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Ph lc 5

TRNG I HC TR VINH KHOA HA HC NG DNG B MN DCDLH&VLNN

TI LIU GING DY
MN THC TP HA L 2
GV bin son: NGUYN TH ANH TH

Tr Vinh, nm 2013

Lu hnh ni b

MC LC Ni dung Trang

Ti liu ging dy Mn Thc tp Ha L 2

BI 1

XC NH DN IN NG LNG CC I CA CHT IN LY MNH V CHT IN LY YU


Mc tiu hc tp: Sau khi hc xong bi ny, ngi hc c th: Xc nh dn in ng lng cc i ca cht in li mnh v cht in li yu. I. C s l thuyt dn in ng lng cc i ca cht in li mnh CH 3COONa, NaCl, HCl c xc nh t dn in cc nng khc nhau nh nh lut Conraus (1) o dn in ring ca cc chui dung dch ca cc cht trn cc nng

bit trc. dn in ng lng c tnh t dn in ring o c theo biu thc (2)

l dn in ring ca nc dng pha dung dch. Nu th b qua

<<

th c

trong biu thc (2). Dng ng thng biu din ph thuc

ri ngoi suy v tung gc (

dn in ng lng cc i ca cht in li yu CH 3COOH khng th xc nh bng phng php trn m c tnh gin tip t dn in ng lng cc i ca cht in li mnh c ion chung nh CH3COONa, NaCl v HCl. II. Ha cht v dng c: KCl 0.1N NaCl 0.1N HCl 0.1N CH3COONa 0.1N My o dn My khuy t Beaker 50ml, 100ml Burette 25ml 1 Pipette 10ml Bnh nh mc 100ml

Ti liu ging dy Mn Thc tp Ha L 2

III. Thc nghim: 1. Chun b cho th nghim: Ra sch tt c m dng c thy tinh, trng bng nc ct.

Ra sch in cc nhiu ln bng nc ct, cho n khi dn ca nc ra cm-1.

xung di 2

Ghi nhn dn ca nc ct dng pha dung dch, lu nc ct phi c cm-1.

dn di 2

Lu : ch dng nc ct cho th nghim. 2. Hiu chnh my Ly 10ml dung dch KCl 0.1M cho vo bnh nh mc 100ml. Thm nc n vch nh mc c dung dch chun KCl 0.01M. a nhit quy chiu ca my o dn v 250C. a h s nhit ca dn v 1.91%. Ly khong 40ml dung dch KCl 0.01M va pha vo cc 50ml. Trng in cc nhiu ln.

b dung dch . Ly li 50ml dung dch chun KCl 0.01M, o v ghi dn

. Ghi nhn hng s in cc K1. Tnh hng s in cc mi K2 theo biu thc:

= K1 .

Chnh hng s in cc v gi tr K2 va tnh c. Chnh h s nhit v 0 dn in hin th l dn nhit th nghim. 3. Xc nh dn in ng lng cc i ca CH3COOH
Ti liu ging dy Mn Thc tp Ha L 2

Pha 100ml dung dch vi nhng nng sau t dung dch CH3COONa 0.1N. 5.00 x 10-2N 1.00 x 10-2N 3.00 x 10-2N 6.00 x 10-3N 1.50 x 10-2N 3.00 x 10-3N

Lu : Th tch dung dch ly pha long khng c di 10ml m bo chnh xc cn thit. Dng buret c chnh xc 0.05ml ly dung dch. Cn la chn cc dung dch dng pha long sao cho t phi ra, trng dng c nht. Ghi s liu dng pha dung dch vo bng.

STT

Dung dch trc pha long Dung dch sau pha long Th tch Th tch sau Nng Nng pha long pha long

dung dch pha vo cc 50ml sch. Nh trng cc bng chnh dung dch s ng.

Cho cc cc ng dung dch va pha vo bnh n nhit. Ch cc cc cng

ngp su trong nc cng tt. Ch cho cc dung dch n nh v nhit phng. Trong lc ch i ra sch in cc bng nc ct cho n khi dn ca nc ra xung di 2cm-1. Trong lc ch n nh nhit hy pha cc chui dung dch k tip tit kim thi gian. o dn ca tng dung dch, bt u t dung dch long nht nh sau. t nh giy lau pha bn ngoi cc l ca in cc thm kh in cc. Tuyt i khng a giy lau vo trong in cc. a in cc vo dung dch sao cho dung dch ngp l trn thnh in cc. Trng in cc vi ln bng cch nng ln v h in cc xung. Ch n khi n nh mi ghi nhn gi tr dn v nhit vo bng. Lu : Nhit ca cc dung dch khng c chnh lch qu
Ti liu ging dy Mn Thc tp Ha L 2

0.1oC. 3

o ln lt t dung dch long n dung dch c. Cht in li: dn in ring ca nc ct: STT CN T(0C)

1. Lp li bc 1 n bc 3 cho NaCl v HCl. 2. Tnh cc i lng cn li trong bng cho mi chui dung dch. Lu n v ca cc i lng.
3. Dng th

cho mi chui dung dch. Dng ng hi quy

tuyn tnh. Tnh phng trnh hi quy. Xc nh dn in ng lng cc i. 4. Ngoi suy ng hi quy v tung gc xc nh dn in ng lng cc i. So snh gi tr ly t th v gi tr t phng trnh hi quy.

Cu hi (bi tp) cng c: 1. Tnh dn in ng lng cc i ca CH3COOH. 2. So snh dn in ng lng cc i thc nghim ca CH 3COONa, NaCl, HCl v CH3COOH vi cc gi tr tra cu t s tay ha l. 3. Hy tnh dn in ng lng ca AgIO 3 298oK, bit dn in ng ca NaIO3, CH3COONa, CH3COOAg 298oK ln lt l 9,11; 9,10; 10,28cm2/om. lg.

Ti liu ging dy Mn Thc tp Ha L 2

BI 2

PHNG PHP CHUN pH NH LNG HN HP ACID H2SO4 V H3PO4


I. C l thuyt s Mc tiu hc tp: Sau khi hc xong bi ny, ngi hc c th: Khi trung ha mt acid (n hay a acid) bng baz mnh, pH tng dn trong qu - nh lng hn hp acid H2SO4 v H3PO4 bng phng php chun pH trnh trung ha. ng pH = f(V) (vi V l th tch dung dch NaOH thm vo) c nhng dng khc nhau th theo acid c trung ha l acid mnh hay acid yu. Vi acid a chc, nu cc chc ca acid c pK a khc nhau qu 4 n v, ta c th trung ha tng chc mt. T gi tr th tch NaOH mi im tng ng, ta suy ra nng tng lng ca acid. Trong bi thc hnh ny, chng ta s tin hnh chun hn hp hai acid H2SO4 v H3PO4 bng dung dch NaOH chun. T s liu thu c, v ng pH = f(V), ng cong ny c hai im un ti hai bc nhy tng ng vi hai im tng ng. im tng ng th nht: chun H 2SO4 v chc th 1 ca H3PO4. im tng ng th 2: chun chc th 2 ca H3PO4. vic xc nh Vt chnh xc, ta c th da vo:

Ti liu ging dy Mn Thc tp Ha L 2

- th pH/V theo Vtb - Tnh 2pH/(V)2 II. Ha cht v dng c Buret Pipete Erlen Becher cc c III. Thc nghim 1. Xc nh nng dung dch chun NaOH Chun li dung dch NaOH 0.1N bng H 2C2O4 0.1N vi ch th phenolphtalein. Np dung dch NaOH vo buret 25ml, dng pipet ly 10ml dung dch acid oxalic 0.1N vo erlen 250ml, thm vo 3 git phenolphtalein. Chun bng dung dch NaOH n khi dung dch xut hin mu hng nht bn trong 30 giy, ghi th tch NaOH tiu tn. Lp li th nghim t nht 3 ln, ly kt qu trung bnh. T tnh ra nng chnh xc ca NaOH.
2. Chun dung dch hn hp H2SO4 v H3PO4

My o pH My khuy t a khuy

NaOH 0.1N Acid oxalic Hn hp H 2SO4 v H3PO4 Phenolphtalein

Bnh nh mc 100 ml C t

a.

Chun th Chun my o pH vi dung dch m l 4; 7; 10

Dng pipet ht 10 ml hn hp phn tch cho vo beaker 100 ml, thm nc ct n ngp in cc (khong n vch 60 ml). Cho c t vo khuy trn u dung dch (trnh ng c t chm in cc), ghi gi tr pH trn my khi s hin ln n nh. Sau , mi ln thm vo 1ml dung dch NaOH (thm khong 20 ln), ghi gi tr pH ng vi th tch NaOH thm vo. T xc nh Vt1 v Vt2 gn ng (ng vi th tch 1ml NaOH thm vo pH tng cao nht). b. Chun tinh Ht 10ml dung dch hn hp cho vo beaker 100ml, thm nc ct n ngp in cc (khong n vch 60ml). Lp li qu trnh nh chun th n khi cch Vt1 gn ng 2ml th mi ln thm vo 0.2ml NaOH. Khi cch Vt1 gn ng 1ml th mi ln thm 0.1ml NaOH. Cho n khi qua Vt1 gn ng 1ml, tng th tch NaOH mi

Ti liu ging dy Mn Thc tp Ha L 2

ln thm l 0.2ml. Khi qua Vt1 gn ng 2ml, thm vo 1ml NaOH. Lm tng t nh trn i vi im tng ng th hai. Ngng chun khi qua im tng ng th hai khong 3ml. Ra sch in cc bng nc ct v ngm in cc trong dung dch KCl c nng thch hp vi in cc. Cu hi (bi tp) cng c: 1. V ng biu din pH = f(V). 2. Tnh Vt1, Vt2, CH2SO4 , CH3PO4 3. Ti sao phi tin hnh chnh m pH trc khi o pH hoc chun pH? 4. Thit lp cng thc tnh nng H2SO4 v H3PO4
\

Bi 3

XC NH TH IN CC OXY HA KH V HNG S CN BNG CA PHN NG OXY HA KH BNG PHNG PHP IN TH K


Mc tiu hc tp: Sau khi hc xong bi ny, ngi hc c th: p dng phng php chun in th xc nh th chun ca in cc oxy ha kh I. C s l thuyt Th chun ca h Fe+3/Fe+2 c xc nh bng phng php chun dung dch Fe+2 bng dung dch KMnO4 chun. y l h oxy ha kh nn in cc ch th phi l in cc Pt. Trong h lun c cn bng ca phn ng oxy ha kh MnO4- + 8H+ + 5Fe2+ Mn2+ + 5Fe3+ + 4H2O Nn th ca hai h Fe+3/Fe+2 v MnO4-,H+/Mn2+ trong dung dch lun bng nhau. Tuy nhin trc tng ng dung dch gm ion Fe+2 d, ion Fe3+ v Mn2+ hnh thnh, nng ion MnO4- rt nh nn cn bng c quyt nh bi nng v th chun ca h Fe+3/Fe+2, v c tnh bi phng trnh Fe3+ + e Fe2+
Ti liu ging dy Mn Thc tp Ha L 2

0 E = E Fe + 3+ , Fe 2 +

2.303RT Fe 3+ lg F Fe 2+

[ [

] ]

Sau tng ng h MnO4-,H+/Mn2+ d nn th ca in cc c quyt nh bi t l nng v th chun ca h MnO4-/Mn2+ MnO4- + 8H+ Mn2+ + 4 H2O
E=E
o MnO4 , Mn 2 + , H + MnO4 H+ 2.303RT + lg 5F Mn 2+

][ ] [ ]

Ni chung trc im tng ng th ca in cc l th ca h kho st nm di cc, sau tng ng l th ca h cht chun nm trn buret. Ti im tng ng th thay i t ngt. im tng ng VE c xc nh t ng chun tch phn hay vi phn. E/mV

V/mL E/V

VE

Hnh 1: ng chun tch phn (trn) v vi phn (di) Cho ti im tng ng nng Fe 3+ t l vi th tch dung dch chun thm vo V. Nng ion Fe2+ lc ban u t l vi th tch tch dung dch chun ti im tng ng Vt, v trc tng ng th t l vi V t V. T biu thc tnh th in cc trc tng ng c dng:
o E = E Fe + 3+ , Fe 2 +

2.303RT V lg F Vt V

Ti liu ging dy Mn Thc tp Ha L 2

Nh vy E s bng Eo ti im V = 1/2Vt. Eo l tung gc ca ng tuyn tnh biu din ph thuc gia E v lg V V . S in t trao i c tnh t h s gc t ca ng ny. II. Ha cht v dng c FeSO4 0.1M KMnO4 0.025M H2SO4 m c KCl 0.1M Giy lc III. Thc nghim Do Fe2+ khng bn, d b oxy ha thnh Fe 3+ nn khng th pha trc dung dch Fe2+ khng cha Fe3+ . dung dch FeSO4 khng cha Fe3+ th phi thm Fe v H2SO4 vo dung dch. Fe s a Fe3+ tr v Fe2+. 2Fe3+ + Fe = 3Fe2+ H2SO4 c tc dng trnh s kt ta ca ion Fe3+, lm chuyn dch cn v pha to Fe2+. Nng Fe2+ trong dung dch s thay i theo thi gian. V vy trc mi th nghim sinh vin phi xc nh li nng Fe2+. 1. Lc ly khong 50 ml dung dch FeSO4 ca phng th nghim. Ly 2 ml cho vo bnh nn. Thm 10 ml nc v 1 ml H 2SO4 m c. Chun bng dung dch KMnO4 0.025N cho n khi dung dch chuyn sang mu hng. Tnh nng FeSO 4. T dung dch ny pha 50 ml FeSO4 0.025N. 2. Ly 10 ml dung dch mi pha v chun li tng t nh trong bc. Ghi nhn th tch tng ng. Lu : H2SO4 m c rt nguy him. Cn thn khi ly H 2SO4 m c. Khng mang H2SO4 m c v ch lm vic. 3. Ly 10 ml dung dch FeSO4 0.025N cho vo beaker 100 ml c c t. Thm 30 ml nc ct v 1 ml H 2SO4 m c. cc ln my khuy t. Rp h thng o nh hnh 2. Ag/AgCl
Volt k

My o in th My khuy t Cc 100 ml Buret 25 ml pipet 10 ml

ng ong Phu thy tinh

Ti liu ging dy Mn Thc tp Ha L 2

kkl v

Pt

FeSO4 0.025N +1 ml H2SO4 Nu dng in cc ORP tch hp th khng cn in cc so snh na. 4. Nh 0.5 ml dung dch KMnO4 0.025N vo dung dch FeSO4. Khuy u. Tt my khuy. Ch th n nh mi ghi nhn gi tr th hin th. Tip tc chun cho ti gn im tng ng Gim lng KMnO 4 thm vo xung cn 0.1 ml. Lp li cho n khi th tng t ngt. Chun tip vi lng KMnO 4 mi ln thm l 0.5 ml. Dng khi tng th tch KMnO4 thm vo gp khong 1.5 ln th tch tng ng.. Ghi s liu vo bng.
5. Dng th Eo v th

theo VKMnO4. Xc nh im tng ng t hai

th trn. Th tch dung dch FeSO4 (ml): Nng dung dch KMnO4: Nhit th nghim: Ln 1 VKMnO4 (ml) Eo (mV)
E / V

Ln 2

Ln 3

6. Tnh lg V V , E Fe t Vt).

3+

, Fe 2 +

o , E Fe

3+

, Fe 2 +

o . Ghi s liu vo bng. Tnh E Fe

3+

, Fe 2 +

trung bnh. (Ch cn tnh Eo cho khong 4 im trc v 4 im sau gn vi im V=


E Fe3+ , Fe 2 +

= Eo + Eso snh

Ly th ca in cc so snh cho trong phn l thuyt


o E Fe3+ , Fe 2 + = E Fe 3+ , Fe 2 +

2.303RT V lg F Vt V

Th tch KMnO4 ti im tng ng (ml): VKMnO4 (ml) Nng dung dch KMnO4: V Eo (mV) lg V V
t

E Fe3+ , Fe 2 +

o E Fe 3+ , Fe 2 +

Ti liu ging dy Mn Thc tp Ha L 2

10

Eo trung bnh: 7. Dng th E Fe


o E Fe 3+ , Fe 2 + t th.

3+

, Fe 2 +

theo lg

V . Xc nh s in t trao i n v Vt V

8. So snh gi tr th in cc, s in t trao i thu c v gi tr l thuyt, t a ra nhn xt v cc phng php o v tnh p dng trong bi thc nghim.
Cu hi (bi tp) cng c: 1. Vit cc phn ng xy ra in cc v vit s pin to thnh trong phn

ng oxi ha kh trn
2. Tnh sut in ng P = 1,013.10 5N.m2, T = 298oK v vit s pin.

Trong xy ra phn ng thun nghch: 2FeCl2 + H3AsO4 + 2HCl 2FeCl3 + HAsO2 + 2H2O Bit: Hot cc cht trong pin: BI 4

XC SUT IN NG V TH IN a Fe =NH 0.02 , a Fe = 0.005 = 0CC .01 , a HPIN = 0.2 , a , a H AsO HAsO = 0.1 , a H O =1 NNG
3+ 2+

Mc tiu hc tp: Sau khi hc xong bi ny, ngi hc c th: Thit lp pin Galvani v o sut in ng ca pin To pin t cc vt liu thng thng

I. C s l thuyt Thit lp pin Daniel Jacobi vi cc nng dung dch khc nhau. o S. (-) Zn| ZnSO4 || Cu SO4| Cu (+) Do Zn hot ng mnh hn Cu nn khi ni mch nguyn t trn phn ng xy ra l Zn + Cu2+ = Zn2+ + Cu Ti in cc Zn xy ra phn ng oxy ha nn in cc Zn l anod. Trn in cc Cu ion Cu2+ b kh v Cu nn in cc Cu l catod. o S phi ni in cc Cu vi cc dng, cn in cc Zn th ni vi cc m ca my o. Khi o S hin th c gi tr dng. Nu rp ngc li S hin th s c gi tr m.
Ti liu ging dy Mn Thc tp Ha L 2

11

S ca pin Daniel Jacobi c tnh bi phng trnh Nernst

(1)

Th ca cc in cc c o nh s tr gip ca in cc so snh Cl -/AgCl, Ag. in cc kho st ng vai tr catod c ni vi cc dng ca my o, cn in cc so snh ng vai tr anod c ni vi cc m ca my o. (2)

Trong

Ein cc kho st =

(3)

T th o c SV cn nhn xt v mi tng quan gia hot tnh ca kim loi v th in cc. Th ca in cc kim loi c tnh nh biu thc
0 E = EM + z+ /M

RT ln a M z + zF

(4)

Trong pin nng khng ti t hai in cc kim loi in cc nm trong dung dch c nng thp s l anod (a1 < a2). o S. (-) Cu | CuSO4 a1 || CuSO4 a2 | Cu (+) (-) Zn | ZnSO4 a1 || ZnSO4 a2 | Zn (+) S ca pin nng khng ti c tnh nh sau:
E= RT a 2 ln (5) zF a1

So snh cc gi tr o c vi cc gi tr l thuyt tnh theo phng trnh Nerst. Hot ca c tnh nh php gn ng th nht Debye-Huykel. ai=fi x Ci (6) lg fi = -0.509 |zi2| (7) (8)
Ti liu ging dy Mn Thc tp Ha L 2

12

Thit lp pin t dy km, dy ng, dy nhm v cc loi qu c c nh c chua, cam, chanh. o S. I. DNG C V HA CHT CuSO4 rn ZnSO4 rn KCl 0.1M Dy Zn, Cu, Fe, Al C chua, cam, chanh Giy nhm nc II. THC NGHIM 1. Chun b thc nghim a. Dng giy nhm nc nh sch cc in cc, v cc dy kim loi b. Pha dung dch CuSO4 v dung dch ZnSO4 0.1M. Pha long 10 ln c cc dung dch nh cho trong bng. ra cc 50 ml. CuSO4 0.1 CuSO4 0.01 CuSO4 0.001 ZnSO4 0.1 ZnSO4 0.01 ZnSO4 0.001 My o in th Cc 100 ml Pipete 10 ml in cc Cu: 2 in cc Zn: 2 Bnh nh mc 100 ml

c. Ly 50 ml dung dch KCl 0.1 M vo cc 100 ml. a in cc so snh clorua bc vo cc. Ch kim tra dung dch trong in cc so snh. Nu dung dch cn th cn chm thm dung dch KCl bo ha. Lu th ca in cc so snh ph thuc vo nng dung dch KCl trong in cc ch khng ph thuc vo nng dung dch KCl trong cc. 2. Xc nh S ca pin Daniel-Jacobi a. Thit lp nguyn t Daniel-Jacobi vi nng dung dch thay i nh cho trong bng ST T CuSO4 (M) ZnSO4 (M) Eo (V) JCuSO4 JZnSO4 fCu2+ fZn2+ aCu2+ aZn2+ Etnh
(V)

Sai s (%)

Ti liu ging dy Mn Thc tp Ha L 2

13

1 2 3 4

0.01 0.01 0.1 0.1

0.1 0.01 0.1 0.01

b. Rp nguyn t in ha nh hnh bn vi in cc Cu (+) nm trong dung dch CuSO4, in cc Zn (-) nm trong dung dch ZnSO 4. Ni hai dung dch bng cu mui aga. c. o S. Ghi kt qu vo bng. d. Tnh lc ion cho cc dung dch. e. Tnh h s hot v hot ca cc ion. f. Tnh S t gi tr hot . g. So snh gi tr o v gi tr tnh. 3. Xc nh th in cc a. Thit lp cc nguyn t trong anod l in cc so snh v catod l in cc Cu hay in cc Zn. Ni dung dch ca in cc kim loi v dung dch KCl bng cu mui aga. b. o S. Ghi kt qu vo bng. c. Tnh th in cc t gi tr o c. d. Nhn xt v mi lin h gia hot tnh kim loi v gi tr th in cc. e. Tnh lc ion cho cc dung dch. f. Tnh h s hot v hot ca cc ion. g. Tnh th in cc t gi tr hot . h. So snh gi tr o v gi tr tnh.
Ti liu ging dy Mn Thc tp Ha L 2

14

STT 1 2 3 4 CuSO4 (M) CuSO4 (M) ZnSO4 (M) ZnSO4 (M) 0.1 0.01 0.1 0.01

Eo (V)

Ec (V)

JM2+

fM2+

aM2+

Etnh (V)

Sai s (%)

4. Xc nh S ca pin nng khng ti a. Thit lp cc pin nng khng ti sau. Ni hai dung dch bng cu mui aga. (-) Cu | CuSO4 0.001 M || CuSO4 0.1 M | Cu (+) (-) Zn | ZnSO4 0.001 M || ZnSO4 0.1 M | Zn (+) b. o S. Ghi kt qu vo bng. c. Tnh lc ion cho cc dung dch. d. Tnh h s hot v hot ca cc ion. e. Tnh S t gi tr hot . f. So snh gi tr o v gi tr tnh. 5. Pin tri cy a. Cm tng cp dy hay ng xu kim loi vo qu chanh, cam hay c chuaCh khng hai kim loi chm nhau. b. Ni hai u kim loi vi cc ca ng h in t. Ch du ca cc cc. Theo di ng h c chy khng. Ghi kt qu vo bng. c. o S. Ghi kt qu vo bng.

Ti liu ging dy Mn Thc tp Ha L 2

15

STT 1 2 3 4

Tri cy Chanh Cam Chui C ..

Anod Fe Zn Zn Al ..

Catod Cu Cu Fe Cu ..

ng h chy

E/V

d. Rp ni tip v song song cc pin. o in th.

Cu hi (bi tp) cng c: 1. Vit cc phng trnh phn ng xy ra cc in cc 2. Hy vit phn ng xy ra trong pin v tnh sut in ng ca pin sau iu kin chun v 25oC (-) Cd|Cd2+|| Cu2+| Cu (+) 3. Nhn xt v kh nng to in th v to dng ca cc pin tri cy trn.

Ti liu ging dy Mn Thc tp Ha L 2

16

BI 5

XC NH G, H, S CA MT PHN NG IN HA
Mc tiu hc tp: Sau khi hc xong bi ny, ngi hc c th: Xc nh nhng c tnh nhit ng hc bng k thut in ha

I. C s l thuyt: Nhit ng hc c lin quan n s thay i nng lng din ra trong qu trnh ha hc v vt l. Nhng nguyn l c bn cho s thay i nng lng ny gm: Nguyn l th nht nhit ng hc (trng thi bo ton nng lng): Nng lng khng t nhin sinh ra cng khng t nhin mt i m ch chuyn ha t dng ny sang dng khc, nhng nng lng ton phn ca h khng i. Trong cc phn ng ha hc, din ra s sp xp li cc nguyn t v cc electron dn n s hnh thnh cht mi. ng thi cc cht cng tng tc vi mi trng xung quanh v chnh iu ny cng lm thay i in th ha hc ca h. Lng nhit ta ra hoc cn cung cp bng bin thin entalpi ca h: H = Hcui Hu Nguyn l th hai nhit ng hc lin quan n qu trnh t din ra ca mt h ha hc. Nguyn l ny c thit lp trn c s quan st nhng qu trnh din ra mt chiu v khng din ra theo chiu ngc li. V d: bn lm ri mt quyn sch xung sn nh quyn sch ny s khng t tr li tay bn. iu ny c p dng vo trong ha hc hoc vt l. Mt qu trnh din ra khng lin quan n xo trn hay mt trt t ca mt h. Nhit ng hc minh ha n mt cch nh lng bng entropi S. S thay i entropi tun theo phng trnh: S = Scui Su Nng lng t do: mt qu trnh t din ra mt nhit v p sut khng i th s bin i nng lng t do c minh ha bng phng trnh: G = H - S (1) Du G lin quan n mt phn ng t din bin: Phn ng din ra theo chiu thun, chiu t din bin l chiu lm gim nng lng t do iu kin ng nhit, ng p .

Ti liu ging dy Mn Thc tp Ha L 2

17

Phn ng t trng thi cn bng . Phn ng khng xy ra, trn nguyn tc, n xy ra theo chiu ngc li Gi tr G, H, S ch ph thuc vo trng thi u v trng thi cui ca h, ch khng ph thuc vo cch bin i ca qu trnh. Do G, H, S l cc hm s trng thi. Vic nghin cu nhng phn ng in ha, cho ta nhng bin php n gin v trc tip cho vic xc nh cc gi tr nhit ng hc bi v nng lng in ha c th sinh ra hoc tiu th cho mt phn ng in ha c th o c rt chnh xc. S thay i nng lng t do ca mt phn ng in ha lin quan n in th E ca h in ha: G = -nFE (2) n: s mol electron trao i cho 1 mol cht phn ng F: hng s Faraday = 96500 coulombs (in tch ca 1 mol in t) Nu in th c o nhng nhit khc nhau, s thay i entropi p sut khng i c biu din bng phng trnh:
S = d ( G ) dT

(3)

Th (2) vo (3):
S = d ( nFE ) dT

S = nF
T (4) ta thy

dE dT

hay dF = S (4)
dT nF

dE dT

l h s gc ca th s ph thuc in th E vo nhit .

Trong th nghim ny, chng ta kho st mt h in ha gm hai in cc Zn 2+ / Zn v Cu2+ /Cu tip xc nhau qua mt cu mui KCl bo ha .
Zn 2e Zn 2+ (Qu trnh oxi ha xy ra anod, cc m ca pin)

Cu2+ +2e Cu2+ + Zn Nernst:

Cu (Qu trnh kh ang xy ra catod, cc dng ca pin) Cu + Zn2+

S ph thuc ca E vo nng , nhit ,... c xc nh bng phng trnh

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Epu = E0pu

a sp RT ln nF atc

(5)

Trong hu ht cc trng hp, hot ng c thay th bi nng . Phng trnh (5) c vit: Epu = E0pu 0,0591 [ sp ] log [tc ] n

(6)

Khi nng Zn2+ v Cu2+ trong dung dch nh nhau th log

[ sp ]
tc

= 0. Trong iu

kin ny, th E ca pin bng vi E0. T E da vo (2) ta tnh c G. Ngoi ra, trong th nghim ny, gi tr th cng c o nhng nhit khc nhau. II. Ha Cht v dng c: Cu mui 2 ming kim loi Zn v Cu Chu thy tinh Volt k Bnh iu nhit III. Thc nghim 1. Chun b cu mui Ha tan 100mg agar-agar (agar,aga) v 500mg KNO 3 vo 5 mL H2O, un nh cho hn hp chy lng ra. Dng ng ht Pasteur cho dung dch cn nng vo mt ng thy tinh hnh ch U. Dung dch s to gel trong khong 10 n 15 pht (khi ngui). 2. Chun b dung dch v in cc Chun b 7 mL mi dung dch CuSO4 0,5M v ZnSO4 0,5M. Ct 2 ming kim loi Zn v Cu c dng hnh ch nht 5x40mm (c sn, sinh vin khng cn ct li). Lu : Kt qu th nghim khng ph thuc vo chnh xc ca nng dung dch. 3. To h in cc phn ng Thit lp pin Gavalni. Ni hai dung dch bng cu mui aga. (-) Zn | ZnSO41 M || CuSO4 1M | Cu (+) agar-agar CuSO4 0,5M KNO3 ZnSO4 0,5M

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4. Kho st nh hng ca in th vo nhit - nhit nc lnh, ngm h trong chu nc (ly nc vi) cho n khi h cn bng nhit (khong 10 pht), ghi nhit dung dch mui ca pin v gi tr sc in ng c trn volt k . - Lm lnh h trong chu nc , khi h cn bng nhit (khong 10 pht), ghi nhit dung dch mui trong pin v gi tr c trn volt k . - Lm nng h n 500C (bng bnh iu nhit hoc bng cch ngm h pin trong mi trng nc nng pha 52 0C, h pin trong mi trng ny i khong 10 pht nhit dung dch ca h pin v mi trng u bng 50 0C, lc ny c t s sc in ng trn volt k) cng i khi h cn bng nhit (15 pht), ghi nhit phng v gi tr trn volt k . - C th c thm vi nhit khc, lu ch c khi h tr nn cn bng nhit . Ch : - Sau khi lm xong th nghim nh em cu mui hnh ch U trong nc nng agar chy lng v ra sch ng nghim hnh ch U ny. - Sau khi th nghim sinh vin nh vn nt volt k. IV. Tnh ton kt qu - Dng excel v th s ph thuc ca E vo nhit . H s gc ca th ny l tr gi ca
dE , thay vo (4) ta c S . Hoc v E theo T (dng giy k ly v), dT

xc nh c dc hay h s gc ca ng thng (xc nh c dE/dT). - Tnh G t (2) - Tnh c t H t S v G t (1)

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Cu hi (bi tp) cng c: 1. Trong nguyn t Galvani : - Ti anol xy ra qu trnh g ? - Ti catod xy ra qu trnh g ? - Dng electron sinh ra nh th no ? 2. Mt pin Cu-Pb cho kt qu th nghim nh sau : T0(0C) E(V) 26,5 0,465 2,5 0,454 80 0,493

Tnh H, S v G 26,50C 3. T cc kt qu th nghim, phn ng no t din bin? Gii thch .

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BI 6

KHO ST MT S H KEO
Mc tiu hc tp: Sau khi hc xong bi ny, ngi hc c th: iu ch v tnh ngng keo t ca mt s h keo. I. C s l thuyt Ho hc cht keo - hay chnh xc hn, ho hc cc h phn tn - nghin cu cc h bao gm mt pha phn tn dng chia nh thnh ht, phn b trong mt mi trng phn tn lin tc. Cc ht c kch thc quy c t 1 m 100 m (10 7 105 cm), ngha l ln hn kch thc phn t, nn h l d th nhng cha ln c th pht hin bng knh hin vi nn h l siu vi d th. Ho hc cht keo cn nghin cu cc h cha cc ht c kch thc ln hn 100 m, c gi l cc h phn tn vi d th hoc cc h phn tn th. Cc h th c gi l huyn ph nu cc ht l pha rn, c gi l nh tng nu cc ht l pha lng v gi l bt nu ht l kh c phn b trong cc mi trng lng. Do cc ht keo c kch thc nh nn chng c b mt ring rt ln. V vy, h keo c nng lng b mt rt ln v khng bn vng nhit ng hc. Cc ht c xu hng lin kt li vi nhau thnh nhng ht ln hn (lm cho b mt ring nh i v nng lng b mt gim) ri lng xung. Qu trnh c gi l s keo t. gi cho cc h keo c bn vng mt mc no ngi ta phi thm vo h cc cht n nh (hay cht lm bn). C ch ca s lm bn trong i a s trng hp l do ht keo hp ph mt loi ion ca cht lm bn, lm tng in tch ca ht keo, khin cho lc y tnh in gia cc ht keo tng ln, ngn cn s lin kt ca cc ht. C hai cch ch to cc h phn tn. Cch th nht l chia nh vt cht cho n khi thu c cc ht c kch thc c ht keo, cc phng php theo cch ny gi l phng php phn tn.V d, ngi ta xay lu hunh ri phn b vo nc, lu hunh l pha phn tn v nc l mi trng phn tn. Cch th hai l tp hp cc phn t, nguyn t hay ion c sn trong mi trng li thnh cc ht c kch thc c ht keo. Cc phng php theo cch ny gi l phng php ngng t. V d, keo AgI c ch to bng cch cho AgNO3 phn ng vi KI. Cc ion Ag + v I trong mi trng s tp hp li thnh cc ht keo AgI.

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Mt iu kin thit yu cho c hai phng php trn l pha phn tn phi thc t khng tan trong mi trng phn tn hay ni cch khc pha phn tn khng c tng tc vi mi trng. Chnh v th m cc h keo ch to bng hai cch trn c gi l h keo k lu. Ngoi ra cn c cc h keo a lu, in hnh l dung dch cc cht cao phn t, trong cc phn t c tng tc vi mi trng v to thnh dung dch tht. V vy, ch to chng ngi ta ch cn cho cht cao phn t vo mi trng thch hp, cht ny s t ho tan vo mi trng . Song nu mi trng l mt dung mi khng tt i vi cht cao phn t th ngi ta vn c th ch to dung dch keo ca cht cao phn t bng phng php phn tn hay ngng t v thu c cc h keo k lu. Ht keo ch to trong mi trng lng thng c cu to phc tp, tu thuc vo iu kin ch to n. Ngy nay, ngi ta quan nim ht keo l mt mixen trung ho in bao gm mt nhn, thng c cu to tinh th, gia v mt lp in kp bao quanh n. Lp kp gm hai bn. Bn trong gm cc ion cng mt du in nm trn b mt ht keo, to cho ht c mt in tch no nn c gi l cc ion quyt nh th hiu. Bn ngoi gm cc ion in tch ngc du va trung ho in tch ca ht keo - l cc ion nghch. Cc ion nghch chu tc dng ca lc ht tnh in, lc hp ph vo b mt ht v lc khuch tn do chuyn ng nhit gy ra, nn c phn b thnh hai lp. Lp trong gm mt s ion nm st b mt ht keo gi l lp hp ph, lp ngoi bao gm s ion nghch cn li, l lp khuch tn. lp ny nng cc ion nghch gim dn t trong ra ngoi v khi lp kp kt thc th nng bng nng cc ion nghch trong dung dch. Ngi ta thng biu din cu to ht keo bng s hay bng cng thc. V d ht keo AgI hnh thnh do phn ng:

vi gi thit KI ly d lm cht lm bn, c s v cng thc c ch ra hnh 1

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Hnh 1: S v cng thc cu to ca mixen ca son AgI trong dung dch KI long Tu thuc vo nng cc ion trong dung dch m lp kp c th dy hay mng. Khi lp kp c chiu dy ln th ht keo bn vng, khi lp kp mng th ht keo tin st li gn nhau khong cch m lc ht tc dng mnh khin cho cc ht lin kt li vi nhau thnh nhng ht ln - l s keo t. Chnh v vy m khi thm cht in li vo h keo thng xy ra s keo t. S keo t bt u xy ra mt nng cht in li ti thiu gi l ngng keo t, c tnh bng s mili mol hoc mili ng lng cht in li trn mt lt dung dch keo. S keo t bi cht in li tun theo quy tc Schultze Hardy. Tc dng keo t ca mt cht in li l do ion ngc du vi du in ca ht keo v tc dng tng ln rt nhanh theo s tng ho tr ca ion . L thuyt cng nh thc nghim ch ra rng ngng keo t t l nghch vi ho tr Z lu tha 6.

S c mt ca mt cht cao phn t thch hp trong mt h keo k lu c th lm tng bn vng ca h keo . Tc dng c gi l tc dng bo v ca cht cao phn t i vi h keo k lu. C ch ca tc dng bo v l do cht cao phn t hp ph ln b mt ht keo, lm thnh mt mng bo v ngn cn s lin kt ca cc ht khi chng n gn nhau. Nh trn, ta bit ht keo thng c in tch nht nh, tu thuc vo bn cht ion quyt nh th hiu. Do , khi t h keo vo mt in trng th cc ht keo tch in s di chuyn v mt cc, l hin tng in di (phn ht di chuyn bao gm: nhn cng lp ion quyt nh th hiu v lp hp ph ca ion nghch); mi trng vi
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phn ion nghch cn li l lp khuch tn s di chuyn v cc khc, l hin tng in thm. Nhng h keo k lu sau khi ch to thng cha cc cht ln, thng l cht in li. Khi nng cht in li ln, chiu dy lp kp gim lm cho bn vng ca h gim i. Mun cho h keo bn vng ngi ta phi loi bt cht in li bng phng php thm tch, ngha l cho h keo vo mt ti mng bn thm, cht in li lt qua mng thot dn khi h, cn cc ht keo c kch thc ln nn khng lt qua mng v gi li trong h. Cng v kch thc ht ln m cc h keo cn c c im l khuch tn rt chm so vi dung dch thc. ch to cc nh tng ngi ta dng phng php phn tn v thng phi thm cht lm bn gi l cht nh ho. C hai loi nh tng: a. Nh tng loi I hay nh tng thun, c pha phn tn l cht lng khng phn cc, mi trng phn tn l nc. b. Nh tng loi II hay nh tng nghch, c pha phn tn l nc, mi trng phn tn l cht lng khng phn cc (thng gi l du). Nh tng loi I c k hiu l D/N (du trong nc), nh tng loi II c k hiu l N/D (nc trong du). Cht nh ho thng l cht hot ng b mt, th d kali oleat, canxi oleat, nhm stearat v.v... II. Dng c v ha cht Bp in Bnh tam gic 250ml ng ong 250ml ng nghim Cc 250ml III. Thc nghim 1.`iu ch h keo Fe(OH)3 Dng ng ong ly 200ml nc ct vo erlenmeyer (bnh nn) 250ml, un si nc trn bp in cch li amian. Tt bp, thm tng git dung dch FeCl 3 1N vo erlenmeyer n khi ht 5 ml. Ta c ta keo dng Fe(OH) 3 mu nu sm, trc khi th dung dch FeCl3 c mu vng).
Ti liu ging dy Mn Thc tp Ha L 2

FeCl 3 1N KCl K2SO4 Tinh bt Trng g Bong bng heo

25

Khi thm ht 5ml th ly bnh keo ra khi bp, ngui trong khng kh . 2. Keo t keo Fe(OH)3 bng cht in li t 10 ng nghim vo gi ng ng nghim. Cho vo cc ng nghim th tch cc dung dch ha cht (mL) theo bng sau:
ng nghim Keo Fe(OH) (mL) Nc ct (mL) Cht in li (mL) Nhn xt 1 5 4,5 0,5 2 5 4 1 3 5 3,5 1,5 4 5 3 2 5 5 2,5 2,5 6 5 2 3 7 5 1,5 3,5 8 5 1 4 9 5 0,5 4,5 10 5 0 5

Cht in li l dung dch KCl 3N. Lp li th nghim vi dung dch cht in li K2SO4 0,01N. Sau khi thm cht in li, mi ng u c lc mnh ri yn 15 pht. Sau quan st ri nh u cng + nhng ng b keo t (ng b c), du tr - nhng ng khng b keo t (ng trong). Tnh ngng keo t cho mi cht in li, tc nng ca cht in li ti thiu trong ng gy nn keo t:
=
v.N .10 3 V

v v N l th tch (mL) v nng ban u (lg/L) ca cht in li ng u tin b keo t. V: l tng th tch ha cht trong ng nghim (10mL). Khi c n v l mmol/L. 3. Keo a lng a. iu ch - Keo tinh bt: cn 0,5 gam tinh bt cho vo cc (becher) 250 mL cha sn 100 mL nc ct. un nh trn bp in, va un va khuy u n khi tinh bt tan ht. Nhc xung ngui. - Keo albumin: ly mt lng trng trng g cho vo cc 250 mL ri thm 100 mL nc ct, khuy u l c keo albumin. (Sinh vin ly trng g t lnh ca phng th nghim). Hai dung dch keo ny c dng tip cho phn b v c di y. b. Thm tch keo Ly 50 mL keo tinh bt cho vo ti thm tch (bng mng bong bng heo).
Ti liu ging dy Mn Thc tp Ha L 2

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(Sinh vin ly bong bng heo t trong t lnh ca phng th nghim. Nu bong bng b ng cng th sinh vin phi ngm bong bng trong nc x ng). Thm tip 10mL dung dch K2SO4 0,1N vo bong bng, dng dy cao su ct kn ming bong bng ri nhng vo erlen 1000mL cha sn 500mL nc ct, khuy lin tc cc nc bn ngoi ti khon 10 pht. Ly vo hai ng nghim, mi ng khong 10mL nc trong bnh thm tch trn (nc ngoi bong bng). Mt ng th nhn bit ion SO4 2- bng dung dch Ba2+ (dung dch BaCl2), mt ng th xem c tinh bt khng bng dung dch I 2 (nhm bit ion SO42-, tinh bt c c thm tch ra khi mng bong bng heo hay khng). Nhn xt kt qu v gii thch. c. Bt Ly vo ba ng ong 100 mL ln lt 5, 10 v 15 mL keo albumin. Thm vo cc ng ln lt 15, 10 v 5 mL nc ct. y nt (hoc bt tay), lc k mi ng trong 5 pht. Ghi th tch hn hp c bt trong mi ng. Th bn ca bt trong mi ng bng cch nhng mt vng dy cao su vo mi ng. Nhc t t vng dy c keo ra ngoi. Ghi thi gian mng keo b t. Nhn xt kt qu. Sau khi th nghim, sinh vin b bong bng heo v phn trng g cn li vo thng rc, t ngoi phng th nghim. Cu hi (bi tp) cng c:
1. Vit phng trnh phn ng iu ch keo Fe(OH)3 2. Vit cng thc cu to ca h keo Fe(OH)3 3. Tnh ngng keo t theo n v mN/L

C.V .1000mN / L Vk + V

V: s mililit dung dch cht in li cho vo dung dch keo. C: Nng dungKHO dch cht in li cho vo. TI LIU THAM
TI LIU THAM KHO BIN SON NI DUNG MN HC:

Vk: S mililit dung dch keo dng keo t.

1. PGS. TS. V Ngc Ban - Gio Trnh Thc Tp Ha L - NXB i Hc Quc Gia H Ni - 2007
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2. TS.Trn Th Ngc Lan - in Ha Hc - i Hc Khoa Hc T Nhin


TI LIU THAM KHO NGH CHO HC VIN:

1. T chuyn ngnh Ha L - Gio Trnh Thc Tp Ha L - Trng i hc Cn Th - 2011

Ti liu ging dy Mn Thc tp Ha L 2

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