TRNG I HC CNG NGHIP TP.

H CH MINH TRUNG TM CNG NGH HA

GIO TRNH THC HNH

HA L NNG CAO

Thnh ph H Ch Minh, thng 6 nm 2006

Mc lc

Ni dung

Trang

BI 1: XC NH ENTAPY CA QU TRNH HA HI CHT LNG........ 5 BI 2: TNG IM SI .............................................................................. 11 BI 3: XC NH NHIT TO THNH CA NC ..................................... 15 BI 4: CN BNG LNG - HI........................................................................ 20 BI 5: SC K KH............................................................................................. 24 BI 6: XC NH TC PHN NG V NNG LNG HOT HA CA PHN NG THY PHN CH3COOC2H5 BNG HCl........................... 40 BI 7: VN TC PHN NG TH HALOGEN............................................... 45 BI 8: DN IN TRONG CHT RN ..................................................... 50 BI 9: PHNG TRNH NERST...................................................................... 57 PH LC ........................................................................................................... 100

Li ni u

Ha l l mt mn hc c s khng th thiu c ca ngnh cng ngh ha hc. Gio trnh thc hnh Ha l nng cao c bin son da trn cu trc chng trnh l thuyt ca mn Ha l 1 v Ha l 2 gm c cc chng nh sau: Nhit ng hc Cn bng ha hc ng hc in ha

C s l thuyt, quy trnh th nghim, tnh ton kt qu v ton b thit b trong gio trnh ny c trang b t tp on Phywe GMBH (c). vic thc tp t c kt qu, sinh vin cn phi nghim tc thc hin cc quy trnh sau: 1. 2. 3. 4. 5. 6. c v nghin cu k bi, hiu cn k cc nguyn l v nhim v ca tng bi trc khi vo thc tp. Kim tra li h thng lp rp thit b ca bi. Khi c thc mc phi hi li gio vin hng dn. m bo kt qu o c chnh xc, cc dng c, thit b trc khi s dng phi c ra sch v sy kh. Khi tin hnh th nghim phi tun th cc iu kin v nhit , p sut, tc dng Cc kt qu o c ca th nghim phi c gio vin k xc nhn trc khi lm bo co. Khng ty sa i cc dy dn, u d hoc s dng my tnh vo mc ch khc m khng c s ng ca gio vin hng dn.

7.

H thng bi th nghim c s dng p sut, bnh gas, kh nn cn phi cn thn khi iu chnh van p sut, trnh va chm mnh, v cc bnh cha kh c th gy tai nn.

8.

Tc phong lm vic nghim tc, khng gy n o trong phng th nghim nh hng n hc tp cng nh cc kt qu o.

Mc d gio trnh v thit b u c chuyn giao t nc ngoi nhng y l ln bin son v ging dy u tin ti Trng i hc Cng Nghip Tp.HCM nn chc chn s cn nhiu thiu st. Rt mong c nhn c s gp ca thy c v cc bn sinh vin gio trnh v phng php ging dy mn Thc hnh Ha l t kt qu tt hn.

Tc gi bin son 1. 2. L Th Thanh Hng Nguyn Hong Minh

BI 1: XC NH ENTAPY CA QU TRNH HA HI CHT LNG

1.

Khi nim lin quan Entapy ca qu trnh bay hi, ngng t v thng hoa, p sut hi,

entropy ca qu trnh ha hi, phng trnh Clapeyron - Clausius, quy lut ca Trouton, nh lut ca nhit ng hc. 2. Nguyn tc Qu trnh ha hi ca cht lng xy ra khi hp th nhit. xc nh entapy ca qu trnh ha hi (H) phi bit khi lng ca cht lng ha hi. Lng nhit hp th tng ng vi qu trnh ha hi c xc nh bng nhit lng k. 3. Nhim v
-

Xc nh nhit ha hi C2H5COOC2H5OH v CH3OH. Tnh ton S ca qu trnh ha hi v ng dng quy lut Trouton tho lun kt qu.

4.

Dng c, ha cht v thit b

Hnh 1: S h thng th nghim

5

- Cobra3 unit - Ngun 12V/ 2A - Cp truyn d liu - Mn hnh hin th nhit - Software - u d nhit Pt - Dng c o nhit lng - Bnh bay hi - in tr - Ngun cung cp vn nng - Cp ni, l = 500mm - Bp khuy t - C t - Thanh , l = 500mm - Kp gc phi - Kp vn nng - Chn , h = 500mm - Cn 620g - Cn 3200g - ng h bm giy - Bnh an ton v p k - Bm chn khng bng nc - Erlen 250 ml, c rng - ng cao su, chn khng d = 6mm - ng cao su, d = 6mm - Bp cao su - Kp ng, d = 12 .20mm - Van kim sot khng kh - Xylanh 20 ml - Kim tim, 0.9 x 70mm - Bnh tia - Dietyl ete 250 ml - Metanol 500 ml - Nc ct

12150.00 12151.99 14602.00 12102.00 14503.61 11759.01 04402.00 04405.00 04450.00 13500.93 07361.05 35720.93 35680.04 02022.20 37697.00 37715.00 37692.00 48852.93 48803.93 03071.01 34170.88 02728.00 36134.00 39286.00 39282.00 39275.03 40995.00 37003.00 02591.03 02597.04 33931.00 30007.25 30142.50 31246.81

1 1 1 1 1 1 1 1 1 1 4 1 1 1 3 3 1 1 1 1 1 1 1 1 1 1 5 1 1 1 1 1 1 1
6

5.

Lp t v vn hnh Lp t dng c nh hnh 1 nhng trong thi gian ny ng ni b

phn gia nhit vo ngun in. Ni u d o nhit vo modul o nhit T1. Khi ng chng trnh Measure trong Windoows v chn Temperature nh cng c o. Chn cc thng s o nh hnh 2. Trong Diagram 1 chn Temperature T0a vi phm vi nhit thch hp v trong X bounds chn auto range. By gi chun li u d nhit ca bn trong Calibrate bng cch nhp gi tr nhit c o bng nhit k ri nhn Calibrate. Sau khi thc hin cc ci t ny, nhn Continue ghi cc gi tr o. Sp xp cc hin th nh bn mong mun. t bnh ha hi kh v sch trong bnh erlen v dng ng tim a 15 ml dung dch s c lm bay hi vo bnh thng qua mt ng thng t nm bn trong bnh. Ni ng kh vo vi van iu khin khng kh bng ng cao su di 5 cm. ng ng kh thot ra bn phi bng nt cao su trnh tht thot cht trong qu trnh bay hi. xc nh khi lng ca bnh ha hi cn chun b cn c chnh xc 0,0001g. Bnh erlen ch n thun l dng c h tr cho bnh ha hi. Cho 900g nc ct ( nhit phng, cn chnh xc 0,1g) vo bnh o nhit lng, cho c t hnh oval vo bnh sau bt bp khuy t nh hnh 1 (khng c bt ngun gia nhit). Cho b phn gia nhit, u d nhit v bnh bay hi vo trong bnh o nhit lng, c nh v tr ca chng. Tho nt cao su ra v ni bnh ha hi vi bm chn khng bng nc thng qua bnh an ton. Ch n khi nhit cn bng khong 10 pht. Bt u o bng cch nhn nt <Start measurement>. Ch nhit trong bnh o nhit lng n nh hoc giao ng khng ng k, m bm chn khng v cn thn m van iu khin khng kh qu trnh bay hi xy ra. Tuy nhin khng nn m qu ln to ra qu trnh sc kh mnh lit l nguyn nhn tr hon qu trnh si. Khi nhit ca nc gim xp x 10C (qu trnh bay hi cn phi c thc hin hon ton) ng van iu khin khng kh v tt bm chn khng. Ngay lp tc tho ng cao su ca bm u ca bnh bay hi v thay vo l nt cao su.
7

Tip tc o v ghi li nhit ca h thng cho n khi cn bng mi c thit lp hay nhit ch dao ng xung quanh mt gi tr. Tip theo xc nh tng nhit lng ca nhit lng k. lm iu ny ta phi cung cp ngun mt chiu 10V. Nhn nt <Reset> sau cm u t do ca ng xon gia nhit vo ngun cung cp in. Lc ny h thng lin tc b t nng v lng nhit cung cp c o. Khi nhit ca nc tng tr li v xp x nhit ban u trc khi bay hi (ng h hin th gi tr nng lng khng nn vt qu 9000 Ws), tt nhit bng cch nhn nt <Stop> trn b ngun, nng lng in c hin th chnh xc trn mn hnh b ngun. Tip tc o thm 3 pht na, sau ngng lu nhit bng cch nhn nt <Stop measurement>. Hnh 3, biu din th ca qu trnh o bng chng trnh measurement khi ngng vic o lng. Nu bn s dng chc nng <survey> t thanh cng c bn c th c c nhng s liu nhit khc nhau. Lun lun lm sch v kh bnh cha cht bay hi trc khi thc hin mt qu trnh o lng mi.

Hnh 2: Thng s o lng <measurement parameters>

Hnh 3: ng cong thi gian v nhit 6. L thuyt Khi cht lng c gia nhit p sut khng i (ng p) n nhit no vt cht s chuyn t pha lng sang pha hi. Nhit si vn khng thay i khi c s b sung thm nhit cho n khi cht lng chuyn ht thnh hi. Nu 1 mol cht lng bay hi, th entapy H tng ln do qu trnh hp th nhit Qv. S chnh lch entapy ny c nh ngha l entapy ca qu trnh bay hi (H) v c gii thch bng nng lng cn ph v cc lin kt trong phn t ca cht lng. S thay i lin tc ca p sut hi s c tc dng chng li p sut bn ngoi. Nu hi c lm lnh, qu trnh ngng t xy ra cng nhit , gi l qu trnh thun nghch. Do , vic tng ln ca entropy S v s ph thuc ca nhit ha hi c th p dng cng thc tnh theo nguyn l 2 ca nhit ng hc:
S = H Tv

(1)

i vi hu ht cc cht lng th ha hi (S) thng nm trong phm vi t 80 n 90 J.mol-1.K-1. Nguyn tc ny c t tn l Trouton c gi tr c bit cho nhng cht lng khng lin kt. Trong th nghim ny th nhit ha hi ca cht lng thp hn nhit si ca n. Trong cch lm ny, cn bng gia pha lng v pha hi b xo trn bng cch loi b lin tc thnh phn ca pha kh. Nhit ha hi c tnh theo cc cng thc sau :
9

H = S.Tv
H = h n

(1.1) (h = - Qv) (2) (3) (4) (4.1)

M m

h = - Ck. Tv Wel= Ck. Tel

Ck = Wel Tel

H = C k .Tv

(5) (5.1)

H = Wel

Tv M Tel m

Trong : TV: Chnh lch nhit ca nc trong sut qu trnh bay hi. Tel : Chnh lch nhit ca nc trong qu trnh cung cp in th. Wel : Nhit lng cung cp to ra chnh lch nhit Tel. Ck: Nhit dung ring ca dng c o nhit lng. n : s mol cht bay hi.

10

BI 2: TNG IM SI

1.

Khi nim lin quan nh lut Raoults, Henrys, hng s nghim si, phng trinh Gibbs -

Hemholtz, 2. Nguyn l Nhit si ca dung dch lun lun cao hn nhit si ca dung mi nguyn cht. Nhit si ca dung dch ph thuc nng ca cht tan. Vic o tng im si ca nc c th xc nh c khi lng phn t ca cht tan. 3. Nhim v Lp bng o s gia tng nhit si ca nc ph thuc v nng ca mui, ur v hydroquinone. Thit lp mi quan h gia tng im si v s vin cht tan cho vo. Xc nh phn t lng ca cht tan thng qua mi lin h gia s tng nhit si v nng . 4. Dng c, ha cht v thit b

11

Hnh 1: S h thng th nghim - Dng c o tng im si - Mn hnh hin th nhit - u d nhit - B iu khin tc un - Bp un - Bnh cu 250ml - Becher 250ml - u ni, GL 25/8 - ng silicon - Chn - Kp gc phi - Ngm kp - Ci v chy - pinchcock - Mung cc nh - Dng c p vin - Cn - Da cn - Phu - Pipet - Bp cao su - NaCl 500g - Ur tinh khit - Hydroquinone 250g - Glycerine, 250ml - Nc ct, 5l 5. Lp t v vn hnh Lp t dung c nh hnh 1. Sy kh v cn bnh bn trong, ghi khi lng (m1). t bnh trong vo trong bnh ngoi sao cho khe h ca ng nh bn trong nm bn di ca khp ni bng cao su silicon. Trong sut qu trnh o, hi nc i vo bnh trong thng qua l bn di, nhng khng c ph ln bnh trong.
12

36820.00 13617.93 11759.04 47557.01 32247.93 35812.15 36004.00 41242.03 39296.00 37694.00 37697.00 37715.00 32604.00 43631.15 33393.00 04403.04 48852.93 45019.05 34459.00 36590.00 39275.03 30155.50 30086.25 30089.25 30084.25 31246.81

1 1 1 1 1 1 1 1 1 1 3 3 3 1 1 1 1 1 1 1 1 1 1 1 1 1

Cho vo bnh cu 150 - 200 ml nc, ri ni chng vi cc b phn lp rp. Ni hai ng silicon vo hai li ra ca bnh ngoi v t 2 u ng vo gia beacher 250 ml. Gn kp (pinchcock) vo ng thp hn dn ra t bnh ngoi nhng lc ny cha kha li. Cho vo bnh trong 40ml nc. ng bnh pha bn trn bng cch t c nh u d nhit . Cht tan phi c kim tra v nn thnh vin truc khi cho vo bnh trong (trnh chng dnh vo thnh bnh). Cn 5 mu mi cht (NaCl, Ur, Hydroquinone), mi mu xp x 700mg. u tin nghin cc cht thnh bt bng chy v ci. Dng b nn, nn chng thnh vin. Cn vin va nn vi chnh xc 1mg. Gia nhit cho dung mi trong bnh cu si ln. Hi dung mi i vo bnh ngoi v gia nhit cho bnh trong. iu chnh tc gia nhit bng b phn iu chnh ngun. Nhit ca bnh trong c hin th trn mn hnh (oC). Sau vi pht khi m nhit trong bnh trong gn t n nhit si v khng cn tng c na, h thp bp un cho n khi ngng si v bt u s ngng t hi t bnh ngoi vo tr li bnh cu. Sau nng bp un ln li. Khi m qu trnh si tr li ban u th ng pinchcock. Ci t nhit bng cch nhn nt <Set 0,00> o s thay i nhit . vic o c tt hn th s chnh lch gia hai ga tr trn mn hnh khng qu 0,01K. Ch cho gi tr hin th n nh. Cn thn m np bnh trong, thm vin u tin ca cht tan ri ng li ngay lp tc. Ban u nhit gim nh sau tng tr li trong lc cht tan s tan ra. Khi gi tr hin th tr li n nh, ghi li kt qu v lp li qu trnh trn cho nhng vin k tip, qu trnh kt thc sau 5 ln o. Th nghim kt thc, u tin m pinchcock, tt bp un. iu quan trng trnh cho dung dch bnh trong b tro xung bnh cu trong khi nhit h xung. Ly bnh trong ra, lm kh b mt ngoi, ly u d nhit ra khi bnh trong v cn li n (m2). Khi lng ca nc lc ny s bng vi gi tr ca ln o c cui cng tr i khi lng ca bnh trng (m1) v khi lng ca 5 vin cht tan. th th hin tng im si theo t s khi lng ca cht tan v khi lng ca nc nh hnh 2. 6. L thuyt

13

Dung dch l cht lng bao gm dung mi v cht tan. Ch c dung mi c th bay hi, p sut hi ca cht tan thc t l bng khng. Vo nm 1886, Raoul a ra nh lut ly chnh tn ng ta: p sut hi ca dung dch chnh l p sut hi ca dung mi nguyn cht vi phn mol ca dung mi.
Ps = n2 P 0 n1 + n 2

Trong : PS :p sut hi ca dung dch. P0: p sut hi ca dung mi nguyn cht. n1,n2: s mol ca dung mi v cht tan.

Hnh 2: tng im si ph thuc vo nng

TS = TS T0

Trong : TS: nhit si dung dch. T0: nhit si dung mi.

T = K S .m ct .1000 M ct .m dm

mct: khi lng dung mi nguyn cht. mdm: khi lng cht tan. Mct: khi lng mol cht tan. Ks: hng s nghim si

14

BI 3: XC NH NHIT TO THNH CA NC

1.

Khi nim lin quan Nguyn l 1 nhit ng hc, nhit ha hc, nhit lng, entapy to

thnh, entapy ca phn ng. 2. Nguyn l Entapy to thnh iu kin tiu chun c lp thnh bng tnh ton entapy ca phn ng. Chng c nh ngha nh l nhit phn ng to thnh mt mol cht t cc n cht p sut khng i. phn ng to thnh din ra mt cch t nhin v nh lng c th entapy tiu chun c th o c trc tip bng nhit lng k. V d s to thnh nc t oxy v hydro. 3. Nhim v Xc nh entapy to thnh ca nc bng cch t 100ml H2 trong dng c o nhit lng bng thy tinh c ng kn. 4. Dng c, ha cht v thit b - Ngun cung cp in th 0 10 KV - Dy ni 1m - ng bao thy tinh - Clorimeter - Xy lanh 100 ml (3 ci) - ng Silicon - hnh ch H - Thanh thp 250mm - Thanh thp 500mm - Thanh thp 750mm - Dng c o nhit v p sut - Nhit k -10.+500C (2 ci) 13670.93 07367.00 02615.00 02615.01 02617.00 39296.00 02009.55 02031.00 02032.00 02033.00 87997.01 38034.00 1 2 1 1 3 1 1 2 1 1 1 2
15

- Knh lp - C t - Thanh nam chm - Phu - Ca nha 1 lit - Cn - Bnh kh hydro - Bnh kh Oxy - Van gim p cho kh oxy - Hai ng thp hnh tr - ng cao su - Nc ct 5. Lp t v vn hnh Lp t dng c nh hnh v:

64598.00 64598.00 46299.02 34457.00 36640.00 48852.93 41775.00 41778.00 33482.00 41774.00 39282.00 31246.81

1 1 1 1 1 1 1 1 1 2

t dng c o nhit lng vo ng bc thy tinh nh c m t trong ti liu hng dn. t np dng c o nhit lng vo khp ni. Np ca dng c o nhit lng c hai ng mao dn c b cong cc gc bn phi ging nh cc ng dn kh, mt trong hai ng mao dn c lp kht bng hai in cc platin. ng mao dn c in cc platin lun lun phi nm bn di khi dng c o nhit lng lp t xong. Cho nc vo ng ong xp x 500g, ri xc nh khi lng ca n bng cn (m1). Cn thn nc vo ng bao ca dng c o nhit lng thng qua 1 trong 2 ng ng pha trn ca dng c o nhit lng (bng phu), ri cn li khi lng ca ng ong (m2). Tnh khi lng mH2O = m1 - m 2. Cho c t vo ng bc bn ngoi ca dng c o nhit lng, cm nhit k vo 2 ng ng ca ng ny. Ni dng c o nhit lng vi 3 xi lanh kh bng van ba chiu v cn thn ni 2 u ng thy tinh bng ng cao su silicon ngn. iu chnh cc nt dng ca gi xylanh sao cho th tch ca n l 100ml. Ni in cc ca dng c o nhit lng n b phn cung cp in th bng cp ni. Bt ngun ca thit b cung cp in th, chc chn rng
16

cc tia in lin tc phng ra ti cc in cc. Bc kim tra ny rt quan trng v trong sut qu trnh chy ca hydro cc tia la lin tc lm tng nguy c n do hnh thnh hn hp n ca kh oxyhydrogen.

Hnh 1: S h thng th nghim Xoay kha ba chiu v tr m, lm y xi lanh kh n 100ml kh oxy t bnh cha kh (ch xylanh cha oxy nm pha trn bn phi ca dng c o nhit lng). Xoay kha ba chiu sao cho xi lanh ni trc tip vi xylanh bn tay tri nm bn kia ca dng c o nhit lng ri bm kh ti lui vi ln. Trong sut giai on ny oxy c trn ln vi khng kh trong dng c o nhit lng cng lc s kn ca dng c o nhit lng s c kim tra (bng cch kim tra th tch kh ca xylanh bn tay tri v tay phi phi bng nhau). Rt tr li 100ml hn hp kh oxy v khng kh vo xylanh pha trn bn tay phi t dng c o nhit lng v m bnh o nhit lng. Lm y xylanh pha di bn tay phi bng 100ml kh hydro ri ng van li. Ghi nhit ban u ca nc (T1). Bt ngun cung cp in th, m kho ba chiu ca xylanh cha kh hydro v n cng lc hai pittng ca 2 xylanh trn v di a kh oxy v hydro vo dng c o nhit lng (trong khong thi gian 4 - 5 giy) cho n khi c hai xylanh u ht kh hon ton.
17

Kh hydro vo trong dng c o nhit lng c t chy bng cc tia la v chy to thnh nc. Hn hp kh oxy v khng kh cn d s thu c trong xylanh bn pha tay tri. Sau khi chy, ng ngay lp tc van ca xylanh cha hydro v tt ngun in. Khuy nc trong ng bc bng cch di chuyn thanh nam chm qua li cho n khi nhit cn bng (nhit trn hai nhit k nh nhau). Ghi li nhit ny (T2), T2 nn cao hn nhit T1 khong 0,5 . Ch ghi nhit phng (T0), p sut kh quyn (P) trn mn hnh LCD. 6. L thuyt Nhit to thnh ca nc (H) c nh ngha nh s thay i entapy h ca mt mol cht v chuyn ha theo phn ng. H2O + 1/2O2 = H2O
h H = p,T

S thay i entapy (h) ca h thng phn ng xy ra y tng ng vi nhit c hp th bi dng c o nhit lng (Qcal) ta c phng trnh: - h = Q cal = m i c i T = m H 2O .c H 2O + C cal T Trong :
m H 2O : khi lng ca nc trong dng c o nhit lng C H 2O : nhit dung ring ca nc (= 4,1868 J.g .K )
-1 -1

Ccal: nhit dung ca dng c o nhit lng (= 410 J.K-1) T = T2 - T1 (K) Mt khc ta c:
n (H 2 ) =
n (H 2 ) : s mol H2

p dng phng trnh trng thi kh l tng:

n (H 2 ) = PV RT

Trong : P: l p sut kh quyn (N.m2)

18

V: l th tch kh H2 (m3) T: nhit phng R: l hng s kh (= 8,314 J.mol-1.K-1) S mol H2 trong 100ml kh (n = 4,065 mol) nhit T = 296,5K v p sut l P = 100,1 KPa, T = 0,45K. Kt qu l nhit to thnh ca phn ng l -277,1 KJ.mol-1 (gi tr = - 286 KJ.mol-1).

19

BI 4: CN BNG LNG - HI

1.

Khi nim lin quan Entropy v entanpy ca qu trnh ha hi, p sut hi, phng trnh

Clapeyron-Clausius, qui tc Trouton - Pictec, nguyn l nhit ng hc. 2. Nguyn l cc nhit khc nhau, p sut ring phn ca pha kh c to ra do cht lng bay hi cng khc nhau. Nu p sut trn b mt cht lng gim, cn bng lng hi c thit lp li bi s bay hi mt phn ca pha lng. 3. Nhim v Xc nh nhit ha hi ca aceton bng cch o p sut hi ti cc nhit khc nhau. 4. Dng c, ha cht v thit b

Hnh 1: S h thng th nghim - Dng c o nhit lng - Mn hnh hin th nhit 04402.00 13617.93 1 1
20

- u d nhit Pt - ng bo v u d - Barometer - u d p sut - Vng m silicon d = 7mm - Vng m silicon d = 2mm - Chn ng h = 750mm - Kp gc phi - Bnh cu 3 c - ng thy tinh thng l = 80mm - Van mt chiu - Bnh an ton v manometer - Bm chn khng bng nc - ng cao su, chn khng d = 6mm - ng ong 50 ml - Phu - Ca nha 1 lit 5. Pipet Bp cao su Acetone 250 ml Gyxrin 250 ml Mui 500g Nc

11759.01 11762.05 07136.00 07136.01 39296.00 39298.00 37694.00 37697.00 35677.15 36701.65 36705.00 34170.88 02728.00 39286.00 36632.00 34457.00 36640.00 36590.00 39275.03 30004.25 30084.25 30155.50

2 1 1 1 1 1 2 3 1 1 1 1 1 3 1 1 1 1 1 1 1 1

Lp t v vn hnh Lp t dng c nh hnh v. Lp vo bnh cu 3 c mt van mt

chiu, mt ng thy tinh ngn, thng v ng bc ngoi bo v u d nhit nh sau: thay 2 ming m GL 25/12 bng 2 ming m GL 25/8. C nh ng thy tinh ngn gia c ca bnh cu. Ni ng thy tinh ny vi adapter bng mt ng silicon nh (d = 7 mm), sau ln lt ni vi u d p sut ca thit b o vi mt ng mng ( d = 2 mm). Ni van mt chiu vi ng cao su n bnh an ton c ni vi bm. Cho 3 git aceton

21

vo bnh bo v bc ngoi tn dng s truyn nhit sau nhng u d nhit ngp trong ng bc ngoi. Cho vo dng c o nhit lng hn hp sinh hn (nc + mui), o nhit ca hn hp sinh hn bng u d nhit . Cho vo bnh cu ba c 50ml aceton, nhng khng nhng chm vo hn hp sinh hn. Lp bm chn khng bng nc v vn hnh to chn khng trong bnh cu cho n khi aceton bt u si. ng van trn bnh cu, h bnh cu ngm vo hn hp sinh hn. Ngay khi nhit h di -50C, m li van mt chiu lng kh tha di chuyn khi bnh cu. Khi p sut xp x 50 hPa (5000 Pa), kha van mt chiu v cn thn m van ba chiu trn bnh an ton khng kh t t i vo. Tt bm chn khng, c p sut trong bnh cu c hin th trn p k. Trong vng 10 pht n c th tng ti a l 2 hPa. (Nn kim tra li cc ch ni). Gia tng nhit trong bnh cu tng bc t 2 - 30C bng cch thm nc vo hn hp sinh hn (dng a khuy u hn hp) hoc ly bt nc mui ra khi bnh o nhit lng. Sau mi ln tng nhit , ch cho n khi cn bng lng hi c thit lp tr li, ghi nhn nhit v p sut hi tng ng ca aceton trong bnh cu. Tip tc th nghim cho n khi nhit t 200C v cho cn thn khng kh vo bng cch m t t kha van mt chiu trn bnh cu. 6. L thuyt p sut hi ph thuc vo nhit v c m t bng phng trnh Clapeyron - Clausius:
H V dP = dT T(Vg Vl )

Trong : P: p sut hi HV: entapy ca qu trnh bay hi Vg, Vl: th tch ca pha kh v pha lng T: nhit (0K) Kt hp vi phng trnh trng thi kh l tng ta c:

22

1 dP H V = P dT RT 2

dP H V dT = R T2 P
lnP = H V +C RT

C: hng s tch phn Hoc:

ln H V P2 = P1 R 1 1 T 2 T1

1 Hnh 2: th hm s lnP = f T

23

BI 5: SC K KH

1.

Khi nim lin quan Sc k, sc ph, phng trnh Nernsts v s phn b (s lng a l

thuyt), u d dn nhit. 2. Nguyn tc Qui trnh sc k cho php tch mt hn hp cc cht vi s c mt ca pha tnh v pha ng.Trong sc k kh pha ng l kh. Pha ng s chuyn hn hp cc cht qua ct tch vi tc dng khng i. Cn bng c thit lp gia pha tnh v cc cht khc nhau do vn tc di chuyn khc nhau ca cc cu t (cn bng ca s phn b, qu trnh hp th, gii hp th). cui ct c mt u d, u d ny c th xc nh c nhng cht khc nhau da trn s khc nhau v tnh dn nhit. Tn hiu ca u d pht ra l hm s theo thi gian (sc ph) S dn nhit khc nhau ca kh mang v cc cht gy ra s bin i ca u d, u d ny c t ti mch cu Wheatstone. Tn hiu in i ra c ghi li ra giy v l mt hm theo thi gian (sc ph). 3. Nhim v Xc nh thi gian lu ca nhng cht khc nhau v biu din s tch sc k ca hn hp kh butane. Tch v nhn bit thnh phn ca hn hp 2 thnh phn gm ethanol v ethylacetat. 4. Dng c, ha cht v thit b Cobra3 unit Ngun cung cp 12V/2A Cp truyn d liu Software Dy ni, l = 250mm mu 12153.00 12151.99 14602.00 14520.61 07360.01 1 1 1 1 1
24

Dy ni, l = 250mm mu xanh B phn iu khin sc k u d sc k ng bao bng thy tinh Ct tch sc k Nt cao su o lu lng bng bt x phng Chn hnh ch H Thanh , l = 750mm Kp gc phi Kp vn nng Xylanh 10 l Xylanh 1 ml Kim tim, 0.45 x 12mm ng thy tinh, thng l = 80 mm Nhit k -101000C ng h bm giy Bnh kh Heli Chn bnh kh He Van gim p B phn gia nhit, 1000C B phn ci t ca b iu nhit B iu nhit dung tch 6l ng cao su, chn khng ng cao su Kp ng d = 812mm Kp ng d = 1220mm Cn Bnh cu 500ml Bm chn khng bng nc Bnh bo v vi p k Mung Phu thy tinh Bp cao su Becher 150ml Van chnh tinh Kh nn n-butan Kh nn iso-butan Bng thy tinh Chromosorb Dinonylphthalate

07360.04 36670.99 36670.10 02615.00 36670.00 02615.03 36675.00 02009.55 37692.00 37697.00 37715.00 02607.00 02593.03 02598.04 36701.65 38056.00 03071.01 41776.00 41774.00 33481.00 08492.93 08492.01 08487.02 39286.00 39282.00 40995.01 40996.01 48852.93 35862.00 02728.00 34170.88 33398.00 34457.00 39275.03 36003.00 33499.00 41773.11 41773.12 31773.03 31514.04 31276.10

1 1 1 1 1 1 1 1 2 6 6 1 1 1 1 1 1 1 1 1 1 1 1 2 6 7 2 1

25

Acetone 250ml Ru etylic tuyt i 500ml Etylacetat 250ml Nc ct 5l Dung dch x phng

30004.25 30008.50 30075.25 31246.81

Hnh 1: S h thng th nghim 5. Lp t v vn hnh Chun b th nghim nh hnh 1. Chun b pha tnh cho ct tch kh bng cch rt aceton vo 10g Chromosorb trong bnh y trn cho ti khi c mt lp mng cht lng pha trn Chromosorb. Thm vo bnh cu trn mt dung dch gm 1,11g dinonylphthalate v 10ml dung dch acetone, lc mnh hn hp trong vi pht. t bnh trong mt a ng nc m v s dng bm chn khng bng nc lm gim p sut trong bnh, lc ny acetone bt u si nh. Ch , gn tephlon xung quanh c bnh cu. thu hi acetone, ta t thm mt bnh an ton vo gia bnh cu v bm chn khng bng nc. Trong sut qu trnh bay hi ca aceton, ta thng xuyn lc bnh cu cho n khi Chromosorb kh li v chuyn mu sng ln ging vi mu Chromosorb ban u. Khi acetone bay hi ht, thu gom acetone t bnh an ton vo bnh thu hi cha cc dung mi hu c. Sau sy Chromosorb 1000C trong vng t 5 - 6 gi. Mt iu ht
26

sc quan trng l pha tnh trong ct sc k phi kh ro hon ton v khng c bt k d l mt lng nh dung mi. pha tnh chun b vo ct bng cch s dng phu v bm chn khng bng nc. lm c iu ngi ta dng mt que nh y bng thy tinh vo mt u ca ct tch. Sau , ni u ng thy tinh vo bm chn khng bng ng cao su v ht kh t ct. Lc ny mt tay gi ct v nghing sao cho phu c gi u ni thy tinh GL18 (u cn li). pha tnh chun b v chia thnh nhiu phn cho vo phu, ngay lp tc n s c ht ngay vo trong ct bng lung khng kh. Cn thn gi ng thy tinh bng tay kia.Ta phi chc chn rng ct phi c u. Khi ct y ta ng u cn li bng bng thy tinh nhng thc hin cho u kia. Tuy nhin khng c n qu cht, nu khng tr lc ca dng kh vn chuyn trong ct tch qu cao khi ct i vo hot ng. Mt khc chng phi chc chn ngn khng kh mang to p lc y pha tnh ra khi ct.

Hnh 2: Cu to ca h thng sc k Lp t ct tch vo trong ng bao thy tinh iu nhit v t chng v tr thng ng bng hai kp thng nm bn tri thanh . Sau ni vi b iu nhit tun hon nm trong b ln bng nha v c th tch l 6l (b iu nhit ), vi ng bao thy tinh bn ngoi bng ng cao su sao cho nc vo ng bao thy tinh bn ngoi t pha di. Dng nc chy xung quanh ct tch v ra ngoi bng mt ng gn nh ct tch.
27

t mt nhit k vo ng thy tinh hnh ng ca ng bao thy tinh bn ngoi kim tra nhit . Trc khi ci t, cn phi kim tra h thng tun hon nc (t b phn iu nhit n ct sc k v ngc li) kim tra h thng ng thi lm y nc trong ng bao thy tinh bn ngoi (trnh to thnh nhiu bt kh). Trong khi lm vic ny, ta kim tra cc l r r trong h thng nc tun hon v loi chng ra nu cn thit. Nu ci t phn ny hot ng ng ta ci t phn cn li ca thit b th nghim theo chui sau y: Ni ng chu p lc t bnh kh He n ng ni thy tinh (1). Do ng ny phi chu p lc cao trong sut qu trnh th nghim nn hai u phi c sit cht bng bng cc kp ng. t u d (5) vo bn trong u ni thy tinh (2) v gi cht bng kp ng. Kt ni u d thng qua ng thy tinh hnh ng (6) c ni vi dng c o bt x phng, trong c sn 1 n 2 ml dung dch x phng. Ta c th thng xuyn thm mt lng nh dung dch x phng vo lu lng kh thng qua bp cao su. Bt x phng c to thnh theo cch ny c th d dng quan st cho vic o vn tc dng kh. Ni u d vi b phn iu khin sc k kh, m n ng vai tr cung cp ngun in v hiu chnh u d thng qua dy cp ng trc. Cn thn: Ch m b phn iu khin khi c kh di chuyn qua trnh lm h u d do qu nhit. Ni Cobra3 Chem - Unit vo cm ca b iu khin. lm iu ny, s dng hai cp ni ni b phn ghi ca thit b iu khin vo thit b Chem - Unit chanel Analog In. Ni Chem - Unit vo u vo ca my tnh bng si dy truyn d liu. Lp mt np cao su kn trn ming ng tim ca ct tch thy tinh nh l septum. Bt h thng iu nhit vi bm tun hon. nhit phng th va tch kh, nhng ni chung ta cn nhit cao hn khi tch hn hp cht lng. Khi nhit t n ngng cn thit lc ny ta mi cho kh (He) t t vo ct tch. iu chnh tc dng kh bng van gim p trn bnh cha He khong 30 ml/pht (o bng dng c o bt x phng). o vn tc ca bt x phng nh sau:
28

Hnh 3: Dng c ly kh n vo bu cao su c cha 2 ml dung dch x phng to mt t bt x phng phn trn ca ng thy tinh. Kh i vo mang theo bong bng ln trn ng. o thi gian mt bt bong bng i t im mc 0 n mc 5 hoc mc 10ml bng ng h bm giy. Tnh vn tc dng kh (ml/pht) t gi tr ny. V d khi mt bt x phng ti mc 10 ml trong 15 giy, ta o vn tc kh trong ct tch l 40 ml/pht. y nc vo erlen c nhm. Ni ng thy tinh trn erlen vi bnh kh (n-butane, iso butane, camping gas) bng ng cao su di. M van kh i vo erlen, n to p lc y nc i vo phu nha gn pha trn erlen. Sau khi y, ng ng vi nt y cao su. ngn khng cho kh b p ra ngoi erlen do p sut ca nc tc ng ln n y phu bng nt cao su. Nt ny s c ly ra sau . 6. Qui trnh

6.1. Tch v xc nh ng phn ca butan Qu trnh tch hn hp butan c thc hin nhit phng. Bt b iu nhit tun hon, nhng khng lm nng nc (ci t nhit 300C). Khi ng chng trnh Measure v chn Cobra 3 Chem - Unit. Ci t s la chn nh sau: Get value every 300 ms trong X - data chn Time bt u v kt thc chng trnh bng bn phm, v trong du Channel chn Voltage (nh hnh 4). Chn hp Preferences chn Voltage v chn ch in th hot ng ch o 3V v cng
29

chn Average over 1 valuve (nh hnh 5). Sau khi ng ca s ny chn ch Displays. Ci t t -0,2 n 1V (nh hnh 6). Trong menu Digital ci hin th Digital 1 l Voltage cc phn khc th off. Mn hnh hin th ny ch ng vai tr iu khin. Trong phn <Analog> chn <off> cho tt c cc hin th, trong khi trong <Diagrams> chn <Line diagram> trong Diagram 1, chn <Voltage> trong Diagram 1a v chn <off> trong Diagram 1b v 1c. Ci t ch <0 300s> v chn <Scroll> (nh hnh 7). ng ca s ny. Kt thc ci t bng <Continue>. Sau mn hnh hin th o c m. M rng s sao cho chim khong 2/3 din tch mn hnh. hin th s din tch bn di ca mn hnh. Cc gi tr o c kim sot ti y. Bt cng tc iu khin vi pht trc khi bt u o (nh, ch bt khi kh mang chy qua, trnh trng hp qu nhit u d). Gi nt Grob v tr mt lt, sau iu chnh n gi tr ng nn 0V. Sau 3 pht, kim tra li mn hnh hin th. Nu cc gi tr o thay i nhiu, th nhn nt Grob 1 ln na. Nu vn cha t ta vn nt Fein t gi tr xp x 0 (V). M van Heli v s dng dng c o bt x phng (vi bu cao su cha 1-2 ml dung dch x phng) iu chnh tc dng Heli 30 ml/ph (10ml/20s). n vo bu cao su to v nh v bt x phng.

Hnh 4
30

 thc hin qu trnh tch sc k kh, trn n-butance v iso-butan trong ng tim 1ml bng kim tim, ht 0,5 ml mi cht t erlen cha kh chun b vo ng tim. Bt u thu thp d liu t my tnh, sau cn thn a su u ng tim vo septum v nhanh chng nhn ng pittong (nu c th hy thc hin ng tc ny vi ln, m bo ton b mu c a vo). Rt ng tim ra khi septum. Ch im bt u tch - thi gian tim - my tnh s bt u ghi li. nhn bit cc peak ring l, chun b trn mt hn hp khc gm 2 kh, nh trong ln u nhng dng 0,2 ml iso-butane v 0,8 ml n-butane, ln sau l 0,8 ml iso-butane v 0,2 ml n-butan. So snh kt qu ca sc k kh vi mng sc ph ban u (pha trn 1:1). Hn hp kh butan trong bnh kh c th tch ra theo cch tng t. Thm vo hn hp kh trn l 2 ng phn n - butane v iso-butan, c tim vo ct tch. Thay i np cao su (septum) sau mt vi ln tim, v n s r r sau vi ln tim. Ngng lu thng kh li trc khi thay i septum.

Hnh 5

31

Hnh 6

Hnh 7 6.2. Tch hn hp etanol v etyl acetat Dng 2 ng tim (1 ml) ly mi cht etanol v etylacetat 1ml cho vo l nh c np. Hn hp ny c cha trong l nh c th bo qun c mt thi gian ngn dng sau ny. Thc hin qu trnh tch kh 800C. Ci t b iu chnh nhit n nhit ny v i cho n khi cp nhit cm trong v ngoi bng thy tinh (glass jacket) n nh 800C. Qui trnh tch sc k kh tip theo hon ton tng t nh m t trong phn 1. Ht 5l hn hp, khng c bong bng, vo trong ng tim 10l. Bt u o, cn thn a kim tim vo su xuyn qua septum, dng tay cn li p

32

nhanh pittng. Ly ng tim ra khi ct nhanh chng (nhng cn thn, kim rt d gy). i vi qu trnh xc nh ester, tim mt hn hp u gm 4l hn hp v 2l tyl acetat. 7. L thuyt: Qu trnh tch sc k ca hn hp cc cht xy ra gia pha tnh l pha m ct sc k c nhi y v pha ng l pha di chuyn vi tc dng kh qua ct tch khng i. Trong sc k kh, pha ng l kh: n c gi l kh mang. i vi qu trnh tch cc cht, cc hm c trng c th c s dng (v d: hp th, phn b, trao i ion, gel thm thu). Sc k kh thng c s dng nh l php ghi sc phn phi. Trong trng hp ny pha tnh bao gm cht rn nn m trn b mt c mt lp cht lng mng m pha tnh c xc nh chnh xc. Trong cc iu kin v ng nhit, ng p quy lut phn b Nernst di y l c s cho vic thit lp cn bng v phn b:
K= aI A a II A

K: h s phn b Nernst

a I : hot ca nguyn liu A pha 1 A a II : hot ca nguyn liu A pha 2 A

Khi mt cht chuyn n ct tch, phn ln cn bng c thit lp cho ph hp vi nguyn tc chn lc hay phn b Craig. Cht hot ng mnh trong pha tnh th s di chuyn qua ct tch chm, ngc li cht ha tan km trong pha tnh th di chuyn nhanh qua ct. Tng t i vi s chng ct, kh nng tch ca mt ct c biu din qua s mm l thuyt. S mm l thuyt cng ln th kh nng tch cng tt hn. S a l thuyt N c th tnh l thng s ca chiu di ct v chiu cao ca a mm l thuyt H:
N = L H

Trong : N: S mm l thuyt
33

L: chiu di ct H: chiu cao tng ng mi mm l thuyt. Chiu cao mm l thuyt c tnh ton trc tip t sc k . Hnh 9 miu t c im v s lng ci m c th c t sc k . Cng ca tn hiu l mt hm theo thi gian. Thi gian ng l thi gian m kh khng c ct gi li cn i qua ct. T sc k chiu cao tng ng ca mm l thuyt c th xc nh c. chnh l kh nng tch ca ct.
H= b2L 16t2 R

Hnh 8

Hnh 9

Thi gian lu th dng xc nh cc cht (nh tnh). Thi gian lu l tnh cht c trng cho mt cht c th nhng iu kin nht nh. Khu vc di mi peak ca mi cht cung cp thng tin nh tnh. Vi nhng mi (peak) nhn, chiu cao mi c th dng tnh trc tip cho vic nh lng. I: t0: tm: Cng ca tn hiu thi gian bt u thi gian ng (thi gian cht)

tRA: thi gian lu ca cht A tRB: thi gian lu ca cht B ba: b rng mt y ca cht A bb: b rng mt y ca cht B 8. L thuyt v kt qu
34

Nhng kt qu s khc nhau vi nhng ct tch khc nhau. Vi nhng iu kin c a ra nh trn th kt qu t c nh sau:

8.1 Qu trnh tch cc ng phn ca butane Hai ng phn ca butane c th tch bi sc k kh, v c v trn sc k (hnh 10 - 16). Khi t l gia cc ng phn l 1:1 th sc k ny (hnh10) c so snh vi nhng sc k khc m trong hn hp kh gm mt kh c thnh phn nhiu hn (hnh11 - 12), c th thy rng thay i lin quan n chiu cao peak. S tng ln ca mi c cho l lin quan n t l 1:1 vi cc ng phn c phn chia vt mc, v gim ca mi cng l do lin quan n s phn chia (gim xung).

Hnh10

Hnh 12

Hnh 11

Hnh 13
35

C th xc nh c rng trong s tch ny iso-butane (mi 2) ra khi ct tch trc n-butane (mi 3) (hnh 11 v 12). Mi 1 ca sc k kh c to ra l do mt lng vt ca kh c tim vo vi mu. Kt qu ca s tch hn hp kh t burner cartidge l sc k vi 5 mi (hnh 13). Mi u tin c th c quy l khng kh. S so snh sc k t hnh 10 n 12 cho php kt lun mi 3 l iso-butane v mi 4 l nbutane. Mi 2 l propane cng c mt trong hn hp kh t. Tnh ng n ca s phn chia ny c th c gii thch bi s di chuyn ca s tch sc k, mi loi hn hp kh t c ha trn vi mt lng nh kh nguyn cht (hnh 14 - 16). Propane khng c dng y nhng v nguyn tc c th tham gia vo qu trnh tch ri. Mt mi sc k na c tm thy trong sc ph t hnh 13 ti 16 (mi 5). l kt qu ca mt lng nh 1,3-butadien, iu ny ph hp vi nhn trn bnh kh, n c cha trong hn hp kh. Kt qu xc nh c trong thc nghim c th gii thch nh sau. Cc ng phn ca butane khc nhau v nhi si. Isobutane l phn t hnh cu c lc tng tc phn t yu v c im si ti -11,70C trong khi n-butane l phn t thng v v vy n c n ra vi lc bm dnh ln hn, kt qu l im si ca n cao hn -0,50C. V vy iso-butane s ra khi ct trc n-butane. S tch ca hn hp kh miu t di y di nhng iu kin nh sau: Nhit ct tch Tc dng kh mang Tng lng kh bm vo Thnh phn ca hn hp kh: Hnh 10: 0,5 ml iso-butane + 0,5 ml n-butane Hnh 11: 0,2 ml iso-butane + 0,8 ml n-butane Hnh 12: 0,8 ml iso-butane + 0,2 ml n-butane Hnh 13: 1,0 ml camping gas Hnh 14: 0,6 ml camping gas + 0,4 ml n-butane Hnh 15: 0,6 ml camping gas + 0,4 ml iso-butane Hnh 16: 0,7 ml camping gas + 0,3 ml khng kh
36

: : :

220C 30 ml/pht,He 1 ml kh/ hn hp kh

Hnh14

Hnh 15 8.2 Qu trnh tch hn hp ethanol v ethylacetat

Hnh 16

S tch hn hp ethanol v ethylacetat (t l v th tch 1:1) cung cp mt sc k vi hai mi (hnh17). Mi 1 trong sc k ny l ethanol v mi 2 l ester. iu ny c th gii thch n gin bng ln tch th hai dng 4l ca hn hp v ht 2l ca ester cho vo xy lanh microlite. Sc k ca qu trnh tch ny miu t mt s khc bit kh ln, ph thuc vo ln ca mi 2 vi mi 1 (hnh18), iu a n mt nhn xt rng mi 2 chnh xc l ester. Php tch sc k ca hn hp ethanol v ethylacetat c din ra di iu kin nh sau: Nhit ct tch : 800C 30ml/pht, He
37

Tc dng kh mang:

Thnh phn ca hn hp phn tch: Hnh 17: 5l hn hp (ethanol/ester = 1/1) Hnh 18: 4l hn hp + 2l ester

Nu nh qu trnh tch sc k kh tch chnh xc theo nhit si th cht c im si thp s c tch ra khi ct trc mt cht c im si cao. C th thy iu trong v d ny, tuy nhin r rng l ethylacetat ra khi ct mun hn ethanol d n c im si nh hn ethanol l 1,44K (im si ca ethylacetat l 77,060C; ethanol l 78,50C). V vy sc k kh cho php tch hn hp ra nhng thnh phn ring l, nhng thnh phn ny khng th tch ri bi qu trnh chng ct, nh l hn hp ng ph hay l hn hp nhng cht c im si tng t nhau. c tnh ca s tch c th c ci thin tt hn bng vic thay i cc ch . 9. Nhng iu cn ch Vic s dng sc k tch cc cht c chng minh l mt phng php tt trong phn tch. Phng php ny c th tch c mt lng rt nh ca hn hp thnh cc thnh phn, v chng c th c nhn bit bi nhng u d thch hp. Trong th nghim c miu t y sc ph c th c tp hp d dng t nhng thnh phn ring bit, v v vy n c nhng li ch ring, l cu trc v cng thc l nhng yu t cn thit ca sc k th sinh vin c th hiu c. Ch pht hin c thc hin bng cch s dng u d da vo mt in tr NST. N nhn bit c mt lng nh kh da vo s khc nhau v dn nhit. Tn hiu pht ra i qua b iu khin vi b khuych i n u vo ca giao din Cobra 3, v sau v th v nh gi. Ct tch kh dng trong sc k kh th c y vi dinonylphthalate, nh c hng dn trn. Mc d ch c ct tch c s dng tch hn hp cc cht, nhng vn s dng glass jacket, n gi cho nhit n nh thng qua b iu nhit tun hon. iu ny rt quan trng v v tr ca cc mi ca cc cht (thi gian lu) ph thuc rt nhiu vo nhit , trong cc yu t th nhit thay i tht thng lm cho ng nn khng c n nh. Heli c th c
38

dng lm kh mang (pha ng) trong php sc k ny. Tc dng kh c th c iu chnh v quan st bng dng c o tc bt x phng. Thnh phn ca kh t c th thay i tht thng. Trong c th khng c propane, hoc c th ch c n-butane. Thnh phn ca kh trong bnh cn phi kim tra trc khi dng kh thc nghim. y chng ta khng tho lun v l thuyt ca phng php sc k. Th nghim ny ch n thun l minh ha r nt cho nhng nguyn tc. Nhng miu t chnh xc hn v bao qut hn s c tm thy trong cc ti liu k thut.

Hnh 17

Hnh 18

39

BI 6: XC NH TC PHN NG V NNG LNG HOT HA CA PHN NG THY PHN CH3COOC2H5 BNG HCl

1.

Khi nim lin quan Tc phn ng, hng s tc phn ng, phn ng bc 1, phn

ng bc 2, phng trnh Arrhenius, nng lng hot ho. 2. Nguyn l Trong dung dch axit, CH3COOC2H5 thy phn thnh C2H5OH v CH3COOH theo bc gi nh l 1. Lng axit to thnh c chun bng phng php chun kim, t phng php ny c th rt ra kt lun nng ca este ph thuc vo thi gian. 3. Nhim v Xc nh hng s tc phn ng cho phn ng thy phn CH3COOC2H5 bng acid HCl 2 nhit khc nhau (hay nhiu hn). Tnh ton nng lng hot ha ca phn ng theo nhit t cc hng s tc o c. 4. Dng c, ha cht v thit b

Hnh 1: S h thng th nghim

40

- ng xon gia nhit - B iu khin ng xon gia nhit - B iu nhit, 6l - ng cao su d = 6mm - Mn hnh hin th nhit - u d nhit NiCr-Ni - ng h bm giy - Bp iu nhit c khuy t - C t l = 15mm - C t l = 30mm - Thanh l = 500mm - Thanh l = 750mm - Buret, 50ml - Kp gc phi - Kp vn nng - ng ong 100 ml - Bnh nh mc, 1000ml - Pipet 5ml - Pipet 100ml - Bp cao su - a thy tinh, 1000ml - Erlen, 250ml, c rng - Erlen, 250ml, c cht - Nt cao su 17/22mm - Becher 250 ml - Phu thy tinh - Bnh tia 500ml - CH3COOH, 250ml - HCl 1M, 1000ml - Dung dch NaOH 1M, 1000ml - Dung dch phenolphtalein 1% - Nc tinh khit 5l

08492.93 08492.01 08487.02 39282.00 07050.00 13615.03 03071.01 35720.93 46299.01 462.99.02 02022.05 37694.00 37720.00 37697.00 37715.00 36629.00 36552.00 36577.00 36582.00 39275.03 46245.00 36134.00 36424.00 39258.00 36013.00 34457.00 33931.00 30075.25 48454.70 48329.70 31714.10 31246.81

1 1 1 2 1 1 1 1 1 1 1 2 1 4 4 1 1 2 1 1 1 2 2 2 1 1 1 1 1 1 1 1
41

5.

Lp t v vn hnh Lp t dng c nh hnh v. Chun b dung dch NaOH 0,2M bng cch ly 200 ml dung dch NaOH

1M cho vo bnh nh mc 1000ml, cho nc ti vch chun. Cho dung dch NaOH 0,2M vo buret. Dng pipet ly 100ml dung dch HCl 0,1M cho vo bnh erlen, y np cho vo b n nh nhit khong 15 pht 350C (T1 ). Cho 5ml dung dch CH3COOC2H5 vo bnh erlen cha HCl, lc vi ln ri t vo b n nhit. C sau cc khong thi gian 10, 20, 30, 40, 50 pht, ly 5ml hn hp cho vo cc erlen c rng cha sn 100 ml nc ct lnh (5 bnh), phn ng s dng ngay lp tc. Chun bng dung dch NaOH 0,2M vi ch th phenolphtalin. Sau khi kt thc chui th nghim th lp li qu trnh trn nhit 450C (T2). Th tch ca NaOH ti thi im t0 ( VNaOH,0 : th tch cn trung ha lng HCl lc ban u) c th c tnh theo l thuyt hoc da vo kt qu th nghim. Xc nh VNaOH,0 chun ht 5ml HCl 0,1M. Xc nh th tch NaOH thi v cng (phn ng chuyn h hon ton) bng cch. em bnh nn cha hn hp cn li cho ln bp, un cch thy (c khuy t) nhit khong 700C trong vng 30 pht. Lm ngui hn hp ri chun bng dung dch NaOH 0,2M nh trn. 6. L thuyt CH3COOC2H5 + H2O Tc phn ng: CH3COOH + C2H5 OH

vR =
Vi:

dCE = k.CE .CW.CK dt

k: hng s tc phn ng. CE, C W, CK: nng ca este, nc v xc tc ti thi im t. V nng H2O v H3O+ l khng i, v vy ta c:
dC E = k 'C E dt
42

Ly tch phn 2 v, ta c:

ln

C E,0 CE

= k't

Nng ca este CE,0 v CE ti thi im t0 v t c th thay bng th tch dung dch NaOH cn cho qu trnh trung ha ca cc mu ti thi im bt u (VNaOH;0 ) , trong qu trnh phn ng (VNaOH ) v sau qu trnh chuyn ha hon ton (VNaOH; ) .
ln VNaOH, VNaOH,0 VNaOH, VNaOH = lnQ = k , t

Trong : VNaOH, : th tch NaOH dng chun thi im t = VNaOH,0 : th tch NaOH dng chun thi im bt u VNaOH : th tch NaOH dng chun thi im t. Th tch VNaOH, 0 v VNaOH, c th c xc nh bng th nghim hoc c tnh bng cch s dng cc phng trnh sau:
VNaOH,0 = C HCl .V1 100 C NaOH 105

Trong : V1: th tch mu (= 5ml) CHCl: nng dung dch HCl (= 1M) CNaOH: nng dung dch NaOH (= 0,2M)
VNaOH, = E .VE .V1 + VNaOH,0 M E .VS .C NaOH

Trong : E: khi lng ring ca este ME: phn t lng este VE: th tch dung dch este VS: th tch ca dung dch (= 105ml) ti thi im t0.

43

Hnh 2: th lnQ theo thi gian t, h s gc ng thng l k Nng lng hot ha c xc nh theo phng trnh Arrhenius:
k = k 0 .e
' EA RT

Trong :

R: Hng s kh (= 8,31441 J.mol-1.K-1) kmax : Hng s trc ly tha i vi 2 cp gi tr bit c hng s vn tc k1 v k2 tng ng vi nhit T1 v T2.
lnk ' = EA + lnk 0 RT EA + lnk 0 RT1 EA + lnk 0 RT2

Ta c:
' lnk 1 =

lnk '2 =

Suy ra:
T1 .T2 k ,2 EA = R ln ' T2 T1 k1

44

BI 7: VN TC PHN NG TH HALOGEN

1.

Khi nim lin quan Tc phn ng, quy lut phn ng bc 1 v 2, dn in.

2.

Nguyn tc Cc nhm halogen alkyl phn ng trao i halogen nhanh trong dung

mi thch hp. Phn ng thay th ny xy ra theo c ch SN2. Vn tc ca chng c th c xc nh mt cch thun li thng qua cc ln o dn in. 3. Nhim v 4. o dn in ca cc dung dch vi cc nng khc nhau ca NaI trong acetone. Xc nh nng ca cc cht ng phn ng ca phn ng propyl bromua vi NaI trong aceton 300C. Xc nh hng s tc phn ng.

Dng c, ha cht v thit b

Hnh 1: S h thng th nghim

45

- Thit b o dn - u d nhit v dn - Bp khuy t - Dng c ci t nhit - C t, l = 25mm - C t, l = 50mm - ng h bm giy - Da cn - Thanh , l = 750mm - Kp gc phi - Kp vn nng - Da thy tinh, 1000ml - Bnh cu 3 c - ng sinh hn - ng thy tinh thng, l = 80mm - Septum - Cn - ng ong 100ml - Xylanh 1ml - Kim tim, 0.6 x 60 mm - Pipet - Bp cao su - Phu - Beaker 50 ml - Mung - ng cao su, d = 6mm - Kp ng, d = 812mm - n - propyl bromide 250ml - NaI 50g - Aceton 250ml 5. Lp t v vn hnh

13701.93 13701.01 35720.93 35721.00 46300.01 46299.03 03071.01 03065.20 02023.20 37697.00 37715.00 46245.00 35677.15 35815.15 36701.65 02615.03 48852.93 36629.00 02593.03 02599.04 36590.00 39275.03 34472.00 36001.00 33398.00 39282.00 40996.01 31756.25 31634.05 30004.25

1 1 1 1 1 1 1 1 1 3 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 4 1 1 1

Th nghim c lp t nh hnh 1. Rt 100ml aceton vo bnh cu y trn c nhng chm vo b cha nc. t c t thch hp bnh cu y trn v b cha nc, bt u khuy. t in cc o dn in
46

vo 1 ci c ca bnh cu, ni in cc vi thit b o dn, la chn chc nng o dn in ring. Ci t b cm bin in t ca my khuy t 350C v bt ngun gia nhit. Khi t n nhit ci t, o dn in ca dung mi nguyn cht m gi tr c th l vi mS/cm. Thm chnh xc 6,805g (4,54.10-2 mol) NaI, chia lm 7 phn, mi phn 0,97g cho vo ci c cn trng ca bnh cu. Sau mi phn cho vo ch mui phn hy hon ton v nhit c thit lp (khng thay i), trc khi o dn in. Ghi li khi lng NaI sau mi ln thm vo v o dn in ri v ng cong dn in theo nng NaI. Khi ton b khi lng NaI c thm vo, bt u thc hin php o. C th ba ca bnh cu c gn ng thy tinh ngn v y cht bng nt cao su. Tim 4,2ml propyl bromua (4,54.10-2 mol 300C) xuyn qua ci nt cao su v ngay lp tc o dn ca dung dch (ti thi im t0). Tip tc o dn trong khong thi gian 5 pht mt ln. Kt thc qu trnh o sau 90 pht. 6. L thuyt Phn ng Finkelstein tin hnh theo c ch phn ng SN2 C3H7Br + I- = C3H7I + BrVn tc ca phn ng ny l 1 hm s ph thuc vo nng ca 2 cht phn ng v n tun theo quy lut phn ng bc 2.
dC PrBr = kC PrBr C I dt

(1)

Trong : gian t

k l hng s tc phn ng CPrBr, CI- l nng propyl bromide v ion I- ti thi

V nng u ca C3H7Br v NaI bng nhau (CPrBr,0 = CNaI,0), nn phng trnh c th c vit nh sau:
dC PrBr = kC 2 = kC 2 PrBr I dt

(2)

Sau khi ly tch phn 2 v ca phng (2) ta c:

1 C PrBr = kt + 1 C PrBr,0

(3)

47

Hnh 2: S ph thuc ca dn in vo nng ca NaI Nng ca NaI cn li trong qu trnh phn ng ti thi im (t) c xc nh bng ng cong chun (hnh 2). T xc nh nng propyl bromide (CPrBr) theo phng trnh sau: CPrBr = CI- = CNaI (4) Ri th v th nng propyl bromide theo thi gian CPrBr - t

Hnh 3: th nng theo thi gian (CPrBr = CI- = CNaI) ca phn ng gia propyl bromide vi I xc nh bc phn ng, v th
1 C PrBr

- t

48

Hnh 4: Xc nh bc phn ng v hng s tc ca phn ng propyl bromide vi I1 C PrBr

Mi quan h tuyn tnh gia

v t c minh ha hnh 4 ti

y c s hin din ca phn ng bc 2. Vi h s gc ca ng thng l hng s tc k = 1,5.10-3 l.mol-1.s-1 (v gi tr k = 1,37.10-3l.mol-1.s-1 2980K) Vn tc ca phn ng Finkelstein ph thuc vo c tnh ca dung mi ban u. V l do ny, nhng chch lch ca cc gi tr o xy ra ty theo tinh khit ca aceton c s dng.

49

BI 8: DN IN TRONG CHT RN

1.

Khi nim lin quan S dn in ca electron v ca ion.

2.

Nguyn tc Xc nh in tr ca cht rn ph thuc vo nhit , n cho bit c

ch v s dn in v thay i in tch trong cht rn. 3. Nhim v Xc nh h s nhit in tr i vi dy st, ng v dy Constantan trong gii hn t nhit phng n 950C. 4. Dng c, ha cht v thit b

Hnh 1: S h thng th nghim

50

Nt mu trng Nt mu vng

sensor dy mu

dy mu

dy mu xanh

Hnh 2: S lp mch in - Cobra3 Unit - Ngun cung cp 12V/ 2A - Cp truyn d liu, RS232 - Phn mm Cobra3 Universal writer - Mn hnh hin th nhit - u d nhit NiCr-Ni - Ngun cung cp vn nng - Bp khuy t - C t, l = 30mm - Thanh , l = 500mm - Thanh , l = 250mm - Kp gc phi - Kp vn nng - Pin cch in - Dy ni, l = 500mm, mu - Dy ni, l = 750mm, mu - Dy ni, l = 750mm, mu xanh - Becher 1000ml 12150.00 12151.99 14602.00 14504.61 07050.00 13615.05 13500.93 35720.93 46299.02 02022.20 02031.00 37697.00 37715.00 07807.00 07361.01 07362.01 07362.04 36017.00 1 1 1 1 1 1 1 1 1 1 1 4 1 2 2 1 1 1
51

- Ko - Dy ng - Dy st - Dy constantan - Nc ct 5. Lp t v vn hnh Lp t thit b th nghim nh hnh 1 v hnh 2.

64798.00 06106.00 06104.00 06100.00 31246.81

1 1 1 1 1

Chun b 3 mu dy kim loi. Tip theo ct mu dy th nht di 30cm v qun mu dy vng quanh cy bt ch, lp li qu trnh trn cho 2 mu cn li. Phi m bo tng vng xon ring l khng c chm vo nhau. Ni mu th nht vo hai kim o cch in v nhng chm n vo trong beaker c cha sn c t v nc ct. Phi chc chn rng mu hon ton ngp trong nc. Ni u d S2 v hai kim cch in vo hai l nh bn di Analog ln 1 ca thit b cobra3 basic unit. Khi ng chng trnh Measure trong windows v chn <Universal writer>. Ci t cc thng s o nh trong hnh 3.

Hnh 3 Di diagram 1 chn <Calculated Channel> t 0 - 5 Ohm, gii hn X: 0 - 15 v <no auto range>. Sau khi thc hin nhng bc trn nhn <Continue> chp nhn cc gi tr c ci t. Sp xp cc hin th nh bn mong mun.
52

 ghi li cc ln o ring bit, ci t in th ca dy ng xp x 0,25V v 1,2V cho dy st v Constantan. Chn tc khuy ca c t va phi. Ghi li im o u tin ti nhit phng bng cch nhp vo <Save value>. o 20 ln ti nhit ny ly gi tr Rc trung bnh. Sau ta tng nhit mi trng bng cch un nng nc di s khuy lin tc. Ghi gi tr o sau mi ln tng 50C. Ta ngng o khi nhit t n 950C v ghi li d liu vi ng dn <File> < Save the measurement as >. th biu din s ph thuc vo nhit ca in tr c th c chun b bng cch nhp vo <Channel modification> trong menu <Analysis>. Ci t cc thng s nh hnh 4.

Hnh 4 Hnh 5 - 7 cho thy in tr ca 3 thanh kim loi ph thuc vo nhit . Di <Display options> ta c th chn <Hide curve> v thay vo s xut hin ng thng hi quy. 6. L thuyt dn in trong cht rn ph thuc vo kiu lin kt cc thnh phn ca cht rn, m ch yu l lin kt kim loi v lin kt ion. Do chng ta phi quan tm n dn electron v dn ion. dn in c quan st trong cc kim loi, hp kim v nhng nguyn liu khc c nh kim nh: graphite, mt vi oxit kim loi, sulfit kim loi Hu ht cc cht bn dn c s dng trong cng ngh in v
53

in t v cc cht c lp cng l cc cht dn in. Tnh dn in ny th lin quan n lin kt kim loi. Trong vn ny, cc electron ngoi cng ca li kim loi th c lin kt yu v c th chuyn ng gia cc ht nhn nguyn t. Tuy nhin cc electron lin kt khng thuc v nguyn t ring bit no, nhng thuc v tt c, lin kt ca chng th khng c nh hng khng gian. Nhng ion linh ng trong li kim loi gy ra s dn in. Thuyt lin kt v s di chuyn ca cc electron trong cht rn gii thch hin tng da trn cc trng thi nng lng khc nhau ca cc electron trong cht rn. Di o dn in c trn 30 bc, t cc cht c lp c dn in bng 1022 1 .cm-1 n 10-8 1 .cm-1 ca cc kim loi tinh khit. dn ion l kh nng dn in ca mt cht bi dng chuyn di ca cc ion. Tt c cc dung dch in phn, mui nng chy v nhng mui rn l cc hp cht ion in hnh u l cc cht dn in ion. Do lin kt bn trong mng li tinh th ion ca cc mui rn, linh ng ca cc ion, do dn in rt nh nhit phng. Bng s gia tng nhit th cc lin kt dn dn yu i, v cc ion tr nn cng ngy cng linh ng hn. Hin tng ny tip tc tng ln ti im nng chy v hn na. S gia tng ca nhit s lm gim in tr sut. iu ny th tri ngc s ph thuc ca dn in vo nhit . Vi cc kim loi th s gia tng ca nhit s khng lm tng s lng hoc linh ng ca cc electron. linh ng gim cng nh vic tng nng lng nhit ca cc ion kim loi s lm tng cc dao ng nhit xung quanh v tr ca n trong mng li tinh th. Kt qu l, c s tng ln tng ng v s va chm ca electron v cc ion kim loi, lm gim chiu di qu o chuyn ng ca cc electron. iu ny s lm gim dn in. T cc gi tr thc nghim ca dng in v hiu in th, in tr R c th c tnh ton theo cng thc:
R= U I

(1)

Trong : U: hiu in th (V) I: Cng dng in (A)

54

Hnh 5: S ph thuc ca in tr vo nhit trong dy st H s dn nhit theo nhit c nh ngha nh l dc ca ng cong ca in tr sut theo nhit .
= R T1 (T2 T1 ) R T2 R T1

(2)

Hnh 6: S ph thuc ca in tr vo nhit trong dy ng

Hnh 7: S ph thuc ca in tr vo nhit trong dy Constantan

55

iu ny ch ng nu ng cong biu din in tr sut so vi nhit l mt ng thng, m ng thng th khng vt qua gii hn ln nht ca nhit . Sau y l cng thc ph hp hn ca s khc nhau v thng s c th c dng. Cng thc sau y ch ra rng s ph thuc ca in tr mi cht ph thuc vo nhit :
= 1 dR R dT

(3)

Nhit tr sut c th tnh ton t gi tr thc nghim:

= 1 R R C T

(4)

Trong : RC : in tr nhit phng

R : dc ca ng thng T

: H s nhit ca in tr

Da vo phng trnh (4) chng ta c, Fe = 4,6.10-3 K-1 v Cu = 4.10-3 K-1.

56

BI 9: PHNG TRNH NERST

1.

Khi nim lin quan S ph thuc ca th in cc vo nng ca dung dch in cc,

in cc oxi ha kh, pin in ha. 2. Nguyn tc Phng trnh Nernst pht biu th in cc ca pin ph thuc vo dung dch v nng (hot ) ca ion . Phng trnh ny c minh ha bng thc nghim khi s dng pin in ha c to thnh t in cc ch th kt hp vi in cc so snh. 3. Nhim v o in th ca in cc platium trong dung dch cha nng bit ca Fe(II) v Fe(III) v hn hp ion [Fe(CN)6]4- v [Fe(CN)6]3-. 4. Tnh th in cc ca in cc so snh nhit th nghim Tnh th in cc chun ca E 0 Fe
3+

, Fe 2 +

ti nhit th nghim.

Dng c, ha cht v thit b

Hnh 1: S h thng th nghim

57

- pH - meter
-

13702.93 18475.00 45206.00 07361.05 13702.01 47334.93 46299.02 37694.00 37697.00 37715.00 45284.01 03065.20 36517.01 48802.93 45019.05 36002.00 36003.00 36552.00 36581.00 34457.00 34459.00 33398.00 39275.03 33931.00 30101.25 30100.10 31246.81

1 1 1 1 1 1 1 2 2 1 1 2 2 1 1 2 4 4 2 2 2 1 1 1 1 1 1

in cc so snh Ag/AgCl/Cl-

- ng bo v in cc platin - Dy ni, l = 500mm, en - in cc Pt - My khuy t - C t - Chn , h = 750mm - Kp gc phi - Kp vn nng - Thanh 2 in cc - Kp gi buret - Buret 50ml - Cn phn tch - Da cn - Becher 100ml - Becher 150ml - Bnh nh mc 1000ml - Pipette 50ml - Phu thy tinh, d = 55mm - Phu thy tinh, d = 80mm - Mung - Bp cao su - Bnh tia - K4 [Fe(CN)6]: 250g - K3 [Fe(CN)4]: 100g - Nc ct 5. Lp t v vn hnh Lp t th nghim nh hnh 1. Chun b dung dch cho th nghim nh sau:

58

Pha dung dch K4[Fe(CN)6] 0,01M: cn chnh xc 4,2239g mui K4[Fe(CN)6].3H2O. Cho K4[Fe(CN)6].3H2O vo bnh nh mc 1lit. Ha tan bng nc ct, sau nh mc n vch chun.

Pha dung dch K4[Fe(CN)6] 0,001M: dng pipet ly 100ml dung dch K4[Fe(CN)6] 0,01M cho vo bnh nh mc 1l, sau nh mc n vch chun bng nc ct.

Pha dung dch K3[Fe(CN)6] 0,01M: cn 3,2925g K3[Fe(CN)6] cho vo bnh nh mc 1l, ha tan bng nc ct, sau nh mc n vch chun.

Pha dung dch K3[Fe(CN)6] 0,001M: dng pipet ly 100ml dung dch K3[Fe(CN)6] 0,01M cho vo bnh nh mc 1l, sau nh mc n vch chun bng nc ct.

S dng 2 ci burette, mt dng cho dung dch Fe(II) 0,001M v mt dng cho dung dch Fe(III) 0,001M, t vo chn gi , trng 2 ln bng dung dch tng ng nh trn v cho dung dch tng ng vo n vch mc. Chun b dung dch mu theo bng 1. t becher cha dung dch mu u tin vo my khuy t v cho c t vo becher. Sau , ni in cc Platin, in cc so snh v u d nhit vo my o pH v nhng chng ngp trong dung dch. Ghi nhit v sc in ng ca pin. Ra sch in cc bng nc ct, lm kh v t chng vo trong dung dch mu k tip, qu trnh ny phi c lm nhanh. Khng nn in cc so snh ngoi dung dch qu lu. Tip tc o cho n ht cc mu. Lp li quy trnh trn vi dung dch 0,01M. Tnh sc in ng ca pin nh l mt hm s:

[Fe(CN )6 ]3 ln [Fe(CN )6 ]4
Bng 1: Chun b cc dung dch mu
Dung dch Fe (II) (ml) Dung dch Fe (III) Dung dch Fe (II) ( ml) (ml) Dung dch Fe (III) ( ml)

49 48 46

1 2 4

20 12 7

30 38 43
59

Dung dch Fe (II) (ml)

Dung dch Fe (III) Dung dch Fe (II) ( ml) (ml)

Dung dch Fe (III) ( ml)

43 38 30 25 6. L thuyt

7 12 20 25

4 2 1

46 48 49

Pin in ha c s dng y, in cc Ag /AgCl/ Cl- c dng lm in cc so snh cung cp mt in th c nh xc nh th ca in cc oxy ha kh. in cc bc clorua gm c mt si dy Ag c bao ph bi AgCl v c nhng trong dung dch KCl c nng xc nh. in cc oxi ho - kh l cp Fe(III)/ Fe(II): [Fe(CN)6]3- + e= [Fe(CN)6]4Thng thng, mt phn ng oxi ho - kh m ion Xz+ nhn n electron thnh ion Y c in tch (z - n)+ c th c th hin nh sau: Xz+(dd) + ne- = Y (zn) mi v phn ng cn bng nhau: x(dd) + n.e (kl) = Y(dd) T nh ngha v ha th, ta c phng trnh sau: x(dd) = x + zFdd e(kl) = e + Fdd Y(dd) = Y + (z-n)Fdd Vi: dd: in th ca dung dch (kl): in th ca in cc kim loi tr i: ha th ca cu t i Kt hp phng trnh (1) v (2), ta c: (2a) (2b) (2c) (1)
+

Trong h thng ny, trng thi cn bng t c khi tng ha th ca

X z + Y(z n)+ + n e = nF dd nF kl

(3)
60

S chch lch in th gia dung dch v kim loi c biu din:

= dd kl =

1 ( Z + Y (z -n) + + n e ) nF x

(4)

in th ion ph thuc vo hot ca ion trong dung dch:

Xz + = 0 z + + RT.lna X Z+ X
Y(z-n)+ = 0 (z-n)+ + RT.lna Y(Z n)+ Y
Phng trnh (4) c th c vit di dng

(5a) (5b)

a 1 0 RT ln X z + X z + 0 (z n) + + n e + Y nF nF a Y(z n) +

(6)

Phng trnh Nernst cho in cc oxi ha kh:

E Fe3+ ,Fe2 + = E 0 3+ ,Fe2 + + Fe

RT a X z + ln nF a Y (z n) +

(7)

Pin c s dng trong th nghim ny l: (-) Ag/ AgCl/ KCl (3M)/ Fe3+, Fe2+/ Pt (+) Th in cc ca in cc dng:
E Fe3+ ,Fe2 + = E 0 3+ ,Fe2 + + Fe RT Fe 3+ ln nF Fe 2+

[ [

] ]

Th in cc ca in cc m:
E Ag/AgCl/Cl = E 0 Ag/AgCl/Cl RT ln Cl nF

[ ]

E0 = E0 + t 25

dE (t 25) dt

Sut in ng ca pin (Epin) l:

E pin = E Fe3+ ,Fe2 + E Ag/AgCl/Cl E pin = E 0 3+ ,Fe 2 + + Fe RT Fe 3+ ln E Ag/AgCl/Cl nF Fe 2+

[ [

] ]

(8)

i vi dung dch long s dng y, hot c thay th bng nng mol. Sc in ng Epin ph thuc vo ln([FeIII]/[FeII]) theo phng trnh ng thng dng (y = ax + b) c h s gc RT/F v tung gc
E 0 3+ ,Fe 2 + E Ag/AgCl/Cl (hnh 2). Nu bit c th ca in cc so snh s dng Fe 61

th th ca in cc chun ca cp oxi ha kh FeIII,FeII c th xc nh c. H s gc ca ng thng (xc nh bi ng hi quy n gin) l 25,2 mV (gi tr RT/F = 25,4mV ti 22oC) T gi tr ca Epin ti giao im trc Y ta c E 0 Fe
3+

, Fe 2 +

E Ag/AgCl/Cl = 172

mV. Ti 200C Ag/ AgCl/ Cl in cc so snh c th 210 mV. T , th oxi ha kh ca in cc chun E0[Fe(CN)6]3-,[Fe(CN)6]4- l 38mV (ti liu: 36mV theo R. Parsons, s tay in ha, Butterworth, London, 1959).

62