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Phn 1: i cng v mu sc v cht mu Chng I: m u Chng 2: i cng v l thuyt mu sc Chng 3: cc h thng so snh mu sc Phn 2: sn xut pigment v c Chng 4:cc phng php sn xut pigment v c Chng 5: k thut sn xut TiO2 t ilmenit Chng 6: k thut sn xut Cr2O3 t qung cromit Chng 7:k thut sn xut mt s pigment v c
Phn 1: i cng v mu sc v cht mu chng 1: M u I.1-Hin tng mu v i tng ca KHMS Chng ta nhn bit c vt cht l do: + vt cht pht ra ngun bc x + vt cht phn x nh sng chiu vo Hai thuc tnh c bn ca vt cht m mt ta c th nhn bit: + hnh dng ca vt cht: o ,thy c +Mu sc ca vt cht: ch cm nhn
1-Hin tng mu
Gm 3 qu trnh chnh: +Vt l: bc x v phn x nng lng +Sinh l: tc ng ca nng lng vo mt +Tm l: mt th cm mu 1.1-qu trnh vt l: nghin cu v nng lng bc x gm : + s pht v truyn nng lng + s phn b nng lng theo xc nh bi phng php khch quan v biu th bi cc n v o vt l
1.2-qu trnh sinh l +Nghin cu s tc ng ca cc ngun bc x ti c quan th gic +Mi quan h gia cu to ca c quan th gic vi cc mu tng ng 1.3 qu trnh tm l: nghin cu qu trnh th cm mu ca h thn kinh thi gic v cc iu kin th cm mu sc ca con ngi nh :tr nh , kinh nghim,thi quen , i tng ca mn tm l mu phc tp
L ht c th xc nh bi cc phng php vt l ph hp,v d soi knh hin vi aggregate Gm cc ht c bn nm gn nhau thng hng, S mt phng tng cng < S ca cc ht agglomerate Gm cc ht c bn lin kt dng gc, cnh v c dng aggregate. S mt phng S cc ht flocculate L cc agglomerate tn ti th huyn ph
S b mt sT
Th tch ht VT s phn b d
Gm S b mt trong v S b mt ngoi
Gm V thc (khng tnh l) v V kh kin Biu thng k % cc kch thc ht
2/ xc nh mt s tnh cht l hc
a-% cht d bay hi: em mu c khi lng m0 (g) sy kh ti khi lng khng i m1 (g) t0 = 1050 2 . Thng thng y l gi tr m w = ( m0 m1).100 / m0 ; % b-%Mt khi nung: i lng ny ty thuc t0 nung v xc nh bng cch o bin thin khi lng nh phn a trn c-%cht tan trong dung mi: em mu c khi lng m0 ha tan(chit) trong dung mi thch hp nhit t , lc ra cn , sy kh , ngui cn khi lng m1 % cht tan = ( m0 m1 ).100 / m0 d- axit hay ba z : cn 100g mu em ha tan trong 1lt nc lc ly dung dch em trung ha bi axit hay ba z e- Xc nh gc sulfat, clorua , dng php phn tch ph hp f Xc nh khi lng ring: Ty theo mc ch ,lnh vc ng dng,cn da trn cc tiu chun cht lng c th xc nh , v d TCVN, tiu chun izo ,tiu chun ngnh,
Kch thc ht
c) phn tch bng sng : ( sng kh hay sng t ) Phng php ny nhanh,n gin nhng khng o c kch thc ht m ch xc nh % phn b ht (khi s dng b sng nhiu kch c l ) v tnh ng knh trung bnh d)Ngoi ra c th dng nhiu phng php khc nh phng php quang ,phng php o cc i lng vt l nh dn din ,.
4/ xc nh din tch b mt
din tch b mt ring l din tch ca mt n v khi lng cht rn. l i lng quan trng v n nh gi kh nng tng tc-hp ph ca pigment +phng php hp ph kh brunauer emmett teller (BET): dng cho ht khng tng tc ha hc vi kh s dng v cc ht nonmicroporous (khng c vi mao qun) +phng php hp th kh carman: cho kh hay lng chy qua lp vt liu xp ( iu kin P cao hay chn khng) v o gim p hay vn tc chy
Bn cht ca nh sng
a/L thuyt sng: as l s truyn nhng dao ng n hi trong khng gian mt cch tun hon Tng t sng c,sng as tun th hai ng /l: a.1-Nguyn l chng cht: +ti im gp dao ng sng bng tng cc dao ng +Khng gy nhiu lon gia chng a.2-Nguyn l hughens: bt c im no nh sng truyn ti u tr thnh ngun th cp
Bn cht ca nh sng
b/ l thuyt ht:nm 1900 Max. Planck ra thuyt lng t nng lng v nm 1908 Anhxtanh ra thuyt photon coi nh sng cu thnh t cc ht ging nhau gi l lng t nh sng hay photon Vi bc x in t n sc c bc sng ,tn s s c nng lng xc nh = h . = h.c / vi h l hng s planck Trong mi mi trng , photon truyn i vi vn tc bng 3.108 m/s v cng ca chm bc x t l vi s photon pht ra trong mt n v thi gian
II.1.2/ cc i lng o bc x 1/ i vi ngun im: a/ thng lng bc x: o kh nng bc x ca ngun thng lng bc x ton phn l ton b nng lng ca ngun pht ra theo mi phng trong mt n v thi gian W=A/t , j/s , erg/s , w +A l nng lng bc x : j ; erg , (1j=107 erg) +t l thi gian , s Nu tnh trn din tch ds ta c thng lng bc x gi ti b mt ds l : dw = dA / t
Cc i lng o bc x
b/ cng bc x:( Ie ) Gc khi : d , steradian (sr) d = ds.cos /r2 , sr o
ds0
n ds
Ie c trng cho kh nng pht x ca ngun theo tng phng. Ie c tr s bng thng lng bc x ca ngun gi i trong mt d Ie = dw / d , J/s.sr hay w/ sr
Cc i lng o bc x 2/ i vi ngun khi bc x : a/ trng bc x: Re ( w/m2 , J / s.m2 ) Re l kh nng bc x ca mt n v din tch xc nh trn b mt ngun pht ra Re=dw / d + d l phn din tch b mt ngun , m2 + dw l thng lng bc x pht ra t d
Cc i lng o bc x b/ chi bc x: Be ( w/ sr .m2 ) +a0-a0 ngun khi +N-M phng pht x a n d +d phn din tch trn a0-a0 N d +dIe cng bc x ca d a +da hnh chiu ca d trn phng N-M da = d .cos Be = dIe / da = dIe / d.cos
0 a 0
Cc i lng o bc x c/ ri nng lng : Ee ( w/m2 ) Ee l i lng vt l c tr s bng thng lng bc x dw gi ti din tch ca mt ds Ee = dw / ds
II.1.3 -qui lut tng tc gia nh sng-vt cht 1/ hin tng phn x-tn x-khc x: xy ra khi chiu cc tia bc x vo vt cht c c tnh : B mt phng ,nhn : phn x (ng hng) B mt li lm,hn hp nhiu cht : tn x, hay thc t l phn x a hng . Qua hai mi trng khc nhau v n : khc x
Tn x Phn x v khc x
Ngun bc x
Cc ngun sng s c ph v khi chng tc ng vo cng mt vt c th cho mu sc nh gi thnh phn ph ca ngun c th da vo khi nim nhit mu T0m ( 0K ) lg a(T,) = 6245 ( 1/T0 1/ T0m ) / + C T0m ca ngun l t0 ca vt en tuyt i c mu trng vi mu ca ngun Khi T0m ph c ngn
II.2. S th cm mu
II.2.1 mt b phn th cm mu a/ cu to ca mt : gm 7 b phn chnh 1/gic mc 5/ vng mc 2/ mng mt v ng t 6/h trung tm(im vng) 3/ thy tinh th( nhn mt) 7/ thn kinh th gic 4/ thy tinh dch ( 99% H2O + anbumin ) Ti vng mc c cc t bo th cm dng que (1,2.108 t bo) v dng n hay dng nn ( 7.106 t bo )
b/ s iu tit ca mt Nhng lng t nh sng c s b hp th vi cc mc .Trong t bo que c nhy ph nh nhau nn khng phn bit mu m ch phn bit mc chiu sng
S hp th
S hp th
blue
green
red
Ph hp th t bo que
,nm
Ph hp th t bo n
,nm
3/ trng R ( lm / m2 )
R l i lng c trng cho kh nng pht sng ca ngun khi - n l quang thng ton phn do phn din tch d ca ngun pht ra R = d / d , lm / m2
4/ chi B , nit ( nt )
B c trng cho s pht sng theo tng phng ca ngun khi . Vy B thay i theo phng chiu (gc ). Nu B khng ph thuc phng chiu ngun c gi l ngun lambe . B = dI / d.cos = dI / da ; (1 nt = 1Cd /1m2 ) nit l chi ca mt mt pht sng c din tch 1m2 pht ra cng sng 1 Cd theo phng vung gc vi n
5/ ri E , lux (lx)
E l i lng vt l c tr s bng quang thng gi ti mt din tch ds E = d / ds ; lm/m2 hay lux (lx) Do d = I . d v d = ds.cos / r2 E = d / ds = I . Cos / r2 lux l ri ca mt mt c din tch 1 m2 nhn c quang thng 1 lumen gi ti
6/ chi ca b mt c chiu ;
Ty thuc : + cng ngun chiu I + tnh cht ca b mt c chiu H s chi lun < chi ca ngun B = B / Blt +B : chi b mt c chiu theo hng gc +Blt : chi ca b mt tn x l tng. Thc t khng c Blt . C th coi b mt ca MgCO3 ( c = 0,96-0,99) hay MgSO4 ( 0,95-0,97) l Blt Do Blt = E / B = . E / i vi nh sng n sc : ,i = B,i / Blt
1/ tng mu v sc mu Tng mu ca mt cht l mu ca n da trn ca bc x n sc tri,cn sc mu biu th phn bc x cn li V d: hn hp R-G vi R tri c tng mu l R v sc mu G ( nu R=G tng mu Y cn sc ch sng ti: vng sm,vng sng) nh ngha: tng mu ca mt cht ch s khc bit v cm gic mu ca mu hu sc vi mu ghi (v sc) c cng sng
2/ chi sng chi ca mu cng chnh l chi ca cc tia bc x hay cc tia phn x ( chi ca b mt c chiu) v c th xc nh khch quan sng l thc o s th cm mu (sng-ti) ca c quan th gic nn ch cm nhn m kh c th xc nh c
3/ thun sc bo ha thun sc xc nh mc sc thi ca mu (hay t l ca mu tri so vi cc mu cn li ) Mu quang ph c thun sc 100% . +ngun bc x: t s d tia tri : di + vt cht : t s B tia tri : Bi bo ha : l cm gic v s khc bit vi mu trng v mu sc .cc mu quang ph c bo ha tng dn t mu vng ti mu tm Vng - vng lc - lc cam lam - -chm -tm
1/ su cao mu :Khi cc i hp th di chuyn v pha : + di hn : Mu tr nn su (sm) hn + ngn hn: Mu tr nn cao hn Cc mu quang ph ( vng kh kin ) c th t tng gim su v cao mu: su mu: Trng- vng chanh- vng- - cnh sen- tm- xanh tm- lc cao mu:
2/ cng mu Ch s m nht ca mu . N ph thuc thnh phn , hm lng cht mu Khi chi cao mu c cng mnh (mu nng ) v ngc li ( mu lnh ) Lu : cng mu khc cao v su mu . Khi chuyn dch su mu cha chc tng cng mu . Khi chuyn dch cao mu cha chc gim cng mu .
II.4. b mt mu mu vt cht
II.4.1 mu vt cht-cc yu t nh hng 1/ mu vt cht: mu sc l mt trong hai thuc tnh cn bn ca vt cht. Mt nhn bit c mu l do t hp ca 3 qu trnh: + c ngun bc x chiu vo vt + vt hp th chn lc cc sng bc x +s th cm mu mt Qu trnh th hai to ra s khc bit v mu sc gia cc vt, khi chiu cc bc x c ngoi vng kh kin vo vt c th pht quang ( hunh ,ln quang)
Bng 2.1: E v mu ca vt
b hp Nng th . lng . nm kj/mol 400-435 299-274 435-480 274-249 480-490 249-244 490-500 244-238 500-560 238-214 560-595 214-200 595-605 200-198 605-750 198-149 Mu ca as b hp th tm Xanh-tm lam Xanh l Lc vng cam Mu ca vt cht Lc-vng vng cam Cnh sen Xanh-tm lam Xanh da tri
2/ cc yu t nh hng ti kh nng hp th as
a/tnh cht lp b mt c chiu
Vt c lp phn x
nh sng tn x
Phn x c hng
b/ chiu dy lp hp th H s hp th : H = ( I I0 ) / I Theo lamber-beer: s hp th tng khi c v x dI = - c.I.dx dI/I = - c dx x Ly xc nh t I0I v t 0 x dI dx Ln I/I0 = - c . X I I Khi xs hp th thun Sc m mu Lu nh lut lamber-beer ch ng c nh
0
c/ kch thc ht Theo l thuyt Mie: da trn phng trnh ca Maxwell tao m hnh gm mt phng sng giao vi vt hnh cu ng hng v phng din quang ,c chit sut n v ch s hp th k . Khi ly phng trnh sng s thu tit din hp th QA v tit din tn x QS . Cc gi tr v hng trn cho bit mi quan h gia kh nng hp th,tn x vi kch thc ht hay gia mu sc vi kch thc ht .
d/ cu trc tinh th S khc bit v cu trc ( v kch thc ht ) s dn ti khc bit v kh nng hp th hay phn x cc bc x chiu vo vt khc bit v mu sc . V d : cacbon dng kim cng , grafit hay than . Trong thc t do pigment thng c dng lm lp ph trang tr hay bo v trn b mt vt nn mu sc ty thuc ch yu vo tnh cht b mt ca vt
II.4.2. bn cht ha hc ca cht mu 1/ electron c s gii thch mu vt cht Trang thi e , linh ng v s chuyn mc nng lng ca e khi b kch thch to ra mu
s2
s1 *
T1*
T0*
s0
Electron. Nng lng chuyn e ca vt t qu o n nh s0 sang qu o kch thch si* nhn c t ngun bc x chiu vo n = Esi Eso = hi . = h.c / i Gi s lp s0 c 2e vi tng spin =0( trng thi singlet ).Khi b kch thch c 1e nhy ln mc s1* nhng spin khng i (trng thi singlet s* ). Nu spin thay i (tng 0) n s mc T0* c nng lng ET* < Es1* v bn hn ( trng thi triplet T0* )
Electron
+ Do e trng thi kch thch khng bn nn sau khong thi gian ngn (10-8 10-9 s ) n tr li qu o s0 km gii phng E dng bc x vi i xc nh. Nu i trong vng kh kin ta s thy mu ca vt cn i ngoi ta thy hin tng hunh quang pht quang hay ln quang
2/ cc cht mu v c
a/ c im chung:mu l do chuyn e (nht l e ho tr) cht v c c mu thng l +Cc cht c mc nng lng gia cc orbitan cha e , orbitan cha e v trng gn nhau, lp v e cha y +Cc cht c nhiu e v c orbitan ha tr cn trng V d : +Ca : 3p6 4s2 : khng mu +Br : 4s2 4p5 : c mu vng cam cht v c khng mu hay mu trng thng l : +cc nguyn t s v p lp y e , cc hp cht kim loi kim, kim th vi phi kim 3 chu k u. V d : NaCl , NaF , CaF2 ,
Cc cht mu v c +Cc cht, hp cht c s khc bit v nng lng gia lp cha e v lp trng qu ln +Cc cht ,hp cht khng cn orbitan (nht l cc orbitan ha tr) trng +Cc hp cht ( ch yu l oxit) ca cc cht nm gia kim loi v phi kim
b/ cc yu t nh hng ti mu cc cht v c b.1/trng thi tn ti:nh hng s chuyn e do + khong cch ion-ion + khong cch nguyn t - nguyn t + khong cch ht nhn electron V d: PbI2 dng dung dch : khng c mu PbI2 dng rn : mu vng Do ion bin dng gim phn cc khong cch cation-anion gimchnh E gimmu
b.2/ s phn cc phn t S phn cc thay i mc nng lng ca e d b kch thch c mu V d : AgCl : mu trng AgI : mu vng AgBr : mu cam
b.3/ trng thi oxy ha Mc oxy ha cng caotc dng phn cc cng ln e d b kch thchc mu v d 1 : + MnO2 : mu xm en + K2MnO4 : mu xanh + KMnO4 : mu tm v d 2 : + V+ : mu xm + V5+ : mu vng cam
c/ kt lun Mu ca cc cht v c b chi phi bi : Trong phn t cc mc nng lng gia cc orbitan ha tr cha e v trng phi gn nhau hay phn t c nhiu e v c orbitan trng Trong phn t c s phn cc mnh hay cation v anion c kh nng phn cc ln
Chng III.cc h thng so snh mu sc III.1. cc nguyn l tng hp mu III.1.1. mu c bn nh ngha : l nhng mu m t chng c th to ra v s v y cc mu khc iu kin : khi phi hp hai mu c bn khng to ra mu c bn th ba V d: (red) lc (green) xanh tm (blue) Mu to t hai mu c bn ( mu hai) nh mu vng t + lc , t ba mu c bn ( mu ba) nh mu en t + lc + xanh tm .
2/Phng php tr mu ( mu vt cht) Khi trn cc mu c bn (mc mu, mu v, sn, in chng mu,) s thu: + mu hai : mu trung gian green black yellow + mu ba : mu en cyan c im:khi thay i cht mu theo cc t l s lun blue red thu mu trung gian ti hn mu c bn magenta
III.1.3 Mu i nhau
Mu i nhau l mu khi hn hp s thu c mu quang ph yellow Quang ph : green + cng mu : mu trng red + tr mu : mu en Quang ph Cc mu i nhau nm cyan magenta i din nhau trn vng mu sc .Mu bt k u c tng hp blue t hai mu bn cnh theo cc phng php cng hay tr
2/ phng php so mu Th hin mu v s lng v gn vi 3 c trng khch quan ca mu C s ca phng php so mu: l c ch 3 thnh phn: mi mu l tng hp ca 3 mu c bn th hin qua 3 s o ( ta mu- TM) Cc c trng ca mu lin h vi nhau qua ta mu u im: chnh xc,th hin mu bt k Nhc :cn thit b ,tru tng v khng cho cm gic mu
2/ ta mu-TM
TM l s lng 3 mu c bn sau khi trn s phc ch c mu cn xem xt trong h thng mu nht nh nh r, , g, , b, hay x, ,y, , z, xc nh TM c hai cch: + o trc tip mu bng my o mu + tnh ton theo thnh phn ph bc x,phn x ta ring: l ta bc x n sc vi chi pht x n v. N ch r cn trn cc mu c bn vi lng ra sao thu mu bc x n sc vi chi pht x n v .Gi tr TR o bng thc nghim v ch o 1 ln. = V. / L tnh TM ta nhn TR vi chi pht x:v d r = .Ber vi bc x c ph phc tp, TM ca n l tng ta n sc tng ng c trong ph . V d r = r
3/ phng trnh mu L kt qu o mu M th hin qua TM di dng phng trnh: mM = rR + gG + bB vi m = r + g + b ; ( m l h s chi ) a/ Xt v cht(sc thi mu):cn bit t l 3 mu c bn ca M l cc ta ca sc (hay ta tng i ) r,g,b ; x,y,z , r = r / m ; g = g / m; b = b / m r + g + b=1 * Nh vy bit sc ca mu ch cn bit 2 trong 3 h s mu r , g , b . M = r .R + g . G + b . B
b/ xt v lng Ta tnh B theo : BM = r .683 + g. 3135 + b .41 n gin ta chn chi ca R lm n v v chuyn chi n v v chi n v tng i, tc br=1 ;bg=4,59 ;bb=0,06 BM = 683 .( r. 1 + g.4,59 + b.0,06 ) Hay : BM = 683. m (r.br + g.bg + b.bb ) t FM = r.br + g.bg + b.bb BM = 683.m.FM Vi FM l chi tng i
BI TP
BI 1: cho mu M c phng trnh : 2M = - 2,35R + 2,80G + 1,55B Xc nh ta sc r , g , b v chi
BI 2: So snh hai mu M1 v M2 c phng trnh 2,8M1 = 1,4 R + 1,05G + 0,35B v 1,6M2 = 0,8R + 0,6G + 0,2B
BI 3 : cho hai mu M1 v M2 c phng trnh M1 = 0,40R + 0,50G + 0,1B v M2 = 0,33R + 0,33G + 0,33B 1/ Xc nh mu hn hp M khi trn M1 v M2 vi lng nh nhau 2/ So snh hai mu M v M1
4/ tnh ta mu Bi ton: tnh ta mu ca bc x pht ra t n hi thy ngn .bc x c dng ph vch gm 4 bc x n sc c , cng sut v TR
, nm Cng sut, w Ta ring 0,2937 0,0001
404,7
435,8 546,1
5,2
9,1 10,5
0,0005
0,0002
-0,0002 0,0192
0,2142
-0,0001 0,0001
578
10,2
0,2300
0,1434
-0,0011
cyan white
magenta
black
0,1,0
G
red R 1,0,0
green yellow
2/ Tam gic mu M t mu di dng im trong mu. Vic tng hp mu theo qui tc cng
G ( 0,1,0)
B (0,0,1)
R (1,0,0)
G546,1
Mu T:
r=0 g = 0,567 b = 1-0,567=0,433
500
T E yellow
435,8
B magenta
700 R
H RGB
Xt mu T nm ti giao im E-T vi GB Ptr mu: T = 0,567 G + 0,433 B (1 ) T thu c khi trn: +cch 1: mu E v mu T +cch 2 : mu B v mu G Gi s to mu T theo cch 1: Theo qui tc ng lin hp ( hay qui tc n by ): Lng mu E trong T Lng mu T trong T T T E-T
;
0,778 0,222
Suy ra:
T = 0,778 E + 0,222T
(2)
;
(3)
nh vy khi thm E vo T s lm gim thun sc v lm nht mu T khi thay E = 0,333R + 0,333G + 0,333B vo (3) v rt gn ta thu ptr mu ca T
Nhn xt
Tam gic mu RGB l h thng tiu chun do CIE a ra nm 1931 (da trn kt qu N/C ca WrightGuid) c hai nhc im ln: +lun c ta m vi bc x n sc (thm ch c 2 ta m vi bc x a sc) +la chn thnh phn mu c bn cn ch quan Kt qu t tnh ton trn chng t khng c mu ph T thun khit ( do cm nhn mu ca mt )
H xyz-tnh ton Tng mu: biu th bi cc h s mu x,y,z chi :xc nh bi y (y h s phn x ) B = 683. y ; nt thun khit ( Pc): chi bc x tri y P = = Nh RGB nu c im muchi tng c mu M(x,y)s tm y M(x,y) trn ng ph cng tng, c Pc cao hn Gi thit bc x n sc c P,c=100% .vyPc ca M
c
Pc
y y
y ( y y0 ) y ( y y0 )
y ( x x0 ) y ( x x0 )
y
500 0,5
520
600
680
700
380
0,5
- x
1,0
H so mu ng tng phn UVW th uvw nhn c khi chiu h xyz ln mt uv hp thnh mt gc nghing khng gian nht nh vi mt xy mi qui tc cng mu,tng hp mu t cc bc x n sc trong xyz u c bo tn trong h uvw mi lin h gia uvw - xyz v TM, h s mu u = 2x/ 3 ; v = y ; w = 1,5y 0,5x + 0,5 z
-4x
U =
x + 15y +3z
V v =
6y
x + 15y + 3z
Ngi ta thng ghi gi tr x , y ln ngay th uv (song lu khong cch cc im mu vi ta x,y trn uv khc vi trn xy)
H thng CIELAB
Vi Xn , Yn , Zn l cc gi tr trn h CIE ca 3 kch thch c bn . S chuyn i X,Y,Z thnh X*,Y*,Z*
X* = 3 X / Xn ; Y* = 3 Y / Yn ; Z* = 3 Z / Zn
Khi gi tr trong cn < 0,008856 cc biu thc trn tr thnh X* = 7,787.X / Xn + 0,138 ; Y* = 7,787 .Y / Yn + 0,138
Z* = 7,787 . Z / Zn + 0,138 a* = 500 ( X* - Y* ) ; b* = 200( Y* - Z*) ; L* = 116 Y* - 16 chnh mu vi mu chun : Eab* = a*2 + b*2 + L*2 Trong : a* = a*T - a*R ; b* = b*T - b*R v L* = L*T - L*R
H CIELAB H CIELAB c u im l c th chia chnh mu thnh 3 thnh phn : + chnh v sng: L* = LT* - LR*
+ chnh v mu sc :
Hab* =
Eab*2-L*2-Cab*2
2/ phng php kh
Tt c cc loi pigment v c khng th iu ch t dung dch hay iu ch t dung dch lm gim cht lng,tng gi thnh, u phi qua con ng nung , nghin trn kh, +V d1: pigment ultramarine c iu ch khi nung hn hp st,soda,than, t0 cao +V d 2: iu ch pigment oxit crom K2Cr2O7 + S = K2SO4 + Cr2O3
a) b) c) d) e) f) g) h) i) j) k) l)
Dredger : my no vt Sieve : sng Bunker : bunke Reichert cones : Xyclon hnh chp nn Spirals : trc vt Magnetic separator : my tch t tnh Dryer : my sy Electrostatic separator: my tch tnh in Shaking table : bn rung lc Dry magnetic separator : My tch t tnh kh Vertical belt conveyer : gu nng Electrostatic separator : my tch tnh in
II. ng dng
+ 3 dng th hnh ca TiO2 : Rutile, Anatase, Brooktile Trong Rutile v Anatase c sn xut lng ln v s dng lm Pigment, sn xut gm s v vt liu in t + TiO2 c tnh tn x tt hn cc loi pigment trng khc v c bn ha hc cao, t c tnh l pigment v c c sn xut lng ln + Mt s lnh vc ng dng pigment TiO2: sn, cht ph, mc in, nha, giy, si tng hp,
di : mu hi vng
- Phn b kch thc ht
II.2 . mu ( trng )
Ty thuc ch yu: - Phng php sn xut - Cu trc mang tinh th - tinh khit (tp l oxyt kim loi chuyn tip lm gim trng ) - Kch thc ht v s phn b ht - Bc sng ca ngun bc x, V d: - Dng Anatase hp th max = 385 nm, Rutile l 415 nm - chnh nng lng dy ha tr v dy dn in : Anatase ( 3,29 ev) Rutile ( 3,05 ev) Khi chiu bc x vng t ngoi Rutile vng hn Anatase
3) 4) 5)
Kt lun
Qu trnh vn cc v xm ha ( chalkinh) l do nc ,bc x c ngn v TiO2 lm xc tc .H ca qu trnh 312 Kj /mol ly t bc x c 385 nm c O2 hin tng vn cc(lightfastness) khng c O2 xm mu (grayinh) ng nhin c hai u c mt H2O
C s k thut ca PP sulfat
Phn ng phn hy FeTiO3+H2SO4 =FeSO4+Ti(SO4)2 +H2O FeTiO3+H2SO4 = FeSO4 +TiOSO4 +H2O Ti(SO4)2 + H2O = TiOSO4 + H2SO4 FeSO4 + H2SO4 + O2 = Fe2(SO4)3 Cc tp ( Zr ,Fe ,) to mui sulfat
Cc iu kin k thut
Nng axit : 92-94 % (oleum 20%SO3) T0 p.ng : 125-1350c (sau tng do Hp) T l H2SO4 / TiO2 : 1,8-2,2 C ht Ilmenit : 40 m Thi gian phn ng : 1-12 gi Khuy trn v sc kh Dung dch sau khi lc b cn khng tan cha mui sulfat Ti,Fe3+,Fe2+,
tan ca Fe2+ < Fe3+ tan ca Fe2+ t thay i theo t Fe2+ kh b thuy phn hn Fe3+ (pH = 5,5 v pH = 2,0
Hai phng php thy phn mui Ti4+ Pha long dung dch Ti4+ Cho mm nhn to Hai phng php to mm nhn to: 1. Ly mt phn dung dch Ti4+ cho tc dng vi NaOH (100g/lt) ti pH = 3. cho hn hp vo dung dch Ti4+cn li (t l 1% TiO2) 2. Cho mt phn TiO2 vo dung dch Ti4+ Nu thy phn t cao (94 110 %) trong 2 4 gi km khuy trn t = 95 96 %
2. L t : C th dng nhiu kiu l : l quay, l tng si, nhng vt liu ch to phi chu c s n mn v kh Nguyn liu vo kh trnh to HCl v H2O trong pha kh Tp (Mg, Ca)Cl2, ZnSiO3 kh bay hi v clo ha s tch t trong l t Khng ngng l t ngt trnh hin tng thiu kt Kh ra khi l (TiCl4, VOCl3,) c lm ngui v tinh ch
Tinh ch TiCl4
+ Lc b mui clorua tp khng tan ,loi b mui tp tan khi chng ct cc t khc nhau (xem bng 5.7 tr 83 CNSXCMVC) + Ngng t kh l theo tng cp h nhit V d : 319C : FeCl3 ngng t 136C : TiCl4 ngng t + B xung cht to kt ta tp (v d thm H2S kt ta Vanadisulfua )
t chy TiCl4
Phn ng: TiCl4 + O2 = TiO2 + Cl2 Lng O2 dng 110-115 % so l thuyt TiCl4 c ha hi v gia nhit 500-10000 B xung 5% AlCl3 to TiO2 dng R ,d nh Nu c SiCl4 hay PCl3 to dng A C th thy phn dd TiCl4 thu TiO2.H2O
Qu trnh ha hc
Lc u p xy ra trong h R K Khi t0 t0 im tecti: h R-L;R-K;R-L;L-L Ty phthc nung,t0,thnh phn phi liu,trong sn phm nung c nhiu cht Phn ng tng: Fe(CrO2)2+Na2CO3+k =Fe2O3+Na2CrO4+CO Mg(CrO2)2+Na2CO3+k=MgO+Na2CrO4+CO2
S tng tc soda-cromit-CaO
Khi t01100 to cromatto otecti vi soda (6550 ,62,5%Na2CO3 )pha lng t0 1000: vp to cromat>vp gia soda vi cc oxit Al,Si,Mg[soda] trong pha L (A) Do [cromat] nn h di chuyn v im cromat
H tng tc CaCrO4+Na2CO3
Nhn xt
D CaCrO4 tan tt trong pha lng ( 80% 10000) nhng [Ca2+] dng lng khng ln v n to pha rn (silicat,aluminat,ferat,..,) Khi t0 thp (CaCO3 cha b phn hy) h gm 3 cu t: + Pha lng: CaCrO4 ,Na2CrO4 ,Na2CO3 + Pha rn:CaCO3 ,CaCrO4 ,Na2Ca(CO3)2 + Dd rn:mNa2CO3nNa2CO3 ;pNa2CrO4qCaCrO4 Pha lng xut hin ngay 6450 .
Nhn xt
Khi t0 thnh phn pha lng s thay i theo ng lin kt cc im tecti Pha lng xut hin ngay t0 <7000 Cc h bc hai (trn cnh gin )cng to dd rn v im tecti Tp silicat cng to hp cht tecti vi mui cromat ( 7700 ,10% silicat )nhng do hm lng thp nn c t trong pha lng Cc tp khc t nh hng ti mc oxiha
a
50
Na2CO3
50
b N CaO
A,%
100
50
t ,min
BI TP
Phi liu a vo l t kiu thng quay sn xut Natricromat (vi tc cp liu C l 5,0 tn / gi ) gm cc nguyn liu sau: + Qung cromit : 50%Cr2O3 ; 10%Fe2O3 ; 5% Al2O3 ; 2%SiO2 + Soda : 98% Na2CO3 ; 2% m + Oxitcanxi : 95% CaO 1/ Tnh % nguyn liu c trong phi liu trn 2/ Tnh hiu sut l P BI GII 1/ Tnh % nguyn liu: Ly c s tnh ton i vi m0= 100 kg qung cromit a) Tnh mc oxihoa Cr2O3 ( A % ): A = 130,4 0,01125 C = 130,4 0,01125 . 5000 = 74,15 % b) Tnh lng soda ( m1): k = 0,7415 m1 = 1,395. k. [ Cr2O3] . 100/ 98 = 1,395 . 0,7415 . 50 .100/98 = 52,78kg
BI TP
c) Tnh CaO (m2) : t l Al2O3 : Fe2O3 = 5 : 10 = 0,5 0,64 m2 = [1,87SiO2 + 1,1 Al2O3 + 0,7 Fe2O3 + 0,26 Cr2O3 ].100/95 = [ 1,87x 2 + 1,1 x 5 + 0,7x10 + 0,26 x 50 ]x100/95 = 30,78 kg d) Tnh % : Tng nhp liu : m = m0 + m1 + m2 = 100 + 52,78 + 30,78 =183,56kg + % qung cromit : (100 . 100) / 183,56 = 54,48 % + % qung sota : (52,78 . 100) / 183,56 = 28,75 % + % CaO : ( 30,78 . 100) / 183,56 = 16,77 % 2/ Tnh P : + Tnh % Cr2O3 trong phi liu : B = 50 . 100 / 183,56 = 27,24 + Hiu sut l P: P = A . B . C . 10-4 = 74,15 . 27,24 . 5000 . 10-4 = 1009,92 kgCr2O3 / gi
Nhn xt
Nu dng nc ha tch: + Mui cromat;aluminat;soda b ha tan + Khong silicat;ferat;alumin-ferat chuyn dng + Oxit magie v hp cht ca n khng tan V d: CaO.SiO2+H2O=Ca(OH)2 +H2SiO3 tng hiu qu c th axit ha dd bng axit yu (CO2) kt ta CaCO3 trit khi dd v trnh mt cromat dng kh tan 3CaO.Al2O3.CaCrO4.12H2O
X l dd cromat
Dd cromat thu c sau khi lc b cn + C c kt tinh mui natricromat + Chuyn ha thnh mui natridicromat + Trao i ion thu mui dicromat khc Do nhu cu v gi tr mui dicromat cao; tan ca n km nn hai phng php sau thng c s dng
C s l ha qu trnh axit ha
P tng: 2CrO42- +2H+2HCrO4- Cr2O72-+H2O;(1) HA H+ + A- ; K1 =[H+].[A-] / [HA] ; (2) HCrO4-H++CrO42-; K2=[H+][CrO42-]/[HCrO4-] Cr2O72- +H2O2HCrO4;K3=[HCrO4]/[Cr2O7] Gi: a l nng mol HA ban u C l nng mol cromat ban u
C s l ha qu trnh axit ha
1/ Khi cc mui khng in ly v tan tt 2k12(1-x)2(a-cx)2+k1k2k3.x(1-x)(acx)=k22k3cx3,(8 Khi dng pp th hay xp x gii pt trn s tnh c x Khi k3 ln ta coi lng ion Cr2O72- nh v thu phng trnh tnh x n gin hn (k1-k2)cx2-(a+c)k1x +k1a =0 Gii phng trnh trn tnh c x
C s l ha
Khi a=c t pt trn ta c X=1/1+ k2/k1 ; (10) Trn th vi tung x ,honh -lgk1 ,khi c dnh k2 v tnh s thay i x=f (-lgk1) ta c : +ng s 1 (khi k2 = 10-7 ) +ng s 2 ( khi k2 = 8.10-7 ) Nhn xt : +Khi k1 ln ( axit mnh) x +Khi t0 k2 x
ng 3: k2 = 10-7 b1 = 0,05 c v a = c
- Lg k1
5/ Kt lun
a/ t0 ch yu nh hng ti tan ca HA v MA cn t s k2 / k1 f ( t0). Khi t0 tan ca kh gim v ca mui thng tng.T (20) thy khi t0 s x ( do b1 v p ) b/ Khi tt c u tan tt x f (nng ) v b1 khi tng nng ( b1 = S / 2c ) .theo (18) x ch tng ng k khi nng v c MA pha rn ( gn ging khi HA tan km ). Cn theo (19) tng nng s x ( khng c MA pha rn ) c/ k1 ( axit cng mnh ) x v ngc li .
CaCO3
5
6 9 H2O
38%CO2
10
CO2 thi 11 11
7
bicromat
bicacbonat
Ch thch
1/ my nghin qung 2/ my trn phi liu 3/ l nung vi 4/ l nung phi liu 5/ thng cha 6/ my nghin bt t 7/ my lc 8/ thit b ra 9/ thit b bay hi 3 cp 10/ thit b bay hi 2 cp 11/ ni hp ( octocla) 12/ my nn kh 13/ my nghin vi
Kh cromat .
Nung hn hp K2Cr2O7 +C+S t l 15:3:2 thu sn phm 82%Cr2O3 . loi b C d c th nung sn phm vi NH4NO3 + NH4NO3 + C = N2 + CO2 + H2O + NH4NO3 +K2CO3 =NH3+ CO2 +KNO3+H2O 3500 khi t l nitrat : oxit = 1 : 10 sau 1 gi hiu sut kh C t 85-90% .Lu nu nung t0 cao xy ra phn ng lm gim hiu sut KNO3 + Cr2O3 = K2CrO4 + N2O3 + NO2
c/ Kt ta bng dd ba z
Phn ng : Cr3+ + OH- = Cr(OH)3 Khi phn ng xy ra t0 cao Cr(OH)3 = Cr2O3.xH2O + H2O Sn phm thu c sau khi lc ra em nung loi ht nc . Lu : do crom hydroxit lng tnh nn khng dng ba z qu d
i cng v Cd pigment
V d : Khi thay mt phn Zn s lm gim cc thng s mng v pigment c mu vng xanh Khi thay bi Hg v Se ty theo hm lng s lm tng kch thc mng v mu chuyn dn sang cam hay Cc mu pigment Cd p do ph phn x tng
3/ ng dng
Cht mu trong sn ,cao su lu ha ,cht do, Mc mu ,nhum,in la ,x phng , Cht mu trong gm ,s, thy tinh, Khi phi trn vi pigment xanh to mu lc Do hp th v phn x nh sng tt nn dng sn xut pin mt tri: cho CdS thng hoa v ngng t trn mt thy tinh ,sau ngm trong dd CuCl to lp Cu2S (pin ny c =16% ) Do c tnh CdS b han ch ng dng
4/ Vn kinh t , mi trng
CdS v cc hp cht t tan nhng khi vo c th chng tch t (nn khng gy c tc thi) v gy tc hi ( ngng cht LD50 ca chut l 10 g / kg ). Pigment Cd hin gi ch yu dng trong cc lnh vc t gy hai trc tip cho con ngi ( s, gm,hi ha ,)
127NaCl
Lc ra X l
300.SA
3.2/tnh cht mu
ZnS hp th nh sng max 700 nm nn c mu trng xanh Do n ca ZnS (2,37) >> n ca nha v cht kt dnh (1,5-1,6) nn c tnh khuych tn as tt. kh nng khuych tn tt nht l ht hnh cu (D=294 nm).BaSO4 c n nh (1,64) nn n ch l extender.Lithopone dng lm cht ph ZnS v lithopone chu mi mn , ch s hp ph du thp, cng mohs thp
3.3 sn xut
Sn xut lithopone: ZnSO4 + BaS = BaSO4 + ZnS ( 29,4%ZnS) Hm lng ZnS c th thay i khi thay i pp iu ch : v d iu ch lithopone 62,5%ZnS ZnSO4+ BaS + ZnCl2 = ZnS + BaSO4 + BaCl2 Sn xut pigment km-vng : Zn2+ + CrO42- = ZnCrO4 Cht thi c x l thu hi Zn v CrO42-
4.2 Cu trc ha hc
L dng khong Aluminosilicat 3 chiu vi cc ion Na+ v S-n nm cc nt mng .Cu trc mng dng Sodalite vi cc khi lp phng kch thc 0,9 nm Thnh phn alumosilicat : Na6Al6Si6O24 khi c S trong mng : Na7Al6Si6O24S3 Mu ca ultra do bn cht ca 2 nhm S to ra +Nhm S3- c di S-S l 0,2nm ,gc 1030 n hp th trung bnh 600nm ( green orange) +Nhm S2- hp th 380nm ( violet-ultra violet) Cu trc bn nht ca ultra khi tng in tch bng o
Cu trc ha hc ca ultra
tng phm cht mu ca ultra cn tng [S] gim [Al] v [Na] . Sn phm ultra c trng c cng thc Na6,9Al5,6Si6,4O24S4,2 c mu xanh m nh . Mng tinh th ca ultra tm v hng hi khc ultra xanh ch chuyn dng mt phn cc nhm S-2 , S-3 thnh S3Cl- v S4 S phn b Si4+ v Al3+ trong mng ultra tng hp v trt t cn ultra t nhin ngc li
t st nung
Felspar soda Na2CO3 Lu hunh S Cht kh ,C
32,0
7,0 29,0 34,5 4,5
30,0
.. 27,0 33,0 3,0
iu ch ultra ultra th
Trn v nghin hn hp ti d 15m ,sau nung trong mi trng kh theo tng cp 3000 : Na2CO3 + S + C = Na2Sx + CO2 7000 mng ca st lc u chuyn sang dng 3 chiu v khi c s xm nhp ca Na2Sx n sang dng sodalite Oxy ha bi khng kh < 5000 loi S d to SO2 . Kh SO2 oxy ha cc ion di-triatomic polysulfua thnh S3- , S2- ,S v natri sulfoxit. Ultra th cha 75% ultra xanh, 23% natrisulfoxit , 2%S v mt t S2-
S sn xut ultramarine .
457caolin
940Na2CO3+Na2SO4
1-10 than
1-10 nha
Phn ng
H2O Lc ra Dd thi
1000 st-blue
nung
33 S