trnh ny, ngi ta thy rng gy bn cng d dng bao nhiuth cng gn cht cht lng WFH cng yu i by nhiu.

    c nh th, ch cn sc cng b mt F(FA) hay sc cng b mt ca H(HA) yu i. Cc b mt khng cc (du , polyester) c mt sc cng b mtyu, cho nn cc cht bo bm cht vo si polyester rt d dng. Tri li, bng sic cc, c sc cng b mt ln hn v v vy n b dy bn du kh khn hn.

    S ty vt bn c cht bo H khi mt b mt F, c biu din bi s hnh 1-7 sau:

    II III

    Hnh 1.7: S ty ra vt bn c cht bo.

    S ty vt bn bao hm i t th II sang th III. Chng ta hy tnh cng cnthit thay i th ny.

    ban u th II, nng lng t do c biu din bng:

    EII = HF + HEKhi vt bn tch khi b mt F, trong th III, nng lng t do c biu

    din bng :EIII = FE +2HE

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    (ta c 2HE bi v trong th III, ngi ta to nn mt phn gii H / E phthm).

    Cng cn thit i t th II sang III bng:WA = EIII EII = FE +2HE (HF + HE) hay

    WA = FE + HE HF (4)

    Theo phng trnh ny, ngi ta thy rng cng cng yu hn (do gt tyd hn), th hai bin s u FE v HE cng yu hn v bin s th ba HF li lnhn. S thm tc nhn b mt l lm gim sc cng b mt (vy l gim FE v HE)v gia tng sc cng giao din HF nh s hp ph ca tc nhn b mt giaodin F, E v H/E.

    Mt khc, cng c th ghi nhn rng trong trng hp si polyester (khng

    cc) b gy bn bi mt cht bo (khng cc), th sc cng giao din HF yu. Vicgy bn ny do kh khn hn trong trng hp bng si trong HF ln hn

    bi v bng si gm phn t c cc.

    Da vo nhng d kin nhit ng hc, ngi ta c th xc nh nhng iukin cn thit gt ty t pht vt bn c cht bo. vt bn t ty, nnglng t do giai on cui ( ty sch ) cn phi km hn giai on u (bnhim bn), ngha l:

    EIII < EII hay

    FE +2HE < HF + HE hay FE + HE < HF

    Vy nu tc nhn b mt, do s hp ph ca n trn si v vt bn, lm gimc sc cng giao din ca chng (so vi nc) n m tng ca chng trthnh km hn sc cng giao din si / vt bn, lc vt bn s t ty i.

    b. C ch Rolling Up.

    Vic ty i cc vt bn bo cng c th c gii thch bi thuyt Rollingup, c Stevenson nhc n vo nm 1953. Chng ta s xem xt s sau:

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    Hnh 1.8: Phng thc Rolling UpVic ty i cc vt bn t th II sang th IV, qua th trung gian III. Khi cn

    bng, hp lc ca ba vect FE ,HE ,HF c biu din bng phng trnh sau y:

    FE = FH + HE. Cos (5)

    suy ra osFE FH

    HE

    C

    = (6)

    ty i cc vt bn, phi bng 180o hay Cos = -1. Trong iu kinny, phng trnh (6) thnh

    1 FE FH

    HE

    = hay HF = FE + HE (7)

    Cht hot ng b mt, do chng c ht trn si v vt bn, lm gim ccsc cng giao din FE v HE theo phng trnh (6) c xc minh trn y. V lc

    , mng du (vt bn bo ) s cun li v tch khi si trong qu trnh git (gitbng tay hay bng my). l c ch Rolling Up.

    c. Ha tan ha.

    C ch Rolling Up ch lin quan n cc vt bn th lng c cht v chyu nh cht hot ng b mt lm gim sc cng giao din. Sau khi c c nng

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    mixen ti hn, th khng cn gim sc cng giao din na, cho nn hiu ngRolling Up khng tng khi c nng ny. Tuy nhin, v ngi ta thy s gitty gia tng nhanh khi vt qu CMC (nng mixen ti hn), ta cn phi nh nmt c ch khc; s ha tan ha. L thuyt ny c a ra trc ht bi Mc

    Bam vo nm 1942, ri li c Ginn, Brown v Harris kim chng li vonm1961. Chng ta ni n hin tng ha tan ha trong phn c tnh ha lca cc tc nhn b mt, vic hnh thnh cc mixen, nh hng ca nhng nhn tkhc nhau trn nng mixen ti hn. Cc phn t ca cc tc nhn b mt kthp vi nhau trong cc dung dch long hnh thnh cc mixen mt nng no c gi l nng mixen ti hn. Trong cc mixen, phn k nc ca

    phn t hot ng b mt quay v pha trong, trong khi phn a nc (nhm ion-ha hay polyoxyetylen) li hng v nc. Rt nhiu trng hp cht khng ha

    tan trong nc nh cc axit bo, ru bo, triglyxerit, hydrocacbon li c hatan bn trong cc mixen. Nu cc phn t c ha tan c cc (chng hn cchydroxyl hay cacboxyl) th cc phn t , ni chung, c tm thy phn anc ca mixen.

    S ha tan ha ch din ra khi nng cht hot ng b mt cao hn sovi nng mixen ti hn(CMC).

    Tm li ty ra tt khng nhng cn gim sc cng b mt (phng thc

    Lanza, c ch Rolling Up) m cn phi tng nng cc hot cht hnh thnhcc mixen (ha tan ha) v c c mt s mixen , ty theo lng vt bn bohin din trong dung dch git ra.

    III.2 Cc c ch khc ca s ty ra.[3]a. S hnh thnh cc pha th trung gian:

    Cc mixen thnh hnh trong dung dch long th nh v hu nh hnh cu.Nu ngi ta gia tng nng cht hot ng b mt, cc mixen tr nn ln hn

    v khng i xng. Sau cng xut hin mt pha mi gi l Pha th trung gian.Pha th trung gian l mt cht lng rt st hay ngay c l nh gel, c cu to bicc mixen c t chc ring bit. Pha th trung gian ny lng chit v cho ra mthnh nhiu x khi tia X quang chiu qua. V l do , ngi ta gi n l tinh thlng.

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    phn giao din vt bn cht bo / nc, cc tc nhn b mt b hp ph do hnh thnh mt tng n dy c cc phn t. Ngi ta c th xem rng nng tc nhn b mt hnh thnh c gia vt bn v dung dch ty mt phan hi, to nn cht lng tinh th hay Pha th trung gian. Sau , pha th trung

    gian ny phng ln ri xp xung do nc thm thu. Vt bn lc y cphn tn trong dung dch ty di dng nh tng hay di dng ha tan hatrong cc mixen.

    Cn lu rng pha th trung gian ch c th c hnh thnh vi nhngcht bo c t nhiu cc, nh cc axit bo hoc ru bo. Vy c ch ty ra nych c c p dng cho nhng vt bn c cc. Mt khc, tng pha th trung gianto nn mt lp mng rt nhn ngn cn dung dch ty mi xm nhp vo trong vt

    bn, iu ny c tc dng lm chm i mt cch ng k vic tch ra v phn tn.Chnh v nhng l do m c ch ny c xem nh l t quan trng trong tintrnh git ty.

    IV. Phn loi cht hot ng b mt.[4]

    Cht hot ng b mt c chia lm 4 loi:

    - Cht hot ng b mt anion.- Cht hot ng b mt cation.

    - Cht hot ng b mt khng ion (NI).- Cht hot ng b mt lng tnh.

    a. Cht hot ng b mt anion:

    Nu nhm hu cc c lin kt bng ha tr cng vi phn k nc cacht hot ng b mt mang in tch m (- COO -, - SO32-, - SO42-...), cht hotng b mt c gi l anion: cc x phng, cc alkylbenzen sulfonat, cc sulfatru bo...l nhng tc nhn b mt anion.

    b. Cht hot ng b mt cation:Ngc li, nu nhm hu cc mang mt in tch dng (- NR1R2R3 +), th

    cht hot ng b mt c gi l cation, chng hn nh clorua dimetyl distearylamoni.

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    Cc cht cation c gi l i nghch vi cht hot ng b mt anion datrn mi quan h in tch. Mt lng nh cht hot ng b mt anion hay thmch cht hot ng b mt khng ion cng c th nng cao vic ty ra.

    c. Cht hot ng b mt khng mang ion (NI):Cht hot ng b mt khng mang ion c nhng nhm hu cc khng ion

    ha trong dung dch nc. Phn k nc gm mch bo. Phn a nc cha nhngnguyn t oxy, nito hoc lu hunh khng ion ho. S ha tan l do cu to nhnglin kt hydro gia cc phn t nc v mt s chc nng ca phn thch nc,chng hn nh chc nng ete ca nhm polyoxyetylen (hin tng hydrat ha).Trong loi ny ch yu l cc dn xut ca polyoxyetylen hoc polyoxypropylennhng cng cn thm vo cc este ca ng,cc alkanolamit.

    d. Cht hot ng b mt lng tnh:

    Cc cht lng tnh l nhng hp cht c mt phn t to nn mt ion lngcc. Chng hn axit xetylamino-axetic trong mi trng nc cho hai th sau y:

    C16H33-N+H2-CH2-COOH (trong mi trng axit) v

    C16H33-NH-CH2-COO- (trong mi trng kim).

    Trong tt c cc phn t y, phn k nc gm mt dy alkyl hay dy bo.

    Chng c biu th bng:CH3-CH2-CH2-CH2--- hay R

    Bn cht hot ng b mt c th k hiu nh sau:

    V. Mt s cht hot ng b mt chnh dng trong ty ra [28,29,30]

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    Trong s 4 loi cht hot ng b mt th hai loi cht hot ng b mtc dng trong sn phm ty ra l cht hot ng b mt loi anionic v chthot ng b mt khng mang ion(NI).

    V.1 Cc anioni:[30]a. Nhng hp cht kiu alkylsulfonat:

    Alkyl bezen sulfonat (ABS). y l cht hot ng b mt thng c sdng nht. C nhng ABS nhnh v ABS thng. ABS nhnh ch cn dng mtvi quc gia v tc phn gii chm bi cc vi sinh vt.

    ABS nhnh:

    SO3-

    C

    CH3

    CH2 C

    CH3

    CH3

    CH3CH2C

    CH3

    CH3

    CH3

    ABS thng (LAS :linear alkylbezen sulfonat):

    (CH2)nCH3 SO3H

    Sulfonol: l hn hp cc mui Natri kiu alkylsulfonat. Sulfonol d ha tantrong nc nng, c kh nng ty ra v thm t nn c dng nu cc loivi xenlulo v git len. Sulfonol c cng thc tng qut nh sau:

    CH SO3Na

    (CH2)n

    (CH2)n

    CH3

    CH3

    b. X phng:

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    X phng l mui ca cc axit bo nh axit stearic, axit oleic, axit palmiticv nhiu axit bo khc na. Cng thc tng qut ca chng l R-COONa. Khi

    phn ly trong nc chng to thnh 2 ion:

    R-COONa R-COO- + Na+

    X phng c u im l c kh nng thm t, kh nng ty ra v kh nngnh ho cao, nhng n c vi nhc im sau:

    - V l mui ca mt axit yu v mt baz mnh nn khi phn ly dung dchx phng c phn ng kim tnh r rt.

    - Dung dch x phng km bn vi tc dng ca cc mui cng (Ca, Mg),nn khi gia cng vi bng nc cng th x phng s b kt ta bm vo vi kh

    sch. Nhng kt ta ny s gy nh hng xu n u mu ca vi v lmgim v p ca mu.

    c. Nhng cht hot ng b mt kiu alkylsulfat:

    Khi sulfo ha kt hp mt s dn xut ca cc axit bo, nu nh nhm sulfokt hp vo nhng hp cht ny bng lin kt este qua nguyn t oxi, th cht thuc c tnh cht hot ng b mt, c cng thc tng qut l R-CO-SO3Na. Tiu

    biu l:

    Avirol: l mui amoni estesulfo ca butyloleat c cng thc sau:

    CH3 (CH2)7 CH

    O SO3NH4

    (CH2)7 COOC4H9

    Avirol c sn xut dng lng snh, d tan trong nc lnh nhng khi lu dung dch c. Do c kh nng ty ra v nh ha tt nn c dng lm chtnh ho du m.

    Sulfat ru bc mt (PAS: primary alcohol sulfate):

    R-CH2-O-SO3-Na vi R= C11 C12

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    iu kin nht nh, mt phn hoc ton b c chuyn ho thnh cc hp chtsulfat khi khng c mt nc v cc cht kim.

    Phn ng ca mt s loi du vi axit sulfuric c th din ra theo mt s

    cch khc nhau, ph thuc vo nhit , s tng hp ca cc cht c a voqu trnh phn ng v ph thuc vo thi gian phn ng. Cc ph ng ch yu tothnh sn phm dng sulfat nhiu hn sulfonat i vi cc loi du thng thng.

    Tc nhn sulfat ha s dng trong qu trnh ny l axit sulfuric. Di tcdng ca axit sulfuric s to ra cc hp cht mono- v dialkylsulfat c tnh chthot ng b mt tt. Ngoi ra cn to ra cc sn phm ph polyme v nha(do strng ngng), nhng cht ny lm gim ng k cht lng cht hot ng b mt.Sn phm chnh trong qu trnh mong mun l monoalkylsulyfat v vy khng

    ch cc phn ng trng hp, nha ho v to thnh dialkylsulfat hoc ete th nng H2SO4 phi khng ch nng thch hp 8090% v tin hnh iu kinnhit thp. Du thng khng tan trong axit v vy s khuych tn du thng thu c qua v c ng vai tr rt quan trng. Cng vi s gii nhit, tc khuych tn s quyt nh vn tc qu trnh. Qu trnh c th tin hnh vi skhuy trn mnh v gii nhit nhanh. Khi thc hin quy trnh ngi ta s dngthit b c cnh khuy v cho t axit vo trnh s tng vt nhit ca phn ngv nh vy trnh c nhng phn ng khng mong mun.

    Cc phn ng chnh xy ra trong qu trnh sulfat ho nh sau:

    H2SO4 85%

    30oC

    HC

    H2C

    C

    CH2

    CH2

    CH

    CCH3

    CH3

    CH3

    O SO3H

    HC

    H2C

    C

    CH

    CH2

    CH

    CCH3

    CH3

    CH3

    HC

    H2C

    C

    CH

    CH

    CCH3

    CH3

    CH3

    -pinen

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    H2SO4 85%

    30oC

    HC

    H2C

    C

    CH2

    CH2

    CH

    CCH3CH3

    HC

    H2C

    C

    CH

    CH

    CCH3

    CH2

    CH3

    HC

    H2C

    C

    CH2

    CH2

    CH

    CCH3

    CH3

    CH3

    O SO3H

    -pinen

    Phn ng ph: [11]

    H2SO4

    28 oC- 32

    HC

    H2C

    C

    CH

    CH2

    CH

    CCH3

    CH3

    CH3

    HC

    H2C

    C

    CH

    CH2

    CH

    CH3

    C

    CH3 CH3

    OH

    OH

    -pinen tecpin hydrat

    VI.2 Oxy ha du thng:[8]

    Cht si bt tt nht lm giu theo phng php tuyn qung kim loimu l du tuyn i t du thng. Mt khi lng ln bt nh, khi lng ngu c kh nng lm ni ln cc ht vt liu c ch v d dng b ph hu. Vic tothnh nhiu bt l do ru terpen c trong du. Nguyn liu ch yu sn xutdu tuyn l t du thng.

    Nh bit -pinen v -pinen l nhng cu t chnh ca du thng, n db oxy ho bi khng kh, -pinen b oxy ho thnh pinol, sau thnh ru

    solrenol, mirtenol. -pinen b oxy ha thnh ru pinenearveal.VI.3 Hydrat ho du thng:[8]

    Khi gia cng du thng bng hn hp axit H2SO4 v toluensulfuaxit th xyra qu trnh hydrat ho pinen to thnh tecpinhydrat.

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    CHNG 2

    THC NGHIM

    I. Tng hp cht hot ng b mtt du thng bng phng phpsulfat hoI.1 Nguyn liu:

    S dng ngun nguyn liu ca Vit Nam, bao gm :- Du thng Qung Ninh

    I.2 Thit b, dng c:- Cc thu tinh 50, 80, 250ml.- ng ong, pipet.

    - Cn phn tch.- My khuy t gia nhit.- Bp in, nhit k.- Bnh tam gic c nt nhm.- T sy- Bnh cu 3 c dung tch 250 ml

    I.3 iu ch:

    Cho vo bnh cu 3 c 100ml du thng, axit H2SO4 cho nh git t t vo

    bnh phn ng khong 13 ml trong thi gian 1 gi. Phn ng c thc hin cc nhit khc nhau, nng khc nhau v thi gian l khc nhau. Phn ngthc hin trn bp khuy t gia nhit. Ban u khi cho axit vo th nhit ca

    phn ng tng ln. Qu trnh sulfat ho tin hnh trong khong thi gian 4 6ting. Dung dch sau qu trnh sulfat ho ta em ra axit bng nc ct v trungha bng Na2CO3 10%

    Cch ra axit:

    - dung dch sau qu trnh sulfat ho vo phu chit.- Sau nc ct vo v lc u cho dung dch tr nn ng nht.- khong t 2 5 pht cho nc ln axit lng xung di y phu ri

    tho b phn nc ny i.- Lm li thao tc ra khong 3 4 ln.

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    - Cho khong t 8 10 ml Na2CO3 10% vo ri lc u trung ha htaxit.

    - Cui cng ra li bng nc ct mt ln na.

    Hnh 2.1: S thit b phn ng v thit b tch chit.

    II. nh gi kh nng ty ra ca cht hot ng b mt iu ch:

    nh gi kh nng ty ra ca cht hot ng b mt c rt nhiu phngphp: o sc cng b mt, phng php o trng ca vi, o nh bn,phng php o trng lng

    Tuy nhin, do lng cn du bm trn vi si rt nh nn khng th dngphng php o trng lng xc nh ty ra. Sau khi nghin cu chng tinhn thy phng php xc nh kh nng ty trng hiu qu nht ca cht ty radng cho vi si l phng php o trng ca vi.

    II.1. To mu th:

    Mu vi ct ra vi kch thc nht nh : di 5cm, rng 5cm. Cho du bmtrn cc mu vi hon ton ging nhau bng phng php nh git nh ng maoqun.

    II.2. Ngm mu xc nh kh nng ty ra:

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    Cho mu vi cn ty vo trong cc ng du thng bin tnh. Tin hnhngm mu trong iu kin nhit khc nhau c khuy, thi gian ngm mu cngkhc nhau.

    Sau ly mu vi ra, ra li mt ln bng nc sch. em mu vi va tyi phi kh v cho vo ti ng mu em i o trng.

    II.3 o trng ca vi (o ti: Vin kinh t k thut dt may)

    - Tiu chun o trng : ISO105J02

    - My o : Gretag Macbeth

    ColorEye 2180 UV

    - Nguyn l ca php o : Php o da trn c s s dng qu cu tch phn.

    nh sng chiu thng vo mu v tn x vo qu cu tch phn. Phn nh sng tqu cu tch phn s c chiu thng ti t bo quang in. Ti , my s tng o cng nh sng c chuyn thnh tn hiu in, tng ng vi cc

    bc sng t 380700nm. Ph thuc vo mc phn x khc nhau ca cc bcsng khc nhau m xy dng c ng cong phn x ca nh sng theo bcsng. Tng ng vi cc v tr trn ng cong, khi t hp li s xc nh cmu.

    III. Xc nh mt s thng s ho l ca cht hot ng b mt: m bo an ton trong qu trnh th nghim v qu trnh bo qun cht

    hot ng b mt, cn phi kim tra mt s thng s ho l ca cht hot ng bmt nh : bay hi, t trng, sc cng b mt, hm lng lu hunh, nht

    III.1. Xc nh bay hi:

    III.1.1. Dng c

    - Cc 80ml.

    - Cn phn tch.

    - ng h o gi.

    III.1.2. Cch tin hnh

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    - Cn ln ly khi lng nc v bnh (m2).

    - Ra sch v sy kh bnh t trng.

    - Cho sn phm cn o vo bnh t trng ri cn ly trng lng ca bnh v

    sn phm (m3). o v ghi li nhit ca sn phm khi cn.T trng sn phm c xc nh bng cng thc:

    3 1

    2 1

    m md

    m m

    =

    Hnh 2.2: S thit b xc nh t trng.III.3. o sc cng b mt ca cht hot ng b mt trong nc:

    Cng vi vic xc nh kh nng ty ca dung dch cht hot ng b mtbng cch o trng ca vi, chng ti cng nghin cu kh nng ty ra thngqua vic o sc cng b mt ca cht hot ng b mt.

    Ta bit rng khi cho mt cht hot ng b mt vo mt vt bn du m thn s hp ph ln b mt phn cch du/nc hoc vi nc lm gim lc bm

    dnh ca du vi b mt. S hp ph cng mnh m th s cng lm gim nhiu sccng b mt ca du trong dung dch cht hot ng b mt v s ty ra cng tt.Vic gim cc sc cng giao din c th hin c th bi tnh lm t.

    III.3.1. Nguyn tc:

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    Hnh 2-2: Thit b o sc cng b mt.

    2. Cch tin hnh :

    u tin chnh cho my t cn bng.

    *Chun b :

    - Nhn nt khi ng my, ch my khi ng xong nhn nt Start.

    - Chn o SCBM.- t cc thng s :

    + Thng s vng l : 6,1858

    + R/r l : 54,2857

    + D/d (t trng ca 2 mi trng khng kh v cht cn o)

    + t nhit tin hnh th nghim.

    *Tin hnh :

    Cho cht lng cn o vo trong cc (1) khong t 130150ml, t vo my,sau dng cn chnh th iu chnh sao cho vng (2) ngp trong cht lngkhong 35mm. Nhn nt Enter thy pht ra ting pip, nhn nt zero tr v gi

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    CHNG 3

    KT QU V THO LUN

    I. Nghin cu cu trc v b mt vi cotton.

    I.1 Cu trc vi cotton.

    nghin cu cu trc ca vi cotton, chng ti tin hnh chp SEM cax bng nguyn cht v mu vi sch. Kt qu nh sau :

    a) b)

    c)Hnh 3.1: nh SEM

    a. B mt ngoi x bng;

    b,c. Mt ct ngang x bng.

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    T bng s liu trn, c th xy dng th biu din mi quan h gia khnng ty ra v nng axit H2SO4.

    89.36 92.71

    86.1975.71

    63.1

    0

    20

    40

    60

    80

    100

    80 85 90 95 98

    Nng axit sulfuric (C%)

    trngcavi(%t

    yra)

    Hnh 3.1: Mi quan h gia kh nng ty ra v nng axit H2SO4

    Nhn xt:

    T th trn cho thy, mu S4 vi 3ml H2SO4 85% cho ta hot tnh ty ratt nht(92,71%). Nng axit m ln qu th c th xy ra cc phn ng ph nh

    phn ng sulfo ho, oxy ho gy vng lm gim hiu sut. Nng axit m nh

    hn cng lm gim hiu sut ca qu trnh sulfat ho. Vy thc nghim chngminh nng axit 85% l tt nht.

    IV.2 nh hng ca lng axit H2SO4

    C nh nng axit H2SO4 85%, thay i lng H2SO4 v thi gian phnng l 5h, nhit phn ng l 30oC. Ta i kho st nh hng ca lng axit nqu trnh sulfat ho.

    Qua qu trnh sulfat ho du thng vi cc nhit khc nhau ta thu c

    kt qu bng s liu sau:Bng 3.3:nh hng ca lng H2SO4 trong phn ng sulfat ho du thng

    (phn ng thc hin 30oC v 5h)Mu Du thng

    (ml)Nng H2SO4

    (%)H2SO4(ml)

    trng ca vi(% ty ra)

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    S6 200 85 2 90.01S7 200 85 3 92.71S8 200 85 4 85.23S9 200 85 5 79.41

    T bng s liu trn ta xy dng th biu din mi quan h gia kh nngty ra v lng axit H2SO4 nh sau:

    90.0192.71

    85.23

    79.41

    70

    75

    80

    85

    90

    95

    2 3 4 5

    Lng axit sulfuric (ml)

    trngcavi(%t

    yra)

    Hnh 3.2: Mi quan h gia kh nng ty ra v lng axit H2SO4

    Nhn xt:

    T th cho ta thy, mu S7 vi 3ml H2SO4 85% cho ta hot tnh ty ra tt

    nht (92,71%). Lng axit m nhiu qu th c th xy ra cc phn ng ph nhphn ng sulfo ho, oxy ho lm gim hiu sut. Nu lng axit m long qu thphn ng xy ra chm do nng tc nhn khng . Vy thc nghim chngminh lng axit 3ml l tt nht.

    IV.3. nh hng ca nhit :C nh lng axit H2SO4 85% l 3ml v thi gian phn ng l 5h kho

    st nh hng ca nhit .

    Qua qu trnh sulfat ho du thng vi cc nhit khc nhau ta thu ckt qu bng s liu sau:Bng 3.4:nh hng ca nhit trong phn ng sulfat ho du thng

    (Vi 3ml H2SO4 85% v thi gian 5h)

    Mu Du thng Nhit phn ng H2SO4 85% trng

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    T th cho ta thy, qu trnh thc hin phn ng sulfat ho thi gian l5h s cho sn phm du thng bin tnh c hot tnh ty ra tt nht l (92,71%).V nu thc hin thi gian phn ng ngn hn th phn ng t hiu sut khngcao, nh hng n kh nng ty ra. Nu thi gian di hn s nh hng n chi

    ph sn xut v xy ra phn ng ph.

    Nh vy iu kin ti u sulfat ho du thng l tin hnh 30oC vi 3mllng H2SO4 85%, trong thi gian 5h.

    IV.5. So snh kh nng ty ra ca du thng sulfat ha v du thng chabin tnh:

    Xt kh nng ty ra ca du thng sulfat ho v du thng cha bin tnh tac bng s liu sau:

    Bng 3.6:Kh nng ty ra ca du thng sulfat ho v du thngcha bin tnh:

    Mu Du thng sulfat ho Du thng cha bin tnh

    trng ca vi(% ty ra)

    92,71 50,36

    Nhn xt:

    Qua bng s liu trn ta thy du thng khi sulfat ho th kh nng ty racao hn nhiu so vi du thng cha bin tnh. Nguyn nhn l do du thngkhng phn cc nn kh nng bm dnh ca cht ny trn b mt vi km. Sau khi

    bin tnh, nhm -O-SO3H s nh vo vng tecpen to nn phn cc mnh, lmcho kh nng bm dnh trn b mt vi si chc hn nn kh nng ty ra tng ln.

    IV.6. Hm lng lu hunh:

    xt xem s c mt ca nhm sulfat c gn vo cc cu t trong du

    thng, sau phn ng sulfat ho, chng ti tin hnh xc nh hm lng luhunh bng phng php t v sau chun . Kt qu c a ra bngdi y:

    Bng 3.7: Mi quan h gia kh nng ty ra v hm lng lu hunh

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    Hnh 3.6: Ph IR ca mu du thng ban u.

    61

    Nicolet 6700 NRX F T-Raman Module Spec trome

    Number of sample scans: 256Resolution: 2.00001064nm excitation laser

    6

    787.1

    886.4

    905.1

    1014.2

    1125

    1196.

    1365.4

    1378.3

    1447.2

    2834.0

    2878.7

    2920.5

    2959.0

    3023.9

    0

    10

    0

    0

    0

    0

    0

    0

    Sample: Dau thong 24-5-07

    Nicolet 6700 NRX FT-Raman Module Spectrome

    Number of sample scans: 256Resolution: 2.00001064nm excitation laser

    ..

    ..

    787.3

    815.4

    873.1

    886.8

    .

    1014.6

    10

    .

    11

    25.1

    1165.5

    1204.

    1219.2

    12

    .

    1

    .

    1364.6

    1377.51

    446.9

    1514.8

    165

    .

    .

    .

    2834.4

    2864.0

    2920.8

    3024.0

    .

    .

    0

    0

    0

    0

    0

    0

    0

    0

    Sample: Dau thong bien tinh 25-4-07

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    (mN/m) (%kl) (cSt) (% ty ra)

    Du thngsulfat ho 0,9043 21,201 2,004 2,734 92.71

    KT LUN

    1. Nghin cu cu trc v b mt ca vi si (ch yu l si cotton). Kt qul: vi si c cu to t rt nhiu b si, b si gm nhiu si, khong cch

    trung bnh gia cc si l 20,8.10

    3

    nm. Mi si vi li c to nn t rt nhiu x,cc x ny sp xp mt cch ngu nhin v to ra mt h thng mao qun cng knh trung bnh l 50 nm. Hn na gia cc b si c khong cch (khongcch trung bnh gia cc b si l 128,89.103nm) v cc b si ny li c xpchng ln nhau to ra dy ca vi. Chnh s sp xp nh vy to ra mt

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    h thng cc l trng, gip cho cht bn d dng i su vo cu trc vi. T tmhiu c c ch bm dnh ca du m trn vi si.

    2. xc nh c thnh phn du thng, cc thng s ho l ca du

    thng, du thng bin tnh theo phng php sulfat ho. T a ra c iukin ti u sulfat ho l 30oC; vi thnh phn nguyn liu 200ml (94% kl) duthng, 3ml (6% kl) axit H2SO4 85%; tin hnh trong 5 gi v hm lng luhunh ti u sau qu trnh sulfat ho l 2,004 %kl.

    3. Vi iu kin thc hin phn ng sulfat ho nh trn c th khng nhrng phn ng xy ra to nhm sulfat theo phn ng cng. Phn ng cng tuntheo quy tc Macconicop. iu ny c gii thch l do m in ca S v O lxp x nhau, cn m in ca O ln hn ca H. Nn H trong lin kt -O-H d

    dng t ra khi H2SO4 to gc sulfat -O-SO3H (tc nhn nucleophyl) hn lt lin kt -O-S- to ra nhm sulfo -SO3H. Vy phn ng xy ra l phn ngsulfat ho. ng thi cn xy ra phn ng ph l hydrat ho .

    4. Cht hot ng b mt thu c t du thng sulfat ho l cu t rt ttphc v cho vic nghin cu tng hp cht ty ra c tnh phn hu sinh hc cao

    TI LIU THAM KHO

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    10. L nh Mi. Vn tinh du, hng liu v trin vng ca n Vit Nam.

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    11.Vn nh , Trnh Thanh oan, Dng Vn Tu, Nguyn Th Nguyt,Nguyn ng Quang, Nguyn Th Thanh, H Cng Xinh, ch bin Hong

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