Gio trnh thc tp ha l

PGS. TS. V Ngc Ban

NXB i hc quc gia H Ni 2007, 101 Tr.

Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc

ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc
v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc

Bi s 1....................................................................................................................................... 4
NHIT HO TAN ..................................................................................................................... 4
Bi s 2..................................................................................................................................... 10
P SUT HI BO HO ...................................................................................................... 10
Bi s 3..................................................................................................................................... 14
HNG S CN BNG .......................................................................................................... 14
Bi s 4..................................................................................................................................... 17
CN BNG LNG HI CA H HAI CU T ................................................................. 17
Bi s 5..................................................................................................................................... 22
TNH TAN HN CH CA CHT LNG ........................................................................... 22
Bi s 6..................................................................................................................................... 30
PHNG PHP HN NGHIM ........................................................................................... 30
Bi s 7..................................................................................................................................... 35
PHNG PHP PHN TCH NHIT................................................................................... 35
Bi s 8..................................................................................................................................... 39
XC NH HNG S TC CA PHN NG BC MT PHN NG GHCH O
NG ................................................................................................................................... 39
Bi s 9..................................................................................................................................... 43
PHN NG THU PHN ESTE........................................................................................... 43
Bi s 10................................................................................................................................... 46
NG HP PH NG NHIT........................................................................................ 46
Bi s 11................................................................................................................................... 52
DN IN CA DUNG DCH CHT IN LI............................................................ 52
Bi s 12................................................................................................................................... 59
SC IN NG CA PIN GANVANI .............................................................................. 59
Bi s 13................................................................................................................................... 68
S VN TI ........................................................................................................................... 68
Bi s 14................................................................................................................................... 74
IU CH CC H KEO V KHO ST MT S TNH CHT CA CHNG............ 74
Bi s 15................................................................................................................................... 81
PHN TCH SA LNG .......................................................................................................... 81
Bi s 16................................................................................................................................... 88
XC NH PHN T KHI CHT POLIME ..................................................................... 88
Ph lc...................................................................................................................................... 93
SAI S CA PHP O PHNG PHP LP BNG V DNG TH TRONG
THC TP HO L .............................................................................................................. 93
 3

Li m u
Ti liu ny bao gm nhng bi thc tp c bn nht thuc chng trnh Thc tp Ho
l, Khoa Ho hc, Trng i hc Khoa hc T nhin, i hc Quc gia H Ni.
Ni dung gm 4 phn chnh:
Nhit ng hc: 7 bi (t bi 1 7).
ng hc: 3 bi (t bi 8 10).
in ho hc: 3 bi (t bi 11 13).
Ho keo, Cao phn t: 3 bi (t bi 14 16).
mi bi u nu r mc ch, c s l thuyt, phng php tin hnh th nghim v cc
yu cu ca bi th nghim. Trong phn ph lc trnh by l thuyt sai s, phng php lp
bng v dng th trong thc tp Ha l.
Ti liu c vit vi s ng gp ca tp th cn b B mn Ho l, tuy c nhiu c
gng nhng khng trnh khi cc thiu st. Chng ti rt mong nhn c nhng kin ng
gp qu bu ca cc bn c.

TC GI
 4

Bi s 1
NHIT HO TAN

Mc ch
1. Xc nh nhit ho tan ca mui KCl trong nc.
2. Xc nh nhit ho tan ca CuSO4, CuSO4.5H2O trong nc v tnh nhit
hirat ho ca CuSO4.5H2O.

L thuyt
1. Nhit ho tan v nhit hirat ho ca mui
Qu trnh ho tan lun lun km theo s gii phng hay hp th nhit tu theo bn cht
ca cht tan v dung mi.
Hiu ng nhit km theo qu trnh ho tan 1 mol cht tan trong mt lng dung mi no
thu c dung dch c nng xc nh c gi l nhit ho tan tch phn. Hiu ng
nhit km theo qu trnh ho tan 1 mol cht tan trong mt lng v cng ln dung dch c
nng xc nh c gi l nhit ho tan vi phn. Bng thc nghim ch o c nhit ho
tan tch phn cn nhit ho tan vi phn c xc nh theo s ph thuc ca nhit ho tan tch
phn vo nng dung dch.
Nhit ho tan c th xem l tng ca hai s hng: nhit chuyn cht tan vo dung dch Hch
v nhit sonvat ho (hay nhit hirat ho nu dung mi l nc) Hs pht sinh do tng tc
gia cc tiu phn cht ho tan vi nhng tiu phn ca dung mi.
Hht = Hch + Hs (1)
Nhit Hs lun lun m v qu trnh sonvat ho lun to nhit cn nhit Hch c th
dng hoc m. i vi cht kh, Hch (nhit ngng t kh vo th tch dung dch) lun m
nn Hht < 0. i vi cht rn, Hch (nhit hp th ph v mng li tinh th v y xa
cc tiu phn trn khong cch ng vi th tch dung dch) lun dng nn du ca Hht s l
du ca s hng no trong (1) chim u th: Ni chung nhng cht rn c cu to mng li
tinh th km bn v c nhiu khuynh hng sonvat ho hay hnh thnh nhng mui ngm
nc... th Hht < 0 (s ha tan to nhit) cn nhng cht c mng tinh th bn v t sonvat
ho th Hht > 0 (s ho tan thu nhit).
Nhit ho tan ca mui tng khi tng lng dung mi, nhng nu 1 mol mui ho tan vo
100 300 mol dung mi th khi pha long thm hiu ng nhit hu nh khng thay i, lng
nhit l nhit ho tan ca mui.
p dng nh lut Hess i vi qu trnh ho tan c th xc nh gin tip hiu ng nhit
ca nhng qu trnh kh o trc tip, v d nh nhit hirat ho cc tinh th ngm nc.
 5

Nhit hirat ho l lng nhit km theo qu trnh to thnh 1 mol mui ngm nc t
mui khan v lng nc tng ng. V d, s to thnh dung dch CuSO4 trong n mol H2O
c th thc hin bng hai kh nng:
1. CuSO4 (r) + 5H2O CuSO4.5H2O (r) + Hhyd
CuSO4.5H2O + (n 5)H2O CuSO4 (dd) + H1.
2. CuSO4 (r) + nH2O CuSO4 (dd) + H2
Theo nh lut Hess ta c:
Hhyd + H1 = H2.
hay Hhyd = H2 H1 = H ht, CuSO 4 H ht,CuSO 4 .5H 2 O (2)

Xc nh bng thc nghim nhit ho tan ca mui khan v mui ngm nc s tnh
c nhit hirat ho.

2. Phng php nhit lng k

Hiu ng nhit ca phn ng ho hc, nhit ho tan, nhit chuyn pha, nhit dung... c
xc nh bng mt dng c gi l nhit lng k.
C nhiu loi nhit lng k, cu trc ca chng rt phong ph ph thuc vo c trng
ca qu trnh nghin cu. S mt nhit lng k n gin nht ch ra trn hnh 1.

Hnh 1
Nhit lng k
1. Bnh nhit lng k; 2. Nhit k; 3. Que khuy;4. mpun;5. Nt lie;6. Cht lng.

Phn ch yu ca nhit lng k l bnh nhit lng k (1) v lp v ngn cn s trao i

nhit ca nhit lng k vi mi trng xung quanh. Bnh nhit lng k thng l mt bnh
oa c y kn bng nt lie (5). Nt c khoan l cm nhit k (2), que khuy (3) v
mpun ng cht nghin cu (4). Nhit k thng dng l nhit k khong hay nhit k
Beckman c chnh xc cao theo di bin thin nhit trong h. mpun l mt ng
nghim thu tinh c y mng d b chc thng cc cht nghin cu ri vo cht lng (6)
cha trong bnh nhit k.
 6

Hiu ng nhit ca qu trnh tin hnh trong nhit lng k c xc nh theo phng
trnh:
q = Ck.t (3)
y: t - bin thin nhit ca h nhit lng k;
Ck - nhit dung ca h nhit lng k (lng nhit cn thit nng nhit lng k ln
o
1 ) thng c gi l hng s nhit lng k.
Ck c th xc nh c bng cch cng nhit dung ca tt c cc b phn ca
nhit lng k tham gia vo s trao i nhit (bnh nhit lng k, nhit k,
que khuy, mpun, cht lng trong nhit lng k v.v...):
Ck = miCi (4)
y mi v Ci l khi lng v nhit dung ring ca cc b phn ca nhit lng k.
Nhng do chnh xc ca vic xc nh Ci khng ln nn cng thc (4) thng khng c
dng tnh Ck. Phng php chnh xc hn tnh Ck l cho tin hnh trong nhit lng k
mt qu trnh m ta bit trc hiu ng nhit q/ ca n. o bin thin nhit t/ tng
ng ca h nhit lng k, s tnh c Ck theo phng trnh:
q'
Ck = (5)
t'
Bin thin nhit t gy ra do qu trnh tin hnh trong nhit lng k c th
xc nh theo hiu nhit trc v sau khi qu trnh xy ra ch trong trng
hp h hon ton khng trao i nhit vi mi trng bn ngoi. Trong thc
t, vic trao i nhit khng th trnh khi nn xc nh bin thin nhit
thc cn phi hiu chnh phn bin thin nhit do h trao i nhit vi
mi trng ngoi. Vic hiu chnh nh vy thng c tin hnh bng
phng php th (xem phn thc nghim). Khi bit t v Ck s tnh c
hiu ng nhit ca qu trnh theo (3).

Tin hnh th nghim

1. Xc nh nhit ho tan ca KCl trong nc
a) Xc nh nhit dung ca h nhit lng k Ck
Ho tan trong nhit lng k mt lng nht nh mui KNO3 bit nhit ho tan
H KNO3 = 8,52 kcal/mol). Xc nh t v tnh Ck theo cng thc (5).

q' g H KNO 3 8,52.g

Ck = = . = (kcal/) (6)
t' M t' M . t'
y g, M l khi lng v khi lng mol ca mui KNO3.
Cch tin hnh:
Dng cn phn tch cn mpun sy kh, ghi khi lng (g1). Cho mui KNO3
nghin tht nh (khong 6 8 g) vo mpun (ch khng mui dnh vo thnh mpun) v
cn li (g2). Lng mui s dng l g = g2 g1. Dng bnh nh mc ly chnh xc 500 ml
nc ct vo bnh nhit lng k. y np bnh cm ng ng cht, nhit k khong v
 7

que khuy. n y bt u tin hnh thc nghim xc nh t. Nh ni phn trn, do

qu trnh ho tan khng th trnh khi s trao i nhit gia h nhit lng k vi mi trng
xung quanh nn thu c gi tr t thc cn phi tnh n s trao i nhit ny. Vi mc
ch th nghim c tin hnh qua ba giai on lin tc:
Giai on u, cha chc thng mpun, khuy u v nh chng 3 pht, sau va
khuy va ghi nhit , 30 giy mt ln. Khi no s thay i nhit theo thi gian u n
(khong 10 15 im thc nghim) th chc thng mpun ng cht nghin cu v giai on
chnh bt u. Do c hiu ng nhit ca qu trnh ho tan nn nhit thay i nhanh. Tip
tc khuy v ghi nhit nh trn. Khi nhit hu nh khng thay i na (mui tan
ht) th giai on chnh kt thc v cng l lc bt u giai on cui, tip tc khuy v ghi
nhit trong vng 5 pht na. (Ch : 3 giai on trn phi lm lin tc, gia cc giai on
khng dng th nghim li).
Da vo cc d kin thu c, v th nhit thi gian (hnh 2). Nu th nghim
tin hnh tt th giai on u (ab) v giai on cui (de) c biu din bng cc on thng.
dc ca cc on thng ph thuc vo tng quan gia nhit h nghin cu v mi
trng xung quanh.
Giai on chnh c xc nh trn th tnh t cc im m ng cong tip xc vi
cc on thng ca giai on u v giai on cui (on bd). Nu cho rng trong na u
ca giai on chnh s trao i nhit ca h nghin cu vi mi trng xung quanh ging nh
giai on u, cn trong na sau ging nh giai on cui th c th ko di on ab v
ed, sau t C l im gia ca BD k ng song song vi trc tung, ng ny ct cc
ng ko di c v c; di ca cc chnh l gi tr t thc cn tm.
Thay t thc tm c vo cng thc (6) trn tnh c Ck.

Hnh 2
Xc nh t thc bng th

b) Xc nh nhit ho tan ca KCl trong nc

Ly chnh xc 500 ml nc ct vo bnh nhit lng k. Cn mpun sy kh. Cho
vo mpun khong 4 6 g KCl ri cn li, tnh c lng cn ca KCl trong mpun. Lp
mpun vo bnh nhit lng k ri tin hnh xc nh t ca qu trnh ho tan KCl ging nh
lm vi KNO3 phn trn. Bit t v Ck tnh c nhit ho tan ca KCl trong nc;
 8

C k . t.M KCl
H KCl =
g KCl

2. Xc nh nhit ho tan ca CuSO4.5H2O v CuSO4

Xc nh nhit ho tan ca CuSO4.5H2O v CuSO4 khan nh lm vi KCl. Lng
CuSO4.5H2O ly khong 8 g, lng CuSO4 khong 5 g. Trc khi cn cc mui phi c
nghin nh trong ci s. Trong trng hp khng c mui CuSO4 khan th ly khong 10 g
mui CuSO4.5H2O nghin trong ci s ri em rang trn bp in (150 180oC) cho n khi
to thnh mui khan mu trng. ngui mui n nhit phng ri em cn.
Qu trnh ho tan mui trong nhit lng k cn khuy mnh hn v cc mui sunfat
ng kh tan.
Sau khi xc nh c nhit ho tan ca hai mui, tnh nhit hirat ca CuSO4.5H2O theo
biu thc (2):
H hyd = H ht, CuSO 4 H ht, CuSO 4 .5H 2 O
Tnh sai s ca cc kt qu th nghim (Ck, Hht). Ghi cc s liu v tnh ton theo bng
1.
Bng 1
KNO3 KCl CuSO4.5H2O CuSO4
Khi lng mpun rng g1
Khi lng mpun c mui g2
Khi lng mui g = g2 g1
t (xc nh t th)
Nhit ho tan Hht (ghi c sai s)

Ghi ch: Cng thc tnh sai s cc kt qu thc nghim

b) Sai s ca vic xc nh Ck
g H KNO 3
Ck = ( y t = t1 t2)
M t
Ly loga hai v: lnCk = lng lnM + ln H KNO3 lnt

dC k dg d(t) dg dt1 dt 2
Ly vi phn: = =
Ck g t g t1 t 2

C k g 2 t
Chuyn sang sai s: = +
Ck g t1 t 2
g l sai s ca php cn (cn phn tch).
t l sai s c nhit (nhit k khong).
c) Sai s ca vic xc nh H
 9

C k tM
H = ( y t = t1 t2)
g
Qua bin i nh trn thu c:
H C k g 2 t
= + +
H Ck g t1 t 2
C k
va tnh c trn
Ck
 10

Bi s 2

P SUT HI BO HO

Mc ch
Nghin cu s ph thuc ca p sut hi bo ho vo nhit v xc nh nhit ho hi
ca cht lng.

L thuyt
p sut hi bo ho l p sut ca hi nm cn bng vi cht lng (hoc vt rn).
S lin quan gia p sut hi bo ho v nhit si ca cht lng c biu th bng
phng trnh Clapeyron - Clausius:
dP H hh
= (1)
dT T(Vh V1 )
y: Hhh l nhit ho hi mol;
Vh, V1 l th tch mol ca hi v lng.
p sut khng ln v nhit xa nhit ti hn c th b qua V1 so vi Vh, ng thi
RT
xem hi tun theo nh lut ca kh l tng (Vh = ), khi phng trnh (1) c dng:
P
dlnP H hh
= (2)
dT RT 2
Trong khong nhit tng i hp c th chp nhn Hhh l khng i, khi tch
phn phng trnh (2) thu c:
H hh 1 1
lgP = + const = A + B (3)
2,303R T T
1
Phng trnh (3) chng t s ph thuc bc nht ca lgP vo . Nu o p sut hi bo
T
1
ho ca cht lng ng vi cc nhit si khc nhau ri lp th lgP = f s thu c
T
mt ng thng (hnh 1), da vo h s gc ca ng thng tnh c nhit ho hi ca
cht lng:
Hhh = 2,303.R.tg (4)
y tg c xc nh t to ca hai im M v N nm chnh xc nht v xa nhau
trn ng biu din. Nu ly hai im nm gn nhau ngha l khi khong nhit hp th
nhit ho hi trung bnh xc nh c s cng gn nhit ho hi thc nhng sai s ca kt
qu s cng ln (xem phn tnh sai s ca nhit ho hi).
 11

Hnh 1
S ph thuc ca lgP vo 1/T

T hnh 1 ta c:
lgP2 lgP1
tg =
1 1

T1 T2
Suy ra:
4,575T1 T2 lg(P2 /P1 )
Hhh = (5)
T2 T1

Tin hnh th nghim

Dng c lp sn (hnh 2) gm 2 phn: phn bay hi cht lng v h thng thay i p
sut.
Phn bay hi cht lng gm mt bnh hai c (1) cha cht lng nghin cu, mt c ni
vi ng sinh hn thng (2), mt c cm nhit k (3) v bnh (4) cha hi ngng ca cht
lng (trong trng hp un si mnh), ngn khng cho hi ngng sang p k (5).
H thng thay i p sut gm my ht chn khng (khng c trong bnh v), bnh iu
p (6) v p k ch U (5).
Khi my ht chn khng chy, m kho (7) v ng kho (8), khng kh b ht dn khi
h, p sut trong h gim i, mc thu ngn nhnh (a) ca p k dng ln v nhnh (b) h
xung, chnh lch chiu cao ca hai ct thu ngn (h) chnh l chnh lch gia p sut
kh quyn v p sut bn trong h, do tnh c p sut ca h:
Ph = (Pkh quyn h) mmHg
Vic tng p sut ca h (n p sut kh quyn) c thc hin bng cch m t t kho
(8) h thng vi khng kh bn ngoi.
 12

8
7

Ti my ht
4 chn khng
2
3

5 h

a
b
6
1
Hnh 2
Dng c xc nh p sut hi bo ho

Th nghim tin hnh nh sau:

Ly benzen n na bnh (1). B vo bnh vi vin bt. Kim tra cc ch ni sao cho
h c kn. Mun vy ng kho (8), m kho (7), cho my chn khng chy. n khi no
p sut trong h h xung cn khong 450 500 mmHg th tt my, ng kho (7) li. Nu
trong vng 10 pht m p sut ca h khng thay i th c th coi h nghin cu l kn v c
th tin hnh th nghim:
Cho nc chy vo ng sinh hn (2). un cch thu bnh (1). Khi cht lng si u, quan
st nhit k thy nhit dng li th ghi ly nhit ny. Xc nh chiu cao h trn p k.
c p sut kh quyn p k thu ngn t trong phng th nghim. Gi tr p sut tnh c
theo biu thc P = Pkq h chnh l p sut hi bo ho ca cht lng nhit si tng ng
(mt cht lng si khi p sut hi ca n bng p sut ngoi).
M kho (8) cho p sut ca h tng ln khong 50 mmHg (chiu cao h gim 25 mmHg).
ng kho (8) li. Xc nh nhit si ca cht lng p sut mi v ghi h tng ng. Tip
tc xc nh nhit si ca cht lng cc p sut khc nhau, mi t tng 50 mmHg, cho
n khi p sut trong h bng p sut kh quyn.
Yu cu 1: Ghi cc kt qu th nghim v tnh ton theo bng 1.
Bng 1
Hnh 2
Dng c xc nh p sut hi bo ho
Chiu cao Nhit si
ct thu p sut hi
p sut c phong v
TT biu Pkq (mmHg)
ngn p bo ho
lgP
1
k h P = pkqh toC T
(mmHg) T

Yu cu 2:
V th lgP = f(1/T)
T th tnh A, B v tnh nhit ho hi ca cht lng nghin cu.
 13

Ghi ch: Cch tnh sai s ca nhit ho hi

Ly loga hai v phng trnh (5)
lnH = ln4,575 + lnT1 + lnT2 + ln(lgP2/P1) ln(T2 T1)
Ly vi phn:
dH dT1 dT2 dln ( P2 / P1 ) d (T2 T1 )
= + +
H T1 T2 2,303 lg(P2 /P1 ) T2 T1
Chuyn sang sai s thu c:
H T1 T T + T2 P1 P2
= + 2 + 1 + +
H T1 T2 T2 T1 P P
2,303P1lg 2 2,303P2 lg 2
P1 P1
V d i vi CCl4:
T1 = 313 K, P1 = 215 mmHg
T2 = 323 K, P2 = 317 mmHg
Sai s ca nhit k (chia n 1o) l 0,5o.
Sai s ca p k (chia n 1 mmHg) l 0,5 mmHg.
Sai s tng i ca nhit ho hi s l:

H 0,5 0,5 0,5 + 0,5 0,5 0,5

= + + + +
H 313 323 323 - 313 2,303.215.0,666 2,303.317.0,666
= 0,0016 + 0,0015 + 0,1 + 0,006 + 0,004 0,1
Kt qu tnh ton cho thy chnh xc ca php o nhit s quyt nh sai s ca
kt qu. Nu khong nhit o cng hp th sai s s cng ln. Nu khong nhit o
tng i rng, v d T2 T1 = 40o th sai s tng i s gim nhng khi vic chp nhn
H khng i trong khong nhit s khng cn chnh xc.
 14

Bi s 3

HNG S CN BNG

Mc ch
Xc nh hng s cn bng ca phn ng:
KI + I2 KI3 (1)
trong dung dch nc

L thuyt
Hng s cn bng ca phn ng (1)
[KI3 ]
Kc = (2)
[KI] [I 2 ]

y k hiu [ ] l nng cc cht khi cn bng.

[I2] c th xc nh nh phng php chun bng Na2S2O3 (vi ch th h tinh bt)
theo phng trnh:
I2 + 2Na2S2O3 Na2S4O6 + 2NaI (3)
Tuy nhin, khi nng I2 b gim theo phn ng (3) th cn bng cu phn ng (1) b
dch chuyn theo chiu phn li KI3 to thnh I2, do khi chun ta khng xc nh c
[I2] m ch xc nh c nng tng cng [I2] + [KI3]. xc nh ring r [I2] cng nh
[KI3] ngi ta s dng nh lut phn b, c th l nghin cu s phn b ca I2 gia dung
dch KI trong nc v trong lp CCl4.
Khi cho I2 v KI vo hn hp nc v CCl4 th sau mt thi gian trong h tn ti hai cn
bng ng thi:
1. Cn bng ca phn ng (1) trong lp dung dch KI trong nc (lp H2O) biu
th bng phng trnh (2).
2. Cn bng phn b ca I2 gia lp nc v lp CCl4 biu th bng phng
trnh:
[I 2 ]CCl4
= Kphn b (4)
[I 2 ]H 2 O
 15

I2 + KI KI3 Lp H2O

I2 Lp CCl4

Nu chun lp CCl4 bng Na2S2O3 s xc nh c [ I 2 ] CCl . Da vo (4) c th tnh

4

c I 2 [ ]H O khi bit Kpb (Kpb xc nh nh nghin cu ring r s phn b ca I2 gia lp

2

H2O v lp CCl4):
[I 2 ] CCl 4
[I 2 ] H 2 O = C1 = (5)
K pb

Nu chun lp H2O bng Na2S2O3 ta xc nh c nng tng cng [I2] + [KI3] =

/
C t xc nh c [KI3]:
1

[KI3] = C1/ C1 (6)

Khi bit nng ban u ca KI (CKI) c th tnh c [KI]:
[KI] = CKI [KI3] = CKI C1 + C1 (7)
Thay (5), (6), (7) vo (2) ta thu c:
C1/ C1
KC = (8)
C1 (CKI C1/ + C1 )

Tin hnh th nghim

1. Xc nh h s phn b ca I2 gia lp CCl4 v lp H2O
Ly vo hai bnh nn nt nhm 1 v 2:
Bnh 1: 150 ml H2O bo ho I2 + 10 ml CCl4;
Bnh 2: 150 ml nc ct + 10 ml CCl4 bo ho I2.
Nt kn hai bnh, lc trong khong 1 gi. Ngng li. Chuyn hn hp sang phu chit 1
v 2, yn v chit ring lp CCl4 vo bnh 1a, 2a cn lp H2O vo bnh 1b, 2b. Dng pipet
ly lp CCl4 (bnh 1a, 2a) 2ml v ly lp H2O (bnh 1b, 2b) 50 ml dung dch cho vo 2
bnh, cho thm khong 5 git h tinh bt v chun bng Na2S2O3 0,01 N. Tin hnh chun
2 ln ly kt qu trung bnh.
Gi s ml Na2S2O3 0,01 N dng chun l V, s ml dung dch mu th l Vo,
nng ng lng ca I2 trong mu th l N ta c: V.0,01 = Vo.N. Mt khc theo phng
trnh phn ng (3): N I 2 = M/2 do nng phn t gam ca I2:
V.0, 01
C= (mol/l) (9)
Vo .2
 16

Ghi cc s liu thu c v cc kt qu tnh theo bng 1.

Bng 1
S ml Na2S2O3 dng chun Bnh 1 Bnh 2

Bnh 1a Bnh 1b Bnh 2a Bnh 2b
(lp CCl4) (lp H2O) (lp CCl4) (lp H2O)
Ln 1
Ln 2
Trung bnh
Nng I2 (mol/l)

Tnh Kpb theo cng thc (4) i vi hai bnh v ly kt qu trung bnh.

2. Xc nh nng cc cht tham gia phn ng v hng s cn bng

Ly vo 3 bnh nn c nt nhm 3, 4, 5:
Bnh 3: 50 ml dung dch KI 0,1 N + 10 ml CCl4 bo ho I2.
Bnh 4: 50 ml dung dch KI 0,05 N + 10 ml CCl4 bo ho I2. Bnh 5: 50 ml dung dch KI
0,1 N + 5 ml CCl4 bo ho I2 + 5 ml CCl4.
Nt kn cc bnh, lc trong khong 1 gi. Ngng li. Chuyn cc hn hp sang phu chit
3, 4, 5 yn, ri chit ring lp CCl4 vo cc bnh 3a, 4a, 5a v lp H2O vo cc bnh 3b, 4b,
5b. Dng pipet ly lp CCl4 (bnh 3a, 4a, 5a) 2 ml dung dch, cho thm khong 5 git h tinh
bt v chun bng dung dch Na2S2O3 0,01N. Tin hnh chun 2 ln ly kt qu trung
bnh. Ly lp H2O (bnh 3b, 4b, 5b), 25 ml dung dch v cng tin hnh chun nh vy.
Ghi cc s liu thu c theo bng 2.
Bng 2
Bnh 3 Bnh 4 Bnh 5
S ml Na2S2O3
dng chun Bnh 3a Bnh 3b Bnh 4a Bnh 4b Bnh 5a Bnh 5b
(lp CCl4) (lp H2O) (lp CCl4) (lp H2O) (lp CCl4) (lp H2O)
Ln 1
Ln 2
Trung bnh

Da vo bng tnh c [I 2 ] CCl 4 v nng tng cng [I2] + [KI3] = C trong lp nc

(i vi mi bnh 3, 4, 5). Da vo cng thc (5) (6) (7) tnh c nng ca cc cht khi
cn bng v Kc ri ly kt qu trung bnh.
K1 + K2 + K3
K =
3
Tnh sai s ca vic xc nh hng s cn bng:
K1 = K1 K ; K2 = K2 K ; K3 = K3 K
K1 + K 2 + K 3
K = ; Kc = K K
3
 17

Bi s 4

CN BNG LNG HI CA H HAI CU T

Mc ch
Xy dng gin cn bng lng - hi ca hai h cht lng ho tan hon ton vo nhau
(benzen - axeton) p sut khng i.

L thuyt
Gin cn bng lng - hi biu th s ph thuc ca p sut hi (khi T= const) hoc ca
nhit si (khi P = const) vo thnh phn dung dch v thnh phn hi cn bng vi dung
dch.
i vi dung dch l tng s ph thuc ca p sut hi vo thnh phn dung dch
tun theo nh lut Raun: p sut hi ring phn Pi ca cu t i bng tch p sut
hi ca cu t i nguyn cht Pio vi nng phn s mol xi ca n trong dung
dch. Vi h hai cu t A v B:
PA = P Ao xA (1)

PB = P Bo xB (2)
P = PA + PB = PAo + (PBo - PAo ) xB (3)
Biu thc (1), (2), (3) chng t p sut hi ring phn ca cc cu t v p sut hi chung
P ca dung dch l tng l nhng hm tuyn tnh ca thnh phn dung dch (cc ng
PAo B, PBo A v P Ao P Bo trn hnh 1).

Hnh 1
S ph thuc ca p sut hi ring phn cc cu
t v p sut hi chung ca dung dch l tng
vo thnh phn
 18

Ni chung thnh phn ca dung dch lng khc vi thnh phn ca pha hi nm cn bng
vi n nn nu biu th s ph thuc ca p sut hi chung vo thnh phn hi s thu c
mt ng cong (ng chm chm trn hnh 1). ng thng P Ao P Bo c gi l ng
lng, trn n h tn ti trng thi lng. ng cong chm chm c gi l ng hi,
vng di n h tn ti trng thi hi. Khu vc nm gia hai ng l vng d th gm hai
pha lng v hi.
i vi dung dch thc p sut hi ring phn hoc p sut hi chung s ln
hn (sai lch dng) hoc nh hn (sai lch m) so vi p sut hi ca dung dch
l tng, theo nh lut Raun. Vi dung dch sai lch dng, ng cong p sut
hi chung s cong ln pha trn, cn vi dung dch sai lch m - cong xung pha
di v gin cn bng lng hi ca cc dung dch ny c dng nh hnh 2a, 2b.
Trong trng hp s sai lch khi dung dch l tng qu ln th trn ng cong
p sut hi chung thnh phn c th xut hin cc i hay cc tiu. Ti nhng
im cc tr p sut hi, thnh phn ca pha lng v pha hi l ng nht (nh lut
Knvalp) nn hn hp ng vi thnh phn ny s c nhit si khng i v
c gi l hn hp ng ph. Gin cn bng lng hi ca cc dung dch c to
thnh hn hp ng ph c ch ra trn hnh 3a, 3b.

Hnh 2
Gin cn bng lng hi ca dung dch
sai lch dng (a) v sai lch m (b)

Hnh 3
Gin cn bng lng hi ca dung dch to thnh hn hp ng ph c cc
i p sut hi (a) v c cc tiu p sut hi (b)

Cc gin trn y l cc gin ng nhit. Trong thc t thng s dng cc gin

cn bng lng hi ng p, biu th s ph thuc ca nhit si vo thnh phn lng v
thnh phn hi cn bng, p sut khng i. Trn hnh 4 biu th mt gin cn bng lng
 19

hi ng p i vi h hai cu t khng to thnh hn hp ng ph. ng cong di biu th

s ph thuc ca nhit si vo thnh phn dung dch, ng cong trn biu th s ph
thuc ca nhit si vo thnh phn pha hi nm cn bng vi dung dch. Khu vc gia hai
ng ng vi cc hn hp d th ca cht lng si v hi bo ho. Mt im bt k nm
trong khu vc c trng cho h gm hai pha lng v hi, v d im K h gm pha lng
thnh phn l v pha hi thnh phn m. Lng tng i ca pha hi v pha lng c xc
nh theo quy tc n by:
Lng pha hi Kl
=
Lng pha lng Km
S nghin cu cc gin cn bng lng - hi c ngha ln i vi cc qu trnh chng
ct phn chia cc cu t trong hn hp.

Hnh 4
Gin nhit si - thnh phn pha lng v pha hi
ca h hai cu t

Gi s xt qu trnh chng ct hn hp c thnh phn x1 (hnh 4). Khi nng n nhit

t1 hn hp s si, phn hi u tin to thnh c thnh phn ng vi im biu din m. Nu ta
ngng phn hi ny s thu c hi ngng c thnh phn y1 giu cu t d bay hi hn (cu
t A), cn hn hp lng ban u s giu cu t km bay hi hn (cu t B). Trong qu trnh
un nng v ngng hi tip tc, dung dch lng ban u ngho A dn dn (theo chiu mi tn
trn ng cong lng). Gi s phn on ct th nht bt u t l v kt thc p. Hn hp
lng ng vi im biu din p c thnh phn x2, nhit si t2 v c thnh phn hi y2. Hn
hp lng cn li trong bnh ct s c thnh phn trung bnh x3 v hi ngng c thnh phn
trung bnh y3 giu A hn x1. Phn on ct th hai bt u vi hn hp lng y3 va ngng
c. Hn hp y3, s si nhit t3 v phn hi u tin bay ra c thnh phn y4 cn giu A
hn y3... C tip tc tin hnh nh vy nhiu ln th c th thu c trong phn hi ngng cu
t A hu nh nguyn cht. Hn hp lng cn li trong bnh s giu B dn, qua nhiu ln ct
s cn li cu t B hu nh nguyn cht.
Trong thc t cc qu trnh chng ct - ngng t c thc hin lin tc trong cc ct
chng ct. Da vo gin cn bng lng - hi c th tnh ton c s a cn thit trong
ct c th chng ct c cc cu t A v B tinh khit.
 20

i vi cc dung dch c to thnh hn hp ng ph, vic chng ct hn hp c thnh

phn d mt cu t so vi hn hp ng ph s cho ta mt cu t tinh khit (cu t d) v hn
hp ng ph. Vic tch cc cu t tinh khit khi hn hp ng ph khng th thc hin bng
chng ct thng thng m phi dng nhng bin php ring.

Tin hnh th nghim

xy dng gin cn bng lng - hi ca h hai cu t (benzen v axeton) p sut
kh quyn, cn xc nh nhit si ca cc cht tinh khit, ca cc dung dch c thnh phn
khc nhau v thnh phn ca pha lng, pha hi ng vi nhit si. Thnh phn pha lng
c chp nhn bng thnh phn dung dch pha ch ban u, cn thnh phn pha hi c
xc nh bng phng php o chit sut ca hi ngng.

1. Chun b dung dch v xy dng ng chun: Chit sut - Thnh phn

Dng pipet (hoc buret) ly vo 7 bnh c nt nhm sy kh cc hn hp c thnh
phn nh bng 1.
Bng 1
S bnh 1 2 3 4 5 6 7
Th tch benzen (ml) 0 4 8 12 16 18 20
Th tch axeton (ml) 20 16 12 8 4 2 0
Thnh phn (% th tch benzen) 0 20 40 60 80 90 100
Chit sut

y nt bnh, lc u. o chit sut ca cc cu t tinh khit v cc hn hp bng khc

x k pb theo s hng dn ca cn b phng th nghim (Lng dung dch cn o chit
sut t nn cc dung dch cn li gi xc nh nhit si). Ghi cc d kin thu c theo
bng mu 1 v dng giy k li xy dng ng chun chit sut - thnh phn.

2. Xc nh nhit si v thnh phn pha hi cn bng

5
Hnh 5
Dng c cn bng lng hi
 21

Tin hnh th nghim

Dng c th nghim (hnh 5) gm mt bnh ct (1) c hai c, mt c cm nhit k (2), c
th hai hi nghing cm sinh hn (3). V sinh hn gn vi c bnh bng nt nhm (4) nn c
th xoay sinh hn sang v tr khc (hnh chm chm) ly hi ngng. Hi ngng c thu
vo cc cn nh c nt nhm (5).
mt dung dch c thnh phn xc nh trn vo bnh (1). B vo bnh vi vin
bt. un cch thu cho n khi dung dch si u, ch khng si mnh qu. C th dng
cch m git cht lng ngng bu nhit k (2) iu khin tc si (khong 30 git
mt pht). Khi no tc si u v nhit n nh th ghi ly gi tr nhit ny (nhit
si trc khi ngng). Xoay nhanh ng sinh hn v v tr ly mu, ly 5 6 git hi ngng vo
cc cn (5) sy kh. y ngay np cc v quay sinh hn v v tr ban u ng thi ghi
nhit trn nhit k (nhit si sau khi ngng). Xc nh chit sut ca hi ngng thu
c. hn hp lng trong bnh (1) vo l cha hn hp thu hi trong phng th nghim.
Lp li qu trnh chng ct i vi cc hn hp pha trn. (i vi cc cht tinh khit ch
cn xc nh nhit si m khng cn ly hi ngng). Da vo ng chun chit sut -
thnh phn ni suy ra thnh phn ca hi ngng v ghi cc kt qa theo bng mu 2.
Bng 2
Thnh phn Nhit si Thnh phn
hn hp lng hi ngng
Trc khi Sau khi Trung Chit sut hi ngng
(% th tch (% th tch
benzen) ngng ngng bnh benzen)
0%
20 %
40 %
60 %
80 %
90 %
100 %

Dng giy k li biu din s ph thuc ca nhit si (trung bnh) vo thnh phn hn hp lng
v thnh phn hi ngng, thu c gin cn bng lng - hi ca h benzen - axeton p sut kh
quyn khng i.
 22

Bi s 5

TNH TAN HN CH CA CHT LNG

Mc ch
Xy dng gin tan ca hai cht lng ho tan hn ch v xc nh nhit
ho tan ti hn.
Xy dng gin tan ca h ba cu t ho tan hn ch.

L thuyt
Cc cht lng c th ho tan hon ton vo nhau (nc - etanol, benzen - cloroform
cacbon tetraclorua...), thc t khng ho tan vo nhau (du ho - nc, nc - thu ngn -
benzen,...) hoc ho tan hn ch vo nhau (phenol - nc, nc - cloroform - axit axetic...).
y chng ta xt trng hp ho tan hn ch.

H hai cu t
1. Gin tan ca h hai cht lng ho tan hn ch

Xt h phenol - nc lm v d. mi nhit , ho tan ca phenol trong nc hoc

ca nc trong phenol c gi tr xc nh. Khi nhit tng, tan ca mi cht trong cht
kia u tng. th biu din nh hng ca nhit n tan ln nhau ca chng P =
const c dng nh hnh 1, trong HK v IK l ng biu din nh hng ca nhit ti
tan ca phenol trong nc v ca nc trong phenol. Hai ng ct nhau ti im K ng
vi nhit tk, trn nhit phenol v nc ho tan vo nhau theo bt k t l no. Nhit
tk c gi l nhit ti hn ca s ho tan.

Hnh 1
Gin tnh tan h phenol - nc
 23

hiu r hn gin , ta xt nhng s bin i xy ra trong h khi thay i thnh phn

hn hp mt nhit nht nh. Gi s ly mt lng nc xc nh nhit t1 (im A
trn gin ). Thm dn phenol vo nc, lc u s thu c mt dung dch ng nht
phenol ho tan trong nc, nhng khi lng phenol thm vo ln (nng dung dch ng
vi im B) nc s bo ho phenol v nu tip tc thm phenol h s tch thnh hai lp: lp
c l dung dch nc bo ho phenol c thnh phn ng vi im B (lp B) v lp mi l
dung dch phenol bo ho nc c thnh phn ng vi im C (lp C). V tan ca nc
vo phenol hoc ca phenol vo nc mi nhit l xc nh, khng ph thuc vo lng
cht tan thm vo, nn vic thm tip tc phenol ch lm thay i lng tng i gia hai
lp m khng lm thay i thnh phn ca hai lp. iu ny c thy r trn gin : khi
thm dn phenol im biu din ca h dch chuyn t B n C trong khi thnh phn ca hai
lp cht lng c biu th bng cc im B v C vn khng thay i. T l khi lng gia
hai lp c xc nh bng quy tc n by, v d ti im biu din M:
Khi lng lp B MC
=
Khi lng lp C MB
Khi thm phenol ti im C, lp B bin mt (MC = 0) v h ch cn mt lp C (dung
dch phenol bo ho nc) v t tr i (t C n D) h l ng th (nc ho tan trong
phenol). Nh vy, nhit t1 cc khu vc AB v CD h l ng th, cn khu vc BC h
l d th.
Khi nng nhit , tan ca phenol trong nc cng nh ca nc trong phenol u
tng nn khu vc d th thu hp dn (EF nhit t2, PQ nhit t3...) v khi nng n
nhit tk th khu vc d th bin mt, t nhit tr ln h lun lun l ng th vi bt
k t l no ca phenol - nc. Nhit tk gi l nhit ho tan ti hn ca h. l nhit
ti hn trn. C nhng h c nhit ti hn di ngha l nhit ti v nhng nhit
thp hn n hai cht lng ho tan hon ton, v d h colodin - nc. Cng c h tn ti c
nhit ti hn trn v di, v d h nicotin - nc. ng cong HKI phn chia h thnh hai
khu vc ng th v d th c gi l ng cong phn lp. Mi im trn ng cong biu
th thnh phn ca cc lp cn bng. V d nhit t1, thnh phn ca hai lp cn bng
c xc nh bi cc im B v C, t2 - bng cc im E v F, t3 - bng cc im P v Q.
Cc ng thng BC, EF, PQ... ni cc im biu din thnh phn ca cc lp cn bng lin
hp c gi l cc ng lin hp. Theo quy tc gn ng ca Alecxep th trung bnh cng
ca thnh phn cc lp lin hp cc nhit khc nhau c phn b trn mt ng thng
v im ct ca ng thng (ng KK trn hnh 1) vi ng phn lp l im ti hn
ca s ho tan. Da vo quy tc c th xc nh chnh xc hn nhit ti hn ca h t
cc d kin thc nghim.

2. Phng php xy dng gin tan ca hai cht lng

Qua phn tch trn nhn thy c th xy dng gin tan ca hai cht lng ho tan
hn ch theo hai cch sau y:
a) Trn ln hai cht lng ri t vo bnh iu nhit nhit t1 (sau t2, t3...)
cho n khi tch hon ton thnh hai lp cn bng. Phn tch nh lng thnh
phn hai lp ny s thu c cc im thc nghim B, C (E, F v P, Q...) t
xy dng c ng cong phn lp.
b) Ly mt hn hp c thnh phn nm trong khu vc d th (v d hn hp N) un
nng n nhit tR hn hp chuyn t d th sang ng th (c sang trong).
 24

Nu un hn hp n nhit cao hn tR ri cho ngui dn th n nhit tR

hn hp chuyn t ng th sang d th (trong sang c). Cn c vo nhit
bt u trong v bt u c s xc nh c im R. Lm th nghim tng t
vi cc hn hp c thnh phn khc nhau s xy dng c ng cong phn
lp.
Cch th hai n gin v thun tin hn nn thng c s dng xy dng gin
tan ca h.

H ba cu t
1. Phng php biu din thnh phn ca h ba cu t

Thnh phn ca h ba cu t c biu din bng gin tam gic u (hnh 2). Ba nh
ca tam gic ng vi ba cu t tinh khit. Cc im nm trn cnh ca tam gic biu th thnh
phn ca cc h hai cu t, cn cc im nm trong tam gic biu th thnh phn h ba cu t.
C hai cch xc nh thnh phn ca cc im ny. Theo phng php Gipx, tng khong
cch h t mt im M bt k nm trong tam gic xung cc cnh (Ma+Mb+Mc) bng ng
cao ca tam gic v c coi l 100%. Thnh phn phn trm ca mt cu t, v d cu t A c
xc nh bng khong cch Ma t im biu din thnh phn ca h M n cnh i din vi nh
A ca tam gic. Theo phng php Rzebum th di ca cnh tam gic c coi l 100%.
Tng di ca cc on thng song song vi cc cnh v xut pht t im biu din thnh phn
ca h M (Ma + Mb+ Mc) bng cnh ca tam gic. Khi thnh phn phn trm ca cu t A
bng on Ma. V Ma = Cb nn xc nh % A, t M k 1 ng song song vi cnh i
din ca A, ng ny s ct cnh biu din %A b, im ct ny cho bit %A. C hai
phng php trn u cho mt kt qu thng nht. D dng nhn thy rng theo cc cch biu
th thnh phn trn tt c cc im biu din nm trn cc ng thng song song vi mt
cnh u c nng % ca cu t i din vi cnh l khng i, cn cc ng thng
xut pht t mt nh xung cc cnh i din, ng vi cc hn hp c thnh phn % ca cu
t ng vi nh thay i cn t l thnh phn % ca hai cu t kia lun khng i.

Hnh 2
Gin tam gic biu din thnh phn h ba cu t
 25

Hnh 3
Gin tan ca h ba cht lng, c mt cp cht lng ho tan hn ch

2. Gin tan ca h ba cu t

Nu cc cu t B v C ho tan hn ch vo nhau cn cu t th ba A ho tan vo chng

khng hn ch th khi thm cu t A vo h s lm tan ln nhau ca hai cu t B v C tng
ln n khi h tr thnh ng th. Axit axetic cloroform - nc l mt h ba cu t thuc
loi ny. Gin tan ca chng c dng nh hnh 3. Nhn vo gin d dng nhn thy
cloroform v nc ho tan hn ch, cn axit axetic ho tan v hn vo cloroform cng nh
vo nc.
Khi thm nc vo cloroform theo ng BC n thnh phn x cloroform s bo ho
nc. Thm tip nc vo h s hnh thnh thm mt lp mi l lp nc bo ho cloroform
c thnh phn y.
Nu thm axit axetic vo h th n c phn b gia hai lp to ra hai dung dch bc ba,
nhng dung dch ny nm cn bng vi nhau, vi iu kin thnh phn chung ca hn hp
nm trong min pha di ng cong xKy. V d, nu thnh phn chung ca hn hp biu
din bng im M th hai pha nm trong cn bng c biu din bng im a v b trn
ng lin hp aMb. Nhng thnh phn chung khc s c nhng ng lin hp khc.
Thng thng cc ng lin hp khng song song vi nhau hoc vi cc cnh ca tam
gic. Cng thm axit vo, thnh phn ca hai pha cn bng cng gn nhau hn v ng lin
hp s ngn hn. Cui cng khi thnh phn ca hai dung dch ng nht, ng lin hp tr
thnh mt im K. im K l im ti hn v thm nhiu axit hn na ch dn ti vic to
thnh mt pha ng th. Tt c cc im pha di ng cong xKy biu din cc hn hp
 26

bc ba, nhng hn hp ny c chia thnh hai pha lng. Cc im nm pha trn ng cong
xKy biu din mt pha lng ng th duy nht.
Khi thm nc vo dung dch cloroform v axit axetic c thnh phn N th thnh phn
chung ca h bin i theo ng NC. Khi thm nc theo ng NP, th ch thu c mt
pha lng ng th trong t s nng phn trm ca cloroform v axit axetic lun lun
bng NA/NB. Khi t ti im P nu thm nc na th s c hai pha lng. Khi lng nc
tng, thnh phn nhng pha ny thay i theo ng PQ. Gia P v Q lng ca pha giu
nc tng cn lng ca pha cha t nc gim. Thnh phn ca mi pha cng thay i nh
nhng giao im ca cc ng lin hp vi ng cong phn lp ch r. T Q n C h
tr thnh ng th.
Cn ch gin tan trn l gin ng p v ng nhit. tan tng h ca
cloroform v nc tng theo nhit v min tn ti hai pha s thu hp hn. nhit
cao th khng ph thuc vo lng tng i ca h ba cu t ch thu c mt pha lng.
C th xc nh thnh phn ca cc lp lng cn bng da vo quy tc kinh nghim.
Theo quy tc ny, cc ng lin hp ni lin thnh phn hai lp cn bng a1 b1, a2 b2, a3 b3
khi ko di s ng quy ti mt im (im K* trn gin hnh 3).

3. Phng php xy dng gin tan h ba cu t

Qua phn tch trn nhn thy c th xy dng gin tan ca h ba cu t bng hai
cch sau y:
a) Ly hn hp hai cht lng ho tan vi nhau, sau thm cht th ba vo cho n
khi h tr thnh d th (vn c).
b) Ly hn hp cht c thnh phn to thnh h d th, sau cho dn cu t th ba
vo h n khi h tr thnh ng th (trong sut).
Xc nh thnh phn ca cc hn hp ng vi s chuyn t ng th thnh d th (trong
sang c) v ngc li (c sang trong) s thu c cc im thc nghim. ng ni cc
im thc nghim chnh l ng cong phn lp trn gin tan h ba cu t.

Tin hnh th nghim

1. Xy dng gin tnh tan ca h phenol - nc

Cho nc v phenol vo tng microburet. thc hin iu cn phi nhng l ng

phenol vo cc nc nng c nhit khong 40 45oC cho phenol chy ra ri rt vo
microburet (tuyt i khng un l cha phenol trc tip trn bp, bng phenol rt nguy
him).
Dng microburet ly vo 6 ng nghim c nh s t 1 n 6 cc hn hp c thnh phn
sau y:
S th t ng nghim 1 2 3 4 5 6
Phenol (ml) 0,6 0,9 1,5 3 3,6 4,2
Nc (ml) 5,4 5,1 4,5 3 2,4 1,8
Thnh phn (% th tch H2O) 90 85 75 40 40 30

Lp nhit k v que khuy vo cc ng nghim theo hnh 4.

 27

Hnh 4
Dng c nghin cu tnh tan hn ch ca hai cht lng

Nhng ng nghim 1 vo cc nc c un nng dn trn bp in (hoc tt hn bng

n cn), khuy hn hp nh v u tay ng thi quan st s thay i nhit v nhng bin
i ca hn hp. Khi no hn hp tr nn trong sut (ng th) th ghi ly nhit ny (t1).
Kim tra kt qu nhn c bng cch nhc ng nghim ra khi cc nc, vn khuy u
tay v quan st khi h bt u c th ghi ly nhit ny (t2). Trn nguyn tc th t1 v t2
phi bng nhau v theo nhit ng hc th cn bng nhit ng khng ph thuc vo phng
thc t cn bng, nhng trn thc t, do s hn ch ca mt nhn v chnh xc khng cao
ca php o nn t1 t2. Nu hai nhit khc nhau khng qu 1o th c th coi kt qu thc
nghim l tt. Gi tr trung bnh ca hai nhit l nhit ho tan hon ton ca h hai cu
t c thnh phn tng ng.
Vi mi ng cn lm ba ln ly kt qu trung bnh v tnh sai s.
Ln lt tin hnh th nghim vi cc ng nghim t 2 n 6 theo cch lm nh trn.
Nhng d kin thu c ghi theo bng mu sau:

Thnh phn Nhit toC

STT ng t1 + t 2 + t 3
nghim
(% T.tch t +t t tb = (vit c sai s)
H2O) Ln TN t1 t2 t= 1 2 3
2
1
1 90 2
3
1
2 85 2
3
1
3 75 2
3
1
4 50 2
3
 28

1
5 40 2
3
1
6 30 2
3

V gin s ph thuc ca nhit ho tan hon ton ca phenol v nc vo thnh

phn hn hp v tm nhit ho tan ti hn ca hn hp ny.

2. Xy dng gin ho tan tng h ca h nc - axit axetic - cloroform

Cho cloroform, axit axetic v nc ln lt vo 3 buret c 50 ml (hoc 25 ml), c vch

chia 0,1. Ly vo 4 bnh nn c nt nhm c 100 ml nhng hn hp c thnh phn nh sau:
S 1 S 2 S 3 S 4
Nc (ml) 9 7,5 6 4
Axit axetic (ml) 1 2,5 4 6

y np bnh li, lc cho hn hp trn u vi nhau. Ly cloroform vo microburet. Cho

cloroform xung tng git mt. Mi ln c mt git ri xung li y np li, lc cho tan ht.
Tip tc n khi bt u thong thy xut hin c (khng nn cho qu n ni cht lng tch
thnh lp). Ghi ly lng cloroform thm vo. Nh vy ta xc nh c mt im thc
nghim trn ng cong tnh tan.
Tin hnh tng t vi ba bnh cn li, ta xc nh c thm 3 im trn gin .
Ly vo 4 bnh nn nhm c 100 ml cc hn hp c thnh phn sau:
S 5 S 6 S 7 S 8
Axit axetic (ml) 1 2,5 4 6
Cloroform (ml) 9 7,5 6 4

y np, lc u cc bnh, dng microburet thm nc vo tng git mt, y nt, lc

cho tan ht, tip tc n khi thong c. Ghi ly lng nc cho vo.
Ln lt lm vi 4 bnh, ta xc nh c thm 4 im na trn gin tnh tan.
- Cch tnh:
xy dng gin tnh tan, cn i tt c s ml ra s gam. Cho bit khi lng ring
(g/cm3) ca cc cht nh sau:
d H2 O = 1; d CH3COOH = 1,05; d CHCl3 = 1,48

T tnh thnh phn phn trm theo khi lng ca ba cht trong cc hn hp tng
ng. Ghi kt qu theo bng mu sau:
STT bnh Nc Axit axetic Cloroform
Bnh s 1
Bnh s 2
Bnh s 3
Bnh s 4
. . . . . . .
 29

Bnh s 8

Da vo bng v gin tan tng h ca h ba cu t ( nhit v p sut khng

i) trn giy milimet tam gic, xin phng th nghim.
Hy rt ra kt lun v tnh tan tng h ca cc cp cht lng:
Axit axetic - nc
Nc - cloroform
Cloroform - axit axetic
Cho bit nh hng ca cc cht th ba khi thm vo cc hn hp hai cu t trn.
 30

Bi s 6

PHNG PHP HN NGHIM

Mc ch
Xc nh khi lng phn t ca cht tan bng phng php hn nghim.
L thuyt
Khi ho tan vo dung mi mt cht tan khng bay hi th mt phn mt thong ca dung
mi b chim bi cc phn t cht tan nn tc bay hi ca dung mi gim i, p sut hi
bo ho ca dung mi trn dung dch s gim so vi dung mi tinh khit, khi xt cng mt
nhit .

1 2
P
P ngoi A B C

F
T
2 1 o o 1 2
T T T Ts Ts Ts

Hnh 1
S ph thuc p sut hi ca dung mi tinh khit
v dung mi trn dung dch vo nhit

S gim p sut hi ca dung mi trn dung dch dn ti s tng nhit si v s gim

nhit ng c ca dung dch. iu ny c thy r trn hnh 1, y cc ng OA,
DB, EC l cc ng p sut hi bo ho ca dung mi tinh khit v ca dung mi trn cc
dung dch 1, dung dch 2 (nng dung dch 1 thp hn dung dch 2). ng OF l ng p
sut hi ca dung mi trn dung mi rn.
V cht lng si khi p sut hi bo ho bng p sut ngoi, cn cht lng ng c khi
p sut hi bo ho trn pha lng bng p sut hi bo ho trn pha rn nm cn bng vi pha
lng, nn honh ca cc im A, B, C s l nhit si v honh ca cc im O, D, E
s l nhit ng c ca dung mi tinh khit v ca dung mi trn cc dung dch 1, dung
dch 2 tng ng. ( xc nh nhit ng c chun cn quy v P ngoi = 1atm) Chng ta
thy r rng:
 31

TSo < TS1 < TS2

T0 > T1 > T2
v tng nhit si cng nh h nhit ng c ca dung dch t l vi nng
ca cht tan trong dung dch, ngha l:
TS = TS TSo = ES.n2 (1)
T = To T = E.n2 (2)
y: ES - hng s nghim si
E - hng s nghim lnh
n2- nng molan ca cht tan (s mol cht tan trong 1000 gam dung mi).
Cc h thc trn ch ng vi cc dung dch v cng long. Da vo nhit ng hc c
th rt ra c:
M 1 R(TSo )2
ES = (3)
1000.H bh

M 1R(To )2
E = (4)
1000.H nc
y: M1- khi lng phn t ca dung mi
Hbh, Hnc - nhit bay hi ring v nhit nng chy ring ca dung mi.
T (3), (4) nhn thy ES, E ch ph thuc bn cht ca dung mi. Cc gi tr ES, E i
vi cc dung mi c xc nh bng thc nghim v cho trong cc S tay Ho l.
Nu gi g1 l s gam dung mi v g2 l s gam cht tan ho trong n, M2 l khi lng
phn t cht tan, d dng xc nh c:
g 2 1000
n2 = . (5)
M 2 g1
Thay gi tr n2 vo (1) v (2) thu c:
E s .g 2 .1000
M2 = (6)
g 1 . t s
E .g 2 .1000
M2 = (7)
g 1 . t
Cc cng thc (6) v (7) l c s xc nh khi lng phn t ca cht tan khng bay
hi, da vo tng nhit si hoc gim nhit ng c ca dung dch. Do vic xc
nh nhit ng c thu c kt qu chnh xc hn so vi xc nh nhit si nn cng
thc (7) thng c dng xc nh khi lng phn t. Phng php xc nh khi lng
phn t ca cht tan da vo h nhit ng c ca dung dch c gi l phng php
hn nghim.
 32

Tin hnh th nghim

Dng c xc nh nhit ng c ca benzen c dng nh hnh 2.

4 5

6
3

Hnh 2
Dng c xc nh h nhit ng c
1. Cc ng nc , 2. ng bao
3. ng nghim ng benzen hoc hn hp nghin cu
4. Nhit k, 5,6. Que khuy.

benzen vo ng nghim (3) cho va ngp bu nhit k (4), (khng nhiu qu khi
tin hnh thc nghim s kh khn) nhit k nn cm gn st y ng.
Cm ng ng benzen vo ng bao, t ng bao vo cc ng nc . Dng que khuy
(6) iu ho nhit trong cc (1). Khuy u que khuy (5), theo di s ch trn nhit k
(4) v ghi nhit , c 30 giy mt ln.
C hai trng hp xy ra
- C hin tng chm ng ca benzen
Khi nhit gim n 5oC benzen vn cha kt tinh v hin tng chm ng xy ra
(nhit gim xung di im ng c cht lng vn cha kt tinh). Khi nhit gim ti
1oC hay 2oC dng que khuy (5) khuy nh. S kt tinh benzen chm ng xy ra. Nhit
benzen tng rt nhanh cho n khi t ti im ng c th dng li. Nhit khng i khi
benzen ang kt tinh v tip tc gim i sau khi benzen kt tinh xong. im dng trn
ng cong nhit - thi gian chnh l nhit ng c ca benzen (hnh 3, ng cong I).
- Khng c hin tng chm ng
Khi t ti 5oC benzen ng c v trong sut qu trnh nhit khng thay i cho n
khi kt tinh hon ton. Sau nhit li gim xung (hnh 3, ng II).
 33

Hnh 3
Dng ng cong kt tinh ca cht lng

I. C hin tng chm ng

II. Khng c hin tng chm ng
xc nh chnh xc nhit ng c, th nghim cn tin hnh sao cho c hin tng
chm ng. Mun vy cht lng phi tinh khit, ng nghim ng cht phi m bo tht kh
khng c vt ca nc v khng c bi bn. Cc cht bn ny nu khng c loi tr s lm
mm kt tinh v do cn tr s xut hin hin tng chm ng.
Sau khi xc nh im ng c ca benzen ta tip tc xc nh nhit ng c ca
dung dch.

Hnh 4
ng cong kt tinh ca dung dch

Cn 25 gam benzen bng cn k thut trong cc c np, 0,150,30 gam naphtalen bng cn
phn tch (ly d kin chnh xc n sai s ca cn) ri ho tan trong benzen ta thu c dung
dch nghin cu.
dung dch vo ng nghim (3) sy kh n khi ngp bu nhit k, y nt, cho vo
ng bao.
Dng que khuy (5) khuy u hn hp v tin hnh theo di nhit thay i sau 30
giy mt ln, khi nhit gim dn n gn 5oC th ngng khuy. Nu ho cht sch hin
tng chm ng xy ra, khi nhit t ti khong 1o 2oC khuy nh benzen bng que
khuy (5), lc nhit tng nhanh v benzen kt tinh.
 34

V ch c benzen kt tinh nn trong qu trnh kt tinh thnh phn dung dch lng thay i,
do nhit khng gi nguyn nh trng hp cht lng tinh khit m gim dn. Lc
ng cong nhit thi gian c dng nh hnh 4.
im cc i trn ng cong kt tinh chnh l nhit ng c ca dung dch c thnh
phn bit.
Bit T o v T ca benzen v dung dch, bit hng s nghim lnh ca benzen l 5,07 c
th tnh c khi lng phn t ca naphtalen. So snh vi l thuyt ta s c kt lun v
chnh xc ca th nghim.
 35

Bi s 7

PHNG PHP PHN TCH NHIT

Mc ch
Xy dng gin nng chy ca h hai cu t bng phng php phn tch nhit.

L thuyt
Gin nng chy ca h hai cu t biu th mi quan h gia nhit nng chy (hay
kt tinh) ca h ph thuc vo thnh phn ca h.
y chng ta nghin cu gin nng chy ca h hai cu t ho tan hon ton trng
thi lng v khng ho tan trng thi rn, trong iu kin p sut khng i. Gin c th
xy dng nh phng php phn tch nhit da trn s nghin cu cc ng cong ngui lnh
(hay un nng) ca cc cu t nguyn cht v cc hn hp.
ng cong ngui lnh ca cu t nguyn cht (hnh 1, ng 1)
Khi un cu t nguyn cht n nhit cao hn nhit nng chy ca n ri lm lnh
th nhit gim dn theo thi gian (on ab). Khi cht lng kt tinh th lng nhit pht ra
trong qu trnh kt tinh b cho lng nhit cht lng mt cho mi trng ngoi v nhit
ca h dng li khng thay i (on bc). Khi qu trnh kt tinh xong th nhit li tip tc
gim (on cd).

Hnh 1
ng cong ngui lnh
1. Cu t tinh khit.
2. Hn hp lng c thnh phn bt k.
3. Hn hp lng c thnh phn hn hp tecti.

C th gii thch ng cong ngui lnh nh quy tc pha ca Gipx:

f=n-k+1 (P = const)
 36

y: f s bc t do; n s cu t; k s pha.
- Trn on ab hoc cd, h gm mt pha lng hoc rn.
f=1-1+1=1
ngha l c mt bin s c th thay i tu m khng lm thay i s pha ca h. V
thnh phn l xc nh (100%) nn nhit phi l bin s thay i.
- Trn on bc h gm 2 pha: lng v rn:
f=1-2+1=0
ngha l khng mt bin s no c th thay i, nhit kt tinh ca cu t tinh khit l
hon ton xc nh (on bc nm ngang).
ng cong ngui lnh ca hn hp lng (hnh 1, ng 2)
Khi lm lnh hn hp lng, nhit gim dn (on ab). n mt nhit no , mt
trong hai cu t bt u kt tinh. Nhit pht ra khi kt tinh lm cho nhit gim chm li
(on bc) v trn ng cong ngui lnh c im gy (im b). Theo quy tc pha, trn on
bc:
f=2-2+1=1
ngha l khi thnh phn thay i th nhit phi thay i (on bc gim chm li nhng
khng nm ngang nh trng hp kt tinh ca cht lng nguyn cht). Theo mc kt tinh
ca mt cu t, nng ca cu t kia trong dung dch lng dn tng ln v n mt nhit
no c hai cu t cng kt tinh, thnh phn ca dung dch lng khi s khng thay i v
s kt tinh xy ra mt nhit hon ton xc nh (on cd). nhit ny h gm ba pha:
hai cu t rn v hn hp lng. Theo quy tc pha, trn on cd:
f=2-3+1=0
ngha l c nhit v thnh phn u khng c thay i. Hn hp lng nm cn bng
vi hai pha rn gi l hn hp tecti v nhit ti c cn bng ba pha l nhit tecti
( t oE ).
Khi hn hp tecti kt tinh xong th nhit ca h li gim (on de).
Nu nghin cu s ngui lnh ca hn hp lng c thnh phn ng bng thnh phn hn
hp tecti th d dng thy rng hn hp s kt tinh nh mt cu t nguyn cht (hnh 1,
ng 3).
Xy dng gin nng chy t cc ng cong ngui lnh
Da vo cc ng cong ngui lnh chng ta bit c:
- Nhit kt tinh ca cc cu t nguyn cht.
- Nhit bt u kt tinh ca cc hn hp lng c thnh phn xc nh.
- Nhit kt tinh ca hn hp tecti.
V th, mt trc l nng cc hn hp nghin cu v mt trc l nhit kt tinh
ca cc hn hp tng ng ta c gin kt tinh hay nng chy ca h hai cu t (hnh 2).
Trn gin , cc ng cong t oA E v t oB E biu th nhit bt u kt tinh ca A v B trong
cc hn hp ph thuc vo thnh phn. Thc ra vi cc d kin thc nghim ta ch v c
 37

cc ng t oA m v t oB n cng vi ng t oE . Ta phi ngoi suy sao cho hai ng ct nhau ti

mt im E no trn ng t oE . im E chnh l im tecti v honh ng vi im E
l thnh phn hn hp tecti ca h nghin cu.

Hnh 2
Gin nng chy, xy dng t cc ng cong ngui lnh

Tin hnh th nghim

Dng c xc nh ng cong ngui lnh ca cht lng c dng nh hnh 3.
Dng cn phn tch ly vo cc ng nghim c nh s, ln lt cc hn hp c thnh
phn (% naphtalen) nh bng sau:
S ng nghim 1 2 3 4 5 6 7
Naphtalen (gam) 4 3,2 2,4 1,8 1 0,4 0
iphenylamin (gam) 0 0,8 1,6 2,2 3 3,6 4
Thnh phn (%) 100 80 60 45 25 10 0

un mt cc nc si, nhng ln lt tng ng vo cho hn hp chy lng, sau ly ra,

lau kh ng nghim v lp vo ng bao theo hnh 3.
Khuy nh hn hp bng que khuy (4) ng thi theo di nhit 1 pht 1 ln (dng
ng h bm giy hay ng h eo tay c kim ch giy cng c). Khi no hn hp ng
cng li th thi khuy nhng vn tip tc theo di nhit cho n khi nhit xung ti 29
30oC th thi.
Dng giy milimet v cc ng cong ngui lnh (nhit - thi gian) tm im dng v
im gy trn cc ng cong ny.
Ln lt lm vi c 7 ng. Vi ng s 1 v ng s 7 cha cc cu t tinh khit th ch cn
theo di nhit n khi xut hin im dng ng vi im kt tinh ca cc cu t
 38

Hnh 3
Dng c xc nh ng cong ngui lnh
1. ng bao thu tinh, 2. ng nghim ng cht nghin cu.
3. Nhit k, 4. Que khuy, 5,6. Nt lie.

Ch :
- Th nghim xc nh ng cong ngui lnh nht thit phi lm trong ng bao.
Khng c cm tay trc tip vo ng nghim ng hn hp, khng c nc
vo ng bao.
- Vic xc nh im bt u kt tinh i vi hn hp c thnh phn bt k rt kh
khn, i hi phi cn thn, chnh xc v t m khi ghi nhit v theo di thi gian.
Khng c b qua mt d kin no, khi v th mi c th tm thy im gy trn
ng cong ngui lnh.
- Sau khi lm mi th nghim nn xy dng ng cong ngui lnh kim tra kt qu,
nu khng tm c cc im c trng phi lm li ngay.
Da vo ng cong ngui lnh i vi 7 ng trn, xy dng gin nng chy ca h
naphtalen - iphenylamin.
Yu cu:
1) Ghi d kin thc nghim theo bng mu sau:
Nhit bt u Nhit kt tinh
ng s % naphtalen
kt tinh hn hp tecti

2) V cc th nhit - thi gian v gin nng chy (nhit - thnh phn) trn
giy milimet. Xc nh thnh phn ca hn hp tecti.
 39

Bi s 8

XC NH HNG S TC CA PHN NG
BC MT PHN NG GHCH O NG

Mc ch
Xc nh hng s tc ca phn ng thy phn saccaroz (phn ng nghch o
ng).

L thuyt
Phn ng thy phn saccaroz xy ra theo phng trnh:
[
H ]+
C12H22O11 + H2O C6H12O6 + C6H12O6 (1)
saccaroz glucoz fructoz
Tc phn ng ph thuc vo nng saccaroz, nc v ion H+ dng lm cht xc
tc. Nhng lng nc dng thc t rt ln nn coi nh khng i, cn nng ion H+ gi
nguyn trong sut thi gian phn ng, v vy phn ng c th xem l bc mt v tc ca
phn ng c xc nh theo phng trnh:
dC
= kC (2)
dt
Ly tch phn (2) thu c hng s tc ca phn ng:
1 Co
k= ln (3)
t Co Cx

y: Co l nng ng ban u
Cx l nng ng tham gia phn ng trong thi gian t
C = Co Cx l nng ng thi im t.
Hng s tc k c th xc nh da vo tnh cht hot ng quang hc ca ng.
ng saccaroz v cc sn phm thy phn ca n u cha cc nguyn t cacbon bt
i xng, v vy chng l nhng cht quang hot. Nu chiu qua dung dch ng mt chm
nh sng phn cc (l nh sng ch dao ng theo mt mt phng) th ng s lm cho mt
phng ny lch i mt gc gi l gc quay mt phng phn cc . ln ca gc quay ph
thuc vo bn cht ca cht quang hot, nng v b dy ca lp dung dch m nh sng
phn cc i qua, ph thuc vo bc sng ca nh sng v vo nhit . nh gi mc
quang hot ca cc cht khc nhau ngi ta a ra khi nim quay ring []: l gc
quay khi c mt chm nh sng phn cc c bc sng xc nh (thng l bc sng vch
quang ph vng ca hi natri 5896 ) i qua lp dung dch dy 10 cm, cha 1 gam cht trong
1 ml dung dch 20oC. Bit c gi tr [], nng C v chiu dy ca lp dung dch l c
 40

th xc nh gc quay theo cng thc = [] C l. ngc li c th theo cng thc xc nh

nng dung dch da vo gc quay.
ng saccaroz, glucoz v fructoz c gc quay tng ng bng: + 66,55o, + 52,56o
v 91,90o.
Nh vy, saccaroz quay mt phng phn cc v pha phi cn hn hp sn phm phn
ng quay mt phng phn cc v pha tri.
Trong qu trnh phn ng gc quay c gim dn, chuyn qua gi tr 0 v t gi tr m,
c ngha l s quay phi mt phng phn cc c chuyn thnh s quay tri. V l m
phn ng (1) cn c gi l phn ng nghch o ng. Hng s tc ca phn ng
nghch o ng thng c xc nh da vo s thay i gc quay trong qu trnh phn
ng.
Nu gi: o l gc quay lc bt u phn ng.
l gc quay lc ng saccaroz chuyn ho hon ton.
t l gc quay thi im t.
th o l bin thin gc quay t lc bt u ti lc kt thc phn ng, t l vi nng
ban u ca ng (Co).
t l bin thin gc quay t thi im t ti lc kt thc phn ng, t l vi nng
cn li ca ng thi im t: (Co Cx).
Thay nhng tr s ny vo phng trnh (3) thu c:
2,303 o
k = lg (4)
t t
Cc gc quay c o nh mt dng c gi l phn cc k (hay ng k), s cu
to ca n c ch ra trn hnh 1.

Hnh 1
S my phn cc k

Phn c bn ca phn cc k l ngun sng 1, knh lc nh sng 2 (ch cho nh sng vng
i qua), lng knh phn cc 3, ng phn cc k 4 v lng knh phn tch 5. Khi nh sng i
qua lng knh phn cc th nhng tia c mt phng dao ng trng vi mt ct chnh ca tinh
th lng knh phn cc c th i qua, l nhng tia phn cc. Nu mt ct chnh ca lng
knh phn cc v lng knh phn tch c t song song th cc tia phn cc cng s qua lng
knh phn tch v th knh 6 s thy nh sng phn b u (hnh 2b). Khi quay lng knh
phn tch (cn lng knh phn cc bt ng) th sng trn th knh s thay i. C th t v
tr phn gia ca mt th knh ti cn hai bn sng (hnh 2a) hoc phn gia th sng cn
hai bn ti (hnh 2c). V tr trung gian gia hai v tr trn c nh sng phn b u (hnh 2b) l
im 0 ca my phn cc k.
Nu sau khi t c im 0 m ta cho dung dch cht hot quang vo ng phn cc k
4 th th knh s thy nhng vng ti sng khc nhau. phc hi v tr 0 ta phi quay
lng knh phn tch i mt gc c gi tr bng gc quay mt phng phn cc ca cht nghin
 41

cu. Mt b phn o gc gn lin vi lng knh phn tch cho php ta c gc quay . Phn
ca gc quay c c theo thang ln (chia t 0o 180o) cn phn l ca , c theo
thang nh (chia t 0 10) v ly theo vch no trng vi vch ca thang chia ln (hnh 3).

Hnh 2 Hnh 3
o
Cch chnh phn cc k Cch ghi gi tr gc quay y = 22,10 .

Tin hnh th nghim

V phn ng tin hnh trong iu kin ng nhit nn trc ht cn iu chnh my
iu nhit nhit nghin cu (30oC). Trong thc t, c th tin hnh iu kin
nhit bng nhit phng. Khi nhit phng c xc nh bng cch o
nhit dung dch phn ng bng nhit k thu ngn, sai s 0,2 0,5oC.
Pha dung dch ng bng cch cn 10 gam ng saccaroz (cn k thut) ri cho
vo bnh nh mc 50 ml v thm nc ct ti vch. Nu dung dch c th phi tin
hnh lc. Chuyn dung dch vo mt bnh nn c 100 ml c nt y. Cho vo mt
bnh nn khc ng 40 ml dung dch HCl 1N. Ngm c hai bnh vo my iu nhit
30oC (nu lm nhit phng th khng cn). Sau khong 10 pht tin hnh o
gc quay.
Gc quay o c xc nh bng cch o gc quay ca dung dch ng khi cha
cho axit vo (khi phn ng thu phn xem nh cha xy ra).
Trng ng phn cc k hai ln bng vi ml dung dch ng va pha. dn dung dch
vo ng ti y, sao cho dung dch to thnh mt mt khum trong ng. Cn thn a ming
knh t ra vo, vn cht np gi ming knh li, ch kim tra khng c trong ng cn
bt kh. Dng giy lc lau kh bn ngoi ng, nht l hai mt knh. Cho ng vo my v o
o/
gc o . Gc o =
/
v khi tin hnh phn ng ta s pha long dung dch ng hai ln
2
bng dung dch axit. Sau khi o xong o, dung dch ng trong ng phn cc k tr li
bnh nn.
Xc nh gc quay t:
Dng pipet ly 40 ml dung dch cho vo bnh nn cha 40 ml dung dch axit. Ghi thi
im trn hai dung dch lm thi im ban u t = 0 (dng ng h bm giy). Lc u hn
hp, ly vi ml hn hp trng ng phn cc k ri rt ngay hn hp vo ng. C sau cc thi
im 5, 10, 15, 20, 30, 50, 70 v 100 pht (k t t = 0) th o gc t mt ln. Cc bc thao
tc nh khi xc nh o. Vic o gc quay cc phi lm tht nhanh bng cch quay phi lng
knh phn tch tm v tr 2b (hnh 2), c gc ng ng vi v tr tm c, lp li cc th
tc trn khi quay tri lng knh phn tch. Gi tr ghi l trung bnh cng ca hai gi tr thu
c.
Xc nh gc quay :
 42

S thu phn saccaroz nhit phng thng kt thc sau vi ngy. xc nh

ngi ta un cch thu hn hp phn ng 70o 80oC trong vng 30 pht, trong bnh tam
gic c lp sinh hn hi lu. Sau lm ngui n nhit 30oC (hoc nhit phng), em o
gc .
Yu cu:
1) Ghi cc s liu thc nghim v tnh ton c theo bng mu sau:

Thi gian o gc quay, tnh t lc bt u o t Hng s tc phn ng

S TT t lg
phn ng (pht) t k

ktb =

2) V th lg (t ) = f(t); nhn xt.

 43

Bi s 9

PHN NG THU PHN ESTE

Mc ch
Xc nh hng s tc phn ng v nng lng hot ng ho ca phn ng thu phn
etyl axetat bng dung dch kim.

L thuyt
Phn ng thu phn etyl axetat xy ra theo phng trnh:
CH3COOC2H5 + NaOH CH3COONa + C2H5OH (1)
y l phn ng bc hai, tc ca phn ng t l thun vi nng este v kim:
dC
= kCeCk (2)
dt
v hng s tc phn ng:
2,303 C oe (C ok C x )
k= lg (3)
t (C ok C oe ) C ok (C oe C x )

y: Coe v Cok l nng ban u ca este v kim.

Cx l nng ca este v kim tham gia phn ng sau thi gian t.
Ce = Coe Cx v Ck = Cok Cx l nng este v kim thi im t.
Bng cch chun lng NaOH cn li trong phn ng tng thi im khc nhau c
th tnh c Cx, t xc nh c k.

Tin hnh th nghim

Ly hai bnh cu y bng dung tch 500 ml c nt y kn (tt nht l nt nhm). Dng
1
bnh nh mc ly 250 ml dung dch este etyl axetat N cho vo mt bnh v 250 ml dung
60
1
dch NaOH N vo bnh kia (lng NaOH dng d m bo phn ng thu phn xy ra
40
hon ton).
y kn hai bnh trnh este bay i v CO2 tan vo dung dch NaOH.
Ngm c hai bnh vo my iu nhit 30oC. Sau 10 15 pht th bt u nhanh bnh
ng dung dch NaOH vo bnh ng este, y nt, lc u hn hp, ghi thi gian xem nh
l lc bt u phn ng. ng thi dng pipet ly nhanh 40 ml hn hp cho vo mt bnh
 44

1 1
nn c 250 ml c sn 25 ml dung dch HCl N. V lng HCl N d so vi NaOH c
40 40
trong 40 ml mu th nn s trung ho ht kim v km hm phn ng li. Bng cch chun
1
axit d trong bnh nn (dng NaOH N vi cht ch th phenolphtalein) c th bit c
40
lng HCl tiu tn trung ho NaOH v do tnh c lng NaOH c trong 40 ml
mu th. D kin thu c ng vi thi im t = 0.
Sau 5, 10, 20, 30, 40, 50 pht k t lc bt u phn ng, li ly ra 40 ml hn hp phn
1
ng cho vo bnh nn c sn 25 ml dung dch HCl N v li chun lng HCl d bng
40
NaOH nh nu trn.
Sau khi ly mu th cui cng ( pht th 50), lp vo bnh phn ng mt sinh hn hi
lu, ri un trong ni cch thu ln ti 70oC v gi nhit ny trong khong na gi.
ngui hn hp phn ng n 30oC v tin hnh ly mu v chun NaOH cn li nh
lm trn. V 70oC phn ng xy ra rt nhanh, do sau 30 pht gi hn hp phn ng
nhit ny ri ngui n 30oC, phn ng xem nh kt thc v d kin thu c ng
vi t = .
xc nh nng lng hot ho ca phn ng cn lp li mt th nghim tng t nh
trn nhng bnh phn ng c t trong my iu nhit 40oC v mu th c ly ra
nhng thi im 3, 5, 10, 15, 20, 30 pht sau lc bt u phn ng. D kin ng vi thi im
t = 0 v t = c th s dng kt qu phn trn.
Cn ch trong sut thi gian th nghim khng c nhc bnh ra khi my iu
nhit.

Tnh ton kt qu
1
Nu gi lng NaOH N dng chun axit d trong bnh nn l n mililit th lng
40
1 1
HCl N tiu tn trung ho NaOH hay lng NaOH N c trong 40 ml mu th nt s
40 40
bng:
nt = 25 n
1
Gi no, nt, n l lng NaOH N c trong 40 ml mu th cc thi im tng ng t =
40
0, t = t v t = th nng ban u ca kim Cok s t l vi no; nng ban u ca este Coe
t l vi
no n (v ta xem phn ng kt thc v lng NaOH ly d so vi este) v nng este
b thu phn sau thi gian t l Cx t l vi no nt, ngha l:
Cok = const.no

Coe = const.(no n)
Cx = const.(no nt)
 45

y const l h s t l biu th s lin h gia nng ng lng ca dung dch

vi s mililit dung dch v c tnh nh sau:
1
V no l s mililit NaOH N c trong 40 ml mu th t = 0 nn ng lng NaOH c
40
trong 40 ml l:
1 1
no . .
40 1000
v nng ng lng ca NaOH trong mu th s l:
1 1 40 1
CN = n o . . : = no
40 1000 1000 1600
1
Nh vy const =
1600
Thay cc gi tr Cok , C oe , Cx trn vo cc phng trnh (3) thu c:

2,303 n (n n )
k= lg t o (4)
t.const.n no ( nt n )

Ghi cc kt qu thc nghim v tnh ton theo bng mu sau:

Thi gian Lng NaOH Lng NaOH c Hng s tc phn ng

Nhit
ly mu th dng chun trong 40 ml mu th k
(oC)
k t t = 0 HCl d, n nt = 25 n

i vi tng nhit phi xc nh gi tr hng s tc trung bnh:

k 1 + k 2 + ... + k n
k=
n
Nng lng hot ng ho ca phn ng E tnh theo phng trnh:
k T2 E 1 1
lg =
k T1 4,575 T1 T2
y: T1 = 30 + 273 = 303 K
T2 = 40 + 273 = 313 K.
 46

Bi s 10

NG HP PH NG NHIT

Mc ch
Nghin cu s hp ph ca axit axetic trong mi trng nc trn than hot tnh v v
cc ng ng nhit hp ph.

L thuyt
Nhng vt c b mt tip xc ln vi pha kh hay pha lng thng c kh nng thu ht
cc cht kh hay cht tan trong pha lng. Nu s thu ht ch xy ra trn b mt ca vt th
gi l s hp ph. V d, khi cho than hot tnh vo dung dch axit axetic CH3COOH th mt
s phn t axit axetic s tp trung (b hp ph) ln trn b mt ca than hot tnh. Than hot
tnh c gi l cht hp ph, axit axetic l cht b hp ph, nc l mi trng trong s
hp ph xy ra. Bng cch o nng axit axetic trc v sau khi hp ph, bit khi lng
cht hp ph m gam ta c th bit c lng axit axetic b hp ph trn b mt 1 gam
than hot tnh.
C nhiu phng trnh thc nghim hoc l thuyt c a ra m t s hp ph
ng nhit. y nu ra mt s phng trnh hay gp:

1. Phng trnh Frendlich (Freundlich)

l phng trnh thc nghim p dng cho s hp ph kh hoc cht tan ln cht hp
ph rn:
A = C (1)
trong : A l lng cht b hp ph bi mt gam cht hp ph (mol/g).
C l nng cht b hp ph khi t cn bng hp ph
(mol/l).
v u l hng s, ring lun lun b hn 1.

2. Phng trnh Lngmua (Langmuir)

l phng trnh c chng minh l thuyt da vo vic nghin cu ng hc ca s hp
ph. Phng trnh c dng:
bC
= max. (2)
1 + bC
l lng cht b hp ph bi mt gam cht hp ph (mol/g).
C l nng cht b hp ph lc cn bng hp ph (mol/A).
 47

max v b l hng s.

3. Phng trnh Gipx (Gibbs)

Khi nghin cu v mt nng lng ca qu trnh hp ph, Gipx chng minh c
phng trnh:
C d
= . (3)
RT dC
Phng trnh nu ln quan h gia i lng hp ph (mol/cm2) v d/dC - l bin
thin sc cng b mt ca dung dch gy nn bi s hp ph cc cht ln b mt ca dung
dch theo s bin thin ca nng dung dch .

4. Phng trnh Siscpxki (Shiskovski)

L phng trnh thc nghim nu ln quan h gia sc cng b mt ca dung dch cht
hot ng b mt vi nng dung dch:
= o aln(1 + bC) (4)
trong o l sc cng b mt ca dung mi nguyn cht, a v b l cc hng s.
Trong bi thc nghim ny ta ch kho st hai phng trnh Frendlich v Lngmua, tnh
cc hng s trong hai phng trnh v v ng biu din ca hai phng trnh (c tn
chung l ng hp ph ng nhit), i chiu kt qu tnh ton vi ng thc nghim.
Phn tch phng trnh Lngmua:
Phng trnh (2) c th vit di dng:
C C
= max = max (5)
1 a + C
+ C
b
trong 1/b thay bng a, l mt hng s.
Nu C << a tc nng C rt b th (5) c th vit:
C
= max (6)
a
Ngha l i lng t l bc nht vo C. ng biu din
C l mt ng thng i qua gc to (hnh 1).
Nu C >> a th (5) chuyn thnh:
= max (7)
ngha l i lng hp ph l mt hng s: khi ng biu din ( vng nng ln)
l mt ng thng song song vi trc honh. cc nng C trung gian, ng biu din l
mt on ng cong. ng biu din (hnh 1) c tn l ng hp ph ng nhit
Lngmua (v th nghim tin hnh mt nhit nht nh).
 48

Hnh 1.
ng hp ph ng nhit Lngmua

tm cc hng s trong phng trnh Lngmua, ngi ta dng phng php th.
Mun vy ta biu din phng trnh (2) di dng khc:
C 1 C
= + (8)
m ax b m ax
Theo phng trnh ny C/ ph thuc bc nht vo C. ng biu din trong h to
C/ C ct trc tung ti M. Ta c:
1
OM =
max b
1
tg =
max
T hai phng trnh ny s tnh c b v max.

Hnh 2.
th tm cc hng s trong phng trnh
Lngmua
 49

Phn tch phng trnh Frendlich

V < 1 nn ng biu din ca phng trnh (1) l mt nhnh ca ng parabol v
c gi l ng hp ph ng nhit Frendlich. ng ny khc ng Lngmua ch
vng nng thp ng biu din khng phi l ng thng i qua gc ca to v
vng nng cao, ng biu din khng t cc i m c xu hng i ln mi, l nhc
im ca phng trnh Frendlich. vng nng trung bnh, hai ng biu din ging nhau.
Hnh 3 biu din ng hp ph ng nhit Frendlich ca axit propionic trn than hot
tnh. Ta thy t im M, ng biu din phn ra hai nhnh: on MB l on tnh trc tip
t phng trnh (1) cn MC l on v theo thc nghim.
cho ng hp ph m t ng phng trnh (1) cn gi thit khng phi l hng s
m l hm s ca nng . nng thp = 1, khi ta s c:
A = C (9)
Cn nng cao hn th = 0, khi ta s c:
A= (10)
V nh vy ta thy (9) ging (6) v (10) ging (7).
tnh cc hng s trong phng trnh Frendlich, ngi ta cng dng phng php
th. Phng trnh Frendlich c th vit di dng:
lg A = lg + lgC

Hnh 3.
ng hp ph axit propionic trn than hot tnh

Hnh 4.
 50

th tm cc hng s trong phng trnh

Frendlich

Nh vy lgA t l bc nht vi lgC. ng biu din trong h ta lgA lgC s ct trc

tung ti N.
Ta c: ON = lg
tg =
T hai phng trnh ny s xc nh c cc hng s v .
Tin hnh th nghim
Phng th nghim c sn dung dch CH3COOH vi nng gn ng 1N, hy pha
c 100 ml cc dung dch c nng gn ng sau y:
0,025N; 0,05N; 0,1N,; 0,2N; 0,4N; 0,5N.
Dng dung dch xt chun (nng 0,05N) chun li cc dung dch trn vi ch th
phenolphtalein v ghi ly cc nng chnh xc.
Ly mi dung dch 50 ml cho vo mt bnh nn c 250 ml ri cn 6 mu than hot tnh,
mi mu 1 gam (cn chnh xc), cho vo bnh nn . Lc 5 pht, yn 25 pht. Lc ri
chun li bng dung dch xt chun dng trn hai ln.
Ch : Khi chun (c hai ln) nn ly dung dch 1; 2: 20ml, dung dch 3: 10ml, dung dch
4: 5 ml, dung dch 5; 6: 2 ml; thm nc ct cho 20 ml (t dung dch 3 tr i) ri mi
chun. Kt qu bng trung bnh cng hai ln chun (sai s phi < 3%).

Tnh ton:
1) Hy tnh s mili ng lng axit b than hot tnh hp ph. Cng thc tnh: x =
50
(Co C) .1000 (mN), trong Co v C l nng axit trc v sau khi hp ph (N).
1000
2) Tnh xem mi gam than hot tnh hp ph bao nhiu mili ng lng axit ?
x
A (hay ) =
m
y A (hay ) l hp ph (mN/g);
m l lng cht hp ph.
3) Ly lgC, lgA, C/.
4) Lp bng s liu theo bng mu nh sau:

A hay C
S TT Nng ban u Co (N) Nng sau C (N) x(mN) lgC lgA
=x/m

Hy v th nh hnh 2 v hnh 4 tm cc hng s trong phng trnh Frendlich v

Lngmua.
 51

Khi bit cc hng s hy lp cc phng trnh:

A = C
bC
= max
1 + bC
V ly mt s nng C tun t tng dn (t 0,05 0,5N), tnh gi tr A v tng ng.
Vit kt qu di dng bng s ri v cc ng hp ph ng nhit cho cc trng hp: 1 -
ng thc nghim; 2 - phng trnh Frendlich v 3 - Lngmua. C nhn xt g v dng ca
cc ng ng nhit hp ph ?
 52

Bi s 11

DN IN CA DUNG DCH CHT IN LI

Mc ch
Xc nh dn in ring, t xc nh dn in ng lng gii hn ca cht
in li mnh, in li v hng s in li ca cht in li yu.

L thuyt
I. dn in ring v dn in ng lng
Kh nng dn in ca mi vt dn c c trng bi dn in L, l i lng
nghch o ca in tr R. Vi mt vt dn c tit din khng i:
l
R= (1)
S
trong l in tr sut; l v S l di v tit din ngang ca vt dn, nn:
1 S S
L= = . (2)
l l
1
i lng = c gi l dn in ring, c th nguyn 1.cm1. Khi l = 1 cm,

2
S = 1 cm th L = , nh vy:
dn in ring ca dung dch in li l dn in ca mt th tch dung dch cht
in li nm gia hai in cc song song c tit din l 1 cm2 v cch nhau 1 cm.
V kh nng dn in ca dung dch in li ph thuc vo bn cht cc ion v s ion c
mt trong mt n v th tch dung dch, nn dn in ring phi ph thuc vo nng
cht in li c trong dung dch (hnh 1).
i vi cht in li mnh, dn in ring cng ln nu nng ca cc ion v tc
tuyt i ca chng cng ln nhng khi tng nng ca cc ion th lc ht gia chng tng
ln, nh hng c th tr nn mnh hn s tng nng ca cht in li v dn in
ring ca dung dch s gim.
i vi cht in li yu, dn in ring tng khng ln khi tng nng . Khi nng
tng ln th dn in ring gim do s gim in li ca dung dch v cc i ca
dn in ring ng vi gi tr cc i ca tch s in li v nng ca dung dch.
thun tin cho vic so snh kh nng dn in ca dung dch cc cht in li khc
nhau ngi ta s dng i lng dn in ng lng .
 53

Hnh 1
S ph thuc ca dn in ring ca mt s dung dch
cht in li vo nng dung dch

dn in ng lng l dn in ca mt th tch dung dch cha ng mt

ng lng gam cht in li nm gia hai in cc song song cch nhau 1 cm. Da vo s
(hnh 2) ta d thy quan h gia dn in ring v dn in ng lng:
1000
= .V.1000 = (3)
C
y: V l th tch ca dung dch tnh bng lt, cha ng mt ng lng gam cht
in li, c gi l pha long.
C l nng ca dung dch (lg/l).
Cng thc (3) cho thy ph thuc vo nng dung dch. Khi pha long dung dch s
tng; khi pha long tng n mt gi tr gii hn no th dn in ng lng t
n gi tr gii hn (hnh 3)

Hnh 2
M hnh m t s lin h gia dn in ring v dn in ng lng
 54

Hnh 3
S ph thuc ca dn in ng lng vo pha long

Theo nh lut Cnrao (Kohlrausch) v s chuyn ng c lp ca cc ion trong dung

dch long:
= + + (4)

y + v l dn in (hay linh ) ca cation v anion.

i vi dung dch cht in li yu, in li v dn in ng lng lin
h vi nhau bng phng trnh:

= (5)

Theo (5) c th xc nh c hng s in li K ca mt cht in li yu da vo dn

in. V d, trong trng hp n gin nht, vi cht in li AB phn li theo s :
AB A+ + B
[A + ] [B ]
K = (6)
[AB]

V [AB] = C(1 ); [A+] = [B] = C nn:

C 2
K = (7)
1
Thay theo phng trnh (5) vo (7) rt ra:
2C
K = (8)
( )

Phng trnh (8) c th vit di dng:

2C
1 = 2 (9)
K

hay, sau khi chia tt c cho , thu c:

 55

1 1 1
= + 2 C (10)
K

1 1
y v 2 l nhng hng s.
K

Nu xy dng th s ph thuc ca 1/ vo C th s thu c mt ng thng v

da vo th xc nh c 1/ v 1/ 2 K ngha l xc nh c dn in ng
lng gii hn v hng s in li K ca cht in li yu.
i vi dung dch long ca cht in li mnh (C < 102 lg/l) dn in ng
lng ph thuc vo nng theo phng trnh:
= A C (11)
trong A l hng s ph thuc vo bn cht ca dung mi, nhit v ho tr ca cht
in li.
Nu xc nh dn in ca dung dch cc nng khc nhau, sau xy dng th
s ph thuc ca vo C s thu c mt ng thng v da vo th s xc nh c
dn in ng lng gii hn ca cht in li mnh.
II. Phng php o dn in
Vic o dn in ca dung dch in li thc t quy v vic o in tr ca chng bng
dng in mt chiu hay xoay chiu. Khi dng dng mt chiu, trn b mt in cc tip xc
vi dung dch c th xy ra phn ng in ho to nn mt in tr gi l in tr phn cc,
lm thay i in tr ca dung dch cn xc nh. trnh in tr phn cc ngi ta dng
cc in cc khng phn cc nh calomen, clorua bc nhng tt hn ht l dng dng xoay
chiu c tn s cao (khong 600 1000 Hertz).
o in tr ngi ta dng cu o Weston (Wheatstone), s ca n ch ra trn hnh
4, trong R1, R2, R3 l in tr bit, Rx l in tr cn xc nh. Theo nh lut Kicxp
(Kirchhoff) v mch r, khi kim in k (2) ch s 0 ngha l khi khng c dng in i qua
mch CD ta c:
R1
Rx = R3. (12)
R2

Hnh 4
S cu o Weston; 1. Ngun in xoay chiu thnh ph;
2. in k.
 56

Hnh 5
S cu o in tr dung dch
1. Ngun in; 2. B phn tng tn s;
3. in tr mu; 4. Con chy;
5. ng nghe; 6. Bnh ng dung dch cn o in tr.
AB - Dy in tr u.

Trong thc t in tr R1, R2 thng c thay bng mt cu dy AB trn c con chy

C (hnh 5), cn in k ch khng (2) c thay th bng ng nghe (5).
Dch chuyn con chy C trn dy AB tm v tr ti ng nghe (5) c m thanh cc tiu.
Khi ta c cn bng cu o v xc nh c in tr ca dung dch Rx:
BC
Rx = R3. (13)
AC
Cu trc bnh ng dung dch cn o dn in c mt ngha quan trng. in tr ca
dung dch khng nhng ph thuc vo nng cht in li, din tch ca in cc v khong
cch gia chng m cn ph thuc vo cch sp t cc in cc v th tch ca dung dch, v
khng phi ch c phn th tch ca dung dch nm gia hai in cc l tham gia vo vic dn
in (hnh 6). V vy hnh dng v cch sp xp in cc trong mi php o phi c gi
nguyn, th tch ca dung dch o cng phi c nh.
Php o dn in thng thc hin trong cc bnh o c cc in cc l nhng l
platin en c gn c nh bng nhng thanh thu tinh vo np bnh o (hnh 7).
Nu khong cch gia hai in cc l l, din tch b mt in cc l S v f l yu t ph
thuc vo c trng hnh hc ca bnh o th in tr ca dung dch c tnh theo cng thc:
1 l
R = f (14)
S
1 l
Suy ra = f (15)
R S
 57

Hnh 6 Hnh 7
Phn b ng sc trong in in cc platin xc nh hng s bnh
trng gia hai in cc song
song

V cc i lng f, l, S l c nh, c trng cho mi bnh o, nn phng trnh (15) c

th vit:
K
= (16)
R
y K l hng s bnh, c th nguyn cm1.
o dn in cn phi xc nh hng s bnh K. Ngi ta xc nh K bng cch o
in tr ca mt dung dch chun bit dn in ring, v d dung dch KCl 0,02N c
=0,0027651.cm1 25oC. o RKCl s xc nh c K theo phng trnh:
K = 0,002765.RKCl (17)
Bit K da vo phng trnh (16) c th xc nh dn in ca dung dch bt k khi o
c in tr ca chng.

Tin hnh th nghim

1. Xc nh hng s bnh K
Hng s bnh K xc nh da vo vic o in tr ca dung dch chun KCl cc nng
khc nhau (0,1; 0,02 v 0,01N).
u tin ra bnh o v in cc 2 3 ln bng nc ct, sau trng 1 2 ln bng mt
t dung dch KCl 0,1N. Dng pipet ly mt lng nht nh dung dch KCl 0,1N (khong 40
50 ml) vo bnh o, sao cho dung dch ngp ht cc in cc. o in tr ca dung dch bng
cu o (hnh 5).
Sau ly 10 ml dung dch KCl 0,1N pha long thnh 50 ml bng nc ct, ta c dung
dch KCl 0,02N.
dung dch nghin cu ra khi bnh, ra bnh o v in cc nh trn. Ly mt th tch
dung dch KCl 0,02N nh th tch dung dch o ln trc vo bnh v o in tr ca dung
dch.
 58

Li pha long gp i dung dch KCl 0,02N thu c dung dch KCl 0,01N v lp li
qu trnh nh trn. Tnh hng s bnh K theo cng thc (17) i vi tng dung dch ri ly kt
qu trung bnh. Cho bit 25oC, vi dung dch KCl 0,1N v 0,01N gi tr ln lt bng
0,01228 v 0,001413 1.cm1.
Khi tnh dn in ring ca cc dung dch in li long cn phi tnh n dn in
ca nc. Vi nc ct ngoi khng kh do c s ho tan ca CO2 v s kim ho ca thu
tinh nn dn in ca n vo khong 106 1.cm1. dn in thc t ca dung dch s
l:
= o c nc
2. Xc nh dn in ng lng gii hn ca dung dch HCl
Pha dung dch HCl 0,1N trong bnh nh mc 50 ml. Tin hnh o in tr ca dung dch
ny. o ba ln ly kt qu trung bnh. Sau pha long dung dch bng nc ct thu
c 100 ml cc dung dch HCl 0,02; 0,01; 0,005; 0,001N. o in tr ca cc dung dch
ny. Mi th nghim o ba ln v sau mi th nghim phi ra bnh o bng nc ct v trng
bng dung dch ta mun o tip.
Tnh dn in ring v dn in ng lng ca cc dung dch. Xy dng th
C ri ngoi suy ng biu din v C 0 tm gi tr .
Ghi cc kt qu o c v tnh ton theo bng mu sau:
in tr dn in
S Nng dung Hng s bnh dn in
o c ng lng
TT dch HCl C (lg/l) K ring C
Rx

3. Xc nh hng s phn li ca axit CH3COOH

Pha 100 ml dung dch CH3COOH c cc nng 0,1; 0,05; 0,01; 0,005 v 0,001N (pha
t dung dch ban u CH3COOH 0,1N bng nc ct). o in tr ca cc dung dch trn,
mi dung dch o ba ln ly kt qu trung bnh.
Tnh dn in ring v dn in ng lng ca cc dung dch. Tnh in li
theo cng thc (5). Cho bit dn in ng lng gii hn ca CH3COOH:
, CH3COOH = , H+ + , CH3COO = 349,8 + 40,9 = 390,7
Da vo cng thc (8) xc nh hng s phn li ca CH3COOH. Ghi cc kt qu o c
v tnh ton theo bng mu sau:
dn
S Nng Hng s in tr dn in in in Hng s phn
TT CH3COOH C (lg/l) bnh K oc Rx ring ng li li K
lng
 59

Bi s 12

SC IN NG CA PIN GANVANI

Mc ch
o sc in ng ca pin anienJacbi v pin Ganvani nng . Xc nh th in cc
ca ng, km v th in cc oxi ho kh.

L thuyt
1. Pin Ganvani
Mt h in ho c kh nng sinh cng in v c dng lm ngun in nng, gi l
pin Ganvani hay pin in.
Trong trng hp n gin nht pin Ganvani bao gm hai in cc kim loi nhng trong
cc dung dch in li, cc dung dch ny c tip xc vi nhau qua mng bn thm hoc qua
cu dn in.
V d pin anien Jacobi:
ZnZnSO4 CuSO4Cu
K hiu mt vch thng ng l ranh gii tip xc gia in cc v dung dch, hai vch
thng ng l ranh gii tip xc gia hai dung dch. Mch ngoi ca pin c khp kn bng
dy dn kim loi.
ch tip xc ca cc pha, cc phn t tch in (ion, electron) s chuyn t pha ny
sang pha khc v trn ranh gii phn chia ca chng hnh thnh lp in kp gm hai lp in
tch bng nhau nhng tri du. S hnh thnh lp in kp lm xut hin cc bc nhy th
gia cc pha tip xc, kt qu l gia cc in cc xut hin mt hiu in th v trn dy dn
ni cc in cc s c dng in.
Cng in ca pin Ganvani do nng lng ca cc phn ng ho hc tin hnh trong pin
chuyn thnh. V d vi pin anien Jacobi, khi pin hot ng, trn in cc km xy ra qu
trnh ho tan km vo dung dch:
Zn Zn2+ + 2e
Cc electron theo mch ngoi chuyn t in cc km n in cc ng v trn in cc
ng xy ra qu trnh kt ta kim loi ng:
Cu 2+ + 2e Cu
Phn ng tng cng xy ra trong pin s l:
Cu 2+ + Zn Cu + Zn2+
 60

Nng lng ca phn ng ny (ho nng) s c chuyn thnh in nng. Khi cc phn
ng in ho xy ra trong pin l thun nghch th cng in thu c l ln nht. Hiu th cc
i o c gia cc in cc khi , c gi l sc in ng ca pin Ganvani, k hiu l E.
2. Sc in ng ca pin Ganvani
Sc in ng E bng tng i s cc bc nhy th xut hin trn ranh gii phn chia
gia cc pha tip xc, bao gm cc bc nhy th trn ranh gii in cc v dung dch (th
in cc ), trn ranh gii tip xc gia in cc v dy dn (th tip xc tx), trn ranh gii
gia hai dung dch c nng khc nhau hoc gia hai dung dch ca cc cht tan khc nhau
(th khuch tn kt).
a) Th in cc ca kim loi nhng trong dung dch mui ca n biu th bng
phng trnh Nernst:
RT
= o + lna Z + (1)
ZF Me

trong : o- th in cc tiu chun, ngha l th in cc ca kim loi khi hot

a Z+ =1; R - hng s kh; F s Faraday; Z - ho tr ca ion kim loi; T - nhit tuyt i.
Me

Trong cc dung dch rt long v trong nhng trng hp khng i hi tht chnh xc,
c th thay hot bng nng , khi phng trnh Nernst c dng:
RT
= o + lnC Z + (2)
ZF Me

Nu thay R = 8,314 J/K.mol; F = 96487 C v chuyn logarit t nhin sang logarit thp
phn, 25oC ta c:
0,059
= o + lnC Z + (3)
Z Me

Gi tr tuyt i ca th in cc tiu chun o cho n nay cha xc nh c bng thc

nghim hoc tnh ton bng l thuyt. Ngi ta xc nh n theo quan h vi in cc hiro c
th in cc tiu chun c chp nhn bng khng (khi a H = 1 , p H = 1atm ). Cc gi tr o
+
2

xc nh nh vy c tm trong cc sch tra cu.

b) Th tip xc tx xut hin do hnh thnh lp in kp trn ranh gii tip xc gia
hai kim loi. Th tip xc c gi tr rt nh, d dng gim khi s dng ch tip
xc nhng kim loi cng mt loi (in cc ng - dy dn ng v.v...).
c) Th khuch tn kt xut hin do tc chuyn ng khc nhau ca cc ion qua
ranh gii tip xc gia hai dung dch. Ngi ta thng lm gim th khuch tn
bng cch cho hai dung dch tip xc vi nhau qua mt cu mui, l mt cu ni
cha dung dch m c (thng l bo ho) ca cc cht in li c tc tuyt
i ca cation v anion gn bng nhau (KCl, NH4NO3, KNO3 v.v...). gi
dung dch mui trong cu ni ngi ta thng cho thm aga, v vy cu mui
cn c gi l cu aga. Do dung dch trong cu mui l m c nn s khuch
tn qua ranh gii tip xc ch yu l do cc ion trong cu mui. Tc khuch
tn ca cc ion ny gn bng nhau nn th khuch tn s trit tiu.
 61

Trong iu kin c th b qua th khuch tn v th tip xc, sc in ng ca pin s

bng hiu cc th in cc, ngha l:
E = + (4)
y l th in cc m, l in cc xy ra qu trnh oxi ho vi s gii phng
electron; + l th ca in cc dng, l in cc xy ra qu trnh kh vi s thu nhn
electron.
Vi pin anien Jacobi, p dng phng trnh (2) ta c:
RT a Cu RT a 2+
E = Cu Zn = oCu oZn + = Eo +
2+
ln ln Cu (5)
2F a Zn 2+
2F a Zn2+

y: Eo - sc in ng ca pin trong iu kin tiu chun, ngha l khi

a Cu2+ = a Zn2+ = 1

Eo = Cu Zn = + 0,34V ( 0,76V) = 1,1 v

o o

25oC, phng trnh (5) c dng:

0,059 a 2+
E = 1,1 + lg Cu (6)
2 a Zn2+
Trong trng hp tng qut, sc in ng ca pin
Me2 / Me2X / Me1X / Me1
c tnh theo phng trnh:

0,059 a Me
1/ Z 1

E= o
o
+ lg 1 / Z 1
(7)
Me 1 Me 2
Z a 2
Me 2
y: Z1 v Z2- ho tr ca cc kim loi Me1 v Me2
Z- s electron trao i.
3. Pin Ganvani ho hc v pin Ganvani nng
Cc pin Ganvani c phn bit thnh pin Ganvani ho hc v pin Ganvani nng .
Sc in ng ca pin Ganvani ho hc xut hin do cc phn ng ho hc xy ra trong
pin. V d v pin Ganvani ho hc l pin anien-Jacobi ( trnh by phn trn). Mt dng
khc ca pin Ganvani ho hc l pin oxi ho - kh. in cc oxi ho - kh gm mt kim loi
tr (Pt, Au, Ir...) nhng trong dung dch cha dng oxi ho v dng kh ca cng mt cht. V
d, in cc Pt/Fe3+, Fe2+ hoc Pt/Sn4+, Sn2+. Th ca chng c biu th bng cc phng
trnh:
RT a 3+
Fe3+ ,Fe2+ = oFe3+ ,Fe2+ + ln Fe (8)
F a Fe2+

RT a 4+
Sn4+ ,Sn2+ = oSn4+ ,Sn2+ + ln Sn (9)
F aSn2+
 62

Nu ghp hai in cc oxi ho - kh trn s thu c pin oxi ho - kh. Trong pin xy ra
phn ng:
2Fe3+ + Sn2+ 2Fe2+ + Sn4+
v sc in ng ca pin xc nh bng phng trnh:
RT a 3+ .a 2+
E = Fe3+ ,Fe2+ Sn4+ ,Sn2+ +
o
ln Fe Sn (10)
F a Fe2+ .a Sn4+

Pin Ganvani nng cu to t cc in cc ca cng mt kim loi c nhng trong

dung dch ca cng mt cht in li nhng c hot khc nhau, v d:
Me/MeA//MeA/Me
a1 a2
hoc t cc in cc c hot ca cht phn ng khc nhau nhng trong cng mt dung
dch, v d pin hn hng v pin kh:
Hg, Me/MeA/Me,Hg (V d: Hg, Cd/CdSO4/Cd, Hg)
a1 a2 a1 a2
+
(Pt) H2/H /H2(Pt)
P1 P2
Trong pin hn hng, hot ca kim loi trong in cc hn hng khc nhau, cn trong
pin kh, p sut ca kh trn cc in cc l khc nhau. Do hot ca cc cht phn ng
cc in cc khc nhau, cc in cc s c th cn bng khng ng nht, dn ti s xut hin
sc in ng ca pin. Cng in ca pin tng ng vi cng lm san bng hot ca cc
cht phn ng trong hai dung dch hoc trn hai in cc (nguyn t hn hng) cng nh
cng lm san bng p sut kh trn in cc (pin kh). Lin quan n iu sc in ng
ca pin Ganvani nng c th tnh theo phng trnh:
RT a
E = ln 1 (11)
ZF a2
RT P
E = ln 1 (12)
ZF P2
4. Phng php o sc in ng ca pin Ganvani
Khi pin Ganvani hot ng, sc in ng ca n s thay i do cc thay i xy ra cc
in cc v trong th tch dung dch. o chnh xc sc in ng ca pin Ganvani ngi ta
s dng phng php b chnh (hay cn gi l phng php i xung), phng php ny cho
php xc nh sc in ng thc ca pin khi khng c dng in i qua pin, ngha l khi cc
phn ng in cc xy ra trong pin l thun nghch.
S nguyn tc ca phng php b chnh o sc in ng ch ra trn hnh 1.
S gm ngun in mt chiu E ni vi hai u ca dy in tr u AB. Ngun in
thng dng l cqui c sc in ng ln hn sc in ng ca pin nghin cu X. Mt cc
ca X ni vi A (cc ny phi cng du vi cc ca cqui ni vi A) cn cc khc ni qua
mt in k ch khng c nhy cao (n 10 8 109 ampe) sau mc vo con chy C.
 63

Hnh 1
S mch in o sc in ng bng phng php i xung
E - ngun in 1 chiu (cqui); X - pin nghin cu;
W - pin tiu chun Weston; AB - dy in tr c tit din u;
P - o in; G - in k ch khng;
K, K/ - ngt in; C - con chy.

Dch chuyn con chy C dc theo dy AB s tm c v tr Cx m ti khng c dng

in qua in k, kim in k ch s khng. Khi gim th ca cqui trn on ACx s
bng sc in ng Ex ca pin nghin cu.
Nu dy in tr AB hon ton ng nht th gim th ca cqui trn mt n v chiu
di ca dy s l Ecqui/AB t suy ra:
ACX
Ex = Ecqui (13)
AB
V ngun in cqui thng hay b st th nn phi chun th Ecqui bng pin tiu chun
Weston c sc in ng Ew khng thay i. Mun th gt o in P sang v tr 1 pin tiu
chun xung i vi cqui. Dch chuyn con chy C n v tr CX/ khng c dng in i
qua in k, khi ta c:
AC X/
Ew = Ecqui (14)
AB
Thay gi tr Eacqui t (14) vo phng trnh (13) thu c:
AC x
Ex = Ew (15)
AC X/
Pin tiu chun Weston c cu to nh sau: (hnh 2)
() (Pt)HgCd, CdSO4.8/3H2O, ddCdSO4 Hg2SO4.Hg(Pt) (+)
Phn ng xy ra trong pin:
Cd + Hg2SO4 + 8/3H2O CdSO4.8/3H2O + 2Hg

(Cd + Hg 22 +
Cd2+ + 2Hg)
 64

2
4
3 1

Pt

Hnh 2
Pin chun Weston
1. Hn hng caimi - thu ngn; (12,5% Cd)
2. CdSO4.8/3H2O rn; 3. Thu ngn;
4. Hg2SO4; 5. Dung dch CdSO4 bo ho

Sc in ng ca pin Weston n nh, rt t thay i theo nhit v vy ngi ta dng

n lm pin tiu chun. 20oC sc in ng ca pin Weston bng 1,0183 V v ph thuc
nhit theo phng trnh sau:
E = 1,0183 4,06.105 (t 20oC)
Nu cho Ew = 1,018, phng trnh (15) c th vit:
AC x
Ew = 1,018 (16)
AC /x
Nh vy, ch cn xc nh cc on A CX/ v ACx - trn cc on gim th cqui
tng ng bng sc in ng ca pin tiu chun v ca pin nghin cu - ta c th xc nh
c sc in ng ca pin nghin cu.
Khi o sc in ng cn ch mt s quy tc sau y
1. sc in ng ca cc ngun in n nh, mi ln dch chuyn con chy C
ch n ngt in K trong mt thi gian ngn. Khi khng o, phi ngt in ca
ngun in Ecqui v ca pin Ex bng hai ngt in K v K (c th thay bng mt
ngt in kp).
2. Khng bao gi o sc in ng ca pin nghin cu ngay sau khi thit lp n, v
gi tr sc in ng ch n nh sau mt thi gian (khong 3 5 pht).
3. Pin tiu chun khng c nm nghing hay ln ngc. Tuyt i khng
on mch, ch dng pin khi cn thit (nu dng lun sc in ng s gim v
khng dng lm pin tiu chun na).
4. Trng hp sc in ng ca pin X qu nh, con chy C phi dch chuyn n
mi cui u dy AB v sai s ca php o s ln. nhn c s b chnh
khng phi hai u m khong gia ca dy AB cn phi mc ni tip thm
 65

vo mch ca pin X mt pin tiu chun v o sc in ng chung Ech, sau tnh

sc in ng ca pin X.
Ex = Ech Ew (17)

Tin hnh th nghim

1. o sc in ng ca pin anien Jacobi
Thit lp pin anien-Jacobi theo s sau:
() Zn // ZnSO4 0,1N/KCl bo ho/CuSO4 0,1N/Cu(+).
in cc km (mt l km tinh khit c 1 cm 10 cm) trc khi dng phi hn hng ho
bng cch nhng in cc vi giy vo dung dch HgNO3. Lau in cc bng giy lc. Nhng
in cc vo cc ng dung dch ZnSO4 0,1N. in cc ng (mt l ng tinh khit c 1 cm
10 cm) trc khi dng phi ly giy rp nh bng v ra sch. Mun tt hn phi m mt
lp ng trn mt in cc. Nhng in cc ng vo dung dch CuSO4 0,1N. Ni hai bn pin
bng cu aga cha KCl bo ho (hnh 3). Sau o sc in ng ca pin bng phng php
b chnh theo s hnh 1.

Zn Cu

dd KCl bo ho

dd ZnSO 4 dd CuSO4
Hnh 3
Pin anien-Jacobi

u tin gt o in P sang v tr 1 mc xung i cqui vi pin chun, tm v tr CX/ .

Xc nh 3 ln ly gi tr trung bnh.
Sau gt o in P sang v tr 2 mc xung i cqui vi pin anien-Jacobi, tm v
tr Cx. Xc nh 3 ln ly gi tr trung bnh.
Cc kt qu thu c v kt qu tnh ton ghi theo bng mu sau:
/ ACx, cm Sc in ng, V Sai s, V
A CX , cm
Eo Elt Eo-Elt

2. Xc nh th in cc ng v km
Mun o th ca in cc ta phi ghp n vi mt in cc chun, v d in cc
calomen c th in cc bit to thnh mt pin in. o sc in ng ca pin ny v sau
tnh ra th ca in cc.
 66

in cc calomen bo ho c s Hg/Hg2Cl2/KCl bo ho.

Trn in cc calomen xy ra phn ng:
2Hg + 2Cl Hg2Cl2 + 2e
Hg Hg+ + e
Th ca in cc bng:
RT
= o + ln a Hg + (18)
F
Trong dung dch calomen bo ho c mt ion Cl. V a Hg+ .a Cl = L (tch s tan) nn

a Hg+ = L t ta c:
aCl

= oHg + / Hg RT ln a Cl
(19)
F
Th ca in cc calomen tnh theo in cc hiro tiu chun, ph thuc vo nng ca
KCl c gi tr sau y:
Hg/Hg2Cl2/KCl 0,1N = 0,3338 0,00007 (t 25o)
Hg/Hg2Cl2/KCl 1N = 0,2800 0,00024 (t 25o)
Hg/Hg2Cl2/KCl bo ho = 0,2438 0,00065 (t 25o)
t = 25oC th ca in cc calomen bo ho bng 0,2438V.
xc nh th in cc ca ng ta thit lp pin in:
() Hg/Hg2Cl2/KCl (b.h)//CuSO4 0,1N/Cu(+)
theo hnh v (hnh 4).

dd KCl Cu

dd KCl bo ho
Bt Hg 2Cl 2
Hg
Pt dd CuSO4
Hnh 4
Pin Ganvani

() Hg/Hg2Cl2/KCl (bh)//CuSO4 0,1N/Cu (+)

Trong pin ny in cc ng mang du dng. Vy sc in ng ca pin:
E = Cu Cal Cu = Cal + E
Tng t, mun xc nh th in cc Zn ta thit lp pin in:
 67

() Zn/ZnSO4 0,1N/KCl (b.h)//Hg2Cl2/Hg(+)

Trong pin ny, in cc Zn mang du m v sc in ng ca pin:
E = Cal Zn Zn = Cal E
Cc kt qu thc nghim ghi theo bng mu sau:
Pin Th in cc
ACX/ , cm ACX, cm Sc in ng, E Sai s o-lt
o lt

3. o sc in ng ca pin Ganvani nng

() Cu/CuSO4 0,001N//CuSO4 0,1N/Cu(+)
T dung dch CuSO4 0,1N pha dung dch CuSO4 0,001N v thit lp pin nng theo s
trn. o sc in ng ca pin, tin hnh o 2 - 3 ln ly kt qu trung bnh. So snh
kt qu E o c vi E l thuyt theo phng trnh (11). Cch o E v cch ghi kt qu thu
c tng t nh lm i vi pin anien-Jacobi.
4. o th in cc oxi ho kh ca h kali ferocyanua- kali fericyanua
Pha dung dch K3Fe(CN)6 0,1M v K4Fe(CN)6 0,1M. Sau trn hai dung dch theo t l
fericyanua bng 10 ln ferocyanua (tng s th tch ca chng l 20 ml), cho hn hp ny vo
cc v cm in cc Pt vo ta c in cc oxi ho - kh. Ghp in cc ny vi in cc
calomen thnh mt pin:
()Hg/Hg2Cl2, KCl(b.h)//Fe3+, Fe2+/Pt(+)
o sc in ng ca pin ny nh o trn v tnh gi tr th in cc oxi ho-kh:
Fe3+ , Fe2+ = E Cal
 68

Bi s 13

S VN TI

Mc ch
Xc nh s vn ti ca cc ion trong dung dch.

L thuyt
Trong dung dch, s chuyn in c thc hin bi cc ion, ng thi mi dng ion
chuyn mt lng in xc nh ph thuc vo nng ca n trong dung dch, vo ho tr v
tc chuyn ng ca ion trong in trng.
Lng in chung chuyn qua dung dch bng tng lng in chuyn bi cc ion:
l = l1 + l2 + ... + ln = li (1)
T s gia lng in do ion i chuyn vi lng in chung i qua dung dch c gi l
s vn ti ca ion i, k hiu l ti:
li
ti = (2)
l i
i vi dung dch cht in li AB phn li theo s :
AB A+ + B
s vn ti ca cation (A+) v anion (B) s l:
lk lA
tk = v tA = (3)
lk + lA lk + lA
tt nhin l: tk + tA = l
V lng in c chuyn bi cc ion t l vi tc chuyn ng ca chng nn s vn
ti c th biu th qua tc tuyt i ca cc ion:
UK UA
tK = ; tA = (4)
UK + UA UK + UA
Mt khc, v dn in ng lng ca ion lin h vi tc ca ion theo phng
trnh i = Ui F (F- s Faraday) nn cng c th biu th s vn ti qua dn in ng
lng:
k A
tK = ; tA = (5)
k + A k + A
 69

(v khi nim dn in ng lng xin xem bi s 11).

S vn ti c xc nh bng thc nghim da vo vic xc nh lng in chuyn qua
dung dch v s thay i nng ca cht in li gn cc in cc.
Gi s xt qu trnh in phn dung dch cht in li AB trn v tng tng bnh in
phn c chia thnh 3 khu vc: khu vc ant, khu vc catt v khu vc gia (hnh 1). Gi
thit khu vc gia nng cht in li khng thay i trong qu trnh in phn.
+
Khu ant Khu gia Khu catt

A+ B
t k lF t A lF

Hnh 1
S vn chuyn ca cc ion
Khi cho mt lng in lF Faraday i qua dung dch, theo nh lut Faraday, trn mi
in cc s tch ra lF ng lng gam cht do s phng in ca cc ion, ng thi s c tk
lF ng lng gam ca cation A+ t khu ant chuyn sang khu catt v tA lF ng lng
gam anion B t khu catt chuyn sang khu ant. Chng ta xt s thay i nng ca cht
in li AB (biu th bng s ng lng gam) trong khu vc ant v catt:
Trong khu ant (cc dng)
S .l.g. anion B chuyn t khu catt sang ... tA lF
S .l.g. cation A+ ri khi khu ant ... tK lF
S .l.g. anion B d ra s phng in trn ant ... tA lF + tK lF = lF
Nh vy, khu ant gim i tK lF ng lng gam cation A+ v lF tA lF = (1 tA). lF =
tK lF ng lng gam anion B, c ngha l nng ca cht in li AB gim i mt lng
CA = tk lF, suy ra:
C A
tK = (6)
lF
Trong khu catt (cc m)
S .l.g. cation A+ chuyn t khu ant sang ... tK lF
S .l.g. anion B ri khi khu catt ... tA lF
S .l.g. cation A+ d ra s phng in trn catt ... tK lF + tA lF = lF
Nh vy khu catt gim i tA lF ng lng gam anion B v lF tK lF = (1 tK). lF =
tA lF ng lng gam cation A+, c ngha l nng ca cht in li AB gim i mt lng
CK = tA lF, suy ra:
 70

C k
tA = (7)
lF
Theo (6) v (7), nu xc nh c CA hoc CK v lng in chuyn qua dung dch
c th xc nh c s vn ti ca cc ion trong dung dch.

Tin hnh th nghim

Mc ch ca th nghim l xc nh s vn ti ca ion H3O+ v SO 24 trong dung dch

H2SO4.
Khi in phn dung dch H2SO4 trn cc in cc tr xy ra cc qu trnh sau y:
Trn catt: 2H3O+ + 2e H2 + 2H2O
Trn ant: 3H2O 2e 1/2O2 + 2H3O+
S chuyn in trong dung dch c thc hin bi cc ion H3O+ v SO 24 . S vn ti ca
chng c xc nh theo cc phng trnh (6) v (7).
C K
t SO 2 =
4
lF

C A
tH + = = 1 t SO 2 (8)
3O
lF 4

gim nng ca H2SO4 khu catt c xc nh bng cch chun , cn lng

in chuyn qua dung dch c xc nh nh culng k ng.
1. Dng c xc nh s vn ti
S dng c xc nh s vn ti c ch ra trn hnh 2. Bnh in phn gm hai cc
1 v 2 cha dung dch in li, c ni vi nhau bng ng xiphng 5 cha y dung dch. Khi
m kho xiphng cho dung dch chy vo hai cc, hai khu vc catt v ant c tch ring
ra, nh c th xc nh ring r s thay i nng dung dch mi khu vc in cc.

Hnh 2
S thit b o s vn ti
A - Ngun in mt chiu; B - Miliampe k; C - Culng k ng;
D - Bnh in phn; 1, 2 - Cc ng dung dch H2SO4 0,02N;
3- Ant ch; 4- Catt ch; 5- ng xiphng; R- Bin tr; K- Ngt in
 71

2. Chun b culng k ng
Culng k ng (hnh 3) gm 3 thanh ng: thanh gia l catt, hai thanh kia l ant,
nhng trong dung dch CuSO4.
Trn ranh gii in cc-dung dch xy ra cc qu trnh sau y:
Cu2+ + 2e Cu (trn catt)
Cu 2e Cu2+ (trn ant)

Hnh 3
Culng k ng

Khi c mt in lng 1 Faraday i qua dung dch th trn catt ng s gii phng 1
ng lng gam ng hay 63,54/2 = 31,77g ng (63,54 l nguyn t gam v 2 l ho tr
ca ng). Nh vy, khi c in lng F Faraday i qua, khi lng ng c gii phng
trn catt s l go = 31,77.F. Nu xc nh c go s xc nh c in lng i qua dung
dch:
go
F = (9)
3 1 ,7 7
31,77 c gi l ng lng ho hc ca ng.
Ngun sai s chnh ca culng k ng l s ho tan mt phn in cc ng trong dung
dch axit (c bit khi c mt oxi ca khng kh), s to thnh oxit ng (I) do phn ng: Cu2+
+ e Cu+ xy ra trn catt trong dung dch trung tnh khi mt dng nh, cng nh s hnh
thnh lp kt ta ng xp d b bong ra khi mt dng cao.V vy, tng chnh xc
ca culng k ng ngi ta s dng dung dch c thnh phn sau:
15 g CuSO4 (hay 23,4 g CuSO4.5H2O)
100 ml nc ct
5 ml ru etylic
5 ml H2SO4 c
v tin hnh s in phn mt dng trn catt trong khong t 2 20 mA/cm2.
Trc khi mc culng k ng vo mch theo s hnh 2 cn phi m catt ng (ph
mt lp ng mi ln trn catt). Cch tin hnh nh sau: nh sch in cc ng bng giy
rp, ra bng nc ct ri trng bng axeton. Lp in cc ng va ra sch vo bnh in
phn (C) ri mc culng k vo mch in theo s hnh 2. iu chnh bin tr R sao cho
 72

mt dng catt trong khong 2 20 mA/cm2. S in phn thng tin hnh vi hiu th
4 6 V trong khong thi gian 30 pht.
Ly catt ng va c m ra ra bng nc ct, trng bng ru etylic, thm nh tay
bng giy lc cho kh nc. Sy kh nhit 40 50oC trong khong 15 pht (nu lm kh
nhit cao hn lp ng mi m s d b oxi ho). ngui ri em cn bng cn phn
tch, ghi khi lng g1.
3. in phn dung dch H2SO4 0,02N
Ra sch hai cc ng dung dch. Ly cc nh t catt vo (cc catt) trng axeton, lau
bng giy lc ri em lm kh. Cn cc catt chnh xc n 0,01 g ghi khi lng g1/ .
H2SO4 0,02N vo 2 cc. t ng xiphng ni hai cc. M kho 5 ca ng xiphng ht
H2SO4 ln y ng xiphng ri ng kho li.
Dng giy rp nh sch 2 in cc ch, ra sch bng nc ct, nhng in cc vo
dung dch ri mc bnh in phn v culng k ng vo mch theo s hnh 2. Sau khi cn
b hng dn kim tra s mc in mi c ng kn mch. iu chnh bin tr R
dng in qua miliampe k l 50 mA. Trong sut thi gian in phn, phi gi cho dng in
khng thay i. in phn tin hnh trong 90 pht.
Trong thi gian in phn, tin hnh xc nh nng ban u ca H2SO4: Dng pipet
ly 10 ml dung dch H2SO4 v chun bng dung dch NaOH 0,02N vi ch th metyl da cam.
Chun
23 ln ly gi tr trung bnh (V1).
Trc khi kt thc th nghim, ngt mch, m kho xiphng cho dung dch axit chy vo
2 cc. Ly catt ra, cn cc catt cha axit, ghi khi lng g 2/ . Khi lng ca axit trong cc
catt s l gK = g 2/ g1/ . i vi dung dch H2SO4 0,02N t trng ca axit bng 1 nn gK s
chnh bng th tch VK ca axit.
Dng pipet ly 10 ml dung dch axit cc catt, chun bng dung dch NaOH 0,02N.
Chun 23 ln, ly gi tr trung bnh (V2). Mt khc, ly catt ng culng k ng em ra
sch thm kh, sy nhit 40 50oC, ngui ri em cn phn tch, ghi khi lng g2.
Ghi y s liu th nghim theo bng sau:
Khi lng culng k ng trc khi in phn, (g1)
Khi lng culng k ng sau khi in phn, (g2)
Khi lng cc khi cha c dung dch axit), (m1)
Khi lng cc khi c dung dch axit), (m2)
Nng NaOH
Th tch dung dch NaOH dng chun 10 ml H2SO4 trc khi in phn (V1)
Th tch dung dch NaOH dng chun 10 ml H2SO4 sau khi in phn (V2)

Khi lng ca lp ng s l go = g2 g1. Bit g0 s xc nh c lF theo (9). gim

nng ca H2SO4 khu catt c xc nh theo cng thc:
V K ( V1 V 2 )
CK = . N.103 .l.g/l (10)
10
 73

y: VK- th tch H2SO4 trong cc catt, ml;

V1 v V2 l th tch dung dch NaOH 0,02N chun 10 ml dung dch H2SO4 trc
v sau khi in phn, ml;
N l nng ng lng ca NaOH.
Bit lF v CK s xc nh c s vn ti ca ion SO 24 v ca ion H+ theo (8).
 74

Bi s 14

IU CH CC H KEO V KHO ST MT
S TNH CHT CA CHNG

Mc ch
iu ch mt s h keo bng phng php phn tn, phng php ngng t v kho st
tnh cht ca chng. Xc nh ngng keo t ca h keo.

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 (107 105 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. Nhng h cha cc ht nh th c tn l SON.
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, son 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.
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 CPT vo mi trng thch hp, cht ny s t ho tan vo mi
 75

trng . Song nu mi trng l mt dung mi ti i vi cht CPT th ngi ta vn c th

ch to dung dch keo ca cht CPT 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:
AgNO3 + KI AgI + KNO3
vi gi thit KI ly d lm cht lm bn, c s v cng thc c ch ra hnh 1.
{mAgI nI -
 (n-x)K +} xK +
 ion

nhn ion nghch
Q..T.H
   

nhn mixen  lp kh.tn
lp hp ph


granun (ht ion

mixen

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.

= K6
Z
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.
 76

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 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...

Tin hnh th nghim

Ch to Son S v Son clphan (nha thng rn) bng phng php th dung
mi
a) Ch to mt dung dch bo ho lu hunh trong ru etylic bng cch lc mnh cho
S ho tan n bo ho ri lng phn S cn tha. Ly 5 ml dung dch ny nh
chm (va nh va khuy) vo 20 ml nc ct. S khng tan trong nc, nn khi
phn tn vo nc, cc phn t lu hunh s ngng t li thnh nhng ht c kch
thc c ht keo. Cht lm bn l mt sn phm oxi ho ru v nhng tp cht vi
lng c sn trong lu hunh. Ht keo lu hunh tch in m v rt d keo t bng
cc cht in li (dng dung dch mt cht in li no , th xem!).
b) Ch to mt dung dch 2% clphan trong ru. Nh t t 2 ml dung dch ny (va
nh va khuy mnh) vo 20 ml nc ct, ta s c Son clphan trong nc. Ht
keo clphan tch in m.
Phng php ch tao Son S v Son clphan nh trn gi l phng php thay th dung
mi, trong nc thay th cho ru lm dung mi cho Son hnh thnh. Phng php thay
th dung mi thuc loi phng php ngng t.
Ch to Son AgI bng phn ng trao i
Son AgI trong nc c ch to bng phn ng sau:
AgNO3 + KI AgI + KNO3
 77

Cht n nh c th l AgNO3 hoc KI. Khi dng d AgNO3, ht keo s tch in dng
do vic hp ph cc ion Ag+ lm ion quyt nh th hiu v khi dng d KI, ht keo s tch
in m do vic hp ph cc ion I lm ion quyt nh th hiu.
Ly vo bnh tam gic (c dung tch 50 100 ml) 20 ml dung dch AgNO3
0,01N. Nh t t vo bnh (va nh va lc) 2 ml dung dch KI 0,01N.
Ly vo bnh tam gic (c trn) 20 ml dung dch KI 0,01N. Nh t t vo 2
ml dung dch AgNO3 0,01N, va nh va lc.
Li ly vo hai bnh, mt bnh ng 20 ml dung dch AgNO3 0,01N, mt bnh
ng 20 ml dung dch KI 0,01N. Trn t t vo nhau.
Nhn xt hin tng trong c ba trng hp? Dng que d in xc nh du ca cc
Son to thnh.
Que d in: Ly 2 tm Zn v Cu (kch thc c 1 cm 5 cm) t cch nhau t 5 10
mm. Ni hai tm vi nhau bng dy dn (hnh 2).
Khi mun d in tch ca ht keo th nhng hai tm vo dung dch keo. Khi ta s
c mt pin vi cc dng l Cu v cc m l Zn. Cc ht keo tch in s di chuyn v cc
cc. Sau khong 15 pht, rt ln quan st xem ht keo bm vo cc no. Xc nh du in
ca ht keo.

Cu Zn

Hnh 2
S que d in

Ch to keo Fe(OH)3 bng phn ng thu phn

Da vo phn ng:
to
FeCl3 + 3 H2O Fe(OH)3 + 3 HCl
un nng (n khong 90oC) 120 ml nc ct trong mt cc 250 ml, nh vo cc tng
git cho n ht 45 ml dung dch FeCl3 2%. un thm vi pht trn bp (khng un si mnh
trnh nc b bc hi nhiu lm nng h keo thay i), nhc ra, ta c son Fe(OH)3 c
mu nu m. H keo c hnh thnh c cng thc cu to nh sau:
{[mFe(OH)3]nFeO+ (n x)Cl}X+ xCl
H keo c quan st bng hp chiu sng thy hnh nn Tin-an. Hy d du in
ca ht keo. Hy thc hin s thm tch bng mng bn thm cellophan (giy bng knh) ngay
sau khi Son iu ch c cn nng (khi lm ngui phn ng din ra theo chiu nghch).
Ch to nh tng v s o pha nh tng
Dng lc c hc (khuy, lc) ch to nh tng du ho (k hiu D) trong nc (k
hiu N). Cht nh ho l natri oleat (tc x phng thng) C17H33COONa. Ly 10 ml dung
 78

dch x phng vo mt bnh nn c 100 ml. Cho vo 10 ml du ho. Lc na ting lin tc,
ta s c nh tng D/N (tc nh tng thun).
Nu thay cho oleat Na, dng oleat Ca th ta s c nh tng N/D (tc nh tng
nghch). Hy nh 20 ml dung dch CaCl2 0,2M vo nh tng thun mi ch to, nhm
chuyn oleat Na thnh oleat Ca tan trong du, lc trong na gi lin tc, nh tng thu c
s l nh tng N/D, cch lm trn gi l cch o pha nh tng. quan st xem nh
tng l thun hay nghch ta dng mt trong hai cch sau y:
a) Ly mt mt knh, nh ln mt git nh tng v mt git nc gn k nhau,
dng que tm gt cho hai git tip xc vi nhau. Ta c nhn xt g?
b) Nu c knh hin vi th ta dng mt cht mu ch tan trong mt cht lng (nc
hoc du). Sudan III tan trong D m khng tan trong N. Trc khi lc hy thm 5
git Sudan III (ho tan sn trong ru). Khi thnh nh tng, ly mt git soi
di knh hin vi s bit D b nhum l pha phn tn hay mi trng phn tn.
Xc nh ngng keo t ca son Fe(OH)3 bng Na2SO4 (hoc K2SO4)
Ly 12 ng nghim nh s ng t 1 n 12, cho vo mi ng 5 ml dung dch Son
Fe(OH)3. T dung dch Na2SO4 ban u c nng 0,01N pha thnh cc dung dch long dn
theo th t sau:
1 2 1
 79

1
1
Ly 1 ml ca mi dung dch va pha cho vo tng ng nghim ng Son Fe(OH)3 theo
th t t 1 n 11. ng th 12 thm 1 ml nc ct. Lc v yn 1 pht. Quan st. Dng ng
th 12 so snh mc c. ng no c hn ng s 12 l c s keo t. Ghi du + vo ng
no c v du vo ng no khng c, theo bng mu sau:
1
. . . . . . . . . . . . . . . . . . . . . . . . . . . (+) . . . . . . . . . . . . . . . . +

V d: Bt u t ng s 8 c s c. C ngha l ngng keo t c tnh t ng s 8 c

pha long 8/4. Lc nng dung dch Na2SO4 c tnh theo cng thc:
8.0,01 2
C = = .10 2 N
12 3
Ngng keo t c tnh theo cng thc:
C.V
= .1000mN / l
VSon + V
V: s mililit dung dch cht in li cho vo dung dch keo.
C: Nng dung dch cht in li cho vo.
VSon: S mililit dung dch keo dng keo t.
Kt qu s tt hn nu chng ta tm ngng keo t chnh xc hn. Cch tin hnh nh
sau:
Pha khong 70 ml dung dch cht in li c nng m th nghim trc xc nh l
nng bt u lm cho h keo c s keo t v gi l dung dch c hn. Cng ly khong 70
ml dung dch cht in li c nng lin ngay trc dung dch trn v gi l dung dch
long hn.
V d: Trong th nghim 1 ng s 8 bt u c. Do dung dch c hn tng ng vi
ng s 8, c s pha long 8/4. Dung dch long hn tng ng vi ng s 7, c s pha long
7/5.
Dng 2 dung dch trn pha thnh 12 dung dch c nng khc nhau nm trong khong
2 nng ca 2 dung dch trn theo bng sau:
1 2
 80

11

Nng dung dch c xc nh theo cng thc:

C 1 V1 + C 2 V 2
C = N/1
V1 + V 2
C1,V1: Nng v s ml dung dch c nng c hn.
C2,V2: Nng v s ml dung dch c nng long hn.
Ly 1 ml t mi dung dch va pha cho vo cc ng nghim cha 5 ml dung dch son
Fe(OH)3, ging nh lm trong th nghim trn.
Quan st v ghi kt qu nh lm trn (ghi du + vo ng c, du vo ng khng
c).
Tnh ngng keo t chnh xc ca Na2SO4 vi Son Fe(OH)3.
 81

Bi s 15

PHN TCH SA LNG

Mc ch
Kho st phn tn v kch thc cc c ht ca h phn tn th.

L thuyt
Cc h thng phn tn phn ln l cc h a phn tn, ngha l nhng h cha nhiu loi
ht c kch thc khc nhau. Cc tnh cht l ho ca h phn tn ph thuc rt nhiu vo
phn tn v kch thc ht ca pha phn tn, v vy vic xc nh s phn b ca cc ht keo
theo kch thc, tm bn knh ca cc ht ln nht, ht nh nht v ht c nhiu nht trong h,
xc nh lng ht c bn knh nm trong mt khong nht nh v.v... l rt cn thit. phng
php phn tch sa lng cho php gii p cc vn .
Trong bi thc nghim ny chng ta kho st s sa lng ca cc ht huyn ph (h phn
tn th hay h vi d th) di tc dng ca trng trng.
Khi ht ri, lc tc dng f ca trng trng ln ht bng:
4 3
f= R (D D)G (1)
3
y: r l bn knh ht
D v d l t khi ca ht v ca mi trng
g l gia tc trng trng
Lc ma st f ca mi trng lm cn tr s ri ca ht:
f = 6RV (2)
y: v l tc ri ca ht
l nht ca mi trng.
Lc u, khi ht bt u ri, v = 0 v f = 0 nhng sau f tng dn theo tc ri cho n
khi f = f th ht s chuyn ng u vi tc v:
2 (D d )g . r2
v =
9

9
Nu t = K ta s c:
2 (D d)g
r2 = Kv (3)
Theo (3) nu xc nh c tc ri ca ht s xc nh c bn knh ca ht.
 82

Nu ta t mt ci a cch mt thong ca h phn tn mt on h, hng ly ht ri

(hnh 1) v gi thit ri c on ht phi mt thi gian t th v = h/t, do ta c:
h
r2 = K. (4)
t
Nh vy, khi bit c t s xc nh c r.
Trong mt h a phn tn c rt nhiu loi ht, mi loi ht phi mt mt khong thi
gian khc nhau i ht on ng h. Sau mt thi gian tm no , k t lc bt u sa
lng, tt c cc ht bn knh rm tnh theo cng thc (4) v tt c cc ht c bn knh ln hn
rm phi ri ht trn a. Ngoi ra cn c mt phn nhng ht c bn knh b hn rm, nhng
do lc u ( thi im t = 0) vn nm gn a nn cng ri ln a. K hiu lng loi
ht c r rm l Qo v lng loi ht c r < rm ri trn a l q, th tng s lng ht ri
trn a sau thi gian tm s l:
Q = Qo + q (5)

Hnh 1
S ri ca cc ht huyn ph

(Cn lu rng sau thi gian tm loi ht c bn knh nh hn rm vn cn l lng trn a

v ang tip tc ri trn a). Ly o hm ca Q theo thi gian t ta c:
dQ dQ o dq
= +
dt dt dt
dq q dQ
Ch rng Qo l hng s v chp nhn = , ta c q = t ; thay vo (5) ta c:
dt t dt
dQ
Q = Qo + t (6)
dt
Nu biu din s ph thuc ca Q theo t s c mt ng gi l ng cong sa lng
(hnh 2).
Lc mi bt u sa lng, thng ch c loi ht bn knh ln nht (rmax) ri ln a cn,
dQ
lng ht sa lng t l vi thi gian ngha l =const, nn ng sa lng l mt on thng
dt
(on OA) v im A ng vi thi gian tmin l thi gian cc ht ln nht ri ht ln a.
dQ
on OO1 l lng ca loi ht rmax. cc thi im t > tmin th const v ng sa lng l
dt
mt ng cong.
Da vo hnh 2 ta c th xc nh c Qo (lng ht c r rm ri ht ln a) v q
(lng ht c r < rm mi ri c 1 phn ln a). Ti thi im t no , ng vi im B trn
 83

dQ
ng cong, gi tr Q = ON v q = t = NM (M l im ct ca tip tuyn ng cong ti
dt
im B vi trc tung). Suy ra Qo = OM. Nh vy k ng tip tuyn vi ng sa lng
mt im ng vi thi im t no s tm c lng ht Qo c bn knh r ri ht ln
a sau thi gian t.
bit cc c trng ca h phn tn ngi ta xy dng ng phn b tch phn v
ng phn b vi phn da vo ng cong sa lng.

Hnh 2
ng cong sa lng

C th, ta chn mt s im tu 1, 2, 3... trn ng cong sa lng, ng vi cc thi gian

t1, t2, t3... ri tnh cc gi tr r1, r2, r3... tng ng. K cc ng tip tuyn vi ng sa lng
ti cc im chn, cc ng ny ct trc tung ti M1, M2, M3... Cc on OM1, OM2,
OM3... chnh l cc gi tr Qo1, Qo2, Qo3... (hnh 3). T cc gi tr v ng phn b tch
phn vi h to Qo r (hnh 4). Mi im (K) trn ng cong cho ta bit lng ht
(Qok) c bn knh bng v ln hn rk hon ton sa lng sau thi gian tk.

Hnh 3 Hnh 4
Xc nh cc gi tr Qo t ng cong sa ln ng phn b tch phn

v ng phn b vi phn t hnh 3 ta tnh lng ht c bn knh trong khong rm rn

no cnh nhau.
Vi cc khong bn knh:
r1 r2 r2 r3 r3 r4 r4 r5...
Ta c lng ht tng ng:
Qo2 Qo1 Qo3 Qo2 Qo4 Qo3 Qo5 Qo4...
 84

Q o Q o
T lp biu thc: ri xy dng th r , thu c ng phn b vi phn
r r
(hnh 5). Cn ch l mi gi tr Qo ng vi hai gi tr rn v rm nn gi tr r v th l
r + rm
rtb = n . ng cong thu c c dng khc nhau tu thuc h kho st.
2
Q o
r

3 4
2

0 r
Hnh 5
Cc loi ng phn b vi phn
1. H gn nh n phn tn; 2. H a phn tn
3. H cha ht c r nh nhiu hn; 4. H cha ht c r ln nhiu hn.

Cc ng ny thng khng xut pht t gc to m bt u bng rmin v kt thc

rmax. Bn knh rmin l bn knh ca ht nh nht trong h, tng ng vi tmax, lc ng cong
sa lng bt u chuyn sang ng thng song song vi trc honh, ngha l lc s sa lng kt
thc. Cn bn knh rmax l bn knh ca ht ln nht trong h, ng vi tmin, khi ng sa lng
bt u chuyn t ng thng sang ng cong (hnh 2).
ng phn b vi phn l mt c trng quan trng cho cc h a phn tn. Da vo cc
i ca ng phn b c th xc nh c bn knh ca ht c nhiu nht trong h. Nu
khong bn knh cng hp v cc i ca ng cong cng cao th h cng gn vi n phn
tn v ngc li (hnh 5).

Tin hnh th nghim

Dng c
xc nh lng cc ht ri trn a, ngi ta dng cn dy xon (cch s dng cn
dy xon, cn b phng th nghim s hng dn). Trn n cn, treo a cn A (hnh 6).
 85

Hnh 6
Cn dy xon (a) v ng ong ng huyn ph (b)

Cch tin hnh

Ly 250 ml nc vo mt ng hnh tr. a cn vo nc, cch mt nc mt
khong cch h, treo a cn vo mc cn dy xon. Xc nh trng lng a cn
trong nc.
Cn 2,5 g t bt mn, vo ng hnh tr ng nc trn, ta thu c huyn ph
t trong nc c nng C (%) bng:
2,5
C= .100% = 1%
250
Dng que khuy mt u c gn a mng c c l u khp b mt v c
ng knh gn bng ng knh ng ng huyn ph, khuy u huyn ph
(a que khuy i ln ri i xung). Treo a cn vo mc cn. Sau khi khuy,
nhanh chng cho a cn vo bnh ng huyn ph xung n su h nh
trc, ri bm ng h, ly l im khng (cn ch t a cn vo chnh
gia bnh, khng st vo thnh bnh v t lc thi khuy cho n khi ly im
khng, khng c qu 15 giy. C th lm ng tc ny vi ln cho thnh
tho ri hy tin hnh ghi kt qu).
Sau cc thi gian sau y hy c cc gi tr trng lng trn cn xon (trng lng a
v cc ht ri trn a trong nc):
0,5 1 2 5 10 15 20 30 50 80 120 pht
Ghi cc kt qu vo bng 1, ct 1, 2. Khi kt qu vi im cui trng nhau th c th
ngng th nghim. Kha cn xon. Ly a cn ra. huyn ph i. Ra sch cc dng c th
nghim.
Phn tnh ton v xy dng th
Tnh lng ht ri trn a tng thi im (Po) Ly s c trn cn xon tr i trng
lng a cn trong nc thu c cc gi tr Po, ghi vo bng 1, ct 3.
Tnh phn trm lng ht ri trn a trong tng thi im (Q%):
Po
Q% = . 100% (7)
Pk
y: Pk- trng lng ht cha trong hnh tr dung dch pha trn a, cn trong nc.
 86

Pk c th tnh da vo lng ht P tng ng, cn trong khng kh:

P = R2hC (8)
R- Bn knh a cn (cm)
h- Chiu cao ct dung dch t a cn n mt nc (cm)
C- Nng phn trm ca huyn ph
V lng ht P cn trong khng kh c gi tr:
P = VD
cn trong nc th theo nh lut Acsimet, lng ht s c trng lng l Pk:
Pk = VD Vd = V(D d)
y: V - th tch ca huyn ph
D - T trng ca ht huyn ph
d - T trng ca nc
Suy ra:
Pk Dd
= (9)
P D
Thay P theo (8) vo (9) thu c:
Dd
Pk = R 2 .h.C. (10)
D
o bn knh a cn R, o chiu cao h, bit t trng ca ht huyn ph s tnh c Pk, t
tnh c Q% theo (7). Ghi kt qu vo bng 1, ct 4.
Bng 1
Trng lng a cn trong nc:.. h = ..... R = ..
t (pht) S c trn cn xon (mg) Po (mg) Q%

V ng cong sa lng trn h to Q% t

V ng phn b tch phn da vo ng cong sa lng. Ly 5 6 im trn ng
cong sa lng ng vi cc thi im khc nhau, im u l im m ng sa
lng bt u chuyn sang ng cong, im cui cng l im m ng sa lng
chuyn sang ng thng song song vi trc honh, khi s sa lng kt thc.
Tnh r theo cc gi tr t trn. Ghi kt qu vo bng 2, ct 3.
T cc im chn trn ng sa lng, k cc ng tip tuyn vi ng sa lng.
im ct ca cc ng tip tuyn vi trc tung cho cc gi tr Qo khc nhau, ghi vo bng 2,
ct 5.
Bng 2
 87

Q o
S TT t (pht) r (cm) r Qo Qo
r
1
2
3
4
5
6

V th vi h to Qo r thu c ng phn b tch phn.

V ng phn b vi phn.

T cc gi tr Qo v r trn, tun t tnh cc gi tr Qo v r, xc nh Q o ghi vo

r
bng 2 ri v th vi h to Q o r thu c ng phn b vi phn.
r

Nhn xt kt qu
Da vo dng ca ng phn b vi phn hy cho kt lun v:
Tnh a phn tn ca h ?
Nhng c ht no c mt nhiu nht trong h kho st ?
Bn knh ca loi ht cha nhiu nht trong h l bao nhiu, n gn rmin hay rmax ?
 88

Bi s 16

XC NH PHN T KHI CHT POLIME

Mc ch
Xc nh phn t khi cao su thin nhin bng phng php o nht.

L thuyt
Phn t khi cht polime c th xc nh bng nhiu phng php khc nhau da vo s
ph thuc ca mt c trng vt l no ca hp cht polime vo phn t khi ca n. Cc
c trng c th l p sut thm thu, phn tn nh sng, nht, gim nhit
ng c, tng nhit si v.v...
Phng php o nht l phng php n gin v mt thc nghim, ng thi cho
php nh gi phn t khi trong khong tng i rng (M = 104106), tuy phng php ny
khng hon ton chnh xc.
Trc ht ta hy xt mt s nh ngha chung v nht nh: nht tuyt i, nht
tng i, nht ring, nht rt gn v nht c trng.
nht tuyt i ()
Theo nh lut Poady, nu mt cht lng chy qua mt mao qun chiu di L(cm), bn
knh r (cm) di tc dng ca p sut P (in/cm2), sau thi gian t chy qua c mt th tch
V, th nht tuyt i c tnh theo cng thc sau:
.P r 4
= t (1)
8LV
Nu cht lng chy qua mao qun ch do tc dng trng lc ca n, th
P = g.H.d (2)
g- gia tc trng trng
H- hiu s mc dung dch trong mao qun
D - t trng dung dch
Thay gi tr P t (2) vo (1) ta c:
.g .H .d .r 4
= t
8LV
in cm 4 .s in.s
n v ca = 2
3
= = poise
cm cm.cm cm 2
Nu cc php o c thc hin cng mt nht k, th cc i lng V, L, H, r l cc
gi tr khng i.
 89

Khi :
= K.d.t ; (3)
trong
.g.H .r4
k =
8 LV
c gi l hng s ca nht k. K c tnh theo thi gian m cht lng c nht bit
sn chy qua nht k.
o
K= (4)
do t o

o, do, to l nht, t trng v thi gian chy ca cht lng chun.

Bit K s xc nh c nht tuyt i ca cht theo h thc (3), trong t l thi
gian chy trung bnh ca dung dch.
nht tng i (t)
xc nh phn t khi ngi ta khng cn bit gi tr nht tuyt i, m ch cn
bit nht tng i ca dung dch.
dd
t = (5)
dm
Mun xc nh nht tng i cn bit thi gian chy qua mao qun ca nht k
nhit xc nh ca cng mt lng dung dch (t) v dung mi (to). Nu xem t trng ca
dung dch v dung mi l bng nhau (khi dung dch tng i long) th t (3) rt ra:
t
t = (6)
to

nht ring (r)

nht ring l t s gia hiu s nht ca dung dch v dung mi trn nht ca
dung mi. nht ring c xc nh bng h thc:
t to
r = = t 1 (7)
to

nht rt gn (rg)
nht rt gn l t s ca nht ring dung dch vi nng ca n (nng ca
dung dch polime thng c biu din bng s gam polime trong 100 ml dung mi):
r
rg = (8)
C
nht c trng ([])
nht c trng l gii hn ca nht rt gn, khi nng ca dung dch tin ti
khng:
 90

r
[] = lim (9)
c 0 C
xc nh phn t khi cht polime ngi ta s dng h thc Mark Houwink biu din
s ph thuc gia nht c trng v phn t khi cht polime.
[] = KM (10)
K v l hng s ph thuc vo bn cht ca dung mi v nhit , thng c gi tr
trong khong 0,5 0,8.
nht c trng c xc nh bng thc nghim nh sau:
Pha mt lot dung dch cht polime c nng phn trm t rt nh n ln dn (nng
cao nht khng qu 1g/100 ml dung mi). Sau khi xc nh nht tng i ca mi

dung dch, tnh nht rt gn cho mi dung dch, ri xy dng th r = f(C) nh trn hnh 1.
C
on thng m ng biu din ct trc tung s cho ta nht c trng. Theo h thc
(10) ta c:
lg[] = lgK + lgM (11)

r
C
Hnh 1
S ph thuc nht rt gn vo nng

Nu bit gi tr ca cc hng s K v , bng thc nghim xc nh [] ta c th tnh

c phn t khi M ca polime.
Gi tr K v i vi mt s h polime - dung mi cho sn trong cc ti liu tra cu. Th
d, vi h Cao su thin nhin Toluen 30oC, K = 5,02.104 v = 0,67.

Tin hnh th nghim

1. M t nht k
C hai loi nht k thng dng trong phng th nghim
a) Nht k Otvan (hnh 2)
Nht k Otvan c hnh cha U, mt bn c mao qun, c ng knh khong 0,6 0,8
mm. Phn trn ca mao qun ni lin vi mt hay hai bu bnh cu th tch khong 12 ml.
 91

Nht k Otvan dng xc nh nht vi tng nng xc nh. Th tch dung dch dng
cho mi mt ln o phi hon ton bng nhau.
b) Nht k Ublt (hnh 3)
Nht k Ublt khc vi nht k Otvan l c thm mt nhnh th ba gn lin vi nhnh
c mao qun qua mt bu cha nh. Nhnh th ba ny c tc dng ngt dng dung dch cui
mao qun, cho nn thi gian dung dch chy qua mao qun khng ph thuc vo lng dung
dch trong bu cha. Nht k Ublt c nhiu u im hn, dng tin li hn, v c th pha
long nng dung dch ngay trong bu cha bng cch cho thm vo mt lng dung mi
tng ng.
Nht k trc khi dng phi ra bng hn hp Sunfocromic, trng li bng cn hoc ete,
em sy kh trong t sy.
A A

B B
l

Hnh 2 Hnh 3
Nht k Otvan Nht k Ublt

Polime trc khi dng phi c tinh ch bng kt ta nhiu ln v em sy kh nhit

50 60oC trong t sy chn khng cho n khi trng lng khng i.
Polime c tinh ch, sy kh pha vo dung mi vi cc nng khc nhau, pha
khong 5 nng , nng ban u khng ln qu 1 g/100 ml.
2. Tin hnh th nghim
Mc ch th nghim l xc nh phn t khi cao su thin nhin nhit 30oC bng
nht k Otvan.
Phng th nghim chun b dung dch cao su trong toluen vi cc nng
0,4%, 0,2%, 0,1%, 0,05%, 0,0025%.
Trng nht k bng toluen.
Dng ng ong ly 7 ml toluen cho vo nhnh phi (nhnh khng c mao qun)
ca nht k, dng qu bp cao su y toluen qua nhnh c mao qun ln qu
mc A mt t, ri tho qu bp cao su cho toluen chy t nhin v dng ng h
bm giy o thi gian toluen chy t ngn A n ngn B. o li 4 5 ln, ly
 92

gi tr trung bnh (ch thi gian mi ln o khng c khc nhau qu 0,2

giy). Gi tr o c l thi gian to.
Tin hnh o cc dung dch t long n c (khng cn trng nht k) nh
lm trn, mi dung dch phi o 4 5 ln ly gi tr t trung bnh.
Cc dung dch trng, dung mi v dung dch o ln vo mt bnh thu hi. Lm
xong th nghim, nht k phi c trng bng toluen nhiu ln. Cc kt qu th nghim ghi
vo bng theo mu di y:
Bng 2

S Thi gian chy r

Nng C(%) t r
TT (giy) C
1 Toluen
2 0,025 % cao su trong toluen
3 0,05 % cao su trong toluen
4 0,1 % cao su trong toluen
5 0,2 % cao su trong toluen
6 0,4 % cao su trong toluen

r
Da vo cc kt qu bng trn xy dng th C xc nh nht c trng []
C
v tnh phn t khi cao su theo (10).
 93

Ph lc
SAI S CA PHP O
PHNG PHP LP BNG
V DNG TH TRONG THC TP HO L

A. Sai s ca php o
Cc kt qu thc nghim bao gi cng c sai s, ngha l lun lun c sai lch gia gi tr
thc ca i lng cn o v gi tr o c. i lng o c ch c ngha khi xc nh c
sai s ca n. Mt khc, tm c nguyn nhn gy ra sai s v hn ch chng nng cao
chnh xc ca php o l rt cn thit. V vy, vn sai s trong th nghim c mt ngha quan
trng.

I. Nguyn nhn gy sai s

Sai s gy ra do cc hn ch ca dng c, do ngi o, do iu kin th nghim.

1. Sai s dng c gy nn do chnh xc ca dng c b hn ch. Th d, dng nhit k c
1
chia 0,1o th bng mt thng ch c th phn bit c n chia, ngha l khong 0,02o;
5
nu phi o s tng nhit khong 5o chng hn, th chnh xc trong trng hp ny khng
th vt qu 0,02 100% = 0,4%. Nu phi cn mt vt c khi lng 50 g trn mt cn k thut
5
c chnh xc l 0,05g th ta phm phi sai s l 0,1% nhng nu cn trn cn phn tch c
chnh xc n 0,0001 g th ch phm sai s 0,0002%.

Sai s dng c cn do nhng sai st trong cu to ca dng c gy nn, th d my c ch

hng, khong chia trn nhit k, trn pipet khng u v.v Trc khi lm th nghim cn phi
kim tra dng c v kp thi sa i cc sai st .

2. Sai s do ch quan ngi o gy nn do ngi lm th nghim c gic quan km nhy

hoc kinh nghim hn ch. Th d, trong s chun mt nhn thiu tinh tng phn bit s
chuyn mu, trong vic o dn in tai khng thnh pht hin chnh xc trng thi cn bng
ca cu o bng ng nghe v.v

3. Sai s do iu kin th nghim thay i l do vic vic kh duy tr mt iu kin bn

ngoi nh nhau khi lp li nhiu ln mt th nghim no , do nhng tr s ca cc php o
khng c tnh lp li.

93
 94

Sai s do dng c my mc khng chnh xc, do phng php o khng chun xc thuc
loi sai s tt nhin. Kt qu ca cc php o thng thay i theo mt hng nht nh, hoc
tng hoc gim. Mun hn ch sai s ny phi tin hnh kim tra chun ho li dng c thit b
nh hiu chnh pipet, buret, cn, nhit k, v.v

Sai s do ch quan ngi o hoc sai s do iu kin th nghim khng n nh thuc loi
sai s ngu nhin. Sai s ngu nhin khng do mt nguyn nhn nht nh no gy ra, kt qu
ca php o thay i ln xn theo c hai chiu, lc tng lc gim, do khi tng s ln o c th
lm gim gi tr sai s ny.

II. Cc php tnh sai s

1. Sai s tuyt i
Khi xc nh i lng A no th hiu s gia gi tr o c a v tr s thc ca A l sai
s tuyt i ca php o:
a = a A (1)
Trong phng trnh trn a l i lng bit t php o, nhng A l gi tr thc ca i
lng li cha bit. Mun xc nh A ta phi tin hnh nhiu ln o i lng cn tm v chp
nhn A l gi tr trung bnh ca cc ln o . Th d ta tin hnh n ln o v thu c cc gi tr
ca A ln lt l a1, a2, a3,an. Ta c:
a 1 + a 2 + ... + a n
A = (2)
n
A c xem l tr s thc ca A. Khi sai s tuyt i ca php o c tnh bng phng
trnh:
a = a A (3)
Mi ln o s c mt sai s tng ng:
a1 = a1 A
a2 = a2 A
a3 = a3 A
... ...
an = an A
Ta thy ngay rng:
a1 + a2 + a3 + + an = 0
V vy, nh gi phn tn ca cc d kin thc nghim ta phi ly trung bnh cc gi tr
tuyt i ca sai s v thu c sai s trung bnh ca php o:
n

a =
a i
; i = 1, 2, n (4)
n
Th d: khi o ch s chit sut (n) ca nc, ta nhn c cc gi tr sau:

94
 95

1,3325; 1,3322; 1,3330; 1,3327; 1,3331

Gi tr chit sut trung bnh:
1,3325 + 1,3322 + 1,3330 + 1,3327 + 1,3331
n= = 1,3327
5
Sai s tuyt i ca cc ln o:
n1 = 1,3325 1,3327 = 0,0002
n2 = 1,3322 1,3327 = 0,0005
n3 = 1,3330 1,3327 = + 0,0003
n4 = 1,3327 1,3327 = 0,0000
n5 = 1,3331 1,3327 = + 0,0004
Sai s trung bnh:
5

n =
ni
= 0,00028
5
Thng thng sai s trung bnh ln hn nhiu so vi sai s dng c. Vi nhng th nghim
ch o c mt ln hoc kt qu cc ln o u trng nhau th ta ly sai s ca dng c.
Ngi ta thng quy c sai s ca dng c bng mt na gi tr ca khong chia nh nht
ca thang o ang s dng.

2. Sai s tng i
Sai s tng i l t l gia sai s tuyt i v gi tr thc ca i lng A phi tm, ngha l
a a a
. Nhng v ta ch bit A hay gi tr a o c nn sai s tng i c tnh bng hay .
A A a
Sai s tng i mi l i lng c trng cho chnh xc thc ca php o.
Th d, dng mt vn k c chnh xc l 0,005 V, ln th nht o th 1 V, ln th hai o
th 0,1 V. Trong c hai ln sai s tuyt i l nh nhau nhng sai s tng i l khc nhau:
a 0,005
Ln 1: = = 0,005 hay 0,005 100% = 0,5%
a 1
a 0,005
Ln 2: = = 0,05 hay 0,05 100% = 5%
a 0,1
R rng l php o th nht c chnh xc cao hn.
Trong nhiu trng hp i lng phi tm c xc nh bng mt phng trnh trong
cha nhiu i lng phi o. Th d, khi lng phn t cht tan c xc nh bng phng
php hn nghim (bi s 6) theo cng thc:
E m 2 .1000
M= (5)
m1 T

95
 96

Trong E l hng s (hng s nghim lnh) cn khi lng dung mi m1, khi lng cht
tan m2, h nhit ng c T (T = To T, y To v T l nhit ng c ca
dung mi v dung dch) l nhng i lng phi o trc tip. Trong trng hp ny sai s ca i
lng phi tm s c tnh nh th no khi bit sai s ca tng i lng o trc tip?
Gi s y l i lng phi tm, f l dng hm lin h gia y vi cc i lng o c trc
tip 1, 2, n:
y = f (1, 2, n)

Do sai s y qu nh so vi i lng phi tm y, nn c th thay y = dy v sai s tng i

y dy dy
= m = dln f (1, 2, n), nh vy tnh sai s tng i ta ly lga t nhin (ln)
y y y
biu thc ca i lng phi tm ri ly vi phn kt qu thu c .

Th d, tnh sai s tng i trong vic xc nh khi lng phn t cht tan theo cng
thc (5) ta ln lt qua cc bc sau:

Ly lga hai v ca phng trnh:

lnM = lnE + lnm2 + ln1000 lnm1 ln( To T)

Ly vi phn biu thc trn:

dM dm 2 dm1 d(To T )
=
M m2 m1 To T

Vi quy c sai s tnh c l sai s cc i (hay gii hn trn ca sai s), khi chuyn t vi
phn sang sai s cc du tr cn c thay bng du cng ta thu c:
M m2 m1 2T
= + + o
M m2 m1 T T

Gi s lng cn ca cht tan m2 = 0,3 g c cn bng cn phn tch sai s 0,0002 g. Khi
lng dung mi m1 = 20 g c cn bng cn k thut sai s 0,05 g. h nhit ng c
T = 0,3o v nhit c o bng nhit k Beckman c chnh xc 0,002oC. V khi xc nh
cc i lng m1, m2 ta u tin hnh 2 ln o (cn khi lng cc khng v cc c dung mi
hoc cht tan) nn sai s ca php cn phi c nhn hai ln, ta c:
M 2 0,0002 2 0,05 2 0,002
= + +
M 0,3 20 0,3
= 0,0013 + 0,005 + 0,013

= 0,019 2%

M
Kt qu cho thy sai s tng i s ph thuc vo chnh xc ca php o nhit .
M
l l do ti sao o nhit chng ta phi dng nhit k Beckman hay nhit k khong. Sai
s ca php cn dung mi l 0,005 nh hn so vi sai s ca php o nhit , nh vy ch cn

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cn dung mi bng cn k thut l chnh xc. Mt khc, nu chng ta cng cn cht tan bng
cn k thut th:
m2 2 0,05
= = 0,33
m2 0,3

Sai s ny vt qu sai s ca nhit . V vy, trong th nghim ta phi dng cn phn tch
cn cht tan.
Th d trn cho thy vic xc nh sai s ca php o cho php ta phn tch c nh hng
ca chnh xc cc php o mi i lng ring n kt qu chung, t c th hn ch nguyn
nhn gy sai s. iu c ngha ln i vi cc cng trnh khoa hc thc nghim.

3. Quy tc lm trn s v cch vit kt qu

Khi xc nh c gi tr trung bnh A ca i lng A v sai s a ca n th kt qu s
c vit nh th no? Chng ta chp nhn quy c sau:
i vi sai s: sai s c lm trn n con s cui cng (tnh t phi qua tri) khc
khng, theo quy c tng ch s cui cng ln mt bc nu nhng s b i bt u bng s ln
hn 5 (hoc s 5 nhng nhng s sau n khc khng), gi nguyn s cui cng khng i nu cc
ch s b i bt u bng s nh hn 5.
Th d: 0,0872 hoc 0,0851 lm trn thnh 0,09
212,5 lm trn thnh 200
i vi gi tr o c: lm trn n cng mt bc vi sai s tuyt i ca n
Th d: Nu sai s tuyt i l 0,09 v kt qu l 1,7325 th s lm trn thnh 1,73.
Nu sai s tuyt i l 200 v kt qu l 8765,3 th lm trn thnh 8800.

Vi hai th d trn ta s c kt qu cui cng ln lt l:

1,73 0,09
8800 200
Mt th d khc, kt qu thu c l:
2,37425 0,02376
sai s tuyt i lm trn thnh 0,02 th gi tr o c lm trn thnh 2,37 v ghi kt qu l:
2,37 0,02
(Sai s v gi tr o c u lm trn n hng phn trm ca n v)
Nu kt qu thu c l: 2327,63 53,7325
sai s tuyt i lm trn thnh 50 th gi tr o c lm trn thnh 2330 v ghi kt qu l:
2330 50

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B. Phng php lp bng v dng th

I. Phng php lp bng

Mi bi thc nghim cn phi bt u t vic thit lp trnh t th nghim v lp cc bng

ghi cc s liu thc nghim.
Thng cc php o u phi cha t nht hai bin s: mt c la chn lm bin s c
lp v mt (hoc nhiu) l bin s ph thuc. Ngi ta thng chn bin s c lp l thi gian,
nhit , p sut, nng v gi tr cc bin s ny c sp xp trong ct theo th t tng dn
hoc gim dn. Pha u ct phi ghi r tn bin s v n v o. Cc con s phi c ghi y
v cn thn, cc du phy gia cc s phi cng nm trn mt ng thng ng v sau du phy
ch c vit cc s l trong phm vi sai s ca php o (th d sai s ca dng c).
Nu cn phi a vo bng gi tr x = a.10n th trong cc hng ch ghi tr s a, cn pha trn
ca ct ghi x.10n. Th d, nng ca dung dch l C = 2,5.103M th trong hng vit 2,5 v
pha trn ca ct vit C.103M. iu ny c ngha l C.103 = 2,5M hay C = 2,5.103M.
Cc s liu ghi trong bng cng phi c quy trn thch hp v nu cng trong mt ct th
cc s liu phi c cng chnh xc (cng mt s cc s l).

II. Phng php dng th

Vic biu din cc s liu thc nghim hay tnh ton bng th cho php ta - mt cch trc
gic - biu th mi tng quan ca cc i lng nghin cu, gip ta c th so snh cc i lng,
thy c s din bin ca cc d kin (nh c cc i, cc tiu, im un khng?), bit c tc
bin thin ca cc i lng, tnh tun hon ca cc i lng v nhiu tnh cht quan trng
khc. Hn na, bng th ngi ta cn thc hin c mt lot nhng tnh ton khc nh ni
suy, ngoi suy, vi phn, tch phn do so vi phng php lp bng, phng php biu din
trn th c nhiu u im hn.
th c v trn giy k vung, tt nht l trn giy milimet in sn. Ngi ta thng
biu th trong h to -cc cc thng s (x) trn trc honh v cc hm s (y) trn trc tung.
ng biu din phi chim hu ht ton b t giy v. Mun vy thang x v y phi bt u t tr
s gn vi tr s b nht lm trn v kt thc bng tr s gn vi tr s ln nht lm trn ca
i lng cho. Th d, nu x thay i t 0,53 0,96 cn y t 4,2 15,6 th trc honh bt u
t 0,50 v kt thc 1,00; cn trc tung bt u bng 4,0 v kt thc bng 16. Nh vy, giao im
ca trc honh v trc tung khng nht thit phi c honh x = 0 v tung y = 0.
Trn cc khong cch u nhau ca trc, nn ly cc s chn, vic s gip ta xc nh
c to ca mt im trn th c d dng v nhanh chng.
T l ca hai trc to c th khc nhau nhng nu ng biu din l thng th nn chn t
l th no cho nghing ca ng biu din xp x 45o so vi trc honh v nu l cc ng
cong th phi chn t l sao cho cc cc i, cc tiu, im un, im gy c biu th r
rng.
im biu din thng c v bng mt du chm v mt vng trn (hoc mt hnh tam
gic, mt hnh vung) bao quanh. Bn knh ca ng trn ny phi ph hp vi chnh xc
ca php o. Th d, chnh xc ca nhit l 0,01oC th bn knh ng trn bao quanh chm

98
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phi v bng 1/100 ca khong ng vi 1o trn trc nhit . (Trong trng hp chnh xc ca
d kin trn trc tung v trn trc honh khc nhau, l ra phi v quanh im biu din mt hnh
bu dc, th ngi ta vn v mt ng trn c bn knh ng vi d kin c chnh xc thp
hn). ng biu din t nht cng phi dnh vo cc ng trn ca cc im biu din, tr
nhng im c xem l bt thng hoc nhng im c chnh xc km hn cc im khc.
ng biu din phi trnh nhng hin tng khng gii thch c nh cc im gy, im t
ct nhau v.v... Nu ng biu din c dng xc nh chnh xc cc gi tr no th cn
c v bng nt nh.
Khi th c dng xc nh cc o hm hay cc h s ca phng trnh ng biu
din hoc ngoi suy ra ngoi gii hn o, nn chuyn s ph thuc hm s thnh ng thng.
Th d, s ph thuc ca p sut hi bo ho P ca cht lng vo nhit T l mt ng cong,
1
nhng nu biu th quan h gia lgP v th ta s c mt ng thng, da vo h s gc ca
T
ng thng ny s xc nh c nhit ho hi ca cht lng v.v
Da vo th c th thc hin cc php ni suy hoc ngoi suy xc nh mt i lng
no . S ni suy cho php tm cc gi tr trung gian ca hm s y ng vi mt thng s x nm
trong gii hn cc gi tr x1xn cho (hnh 1), cn s ngoi suy cho php tm mt gi tr ca
hm s y ng vi mt thng s x nm ngoi gii hn ca cc gi tr x1xn cho (hnh 2).

x1 x xn x x1 xn
Hnh 1. Ni suy bng th Hnh 2. Ngoi suy bng th

Php ngoi suy ch c php thc hin khi tng quan hm s v bin s vn ng c
ngoi phm vi ca php o c tin hnh. chnh xc ca php ngoi suy khng cao, nht l
i vi cc gi tr x nm xa cc gi tr x1 xn cho, tuy nhin, trong mt s trng hp, vn
l phng php thc nghim khng th thay th c.
Php vi phn th c tin hnh bng cch v mt tip tuyn ti im cho trn ng
dy dy
cong = tg. Gc to bi tip tuyn vi hng dng ca trc x. o hm c xc
dx dx
nh bng t s gia cc cnh ca mt tam gic vung (xem hnh 3). ln ca cc cnh ca tam
gic phi c tnh ra n v ca thang t l. V d, trong hnh 3:
dy ab
=
dx cb

a
y

99
ydx
2

y1 1
y2
 100

) b
c
x
Hnh 3. Vi phn th Hnh 4. Tch phn th

Php tch phn th a ti vic xc nh din tch nm di ng cong v gii hn bi

hai tung (th d hai tung y1 v y2 trn hnh 4).
C nhiu phng php tch phn th song n gin hn c vn l phng php s dng
mt thit b chuyn dng c gi l planimet. Thng thng ton b b mt di ng cong
c chia nh thnh nhng di hp c b rng bng nhau. Mi di hp
ny c xem l nhng hnh thang c mt cnh cong c chp nhn l thng. Ngi ta cn c
th chia din tch di ng cong theo mt cch khc: k nhng on thng song song vi trc
honh sao cho din tch cc tam gic (phn gch cho trn hnh 5) pha trn v pha di
ng cong phi bng nhau. Khi tng din tch cc hnh ch nht chnh l din tch phi tm.

x
Hnh 5. Cch tch phn th

c hai phng php tch phn th, kt qu thu c phi c chuyn t kch thc
hnh hc (cm2 chng hn) sang n v o tng ng vi thang t l.

100