Bài tập hóa lý

Bi tp ha l c s rt gn
Su tm v trnh by: Don Trng C
BI TP HO L C S
MC LC
Chng 1: Nguyn l I nhit ng hc..2
Chng 2: Nguyn l II nhit ng hc..7
Chng 3: Cn bng ha hc..13
Chng 4: Cn bng pha..22
Chng 5: Dung dch v cn bng dung dch - hi..27
Chng 6: Cn bng gia dung dch lng v pha rn........34
Chng 7: in ha hc...40
Chng 8: ng ha hc118
Chng 9: Hp ph v ha keo.........................................58
Chng 1
NGUYN L I NHIT NG HC
1.1. Nguyn l I nhit ng hc

1.1.1. Nhit v cng
Nhit v cng l hai hnh thc truyn nng lng ca h. Cng k
hiu l A v nhit k hiu l Q.
Quy c du
Cng A
Nhit Q
H sinh
>0
<0
H nhn
<0
>0
1.1.2. Nguyn l I nhit ng hc
Biu thc ca nguyn l I nhit ng hc:
U = Q - A
Khi p dng cho mt qu trnh v cng nh:
dU = Q - A
dng tch phn nguyn l I c th c vit:
V2
U Q PdV
V1
1.1.3. p dng nguyn l I cho mt s qu trnh.

1.1.3.1. Qu trnh ng tch: V = const, dV = 0.
V2
A v PdV 0
V1
T ta c: QV = U
1.1.3.2. Qu trnh ng p: P = const, dP = 0.
Ap = P.(V2 - V1) = P.V
Do :
Qp = U + PV = (U + PV) = H
1.1.3.3. Qu trnh ng p ca kh l tng
T phng trnh trng thi kh l tng: PV = nRT
Ta c:
Ap = PV = nRT
Up = Qp nRT
1.1.3.4. Qu trnh dn n ng nhit ca kh l tng

Bin thin ni nng khi dn n ng nhit (T = const) kh l tng l
bng khng nn:
Q T A T nRTln
V2
P
nRTln 1
V1
P2
Trong :
P1: p sut trng thi u.
P2: p sut trng thi cui.
1.1.3.5. Nhit chuyn pha
cp
T
Trong :
cp: nhit chuyn pha (cal hoc J)
nc = -, hh = -ngt
Ghi ch:
R l hng s kh l tng v c cc gi tr sau:
R = 1,987 cal/mol.K = 8,314 J/mol.K
R = 0,082 lit.atm/mol.K
1 cal = 4,18 J; 1 l.atm = 101,3 J = 24,2 cal
1.2. nh lut Hess
1.2.1. Ni dung nh lut
Trong qu trnh ng p hoc ng tch, nhit phn ng ch ph thuc
vo trng thi u v trng thi cui m khng ph thuc vo cc trng thi
trung gian.
Biu thc ca nh lut Hess:
QV = U v Qp = H
Trong :
U: nhit phn ng ng tch.
H: nhit phn ng ng p.
Khi qu trnh xy ra iu kin tiu chun ta c nhit phn ng tiu
chun: H0298, U0298.
i vi cc qu trnh xy ra khi c mt cc cht kh (c xem l kh
l tng), ta c:
H = U + RTn
Vi n l bin thin s mol kh ca qu trnh.
1.2.2. Cc h qu ca nh lut Hess
Nhit phn ng nghch bng nhng tri du vi nhit phn ng thun.

Hnghch = - Hthun
Nhit phn ng bng tng nhit sinh ca cc cht to thnh tr i tng

nhit sinh ca cc cht tham gia phn ng.
s
s
H phn ng = H sp - H tc
Nhit phn ng bng tng nhit chy ca cc cht tham gia phn ng
tr i tng nhit chy ca cc cht to thnh.
H phn ng = Hchtc - Hchsp
Ghi ch: Nhit to thnh tiu chun (H0298, tt), nhit t chy tiu
chun (H0298,c ) c cho sn trong s tay ha l.
1.3. Nhit dung
1.3.1. nh ngha
Q
H
Cp

dP P T P
Q
U
Nhit dung ng tch: C v

dT V T V
Nhit dung ng p:
Mi lin h: Cp - Cv = R
Nhit lng Q c tnh:
T2
T2
Q m CdT hoc Q n CdT

T1
T1
nh hng ca nhit n nhit dung

S ph thuc vo nhit ca nhit dung c biu din bng cc
cng thc thc nghim di dng cc hm s:
2
Cp = a0 + a1.T + a2.T
-2
Hoc Cp = a0 + a1.T + a-2.T
Trong : a0, a1, a2, a-2 l cc h s thc nghim c th tra gi tr ca
chng trong s tay ha l.
1.2.2. nh lut Kirchhoff
Hiu ng nhit ca phn ng ph thuc vo nhit c biu din
bi nh lut Kirchhoff:
1.3.2.
C p
T P
U
Hoc
C v
T V

Sau khi ly tch phn ta c:
T
H T H 0 C p dT
0
Nu ly tch phn t T1 n T2 ta c:
T2
H T2 H T1 C p dT
T1
1.4. Bi tp mu
0
V d 1: Tnh bin thin ni nng khi lm bay hi 10g nc 20 C. Chp
nhn hi nc nh kh l tng v b qua th tch nc lng. Nhit ha hi
0
ca nc 20 C bng 2451,824 J/g.
Gii
Nhit lng cn cung cp lm ha hi 10g nc l:
Q = m. = 10. 2451,824 = 24518,24 (J)
Cng sinh ra ca qu trnh ha hi l:
A = P.V = P(Vh - Vl) = PVh
=
nRT
10
8,314 293 1353,33 (J)
18
Bin thin ni nng l:

U = Q A = 23165 (J)
0
V d 2: Cho 450g hi nc ngng t 100 C di p sut khng i 1
atm. Nhit ha hi ca nc nhit ny bng 539 cal/g. Tnh A, Q v U
ca qu trnh.
Gii
Nhit lng ta ra khi ngng t l:
Q = m.ng. t = 450. (- 539) = - 242550 (cal)
Cng ca qu trnh:
A = P.V = P. (Vl - Vh) = - P.Vh = - nRT
=
450
1,987 373 18529(cal)
18
Bin thin ni nng ca qu trnh l:

U = Q A = - 224021 (cal)
V d 3: Cho phn ng xy ra p sut khng i:
2H2 + CO = CH3OH(k)
nhit to thnh tiu chun 298K ca CO v CH3OH(k) bng -110,5 v 201,2 kJ/mol. Nhit dung mol ng p ca cc cht l mt hm ca nhit :
-3
Cp (H2) = 27,28 + 3,26.10 T
(J/mol.K)
-3
Cp (CO) = 28,41 + 4,1.10 T
(J/mol.K)
-3
Cp (CH3OH)k = 15,28 + 105,2.10 T
(J/mol.K)
0
Tnh H ca phn ng 298 v 500K?
Gii
Nhit phn ng 298K l:
0
H 298 = - 201,2 - (-110,5) = - 90,7 (KJ)
Bin thin nhit dung:
Cp = Cp(CH3OH) Cp(CO) 2Cp(H2)
= - 67,69 + 94,58. 10-3T (J/K)
Nhit phn ng 500K l :
H = Qp = n.Cp. (T2 T1)
PV PV
n.C p 2 1
nR
nR
100
0,082 273
37,1
1 0,2.10 3 44
0,082
1
J
A = PV = P(V2 V1)
100
0,082 273
3
44
8,314 15120 J
1 0,2.10
1
0,082
500
0
H 500
H 0298 C p dT
298
500
90,7.103
67,69 94,58.10
T dT
298
= - 96750,42 (J)
0
V d 4: Cho 100g kh CO2 (c xem nh l kh l tng) 0 C v
5
1,013.10 Pa. Xc nh Q, A, U v H trong cc qu trnh sau. Bit Cp =
37,1 J/mol.K.
3
a.
Dn n ng nhit ti th tch 0,2 m .
3
b.
Dn ng p ti 0,2 m .
c.
un nng ng tch ti khi p sut bng 2,026.105 Pa.
Gii
3
a.
Dn n ng nhit (T = const) ti th tch 0,2m .
V
PV2
Q T A T nRTln 2 nRTln
V1
nRT
100
1 0,2.103
8,314 273.ln
7061 (J)
100
44
0,082 273
44
b.
U = 0
3
Dn n ng p (P = const) ti 0,2m .
c.
U = Q A = 67469 - 15120 = 52349 (J)

5
un nng ng tch (V = const) ti p sut bng 2,026.10 Pa (2 atm)
A=0
C v = Cp - R = 37,1 - 8,314 = 28,786 (J/mol.K)
U = Qv = n.Cv.(T2 T1)
P2 P1
T2 T1
P
2
T2 2 T1 273 546K
P1
1
Ta c:
Suy ra: U = Qv = 1 28,786(546 - 273) = 7859 (J)

H = U + PV = 7859 (J)
V d 5: Mt kh l tng no c nhit dung mol ng tch mi nhit
c Cv = 2,5R (R l hng s kh). Tnh Q, A, U v H khi mt mol kh ny
thc hin cc qu trnh sau y:
a.
Dn n thun nghch ng p p sut 1atm t 20dm3 n 40dm3.
b.
Bin i thun nghch ng tch t trng thi (1atm; 40dm3) n
3
(0,5atm; 40dm ).
0
c.
Nn thun nghch ng nhit t 0,5 atm n 1 atm 25 C.
Gii
a.
Dn n thun nghch ng p (P = const).

V d 6: Tnh nhit to thnh ca etan bit:
0
Cgr + O2 = CO2
H 298 = -393,5 KJ
0
H2 + 1/2O2 = H2O(l)
H 298 = -285 KJ
0
2C2H6 + 7O2 = 4 CO2 + H2O(l) H 298 = -3119,6 KJ
Gii
Cgr + O2 = CO2
(1)
H2 + 1/2O2 = H2O(l)
(2)
2C2H6 + 7O2 = 4CO2 + 6H2O(l)
(3)
Nhit to thnh C2H6 l:
2C + 3H2 = C2H6
(4)
0
0
0
0
H 298(4) = 4H 298(1) + 6H 298(2) - H 298(3)
0
H 298(4) = 4(-393,5) + 6(-285) - (-3119,6) = 164,4 (KJ)
V d 7. Tnh Q, A, U ca qu trnh nn ng nhit, thun nghch 3 mol kh
0
He t 1atm n 5 atm 400 K.
Gii
Nhit v cng ca qu trnh:
Tnh cng A:
V2
A PdV PV2 V1 1.40 20 20l.atm

V1
20
8,314
2028 (J)
0,082
Tnh nhit lng Q:

T
2
P V PV
Q p C p dT C p .T2 T1 C p 2 1
R
R
T1
3,5R
40 20 70 (l.atm)
R
70
b.
8,314
7097
0,082
(J)
Q T A T nRTln
Bin thin ni nng:

U = Q A = 5069 (J)
Bin thin entapy
H = Qp = 7097 (J)
Dn n thun nghch ng tch (V = const).
A=0
Nhit lng:
U = 0
0
0
V d 8. Cho phn ng: 1/2N2 + 1/2O2 = NO. 25 C, 1atm c H 298 =
90,37 kJ. Xc nh nhit phn ng 558K, bit nhit dung mol ng p ca
-1 -1
1 mol N2, O2 v NO ln lt l 29,12; 29,36 v 29,86 J.mol .K .
Gii
Hiu ng nhit ca phn ng 558K l:
2
P V PV
Q v C v dT C v .T2 T1 C v 2 1
R
R
T1
2,5R
400,5 1 50 (l.atm)
R
50
c.
8,314
5069
0,082
U = Qv = - 5069 (J)
Nn ng nhit (T = const)
Q T A T nRTln
558
H 0558 H 0298 Cp dT
298
(J)
U = 0
P1
0,5
1 8,314 298 ln
1717
P2
1
P1
1
3 8,314 400ln 16057(J)
P2
5
(J)
Trong :
-1
Cp = 29,86 1/2(29,12) 1/2(29,36) = 0,62 (J.K )
0
-3
H 558 = 90,37 + 0,62.(558 - 298).10 = 90,5312 (KJ)
1.5. Bi tp t gii
1.
Xc nh bin thin ni nng khi lm ha hi 20g etanol ti nhit
si, bit nhit ha hi ring ca etanol bng 857,7 J/g v th tch hi
3
ti nhit si bng 607 cm /g (b qua th tch pha lng).
S: 2,54 kJ
2.
Tnh H v U cho cc qu trnh sau y:
a.
Mt mol nc ng c 00C v 1 atm;
b.
Mt mol nc si 1000C v 1 atm.
Bit rng nhit ng c v nhit ha hi ca 1 mol nc bng -6,01
kJ v 40,79 kJ, th tch mol ca nc v nc lng bng 0,0195 v
0,0180 lit. Chp nhn hi nc l kh l tng.
S: a. H = U = -6,01 kJ
b. H = 37,7 kJ; U = 40,79 kJ
3.
Nhit sinh ca H2O(l) v ca CO2 ln lt l -285,8 v -393,5 kJ/mol
0
25 C, 1 atm. Cng iu kin ny nhit t chy ca CH4 bng 890,3 kJ/mol. Tnh nhit to thnh ca CH4 t cc nguyn t iu
kin ng p v ng tch.
S: -74,8 kJ/mol; 72,41 kJ/mol
4.
Tnh nhit to thnh chun ca CS2 lng da vo cc d liu sau:
S(mon) + O2 = SO2
H1 = -296,9 kJ
CS2(l) + 3O2 = CO2 + 2SO2 H2 = -1109 kJ
C(gr) + O2 = CO2
H3 = -393,5 kJ
S: 121,7 KJ
5.
Trn c s cc d liu sau, hy tnh nhit to thnh ca Al2Cl6 (r)
khan:
0
2Al + 6HCl(l) = Al2Cl6(l) + 3H2 H 298 = -1003,2 kJ
0
H2 + Cl2 = 2HCl(k)
H 298 = -184,1 kJ
0
HCl(k) = HCl(l)
H 298 = -72,45 kJ
0
Al 2Cl 6(r) = Al2Cl6(l)
H 298 = -643,1 kJ
S: 1347,1 kJ
6.
Tnh nhit phn ng:
H2(k) + S(r) + 2O2(k) + 5H2O(l) = H2SO4.5H2O(dd)
Bit nhit sinh ca H2SO4(l) l -193,75 Kcal/mol v nhit ha tan
H2SO4(l) vi 5 mol nc l -13,6 Kcal.
S: -207,35 Kcal
0
7.
Cho 100 gam kh nit iu kin chun (1atm, 25 C), CP(N2) = 3,262
cal/mol.K. Tnh gi tr ca cc i lng Q, A v U trong cc qu
trnh sau:
a.
Nn ng tch ti 1,5 atm.
b.
Dn n ng p ti th tch gp i th tch ban u.
c.
Dn n ng nhit ti th tch 200lt.
d.
Dn n on nhit ti th tch 200lt.
S: a. Qv = 2424 cal; b. QP = 8786 cal, AP = 1937 cal
c. QT = AT = 1775 cal; d. U = A = 1480 cal
0
8.
25 C phn ng tng hp NH3.
N2(k) +
3H2(k) =
2NH3(k)

0
0
0
-11,04
H 298,tt (kcal/mol)
V nhit dung ca cc cht:
CP (N2) = 6,65 + 10-3T
(cal.mol-1.K-1)
-3
-1 -1
CP (H2) = 6,85 + 0,28.10 T
(cal.mol .K )
-3
-1 -1
CP (NH3) = 5,92 + 9,96.10 T (cal.mol .K )
0
0
Xc nh hm s H T = f(T) v tnh H 1000 ca phn ng?
0
S: H T = -18,22 15,36.10-3T + 8.10-6T2 (Kcal)
H0 = -25,58 Kcal
Chng 2
T2
Nu qu trnh ng tch:
T1
NGUYN L II NHIT NG HC
i vi qu trnh chuyn pha nh qu trnh nng chy, qu trnh ha
-1
-1
-1
i vi kh l tng:
Ta c:
Du = khi qu trnh l thun nghch.

Du > khi qu trnh l bt thun nghch.
2.1.3. Tiu chun xt chiu trong h c lp
Trong h c lp (on nhit)
Nu dS > 0
: Qu trnh t xy ra
2
Nu dS = 0 hay d S < 0: Qu trnh t cn bng

2.1.4. Bin thin entropy ca mt s qu trnh thun nghch
2.1.4.1. Qu trnh ng p hoc ng tch
S C p
T1
dT
T
Shh
Q T nRTln
hh
Thh
V2
V1
QT
V
P
nRln 2 nRln 1
T
V1
P2
Tchph
S T
C Rp1
Thh
C lp
Tnc
hoc
T2
hay
Bin thin entropy nhit bt k c th tnh bng phng trnh:
T2
dT
S C
T
T1
nc
Tnc
-1
Q
T
Nu qu trnh ng p:
HT
T
T
S nc
Entropy c o bng n v cal.mol .K hay J.mol .K

2.1.2. Biu thc ton ca nguyn l II
dS
QT
T
hi
dS
hay
dT
T
2.1.4.2. Qu trnh ng nhit

Trong qu trnh thun nghch ng nhit, ta c th p dng:
2.1. Nguyn l II nhit ng hc

2.1.1. nh ngha entropy
Trong qu trnh thun nghch, bin thin entropy khi chuyn h t
trng thi 1 sang trng thi 2 c xc nh bng phng trnh:
Q
T
Q
S TN
T
S C v
Tnc
dT chph
dT nc
C Rp 2
T Tchph Tchph
T Tnc
dT hh T k dT
Cp
T Thh Thh
T
ST C p
dT
T
T
Trong :
C Rp1 : nhit dung trng thi rn 1

7

T2
CRp 2 : nhit dung trng thi rn 2

Bin thin entropy tiu chun ca cc phn ng c xc nh bng
phng trnh:
S 0298 S 0298(sp) S 0298(tc)

Th nhit ng
Cc th nhit ng bao gm: ni nng, entapy, nng lng t do v
th ng p.
Nng lng t do F v th ng p G c nh ngha bi cc
phng trnh sau:
F = U - TS
G = H - TS
Ti mt nhit xc nh, bin thin th ng p v ng tch c
biu din bng phng trnh sau:
F = U - TS
G = H - TS
V
G = Gcui - Gu
F = Fcui - Fu
0
Th ng p to thnh tiu chun ca cc cht (G 298) c th tra
trong s tay ha l.
2.2.1. Xt chiu trong h ng nhit, ng p
Trong h ng nhit, ng p
Nu dG < 0
: Qu trnh t xy ra
Nu dG = 0 hay d2G > 0 : Qu trnh t cn bng

2.2.2. Xt chiu trong h ng nhit, ng tch
Trong h ng nhit, ng tch
Nu dF < 0
: Qu trnh t xy ra
2
Nu dF = 0 hay d F > 0 : Qu trnh t cn bng

2.3. Bi tp mu
V d 1. Tnh bin thin entropy khi un nng thun nghch 16 kg O2 t 273K
n 373K trong cc iu kin sau:
a.
ng p
b.
ng tch
Xem O2 l kh l tng v nhit dung mol Cv = 3R/2.
Gii
a.
i vi qu trnh ng p
Cp = Cv + R = 5R/2
2.2.
S n C p
T1
b.
dT 16.103 5
373
1,987.ln
775cal/K
T
32
2
273
i vi qu trnh ng tch
T2
S n C v
T1
dT 16.103 3
373
1,987.ln
465cal/K
T
32
2
273
V d 2. Xc nh nhit lc cn bng nhit v bin thin entropy khi trn

0
0
1g nc 0 C vi 10g nc 100 C. Cho bit nhit nng chy ca
bng 334,4 J/g v nhit dung ring ca nc bng 4,18 J/g.K.
Gii
Gi T (K) l nhit ca h sau khi trn. Gi s h l c lp.
Ta c phng trnh:
Nhit lng ta ra = Nhit lng thu vo
- Qta = Qthu hay Q3 = Q1 + Q2
- 10.4,18.(T - 373) = 334,4 + 1.4,18.(T - 273)
T = 356,64 (K)
Bin thin entropy ca h:

S = S1 + S2 + S3
Vi:
S1
nc 334,4
1,225(J/K)
Tnc
273
356,64
S 2 1.
4,18
273
dT
1,117(J/K)
T
356,64
S 3 10.
373
4,18
dT
1,875(J/K)
T
S = 0,467 (J/K)
V d 3. Tnh bin thin entropy ca qu trnh nn ng nhit, thun nghch.
a.
1 mol oxy t P1 = 0,001atm n P2 = 0,01atm.
b.
1 mol mtan t P1 = 0,1 atm n P2 = 1 atm.
Trong hai trng hp trn kh c xem l l tng.
Gii
a.
b.
P1
1,987.ln0,1 4,575(cal/K)
P2
P
S nRln 1 1,987.ln0,1 4,575(cal/K)
P2
V2
13,32(cal/K)
V1
V
S 2 nR.ln 2' 7,46(cal/K)
V1
S nRln
V d 4. Xc nh bin thin entropy ca qu trnh chuyn 2g nc lng

00C thnh hi 1200C di p sut 1 atm. Bit nhit ha hi ca nc
0
-3
100 C l 2,255 (kJ/g), nhit dung mol ca hi nc Cp,h = 30,13 + 11,3.10 T
(J/mol.K) v nhit dung ca nc lng l Cp,l = 75, 30 J/mol K.
Gii
Bin thin etropy ca qu trnh

S = S1 + S2 + S3
373
2
dT
75,3
2,61(J/K)
18 273
T
2 2255
S2
12,09(J/K)
373
2 393
dT
S1 30,13 11,3.10-3 T
0,2(J/K)
18 373
T
S1
Vy S = 20,78 (cal/K)
0
V d 6. Tnh U, H v S ca qu trnh chuyn 1 mol H2O lng 25 C v
0
1 atm thnh hi nc 100 C, 1 atm. Cho bit nhit dung mol ca nc
lng l 75,24 J/mol.K v nhit ha hi ca nc l 40629,6 J/mol.
Gii
Nhit lng cn cung cp
373
Vi
S1 nR.ln
S = 14,9 (J/K)
3
V d 5. Mt bnh kn hai ngn, ngn th nht c th tch 0,1 m cha oxi,
3
ngn th hai c th tch 0,4 m cha Nit. Hai ngn u cng mt iu
kin nhit l 170C v p sut 1,013.105 N/m2. Tnh bin thin entropy khi
cho hai kh khuch tn vo nhau.
Gii
3
Khi hai kh khuch tn vo nhau, th tch ca hn hp V2 = 0,5 m
Bin thin entropy ca h:

S =S1 + S2
Vi S1: bin thin entropy ca kh Oxy khi khuch tn
S2: bin thin entropy ca kh Nit khi khuch tn
Q p Q1 Q 2 75,24dT hh
298
Q p 75,24(373 298) 40629,6 46272,69(J)

Cng ca qu trnh
A A1 A2 0 PV nRT2 1 8,314 373 3101,1J

Ni nng
U = Q A = 43171,5 (J)
H = Qp = 4627,6 (J)
Bin thin entropy ca qu trnh
373
S S1 S 2
298
Cp
dT hh
T Thh
373 40629,6
75,24ln
125,8 J/K
298
373
V d 7. Cho phn ng c cc s liu sau:
3Fe(r) + 4H2O(h) = Fe3O4(r) + 4H2(k)
0
H 298 t.t
(Kcal/mol)
-57,8
-267
a.
b.
c.
a.
S0298
6,49
45,1
3,5
32,21
(cal/mol.K)
-3
Cp(Fe)
= 4,13 + 6,38.10 .T
(cal/mol.K)
-3
Cp(H2Oh) = 2,7 + 1.10 .T
(cal/mol.K)
-3
Cp(Fe3O4) = 39,92 + 18,86.10 .T
(cal/mol.K)
-3
Cp(H2)
= 6,95 - 0,2.10 .T
(cal/mol.K)
0
Tnh hiu ng nhit ng p v ng tch 25 C v 1atm?
Tnh hiu ng nhit ng p v ng tch 1000K?
Xt chiu phn ng 250C v 1atm?
Gii
Phn ng: 3Fe(r) + 4H2O(h) = Fe3O4(r) + 4H2(k)
Tnh H0298 = -267 - 4.(-57,8) = - 35,8 Kcal.
Tnh U0298 = H0298 - nR.T vi n = 4 - 4 = 0
Do U0298 = H0298 = -35,8 Kcal
1000
b.
0
1000
Tnh H
0
298
= H
Cp.dT
298
Cp = [4.Cp(H2) + Cp(Fe3O4)] [4.Cp(H2O) + 3.Cp(Fe)]

Cp = 44,53 - 5,08.10-3.T
Ta c:
1000
0
1000 =
-35800 +
(44,53 5,08.10
.T)dT
Tnh bin thin entropy ca qu trnh un nng 2 mol Nit (c xem

l l tng) t 300K n 600K di p sut kh quyn trong 2 trng
hp:
a.
ng p
b.
ng tch
Bit rng nhit dung Cp ca Nit trong khong nhit 300 - 600K
-3
c cho bng phng trnh: Cp = 27 + 6.10 T (J/mol.K).
S: 41 J/K; 29,5 J/K
3.
Tnh bin thin entopy ca qu trnh trn 10g nc 00C vi 50g
nc lng 400C trong h c lp. Cho bit nhit nng chy ca nc
bng 334,4 J/g, nhit dung ring ca nc lng bng 4,18 J/g.
2.
Tnh bin thin entropy ca phn ng:

4 Fe + 3O2 = 2Fe2O3.
0
Cho bit S 298 ca Fe, O2 v Fe2O3 tng ng bng 27,3; 205 v 87,4
J/mol.K.
5.
Hy d on du ca S trong cc phn ng sau:
a.
CaCO3(r) = CaO(r) + CO2(r)
b.
NH3(k) + HCl(k) = NH4Cl(r)
c.
BaO(r) + CO2(k) = BaCO3(r)
S: a. S > 0; b. S < 0; c. S < 0
4.
Tnh G 298 khi to thnh 1 mol nc lng bit cc gi tr entropy tiu

chun ca H2, O2 v H2O ln lt bng 130; 684; v 69,91 J/mol.K v
0
nhit to thnh nc lng 25 C l -285,83 KJ/mol.
6.
298
c.
2.4.
1.
= - 6854,37 (cal)
U01000 = H01000 - nRT vi n = 4 - 4 = 0
0
0
U 1000 = H 1000 = - 6854,37 (cal)
Xt chiu phn ng ktc t cng thc:
0
0
0
G 298 = H 298 T.S 298.
Trong :
0
S 298 = (4x32,21 + 35) (4x45,1 + 3x6,49)
= - 36,03 (cal)
0
G 298 = -35800 + 298x36,03 = - 25063,06 (cal)
0
V: G 298 < 0 nn phn ng t din bin.
Bi tp t gii
Tnh bin thin entropy ca qu trnh un nng ng p 1 mol KBr t
298 n 500K, bit rng trong khong nhit : Cp(KBr) = 11,56 +
-3
3,32.10 T cal/mol.
S: 6,65 cal/mol.K
S:
7.
Tnh
bit:
S
0
298
S0298, H0298
(J/mol.K)
H 0tt,298 ( KJ/mol)
v G
0
298
ca phn ng phn hy nhit CaCO3
CaCO3 =
92,9
-1206,90
S:
G 0298 = -237,154 kJ
CaO
38,1
-635,10
CO2
213,7
-393,50
S o298 = 158,9 J/K; Ho298 = 178,30 kJ;

Go298 = 130,90 kJ
10
8.
Cho phn ng: CO(k) + H2O(k) = CO2(k) + H2(k), c nhng gi tr bin

thin entanpy v bin thin entropy tiu chun 300K v 1200K nh
sau:
0
H300
41,16 KJ/mol
0
S300 42,40 J/K
0
H1200
32,93 KJ/mol
0
S1200 29,60 J/K
Phn ng xy ra theo chiu no 300K v 1200K?

0
S: G 300 28,44 KJ; G1200 2590J

9.
Cho phn ng: CH4(k) + H2O(k) = CO(k) + 3H2(k).
Cho bit nhit to thnh chun ca CH4(k), H2O(h) v CO(k) ln lt l 74,8; -241,8; -110,5 KJ/mol. Entropy tiu chun ca CH4(k), H2O(h) v CO(k)
0
0
ln lt l 186,2; 188,7 v 197,6 J/mol.K. (Trong tnh ton gi s H v S
khng ph thuc nhit ).
0
a.
Tnh G v xt chiu ca phn ng 373K.
b.
Ti nhit no th phn ng t xy ra.
0
5
S: a. G = 1,26.10 J/mol; b. T> 961K
10. Cho phn ng v cc s liu sau:
COCl2(k) = Cl2(k) + CO(k)
- 53,3
0
-26,42
H0298 t.t (Kcal/mol)
S0298 (cal/mol.K)
69,13
53,28
47,3
Cp(CO) = 6,96 (cal /mol.K)
Cp(COCl2) = 14,51 (cal /mol.K)
Cp(Cl2)
= 8,11 (cal /mol.K)
a. Tnh
hiu ng nhit ng p v ng tch ca phn ng
250C?
b. Xt chiu phn ng 250C?
c. Tnh hiu ng nhit ng p ca phn ng 1000K?
0
0
S: a. H = 26,88 Kcal, U = 26287,87 cal
0
0
b. S = 31,45 cal/K, G = 17507,9 cal
0
c. H = 26486,88 cal
0
11. Tnh nhit lng cn thit lm nng chy 90 gam nc 0 C
0
v sau nng nhit ln 25 C. Cho bit nhit nng chy ca nc
00C l 1434,6 cal/mol, nhit dung ca nc lng ph thuc vo
nhit theo hm s: Cp = 7,20 + 2,7.10-3T (cal.mol -1.K-1).
S: Q = 8169,4 cal
Tnh bin thin entropy ca qu trnh ng c benzen di p sut

1atm trong 2 trng hp:
0
a.
ng c thun nghch 5 C bit nhit ng c ca benzen l
-2370 cal/mol.
0
b.
ng c bt thun nghch -5 C.
Bit nhit dung ca Benzen lng v rn ln lt l 30,3 v 29,3
cal/mol.K.
S: a. S = 0 cal/K ; b. S = 0,31 cal/K
13. Cho phn ng v cc s liu sau:
FeO(r) + CO(k) = CO2(k) + Fe(r)
12.
0
-63,7
-26,42
-94,052
0
H 298 t.t
(Kcal/mol)
0
S 298
1,36
47,3
51,06
6,49
(cal/mol.K)
Cp(Fe) = 4,13 + 6,38.10-3.T
(cal/mol.K)
Cp(CO) = 6,34 + 1,84. 10-3.T (cal/mol.K)
-3
Cp(FeO) = 12,62 + 1,50.10 .T (cal/mol.K)
-3
Cp(CO2) = 10,55 + 2,16.10 .T
(cal/mol.K)
a. Tnh0 hiu ng nhit ng p v ng tch ca phn ng
298 K?
b. Tnh 0hiu ng nhit ng p v ng tch ca phn ng
1000 K?
c. Xt chiu phn ng iu kin tiu chun.
d. Xt chiu phn ng 1000K xem entropy khng thay i theo
nhit .
0
0
S: a. H 298 = U 298 = -3932 cal
0
0
b. H 1000 = U 1000 = -4567 cal
14.
Cho phn ng v cc s liu sau:

C(r) + CO2(k) = 2CO(k)
0
S 298 (cal/mol.K)
1,36
0
0
298 (Kcal/mol)
Cp(CO) = 6,96 (cal /mol.K)
Cp(Cgr)
= 2,07 (cal /mol.K)
Cp(CO2) = 8,88 (cal /mol.K)
51,06
-94,052
47,3
-26,42
11
a.
b.
c.

0
Tnh hiu ng nhit ng p v ng tch ca phn ng 25 C

v 1atm.
0
Xt chiu phn ng 25 C v 1atm.
Tnh hiu ng nhit ng p ca phn ng 1000K.
S: a. H0298 = 41212 cal; U0298 = 40619 cal
c. H01000 = 43297 cal
12
Chng 3
Ti nhit khng i, ta c:
Vi
CN BNG HA HC
G0T RTlnKP
p
3.1.
Hng s cn bng
3.1.1. Cc loi hng s cn bng
Phn ng: aA(k) + bB(k)
cC(k) + dD(k)
Hng s cn bng tnh theo p sut :
P c .P d
K P Ca Db
PA .PB
cb
Hng s cn bng tnh theo nng mol/l:
C c .C d
K C Ca Db
C A .C B
P
K x .P n K n .
n i
P C (RT)
x .P
n
ni
3
PCO
2
3
PCO
3.2.2.
Mi quan h ca cc hng s cn bng:

n
Nu P > KP: phn ng xy ra theo chiu nghch

Nu P < KP: phn ng xy ra theo chiu thun
Nu P = KP: phn ng t cn bng
Hng s cn bng: K P
d
D
b
B
n .n
K n
n .n cb
K P K C .RT
Nu cc phn ng xy ra trong cc h d th m cc cht trong pha

rn hoc pha lng khng to thnh dung dch th biu thc nh ngha hng
s cn bng khng c mt cc cht rn v cht lng.
V d: Fe2O3(r) + 3CO(k) = 2Fe(r) + 3CO2(k)
cb
Hng s cn bng tnh theo s mol:

c
C
a
A
G T RTln KPP
3.2. Cn bng trong h d th

3.2.1. Biu din hng s cn bng
Hng s cn bng tnh theo phn mol:
x c .x d
K x Ca Db
x A .x B
PCc .PDd
PAa .PBb
Trong : PA, PB, PC, PD l p sut ring phn ti thi im bt k
Ch :
cb
GT G0T RTln P
cb
n l bin thin s mol kh ca h.

n = (c + d) (a + b)
Nu n = 0 ta c Kp = KC = Kx = Kn
3.1.2. Phng trnh ng nhit Vant Hoff
Xt phn ng: aA(k) + bB(k)
cC(k) + dD(k)
p sut phn ly
p sut hi do s phn ly ca mt cht to thnh l c trng cho
cht mi nhit c gi l p sut phn ly.
V d: CaCO3(r) = CaO(r) + CO2(k)
p sut phn ly: PCO K P
2
3.2.3.
phn ly
phn ly l lng cht phn ly so vi lng cht ban u:
n
no
n: lng cht phn ly
13
no: lng cht ban u

3.3. Cc yu t nh hng n hng s cn bng
3.3.1. nh hng ca nhit n hng s cn bng
T phng trnh ng p Vant Hoff
dlnK P
H
dT
RT 2
K pT2
H 1
1
ln

K pT1
R T2 T1
dlnKP
0 : nh vy khi nhit
Nu phn ng thu nhit, H > 0
dT
tng, gi tr Kp cng tng, phn ng dch chuyn theo chiu thun.
dlnKP
0 : nh vy khi nhit
dT
tng, gi tr Kp s gim, phn ng dch chuyn theo chiu nghch.

3.3.2. nh hng ca p sut
Ti nhit khng i ta c: K p K x .P
n
n
const
Nu n > 0: Khi tng p sut P, gi tr P cng tng, do Kx gim,

cn bng s dch chuyn theo chiu nghch.
Nu n < 0: Khi tng p sut P, gi tr Pn gim, do Kx tng, cn
bng dch chuyn theo chiu thun.
Nu n = 0: th Kp = Kx = const. Khi p sut chung P khng nh
hng g n cn bng phn ng.
3.4. Bi tp mu
V d 1. Hng s cn bng ca phn ng:
CO(k) + H2O(h)
CO2(k) + H2(k) 800K l 4,12.
un hn hp cha 20% CO v 80% H2O (% khi lng) n 800K.
Xc nh lng hydro sinh ra nu dng 1 kg nc.
Gii
Gi x l s mol ca H2O tham gia phn ng.
CO
+ H2O
CO2 + H2
1000
18
Trong khong nhit nh t T1 n T2, xem H khng i. Ly tch

phn 2 v, ta c:
Nu phn ng ta nhit, H < 0,
250
28
250
x)
28
1000
x)
18
V n = 0, ta c hng s cn bng:
KP Kn
n CO 2 .n H 2
n CO .n H 2O
x2
4,12
250
1000
x .
x
28
18
Gii phng trnh ta c: x = 8,55 (mol)

Vy khi lng H2 sinh ra: m = 17,1 (g)
0
V d 2. 200 C hng s cn bng Kp ca phn ng dehydro ha ru
Isopropylic trong pha kh:
CH3CHOHCH3(k)
H3CCOCH3(k) + H2
4
0
bng 6,92.10 Pa. Tnh phn ly ca ru 200 C v di p sut
4
9,7.10 Pa. (Khi tnh chp nhn hn hp kh tun theo nh lut kh l tng).
Gii
Gi a l s mol ban u ca CH3CHOHCH3.
x l s mol CH3CHOHCH3 phn ly, ta c:
CH3CHOHCH3(k)
H3CCOCH3(k) + H2
a
x
0
x
0
x
(a x)
Tng s mol cc cht lc cn bng:
P
K P K n .
n i
0,97.x 2
a2 x 2
ni a x
x.x P

.
vi n = 1
a x a x
cb
0,692
x = 0,764a
14
Vy phn ly:

c.
x
0,764
a
V d 3. un nng ti 445 C mt bnh kn cha 8 mol I2 v 5,3 mol H2 th to

ra 9,5 mol HI lc cn bng. Xc nh lng HI thu c khi xut pht t 8
mol I2 v 3 mol H2.
Gii
Gi x l s mol H2 tham gia phn ng:
H2 +
I2
2HI
Ban u
Phn ng
5,3
x
8
x
0
2x
Cn bng
(5,3 x)
(8 x)
Theo bi: 2x = 9,5 x = 4,75 (mol)
Hng s cn bng:
Kn
a.
Ban u
Phn ng
3
y
Kn
4y
50,49
3 y 8 y
y = 2,87
S mol HI to thnh: nHI = 5,74 (mol)
V d 4. Hng s cn bng ca phn ng:
PCl 3(k) + Cl2(k)
PCl5(k)
-1
500K l KP = 3 atm .
a.
Tnh phn ly ca PCl5 1atm v 8 atm.
b.
p sut no, phn ly l 10%.
Cn bng
a(1-)
KP K n
ni
0
a
0
a
2 2
a P
a1 a1
Vi n = 1, ni = a(1+)
0
2y
P. 2
1
1
3
3P = 1 -
1 3P
Vi P = 1 atm 0,5
Cn bng
(3 y)
(8 y)
2y
V nhit khng i nn hng s cn bng cng khng i:
2
a
a
Ta c
2HI
8
y
Ban u
Phn ng
2x
n 2HI
4x 2
50,49
n H 2 .n I 2 5,3 x 8 x
Hn hp 8 mol I2 v 3 mol H2.

H2 +
I2
Phi thm bao nhiu mol Cl2 vo 1mol PCl5 phn ly ca PCl5
8 atm l 10%.
Gii
Tnh phn ly ca PCl 5
Gi a l s mol PCl 5 ban u
l phn ly ca PCl 5, ta c:
PCl5(k)
PCl3(k) + Cl 2(k)
b.
c.
Vi P = 8 atm 0,2
p sut no phn ly l 10%
Ta c
P. 2 1
1 2 3
0,1 2.P
1
2
3
1 0,1
P = 33 atm
Lng Cl 2 cn thm vo
Gi b l s mol Cl 2 cn thm vo:
15
PCl5(k)
Ban u
Phn ng
Cn bng

n
PCl3(k) + Cl2(k)
1
0,1
0
0,1
0,9
0,1
b
0,1
(b + 0,1)
Ta c: K P K n
n
i
0,1. b 0,1 8 1
0,9
b 1,1 3
b = 0,5 (mol)
V d 5. C th iu ch Cl2 bng phn ng
4HCl(k) + O2 = 2H2O(h) + 2Cl2
0
Xc nh HSCB KP ca phn ng 386 C, bit rng nhit v p
sut 1 atm, khi cho mt mol HCl tc dng vi 0,48 mol O2 th khi cn bng s
c 0,402 mol Cl2.
Gii
Gi x l s mol O2 tham gia phn ng.
Tng s mol lc cn bng:
ni 1,48 x ; n = -1
2
2
P
2x .2x
KP
4
0,48 x . 1 4x n i cb
KP
1
4x
0,48
x
0
2x
0
2x
(1 - 4x)
(0,48 - x)
2x
2x
1,315
x
Hng s cn bng:
0
x
(1,315 - x)
Theo bi ta c: x = 1,255 (atm)
Hng s cn bng:
PH4 2
1,255
1,91.10 5
1,315 1,255
PH4 2O
Gi x l p sut ring phn ca H2 lc cn bng:

3Fe + 4H2O(h)
Fe3O4(r) + 4H2
3
x
K P K n .
n
i cb
-1
(atm )
V d 6. Cho Fe d tc dng vi hi nc theo phn ng:

3Fe + 4H2O(h) = Fe3O4(r) + 4H2
0
200 C nu p sut ban u ca hi nc l 1,315 atm, th khi cn
bng p sut ring phn ca hydro l 1,255 atm. Xc nh lng hydro to
thnh khi cho hi nc 3atm vo bnh 2 lit cha st d nhit .
Gii
Gi x l s mol H2O tham gia phn ng:
3Fe + 4H2O(h)
Fe3O4(r) + 4H2
KP
Theo bi ta c: 2x = 0,402 x = 0,201 (mol)

4HCl(k) + O2
2H2O(k) + 2Cl2(k)
0,402 4 1 1 81,2
0,279 . 0,196 4 1,279
0
x
(3 x)
x
KP
PH4 2
PH4 2O
x
5
1,91.10
3 x
16
x = 2,863 (atm)
S mol kh H2 sinh ra:
CO + 2H2 = CH3OH(k)
CO + 2H2 = CH3OH(l)
P.V
2,863 2
0,148
RT 0,082 473
m H2 2 0,148 0,296(g)
PV nRT n
Khi lng kh H2 sinh ra:
(mol)
V d 7. p sut tng cng do phn ng nhit phn

2FeSO4(r) = Fe2O3(r) + SO2(k) + SO3(k)
nhit 929K l 0,9 atm.
a.
Tnh hng s cn bng KP 929K ca phn ng.
b.
Tnh p sut tng cng khi cn bng nu cho d FeSO4 vo bnh c
SO2 vi p sut u l 0,6 atm 929K.
Gii
a.
Hng s cn bng:
K p PSO .PSO 0,45 0,45 0,2025 (atm2)
2
b.
K P(2)
Ta c:
K P(1)
p sut tng cng:

Gi x l s mol ca SO3 sinh ra:
2FeSO4
Fe2O3(r) + SO2 +
Suy ra:
SO3
0,6
x
0
x
(0,6 + x)
x
K p PSO2 .PSO3 x.0,6 x 0,2025

x2 + 0,6x - 0,2025 = 0
x = 0,24 (atm)
p sut ca hn hp:
P PSO2 PSO3 0,24 084 1,08 (atm)

V d 8. Tnh HSCB KP 250C ca phn ng
CO + 2H2 = CH3OH(k)
bit rng nng lng t do chun Go i vi phn ng
CO + 2H2 = CH3OH(l)
0
bng -29,1 KJ/mol v p sut hi ca metanol 25 C bng 16200 Pa.
Gii
1
PCO .PH22
PCH3OH
PCO .PH22
0
Mt khc: G (2)
RTlnK
(1)
(2)
PCH3OH .K P(2)
P(2)
G0(2)
K P(2) exp
RT
29,1.10 3
126168 (atm-3)
exp
8,314
298
K P(1)
16200
126168 20177
1,013.105
-2
(atm )
V d 9. Hng s cn bng 1000K ca phn ng:

-21
2H2O(h) = 2H2 + O2 l KP = 7,76.10 atm.
-18
p sut phn ly ca FeO nhit l 3,1.10 atm. Hy xc nh HSCB
KP 1000K ca phn ng
FeO(r) + H2 = Fe(r) + H2O(h)
Gii
2H2O(h) = 2H2 + O2
(1)
2FeO(r) = 2Fe(r) + O2
(2)
FeO(r) + H2 = Fe(r) + H2O(h)
(3)
Ta c: 2p. (3) = p. (2) - p. (1)
G0(3) = G0(2) - G0(1)
2RTlnKP(3) RTlnKP(2) RTlnKP(1)
2lnK P(3) lnK P(2) lnK P(1)

K 2P(3)
K P(2)
K P(1)
M: Kp(1) = 7,76.10
-21
(atm)
17
Kp(2) = 3,1.10-18 (atm)

Suy ra: K P(3)
K P(2)
K P(1)
Gi x l s mol COF2 tham gia phn ng:

2COF2(k)
CO2 + CF4(k)
3,1.10 18
19,99
7,76.10 21
a
x
V d 10. Cho phn ng:

CuSO4.3H2O(r) = CuSO4(r) + 3H2O(h)
0
-6
3
bit hng s cn bng KP 25 C l 10 atm . Tnh lng hi nc ti thiu
o
phi thm vo bnh 2 lt 25 C chuyn hon ton 0,01 mol CuSO4 thnh
CuSO4.3H2O.
Gii
Gi x l mol H2O thm vo:
CuSO4.3H2O(r)
CuSO4(r) + 3H2O(h)
Ban u
Phn ng
0,01
0,01
(a x)
Tng s mol lc cn bng:
KP K n
Hng s cn bng:
P
Kp Kn
n
i
1
3
x 0,03
RT
b.
2
1
0,082 298 x 0,03 10 2

2
nCO2 .n CF4
1
10 6
x 3,08.10 (mol)
o
V d 11. Cho kh COF2 qua xc tc 1000 C s xy ra phn ng
2COF2(k)
CO2 + CF4(k)
Lm lnh nhanh hn hp cn bng ri cho qua dung dch Ba(OH)2 hp
thu COF2 v CO2 th c 500 ml hn hp cn bng s cn li 200ml khng b
hp thu.
a.
Tnh HSCB KP ca phn ng.
o
o
o
o
o
b.
Bit KP tng 1% khi tng 1 C ln cn 1000 C, tnh H , S v G
o
ca phn ng 1000 C.
Gii
a.
Tnh HSCB KP ca phn ng
ni a
V n = 0, hng s cn bng:
(x - 0,03)
x 0,03 (mol)
n
x
2
x
2
x
n
V
2 200 x 4a
Ta c: CF4 CF4
a 500
5
n i Vi
x
0,03
Cn bng
0,00
Tng s mol ti thi im cn bng:
x
2
x
2
2
nCOF
2
o
x
4a2

2
2 25
4
a2
a x
25
o
Kp tng 10% khi tng 1 C ln cn 1000 C.

o
Hng s cn bng KP 1001 C:
Kp = 4 + 0,04 = 4,04
ln
Ta c:
K p(T1 )
4,04
K p(T1 ) 1,987ln 4
32065 (cal)
1 1
1
1
T2 T1
1274 1273
0
G 1000
RTlnK
Ta li c:
1
1

T2 T1
K p(T2 )
Rln
0
H1000
0
H 1000
K p(T2 )
0
G 1000
p(1000)
0
= H
1000
1,987 1273 ln4 3507 (cal)

0
1000
- TS
18
0
1000
0
0
H1000
G1000
32065 3507
27,94
T
1273
(cal/K)
V d 12. 1000K hng s cn bng ca phn ng:

C(gr) + CO2(k)
2CO(k)
l Kp =1,85 atm v hiu ng trung bnh l 41130 cal. Xc nh thnh phn
pha kh cn bng ti 1000K v 1200K bit p sut tng cng l 1atm.
Gii
1000K: gi xCO v x CO l phn mol ca cc kh cn bng:
2
Ta c, hng s cn bng:
Suy ra:
K Kx .n
x
x CO 2
M: x CO x CO 1
2
vi n = 2 1 =1
2
CO
xCO2 1 xCO
2
x CO
K
1 x CO
2
2
CO
1,85.xCO 1,85 0
Gii phng trnh ta c: xCO= 0,72 v x CO = 0,28.
2
ln
ln
K , 2
K ,1
K ,1200
1,85
(1)
b.
1
1
R 2 1
Biu th = f(T) di dng mt hm ca nhit .

Tnh Kp 1270C.
Gii
a.
Tnh G0, H0, Kp 250C ca phn ng:
H0298 = -393,13 + 0 + 110,43 + 219,03 = -63,67 (KJ)
G0298 = -394 + 0 + 137,14 + 198,14 = -67,72 (KJ)

Hng s cn bng:
b.
c.
lnK P
Vy x CO K.xCO K 0
Vi Kp = 1,85 atm
CO
CO2
Pb
PbO
0
-110,43
-393,13
0
-219,03
H 298,tt
(KJ/mol)
0
-137,14
-394,00
0
-189,14
G 298
(KJ/mol)
Cp,298
29,05
36,61
26,50
46,27
(J/mol.K)
0
Chp nhn nhit dung khng thay i trong khong nhit 25 -127 C.
0
0
0
a.
Tnh G , H , Kp 25 C ca phn ng:
PbO(r) + CO(k) = Pb(r) + CO2(k)
x 2CO 58,28.xCO 58,28 0

Gii phng trnh ta c: xCO = 0,98 x CO = 0,02
2
11
Kp = 7,4.10 (atm)
0
Biu th di dng mt hm ca T.
Cp,298 = 36,61 + 26,50 29,05 46,27
= - 12,21 (J/K)
0 0298
(12,21) d
298
41130 1
1
1,987 1200 1000
Ta tnh c:
KP,1200 = 58,28 atm
Thay vo phng trnh (1) c:
G 0298
67,72.10 3
27,33
RT
8,314 298
298
63670
(12,21)d 63670 12,21( 298)
60031,42 12,21 (J)

c.
Tnh Kp 127 C
ln
P,T2
P,T1
1
1
R 2 1
V d 13. Cho cc d kin sau:
19
ln
K p, T2
K p, T1

T
63670 1
1
6,55
8,314 400 298
d.
Vy
V d 14. Cho phn ng v cc s liu tng ng sau:

Ckc (r) + 2H2(k) =
CH4(k)
c.
d.
a.
b.
0
0,453
0
-7,093
H 298
(Kcal/mol)
0
0,568
31,21
44,50
S 298
(cal/mol.K)
Cp
2,18
6,52
4,170
(cal/mol. K)
0
Hy xc nh G 298 v Kp298 ca phn ng trn.
0
25 C khi trn 0,55 mol kh CH4 vi 0,1 mol kh H2 trong bnh cha
Ckc rn (d), th phn ng xy ra theo chiu no nu p sut tng
cng gi khng i 1 atm? Gii thch.
Kh H2 c nn vo bnh c cha Ckc rn d iu kin p sut 1
atm v nhit 298K. Hy xc nh p sut ring phn ca CH4 khi
cn bng nhit p sut trn.
0
Thit lp phng trnh H = f(T) (phng trnh ch c s v T) v tnh
0
0
H 1000 K.
Gii
0
H 298(p) = -7,093 0,453 = -7,546 (Kcal)
0
S 298(p) = 44,50 0,568 2x31,21 = -18,488 (cal)
0
G 298 = -7546 + 298x18,488 = -2036,576 (cal)
-1
KP298 = 31,169 (atm )
p n
n
i
0,55
1
2
0,1 0,1 0,55
35,75(atm 1 )
p > Kp suy ra phn ng xy ra theo chiu nghch.

c.
Kp
PCH 4
PH2 2
0
H1000
11,05 1000 4253,1 15303,1 (cal)
3.5.
1.
2.
= - 15,3031 (Kcal)
Bi tp t gii
0
Ti 50 C v p sut 0,344 atm, phn ly ca N2O4 thnh NO2 l
63%. Xc nh KP v KC.
S: Kp = 0,867 (atm); KC= 0,034 (mol/l)
630C hng s cn bng KP ca phn ng:
N2O4
2NO2 l 1,27. Xc nh thnh phn hn hp cn bng
khi:
a.
b.
p sut chung bng 1atm.

p sut chung bng 10 atm.
S: a. 65,8% NO2; 34,2% N2O4

b. 29,8% NO2; 70,2% N2O4
3.
un 746g I2 vi 16,2g H2 trong mt bnh kn c th tch 1000 lit n
0
420 C th cn bng thu c 721g HI. Nu thm vo hn hp u
1000g I2 v 5g H2 th lng HI to thnh l bao nhiu?
S: 1582 g
4.
Xc nh hng s cn bng Kp ca phn ng sau 700K
SO2 + 1/2O2 = SO3
Bit rng 500K hng s cn bng Kp = 2,138.105 atm -1/2 v hiu
ng nhit trung bnh trong khong nhit 500 700K l -23400 cal.
S: 2,6.10+2 atm-1/2
5.
1000K hng s cn bng ca phn ng:
2SO3(k) + O2(k)
2SO3(k)
C hng s cn bng KP = 3,5 atm-1. Tnh p sut ring phn lc cn
bng ca SO2 v SO3 nu p sut chung ca h bng 1 atm v p sut cn
bng ca O2 l 0,1 atm.
S: PSO 2 0,75 atm , PSO 0,15 atm
3
6.
Ta c PCH 4 PH 2 1 31,169P
Ta c
H0T 11,05T 4253,1 (cal)
31,169 PCH 4 31,169P H2 2

2
H2
C p dT 7546 11,05(T 298)
298
,400 e 6,55 7,4.1011 1,055.109 (atm)
a.
b.
H0T H0298
PH 2 1 0
PH2 0,164(atm),PCH4 0,836(atm)
Tnh G v hng s cn bng Kp 25 C ca phn ng sau:

NO + O3
NO2 + O2 .
Cho bit cc s liu sau:
NO2
O2
NO
O3
20
H 0298, tt (KJ/mol)
S
0
298
(J/mol.K)
33,81
240,35

0
240,82
90,25
210,25
142,12
S.
237,42
34
S: Kp= 5.10
0
0
7.
298K phn ng: NO + 1/2O2 = NO2, c G = -34,82 (KJ) v H
= -56,34 (KJ). Xc nh hng s cn bng ca phn ng 298K v
598K.
S: Kp= 1,3.106 2980K v Kp= 12 5980K
8.
nhit T v p sut P xc nh, mt hn hp kh cn bng gm 3
mol N2, 1 mol H2 v 1 mol NH3.
a.
Xc nh hng s cn bng Kx ca phn ng.
3H2(k) + N2(k)
2NH3(k)
b.
Cn bng s dch chuyn theo chiu no, khi thm 0,1 mol N2
vo hn hp cn bng T v P khng i.
S: a. Kx= 8,33; b. Kx = 8,39
9.
Hng s cn bng ca phn ng:
PCl3(k) + Cl 2(k)
PCl5 (k) 500K l KP = 3 atm-1.
a.
Tnh phn ly ca PCl5 2 atm v 20 atm.
b.
p sut no, phn ly l 15%.
S: a. 44,7%; 13%; b. 14,48 atm
10. Cho phn ng thy phn este axetat etyl.
CH3COOC2H5 + H2O
CH3COOH + C2H5OH
Nu ban u s mol ca este bng s mol nc th khi cn bng c
1/3 lng este b thy phn.
a.
Xc nh hng s cn bng ca phn ng thy phn.
b.
Tnh s mol este b thy phn khi s mol nc ln gp 10 ln
s mol este.
c.
Tnh t l mol gia nc v este khi cn bng 99% este b
thy phn.
S: a. Kn = 0,15; b. 75,9%; c. 393 ln
11. Cho phn ng:
C2H4(k)
+ H2(k)
C2H6(k)
Lp cng thc tnh s mol ca C2H6 trong hn hp cn bng theo s
mol ban u ca C2H4 l a, ca H2 l b, hng s cn bng Kp v p sut cn
bng ca h l P.
ab
a b 2
4
abPK P
P.K P 1
Cho phn ng: CO + Cl2

COCl2
C phng trnh m t s ph thuc ca Kp vo nhit T l:
lgKp(atm) = 5020/T 1,75lgT 1,158.
a. Tm phng trnh m t s ph thuc nhit : G0T = f(T) v
H0T = g(T).
b. Tnh G0, H0, S0 v hng s cn bng KP, KC 700K.
c. Hn hp phn ng sau s xy ra theo chiu no 1atm v
700K:
2 mol CO; 5 mol Cl2 v mol 3 COCl2.
0,4 mol CO; 1,6 mol Cl2 v 8 mol COCl2.

13. C th iu ch Cl 2 bng phn ng:
4HCl(k) + O2
2H2O(h) + 2Cl2
0
Xc nh HSCB KP ca phn ng 386 C, bit rng nhit v
p sut 1 atm, khi cho 1 mol HCl tc dng vi 0,5 mol O2 th khi cn bng s
c 0,4 mol Cl 2.
S: Kp = 69,3 atm-1
0
14. 40 C, hng s cn bng ca phn ng:
LiCl.3NH3(r)
LiCl.NH3(r) + 2NH3(k)
2
l Kp = 9 atm , nhit ny phi thm bao nhiu mol NH3 vo mt bnh c
th tch 5 lit cha 0,1mol LiCl.NH3(r) tt c LiCl.NH3(r) chuyn thnh
LiCl.3NH3(r).
12.
21
Chng 4
CN BNG PHA
Mt s khi nim c bn
Pha: l tp hp nhng phn ng th ca mt h, c cng thnh phn

ha hc v tnh cht l ha mi im. S pha k hiu l f
S cu t: l s ti thiu hp phn to ra h. K hiu l k
t do ca mt h l thng s nhit ng c lp xc nh h
cn bng. K hiu l c.
4.2. Qui tc pha Gibbs
Bc t do ca h:
c=k-f +n
Trong :
k: s cu t
f: s pha
n: s thng s bn ngoi tc ng ln h
4.3. Gin pha v cc qui tc cn bng pha
4.3.1. Biu din thnh phn ca h 2 cu t
Thnh phn ca cc cu t trn gin pha thng dng l phn mol
xi hay phn trm khi lng yi. Trong h hai cu t, dng mt on thng
c chia thnh 100% nh sau:
4.1.
Hnh 4.1. Gin pha h hai cu t

Trn trc to ch cn biu din cho mt cu t v thnh phn ca
cu t cn li c xc nh theo cng thc: xA + xB = 1 hay y1 + y2 = 100%
Khi im biu din ca h cng gn cu t no th hm lng ca cu
t cng ln.
4.3.2. Biu din thnh phn ca h 3 cu t
Thnh phn ca h 3 cu t thng c biu din bng mt tam
gic u nh sau:
Hnh 4.2. Gin pha h ba cu t

Ba nh ca tam gic l ba im h ca cc cu t nguyn cht A, B
v C.
Ba cnh ca tam gic biu din ba h hai cu t tng ng l AB, AC

v BC.
Mi im trong tam gic biu din h 3 cu t.

Cch biu din im P(40%A, 40%B, 20%C) trn gin tam gic
u ABC.
Trn cnh AC, ta v ng thng i qua im 40% v song song vi
cnh BC.
Trn cnh AB, ta v ng thng i qua im 40% v song song vi
cnh AC.
Trn cnh BC, ta v ng thng i qua im 20% v song song vi
cnh AB.
Ta thy 3 ng thng trn ct nhau ti P. Vy P l im biu din
ca h c thnh phn (40%A, 40%B, 20%C).
4.4. Cc qui tc ca gin pha
4.4.1. Qui tc lin tc
22
Hnh 4.5. Minh ha quy tc n by

p dng quy tc n by, ta c:
g M HN
g N HM
Hnh 4.3. Gin nhit - thi gian ca cht nguyn cht.

Cc ng hoc cc mt trn gin pha biu din s ph thuc
gia cc thng s nhit ng ca h s lin tc nu trong h khng xy ra
s bin i cht, s thay i s pha hoc dng cc pha.
Nh vy ta c th suy ra, nu trong h c s thay i v pha hay s thay i
v dng pha th trn cc ng hay cc mt s xut hin cc im gy, lm
cho th khng cn lin tc.
4.4.2. Qui tc ng thng lin hp
Trong iu kin ng nhit v ng p nu h phn chia thnh hai h
con (hay c sinh ra t hai h con) th im biu din ca ba h ny phi
nm trn cng mt ng thng, ng thng ny gi l ng thng lin
hp.
Hnh 4.4. Minh ha quy tc ng thng lin hip

V d: h H = h M + h N. Th im biu din cc h H, M v N nm
thng hng.
4.4.3. Qui tc n by
Nu c ba im h lin hp M, H v N th lng tng i ca chng
c tnh theo qui tc n by nh sau:
Trong : gM: Khi lng ca h M

gN: Khi lng ca h N
4.4.4. Qui tc khi tm
Nu mt h gm n h con th im biu din ca n phi nm khi
tm vt l ca a gic c nh l cc im biu din ca n h con.
V d: H H gm ba h con l H1, H2 v H3. vi khi lng tng ng
l:
g = g1 + g2 + g3
Hnh 4.6. Minh ha quy tc khi tm

Nh vy, H phi nm khi tm vt l ca tam gic H1H2H3. u tin
ta xc nh im biu din ca h K, tha mn iu kin:
H K = h H1 + h H2
v
g1 H2K
g2 H1K
Tip theo ta xc nh im H tha mn iu kin sau:

H H = h K
+
h H3
23
v
4.5.
gK g1 g2 HH3
g3
g3
KH
nh hng ca p sut n nhit chuyn pha

Phng trnh Clausius Claypeyron I:
dT T.V
dP
Trong :
T: nhit chuyn pha (K)
: nhit chuyn pha (cal/mol hoc J/mol)
V = V2 V1: bin thin th tch (ml)
Nu V c tnh bng ml, c tnh bng cal v 1cal = 41,3
ml.atm, nn phng trnh Clausius Claypeyron tr thnh:
dT T.V
dP 41,3.
4.6.
nh hng ca nhit n p sut hi bo ha

Phng trnh Clausius Claypeyron II
dlnP
dT RT2

p dng phng trnh:
Vi: V = Vlng Vrn

= 1,001 1,098 = - 0,097 (ml/g)
Hoc: V = 18.(- 0,097) = -1,746 (ml/mol)
dT 273 1,746
0,0081 (K/atm)
dP 1434,6 41,3
Nh vy, c tng p sut ln 1 atm th nhit nng chy ca nc
gim 0,0081K. Mt cch gn ng, 4atm, nhit nng chy ca nc
l:
T = 273 + (-0,0081) x (4 - 1)
0
= 272,9757K = - 0,0243 C
V d 2. Tnh nhit si ca nc 2 atm, bit nhit ha hi ca n l
538,1 cal/g (coi nhit ha hi khng thay i trong khang t 1 atm n 2
atm).
Gii
Nhit ha hi: = 538,1x18 = 9685,8 (cal/mol)
p dng cng thc:
Ly tch phn 2 v, ta c:
P
1
1
ln 2

P1
R T2 T1
Trong :
T: nhit (K)
P: p sut (atm)
: nhit ha hi (cal/mol hoc J/mol)
R: l hng s kh
4.7. Bi tp mu
0
V d 1. 0 C nhit nng chy ca nc l 1434,6 cal/mol. Th tch
ring ca nc v nc lng ln lt l 1,098 v 1,001 ml/g. Xc nh h
s nh hng ca p sut n nhit nng chy ca nc v tnh nhit
nng chy ca nc 4 atm.
Gii
dT T.V
dP
ln
ln
P2
1
1

P1
R T2 T1
2
9685,8 1
1
1
1,987 T 100 273
T tnh c: T = 394K = 1210C

V d 3. Tnh nhit nng chy ca 1 mol diphenylamin nu 1kg diphenylamin
-5 3
-7
nng chy lm tng th tch ln 9,58.10 m cho bit dT/dP = 2,67.10
2
0
K.m /N. Nhit nng chy ca diphenylamin l 54 C, khi lng mol ca
cht ny l 169.
Gii
p dng cng thc:
dT T.V
dP
24
T.V
dT
dP
273 54 169 9,58.105

1000
2,67.107
19,83.103
(J/mol)
V d 4. p sut hi bo ha ca axit xyanhydric HCN ph thuc vo nhit

theo phng trnh:
lgP(mmHg) 7,04
1237
T
Xc nh nhit si v nhit ha hi ca n iu kin thng.

Gii
Nhit si ca axit HCN p sut 760 mmHg:
Ta c:
lg(760) 7,04
1237
T
T = 297,4K
0
Vy nhit si ca axit HCN l 24,4 C.
Ly o hm hai v phng trnh theo T, ta c:
dlgP 1237
2
dT
T
M:
Suy ra:
dlgP
dT
4,575.T2
1237
2
2
4,575.T
T
mAo = 20% 200 = 40 (g)

Phn trm ca cht C trong lp th 1:
%C = 100 - 50 - 20 = 30 (%)
Vy im biu din ca lp 1: I1 (50%A, 20%B, 30%C)
Khi lng lp th 2:
m = 200 60 = 140 (g)
Khi lng ca cht A trong lp th 1:
mA1 = 50% 60 = 30 (g)
Khi lng ca cht A trong lp th 2:
mA2 = 40 - 30 = 10 (g)
Khi lng ca cht B trong lp th 2:
mB2 = 80% 140 = 112 (g)
Khi lng ca cht C trong lp th 2
mC2 = 140 - 122 = 17 (g)
im biu in lp 2: I2 (7,15%A, 80%B,12,85%C)
V d 6. Khi lng ring ca phenol dng rn v dng lng ln lt l 1,072
v 1,056 g/ml, nhit nng chy ca phenol l 24,93 cal/g, nhit kt tinh
0
ca n 1 atm l 41 C. Tnh nhit nng chy ca phenol 500 atm.
Gii
p dng phng trnh:
Vi:
Ta c:
= 5659 (cal/mol)
V d 5. Trn 200g hn hp gm 3 cht A, B, C cha 20% A, khi cn bng

hn hp chia lm hai lp.
Lp th nht c khi lng 60g v bao gm 50% A v 20% B.
Lp th hai cha 80%B.

Hy xc nh im biu din ca ba cu t A, B, C trn gin tam
gic u trong hai lp trn.
Gii
c gi t v hnh
Khi lng ca cht A trong hn hp ban u:
dT T.V
dP
1
1
0,014 (mol/g)
1,056 1,072
dT 314 0,014
4,26.10 3
dP 24,93 41,3
(K/atm)
Nh vy, c tng p sut ln 1 atm th nhit nng chy ca phenol

-3
tng 4,26.10 K. Mt cch gn ng, 500atm, nhit nng chy ca
phenol l:
-3
T = 314 + 4,26.10 (500 - 1)
0
= 316,13K = 43,13 C
V d 7. p sut thng, nhit si ca nc v cloroform ln lt l
0
0
100 C v 60 C, nhit ha hi tng ng l 12,0 v 7,0 kcal/mol. Tnh nhit
m 2 cht lng trn c cng p sut?
Gii
Gi T l nhit m ti 2 cht lng c cng p sut:
25
Ta c:

8.
1 1
1 1
1 2
T1 T
T2 T
0
Vi: 1 = 12 (Kcal/mol), T1 = 273 + 100 = 373 K

0
2 = 7 (Kcal/mol), T2 = 273 + 60 = 333 K
Th cc gi tr vo phng trnh trn, ta c:
9.
Tnh p sut cn thit nhit si ca nc t c 1200C. Cho

bit nhit ha hi ca nc l 539 cal/g.
S: P = 2 atm
Cho gin pha ca h 3 cu t (hnh di). Xc nh thnh phn
ca A, B, C khi im h chung l im P v hy kt lun v thnh
phn ca A, B khi im h dch chuyn theo ng thng ni t nh
C vi im I.
1
1
1
1
12
7

373 T
333 T
4.8.
1.
2.
3.
4.
5.
6.
7.
Suy ra: T = 448,40K

Bi tp t gii
0
Xc nh nhit ha hi ca H2O 4 atm nu 100 C nhit ha hi
ca nc bng 2254,757 J/g.
Xc nh nhit si ca benzoatetyl (C9H10O2) p sut 200 mmHg
0
bit rng nhit si chun ca benzoatetyl l 213 C v nhit ha hi
bng 44157,52 (J/mol).
S: T = 433,10K
0
Nhit nng chy chun ca Bi l 271 C. iu kin khi lng
3
ring ca Bi rn v lng l 9,673 v 10 g/cm . Mt khc khi p sut
tng ln 1 atm th nhit nng chy gim i 0,00354K. Tnh nhit
nng chy ca Bi.
S: 11 kJ/mol.
0
Ti 127 C HgI2 b chuyn dng th hnh t dng sang dng vng.
3
-1
Nhit chuyn ha l 1250 J/mol, V = 5,4 cm .mol , dng c t
0
trng ln hn dng vng. Xc nh dT/dP ti 127 C.
-6
S: -1,73.10 K/Pa
Khi un nng lu hunh rombic chuyn thnh lu hunh n t km
3
theo bin thin th tch V = 0,0000138 m /kg. Nhit chuyn ha
chun bng 96,70C v dT/dP = 3,25.10-7 K/Pa. Xc nh nhit chuyn
pha.
S: = 501,24 kJ/kg
Xc nh th tch ring ca thic lng ti nhit nng chy chun
0
232 C nu nhit nng chy ring l 59,413 J/g, khi lng ring ca
3
-8
thic rn l 7,18 g/cm v dT/dP = 3,2567.10 K/Pa.
3
S: 0,147 cm /g
0
200 mmHg metanol si 34,7 C cn khi tng p sut ln gp i
0
th nhit si l 49,9 C. Tnh nhit si chun ca metanol.
S: 65,40C
10.
S: %A = 40%, %B = 40%, %C = 20%

Nc nguyn cht c th tn ti 9 dng pha khc nhau (kh, lng v
7 dng rn). Tnh s pha ti a ca nc c th ng thi nm cn
bng vi nhau.
26
Chng 5
Hng s cn bng:
DUNG DCH V CN BNG
DUNG DCH - HI
5.1.
Do ta c:
gi
100(%)
g 1 g 2 ... g n
CM
Nng mol/lit:
Nng ng lng gam (lg/l):
Cm
CN
n'
V
n ct
1000
m dm
Nng molan (Cm):
ni
Nng phn mol: x i
ni
1
1
lnx i 0
i
R T T
n
V
lnKp
i
T
2
RT
Ly tch phn phng trnh, ta c:
Cch biu din thnh phn ca dung dch

Nng phn trm khi lng (%):
C %,i
x i (dd)
x i (kh)
CN = z.CM (z: s in tch trao i trong phn ng)

5.2. S ha tan ca kh trong cht lng
5.2.1. nh hng ca p sut n tan ca cc kh trong cht lng
nh lut Henry: nhit khng i, ha tan ca mt kh trong
mt cht lng t l thun vi p sut ring phn ca kh trn pha lng
xi = kH.Pi
Trong :
kH l hng s Henry
Pi l p sut hi ca pha kh trn pha lng
5.2.2. nh hng ca nhit n ha tan ca kh trong cht
lng, phng trnh Sreder
Xt cn bng:
i (kh) = i (dung dch c nng xi) + Hha tan
Vi: T l nhit ngng t (nhit si)

5.3. S ha tan ca cht lng trong cht lng v cn bng dung dch hi
5.3.1. H dung dch l tng tan ln v hn
5.3.1.1. p sut hi - nh lut Raoul
p sut hi bo ha ca mi cu t bt k t l thun vi phn phn
t ca n trong dung dch.
Pi k R .x li
Pi0
Khi dung dch ch c cu t i (dung dch i nguyn cht): xi = 1 v kR =
Pi Pi0 .x il
i vi dung dch thc, nh lut Raoult ch c th p dng cho dung
0
mi ca dung dch v cng long: P1 P1 .x 1

5.3.1.2. Gin p sut - thnh phn (P - x)
p dng nh lut Raoult cho dung dch l tng ca hai cu t (A - B):
PA PA0 .xlA PA0 . 1 x lB

0
B
PB P .x
l
B
(1)
(2)
p sut tng ca h l:
P = PA + PB
PA0 . 1 x Bl PB0 .x lB
0
A
P PB0 PA0 .x lB
(3)
Nu ta biu din cc phng trnh (1), (2) v (3) ln th p sut - thnh
phn (P - x) ta c hnh 5.1.
27
Hnh 5.1. Gin p sut hi (P - x) ca dung dch 2 cu t l tng

5.3.1.3. Thnh phn pha hi nh lut Konovalop I
Xt h dung dch l tng ca hai cu t A v B nm cn bng vi
pha hi ca chng.
Theo nh lut Raoult ta c:
0
l
l
xh
B PB x B . x B (nh lut Konovalop I)
0
l
xh
x lA
A PA x A
P0
Trong B v c gi l h s tch hay h s chng ct
PA0
5.3.1.4. Gin thnh phn hi thnh phn lng
T nh lut Konovalop I, ta bin i rt ra biu thc:
xh
B
.x l
B
.x l
B
x h x h x l .x l
(1 x l ) .x l
A
B
A
B
B
B
l
.x
B
xh
(4)
B
1 1.x l
B
Biu din phng trnh (4) ln th (x - x) ta c cc ng trn hnh 5.2.
Hnh 5.2. Gin (x-x) ca h hai cu t A-B

5.3.2. H dung dch thc tan ln v hn
5.3.2.1. p sut hi
Dung dch sai lch dng c p sut hi trn dung dch ln hn p

sut hi tnh theo nh lut Raoult.
Dung dch sai lch m c p sut hi trn dung dch nh hn p sut

hi tnh theo nh lut Raoult.
5.3.2.2. Thnh phn pha hi, nh lut Konovalop II
i vi nhng h c thnh phn ng vi im cc tr trn ng p
sut hi tng cng (P - x) th pha lng v pha hi cn bng c cng thnh
phn.
x lgB x hB
5.3.3.
H hai cht lng hon ton khng tan ln
5.3.3.1. Tnh cht
Thnh phn ca pha hi cng ch ph thuc vo nhit m khng

ph thuc vo thnh phn ca hn hp lng.
x hB PB PB0
f(T)
x hA PA PA0
Nhit si ca hn hp cng khng ph thuc vo thnh phn, n
nh hn nhit si ca mi cu t v ch ph thuc vo p sut bn
ngoi.
Trong qu trnh si, nhit si ca hn hp s gi nguyn cho n

khi mt trong hai cu t chuyn ht thnh hi, th nhit si ca h
s tng vt n nhit si ca cu t cn li.
5.3.3.2. Chng ct li cun theo hi nc
28
g H 2O
Trong :
PH02O
PH0 2 O
PA0
0
A

m H 2O
18
MA
M:
18
x H 2O
m H 2O
ln lt l p sut hi ca nc v ca cht
18
A.
m gly
0,997
92
m gly 0,014mH2O
5.3.3.3. nh lut phn b
Suy ra:
nhit v p sut khng i, t s nng ca mt cht tan trong

hai dung mi khng tan ln l mt hng s khng ph thuc vo lng
tng i ca cht tan v dung mi.
Nng phn trm ca dung dch glycerin
C%
C Y/A
K
C Y/B
CY/A, CY/B: l nng ca cht tan Y trong dung mi A v trong dung
mi B.
K: h s phn b
5.4. Bi tp mu
0
V d 1: Tnh p sut hi ca dung dch ng (C12H22O11) 5% 100 C v
nng % ca dung dch glycerin trong nc c p sut hi bng p
sut hi ca dung dch ng 5%.
Gii
p sut hi ca dung dch ng:
P 760
P PH02O .xH2O
m gly m H 2O
100
0,014m H 2 O
0,014m H 2O m H 2 O
100 1,38 (%)
V d 2. 123,3 C bromobenzen (1) v clorobenzen (2) c p sut hi bo

ha tng ng bng 400 v 762 mmHg. Hai cu t ny to vi nhau mt
dung dch xem nh l tng. Xc nh:
0
a.
Thnh phn dung dch 123,3 C di p sut kh quyn 760mmHg.
b.
T s mol ca clorobenzen v bromobenzen trong pha hi trn dung
dch c thnh phn 10% mol clorobenzen.
Gii
Hai cu t ny to vi nhau mt dung dch l tng nn:
P P1 P2 P10 .x1l P20 .x l2 P20 P10 P20 x1l
95
18
95 5
18 342
758 (mmHg)
a.
P
0
H2O
Thnh phn hn hp 123,3 C di p sut kh quyn 760mmHg
P P20
760 762
x 0
0,00552
0
P1 P2 400 762
x l2 1 x 1l 0,9948
l
1
Dung dch glycerin:
P PH02O .xH2O x H 2O
m gly
758
0,997
760
b.
Vy thnh phn ca Bromobenzen l: 0,00552

thnh phn ca Clorobenzen l: 0,9948
T s mol ca clorobenzen v bromobenzen
x h2 P02 x l2 760 0,1
0,21
x 1h P01 x 1l 400 0,9
29
V d 3. Benzen v toluen to vi nhau mt dung dch xem nh l tng.

300C p sut hi ca benzen bng 120,2 mmHg, ca toluen bng 36,7
mmHg. Xc nh:
a.
p sut hi ring phn ca tng cu t.
b.
p sut hi ca dung dch.
Nu dung dch c hnh thnh t s trn 100g benzen v 100g toluen.
Gii
a.
p sut hi ring phn ca tng cu t
Phn mol ca benzen:
100
nB
78
xB
0,54
n B n T 100 100
78 92
nE
Phn ca etanol: x E
Phn ca metanol: x M
b.
2,1739
0,41
2,1739 3,125
3,125
0,59
2,1739 3,125
PE PE0 xlE 44,5 0,41 18,245(mmHg)

l
PM PM0 xM
88,7 0,59 52,333(mmHg)
Phn mol ca toluen:
c.
100
nT
92
xT
0,46
100
100
nB nT
78 92
P = 18,245 + 52,333 = 70,578 (mmHg)

Phn mol ca metanol trong pha hi:
88,7
0,59
44,5
h
xM
0,7415
88,7
1 ( 1)x lM
1
1 0,59
44,5
l
.xM
p sut hi ca Benzen:
PB PB0 .x B 120,2 0,54 64,908 (mmHg)

p sut hi ca Toluen:
PT PT0 .x T 36,7 0,46 16,882 (mmHg)

b.
100
2,1739(mol)
46
100
3,125(mol)
S mol metanol: nM
32
S mol etanol:
Xc nh p sut hi ca dung dch
P PB PT 64,90816,882 81,79 (mmHg)

o
V d 4. Etanol v metanol to thnh dung dch xem nh l tng. 20 C

p sut hi bo ha ca etanol v metanol ln lt l 44,5 v 88,7 mmHg.
a.
Tnh thnh phn mol cc cht trong dung dch cha 100g etanol v
100g metanol.
b.
Xc nh cc p sut ring phn v p sut tng ca dung dch.
c.
Tnh phn mol ca metanol trong pha hi nm cn bng vi dung dch
trn.
Gii
a.
Phn mol mi cht
V d 5. Hn hp SnCl4 (1) v CCl 4 (2) tun theo qui lut ca dung dch l
tng. 90oC p sut hi bo ha ca SnCl4 v CCl4 ln lt l 362 mmHg
v 1112 mmHg. Di p sut chun 760mmHg, SnCl 4 si 1140C v CCl4
o
si 77 C:
a.
Xy dng gin thnh phn - p sut ca cc cu t v xc nh
trn gin p sut P1, P2 v P ca hn hp c phn mol ca CCl 4 l
0,7.
0
b.
Xc nh thnh phn hn hp SnCl 4 - CCl 4 si 90 C di p sut
760mmHg.
c.
Xc nh thnh phn hi ti 900C.
Gii
a.
Xy dng gin thnh phn - p sut
30
P
(mmHg)
a.
3
779,1
362
2
b.
PA0 .xlA PB0 .xlB
PA0
PB0
x Bl
0,7
CCl4
PSnCl 4
362 0,3 108,6
Ta c:
PCCl 4
b.
1112 0,7 779,1 (mmHg)
ln
Pt P20 760 1112
0,47
x1 0
P1 P20 362 1112
Vy thnh phn ca SnCl 4 l 0,47

Thnh phn ca CCl4 l 0,53
Xc nh thnh phn hi
x h2
x 1h
P02
P01
x l2
x 1l
PA0 298
A
R
1
1

T2 T1
(1)
PB0373
PB0298
B
R
1
1
T2 T1
(2)
Ly phng trnh (1) (2), ta c:
Ta c: Pt P1 x1 P2 x 2 P2 P1 P2 x1
c.
PA0 373
Tng t i vi cht B:
p sut ca hn hp:
P = 108,6 + 779,1 = 887,7 (mmHg)
Xc nh thnh phn hn hp SnCl 4 - CCl 4
0
ln
(mmHg)
p sut ca CCl 4:
0
PCCl
.x CCl 4
4
P2 1
1

P1
R T2 T1
i vi cht A:
Hnh 5.3. Gin p sut - thnh phn P - x

p sut ca SnCl 4:
0
PSnCl
. 1 0,7
4
0,75
3
0,25
100 C:
p dng cng thc: ln
x lA
108,6
SnCl4
Ta c: PA PA .x A v PB PB .x B
Theo bi ta c: PA = PB
1112
Gii
250C:
1112 0,53
3,464
362 0,47
1 PA0 373

0,507
3 PB0373
PA0 373
1,52
PB0373
V d 6. Mt dung dch l tng ca A v B cha 25% mol A. 25 C, hi

cn bng ca n cha 50% mol A. Nhit ha hi ca A v B ln lt l 5 v
7 Kcal/mol. Tnh t s p sut hi bo ha ca A v B khi nguyn cht
0
0
25 C v 100 C.
PA0 373 PB0298 1

1 1
ln 0
0
A
PB373 PA 298 R B
T2 T1
PA0 373 PB0298

1 7000 5000 298 373
ln 0
PB373 PA0 298 1,987

298 373
31
V d 7. 800C p sut hi bo ha ca A nguyn cht v B nguyn cht

ln lt l 100 v 600 mmHg.
a.
Hy v th p sut - thnh phn (P - x) ca dung dch l tng A B.
b.
Tm thnh phn ca A v B sao cho ti p sut ca A v B bng
nhau.
Gii
a.
Gin P - x (hnh 5.4)
PA PA0 .xlA 100x lA

PA PB0 .xBl 600x lB
Pt PB0 PA0 PB0 x lA
2.
3.
(1)
(2)
600
500 x lA
4.
(3)
5.
6.
b.
5.5.
1.
Hnh 5.4. Gin p sut - thnh phn P - x

Thnh phn cu t A v B.
Ta c:
PA = PB
100.xlA 600 1 x lA
xlA
0,.857 v
x Bl
0,143
Bi tp t gii
250C p sut hi bo ha ca nc nguyn cht l 23,7 mmHg.
Tnh p sut hi trn dung dch cha 10% glyxerin trong nc nhit
.
S: 23,2 mmHg
7.
500C, dung dch l tng bao gm 1 mol cht A v 2 mol cht B c

p sut tng cng l 250 mmHg. Thm 1 mol cht A vo dung dch
trn th p sut tng cng l 300 mmHg. Hy xc nh p sut hi bo
0
ha ca A v B nguyn cht 50 C.
S: 450 v 150mmHg
Xem dung dch ca CCl4 v SnCl4 l dung dch l tng. Tnh thnh
0
phn ca dung dch si 100 C di p sut 760 mmHg v tnh
0
thnh phn ca bong bng hi u tin, bit rng 100 C p sut hi
bo ha ca CCl 4 v SnCl4 ln lt l 1450 v 500 mmHg.
S: 0,274 v 0,522
0
Xt dung dch toluen benzen cha 70% khi lng benzen 30 C.
Hy xc nh:
a.
Cc p sut phn v p sut tng cng ca dung dch
b.
Thnh phn ca pha hi nm cn bng vi dung dch trn.
0
Bit rng 30 C p sut hi bo ha ca benzen v toluen ln lt l
120,2 v 36,7 mmHg.
S: a. 88,2 ; 9,8 ; 98,0 mmHg; b. 0,9 ; 0,1
Mt dung dch cha 0,5 mol propanol v 0,5 mol etanol c chng
0
cho n khi nhit si ca dung dch l 90 C. p sut hi ca phn
0
ngng t thu c l 1066 mmHg (cng o nhit 90 C). Xem
0
dung dch l l tng v bit rng 90 C p sut hi bo ha ca
propanol v etanol ln lt l 574 v 1190 mmHg. Hy tnh:
a.
Thnh phn mol ca dung dch cn li trong bnh chng
b.
Thnh phn mol ca phn ngng t.
c.
S mol etanol ha hi.
S: a. x = 0,3 ; b. x = 0,8 ; c. 0,32 mol etanol
0
50 C p sut hi ca n - hecxan v n - pentan ln lt l 400 v
1200 mmHg.
a.
Tnh p sut hi ca dung dch cha 50% (khi lng) ca npentan.
b.
Xc nh phn mol ca n - hecxan trong pha hi.
c.
Xc nh thnh phn ca hai cu t trn trong pha lng p
sut hi ca chng bng nhau.
Tnh p sut hi bo ha ca dung dch 5g ng glucose (C6H12O6)
0
trong 180g nc 20 C. Bit rng nhit ny p sut hi bo ha
ca nc 17,5 mmHg.
32
8.
9.
200C p sut hi bo ha ca dung dch cha 52,8g A v 180g H2 O

l 16,5 mmHg. Xc nh khi lng phn t ca A, bit rng nhit
ny p sut hi bo ha ca nc l 17,5 mmHg.
Xc nh phn mol ca dung dch cha 20% A (M = 46), 30% B (M
=18) v 50% C (M = 60) v khi lng.
33
Chng 6
CN BNG GIA DUNG DCH
LNG V PHA RN
6.1. Tnh cht ca dung dch long cc cht tan khng bay hi
6.1.1. gim p sut hi ca dung dch
gim tng i p sut hi ca dung dch bng tng phn phn t
ca cc cht tan khng bay hi trong dung dch.
P 0 P P
0 x
P0
P
Trong :
0
P : p sut hi ca dung mi nguyn cht
P: p sut hi ca dung dch
x: phn mol ca cht tan
6.1.2. tng im si v h im kt tinh
ng OC m t p sut hi trn dung mi rn nguyn cht.
ng OA m t p sut hi trn dung mi lng nguyn cht.
ng OB m t nh hng ca p sut bn ngoi n nhit nng

chy ca dung mi nguyn cht.
tng im si v h im kt tinh ca cc dung dch cht tan
khng bay hi t l thun vi nng ca dung dch.
T = K. Cm
Vi:
Cm: Nng molan ca dung dch.
K: Hng s nghim si Ks hay hng s nghim ng K
Hnh 6.1. Gii thch tng im si v h im kt tinh
R.T02 .M
1000
Trong :
R: hng s kh
T0: nhit chuyn pha
M: phn t lng
: nhit chuyn pha
6.1.3. p sut thm thu
p sut thm thu ca dung dch c nng xc nh l p sut ph
phi tc ng ln mt mng bn thm nm phn cch gia dung dch v
dung mi nguyn cht dung dch ny c th nm cn bng thy tnh vi
dung mi (qua mng bn thm).
= CRT
Trong :
: p sut thm thu
C: Nng dung dch (mol/l)
R: hng s kh
T: nhit tuyt i
34
S kt tinh ca dung dch hai cu t. H khng to dung dch

rn, khng to hp cht ha hc
6.2.1. Gin nhit - thnh phn (T - x)
Cc im a, b tng ng vi nhit kt tinh ca cc cu t A v B

nguyn cht.
ng aeb c gi l ng lng.
ng arAr Bb c gi l ng rn.
Vng nm trn ng lng h ch c mt pha lng LA-B
Vng nm pha di ng rn, h bao gm hai Pha rn: rn A v

rn B (RA, RB).
Vng nm gia ng lng v ng rn h tn ti cn bng ca hai

pha: RA L hoc L - RB.
6.2.
Hnh 6.3. Qu trnh a nhit ca h Q

H H = pha lng e + h rn chung RC
H rn chung RC = pha rnA + pha rn B
Hn hp eutecti
p sut khng i, hn hp eutecti s kt tinh nhit khng i
theo ng thnh phn ca n. Hn hp eutecti c tnh cht ging nh mt
hp cht ha hc, song n khng phi l mt hp cht ha hc m n ch l
mt hn hp gm nhng tinh th rt nh, rt mn ca hai pha rn A v rn B
nguyn cht kt tinh xen k vo nhau.
6.2.4. Php phn tch nhit
6.2.3.
6.2.2.
Hnh 6.2. Gin (T-x) ca h hai cu t, cn bng lng rn.

Kho st qu trnh a nhit
Ti nhit T2: H Q2 = lng l2 + rn r2
35
Hai im e1 v e2 tng ng l cc im eutecti ca h A - D v h D

- B.
6.4. Bi tp mu
V d 1. Bng im ca dung dch nc cha mt cht tan khng bay hi l
0
-1,5 C. Xc nh:
a.
Nhit si ca dung dch.
b.
p sut hi ca dung dch 250C.
Cho bit hng s nghim lnh ca nc l 1,86 v hng s nghim si ca
0
nc l 0,513. p sut hi ca nc nguyn cht 25 C l 23,76 mmHg.
Gii
0
a.
h im ng c ca dung dch: T = 1,5 C
Ta c:
Hnh 6.4. Minh ha php phn tch nhit
Lp 6 h c cng khi lng vi thnh phn ca cu t B thay i t
0% n 100%. Lm nng chy tng h ri h dn nhit , quan st s thay
i nhit theo thi gian v v cc ng ngui lnh (T - t).
6.3. H hai cu t khng to dung dch rn, khi kt tinh to thnh hp
cht ha hc bn
T K .Cm
T
1,5
Cm
0,806
K
1,86
(mol/1000g)
tng im si:
TS KS .Cm 0,513 0,806 0,414(0C)

b.
Nhit si ca dung dch:

0
Tdd = 100 + 0,414 = 100,414 ( C)
p sut hi ca dung dch
1000
18
P P0 .x 23,76
23,42 (mmHg)
1000
0,806
18
Hnh 6.5. Gin (T-x) h 2 cu t to hp cht hoa hc bn

D l hp cht ha hc ca A v B.
ng ae1 l ng kt tinh ca cht rn A.
ng e1de2 l ng kt tinh ca cht rn D.
ng e2b l ng kt tinh ca cht rn B.
V d 2. 200C p sut hi nc l 17,54 mmHg v p sut hi ca dung

dch cha cht tan khng bay hi l 17,22 mmHg. Xc nh p sut thm
0
thu ca dung dch 40 C nu t trng ca dung dch ti nhit ny l
3
1,01 g/cm v khi lng mol phn t ca cht tan l 60.
Gii
Ta c:
P 17,54 17,22
0,018
P0
17,54
36

b.
m ct
60
M
x
0,018
m ct m H2O
60
18
Gi s m ct m H O 100 (g)
2
(1)
a.
(2)
m H 2O 100 m ct
b.
T (1) v (2), ta c: mct = 5,75 (g)

Th tch ca dung dch:
m
100
V dd
99
d
1,01
(ml)
Nng ca dung dch:
CM
5,75
n
60 1000 0,968
V
99
m l HR c
0,2
4
mr
He
0,25 5
Ta c : ml + mr = 90 g
ml = 40 g; mr = 50 g
Khi lng ca rn A v rn B
m RA
(mol/l)
p sut thm thu:

= CRT = 0,968x0,082x(273 + 40) = 24,84 (atm)
V d 3. Gin kt tinh (T-x) ca h hai cu t A - B c cho trong hnh
sau.
a.
Lm lnh 90g h Q, khi im h nm ti H, c A v B kt tinh mt

phn v im rn chung (gm c rn A v rn B) nm ti RC. Tnh
lng rn A v rn B kt tinh v lng lng eutecti cn li.
Gii
S pha v bc t do ca h
Vng I: f = 1, c = k f + 1 = 2
Vng II: f = 2, c = k f + 1 = 1
Ti im eutecti: f = 3, c = k f + 1 = 0.
Khi lng ca pha rn v pha lng
m RB
R C R B 0,8
4
R C R A 0,2
Ta c RA + RB = 50 g
RA = 40 g
RB = 10 g
V d 5. Gin kt tinh (T - x) ca h hai cu t A - B c cho trong hnh
sau. Lm lnh 110 gam h Q.
a.
Xc nh s pha v bc t do ca h ti cc vng I, II v nhit kt
tinh ca cu t A, B nguyn cht.
b.
Xc nh nhit bt u kt tinh ca h Q. Khi im h nm ti H c
A v B kt tinh mt phn v im rn chung (gm rn A v rn B)
nm ti RC. Tnh lng rn A v rn B kt tinh v lng lng
eutecti cn li.
c.
Tnh lng lng eutecti ti a thu c t h trn.
Tnh s pha v bc t do ca h ti cc vng I, II, III v ti im

eutecti.
37

c.
Khi lng eutecti ti a khi RC trng vi RB
m l(e)
m Rc
6.5.
1.
a.
b.
HR B 0,3 3
He
0,4 4
ml(e) + mRc = 110

Gii h ta c: ml(e) = 62,86 (g)
Bi tp t gii
Gin kt tinh ca Sb v Pb c dng nh hnh v. Lm lnh 200g h
Q.
a.
M t gin pha ca h hai cu t trn.
b.
Xc nh bc t do ca vng (I), (II) v ti im e.
Gii
S pha v bc t do ca cc vng
Vng I: f = 1, c = 2
Vng II: f = 2, c = 1
0
Nhit kt tinh A: 450 C
0
Nhit kt tinh B: 700 C
0
Nhit bt u kt tinh: 600 C
Ta c h pt:
m Rc
m le
He
0,4 8
HR c 0,15 3
mRc + mle = 110

Gii h ta c: mRc = 80 (g), mle = 30 (g)
rn A v rn B.
Ta c h pt:
m RA
m RB
R C R B 0,15 3
R C R A 0,85 17
mRa + mRb = 80
Gii h ta c: mRb = 68 (g); mRa = 12 (g).
Khi im h Q trng vi im H. Hy xc nh khi lng ca

pha lng v pha rn.
d.
Khi h Q kt tinh hon ton, hy xc nh lng eutectic thu
c.
S: c. mr = 85,7g; ml = 114,3g ; d. me = 94,11g
V gin pha ca h Sb - Pb da vo cc d kin thc nghim sau:
Thnh phn hn hp lng
Nhit bt u
(% khi lng)
0
Kt tinh ( C)
Sb
Pb
100
0
632
80
20
580
60
40
520
c.
Khi
lng
2.
38
3.
4.
5.
40
60
433
20
80
300
10
90
273
0
100
326
a.
Xc nh thnh phn eutecti.
b.
Xc nh khi lng Sb tch ra nu 10kg hn hp lng cha
40% Pb c lm ngui ti 4330C.
S: a. 87%Pb v 13%Sb; b. mSb = 5kg
Gin kt tinh ca h A - B c dng nh hnh di. Lm lnh 100g
h Q. Khi im h nm H. C A v B kt tinh mt phn. im rn
chung nm ti R.
a.
Xc nh lng A v B kt tinh v lng lng eutecti cn li.
b.
Tnh lng eutecti ti a thu c.
c.
Phi trn A v B vi thnh phn nh th no thu c hn
hp A v B ng thi kt tinh.
6.
7.
ca dung dch l 1g/cm3, hng s nghim lnh v hng s nghim si

ca nc tng ng 1,86 v 0,513.
S: Tkt = -0,930C; Ts = 100,260C; = 11,2 atm
0
0
Benzen ng c 5,42 C v si 81,1 C. Nhit ha hi ti im si
bng 399J/g. Dung dch cha 12,8g naphtalen trong 1kg benzen ng
0
c 4,91 C.
a.
Xc nh nhit si ca dung dch ny.
0
b.
Tnh p sut hi ca benzen trn dung dch 81,1 C.
c.
Tnh nhit nng chy ring ca benzen.
0
S: a. 81,36 C; b. 754.1mmHg; c. 128,24 J/g
0
Acid acetic k thut ng c 16,4 C. Bng im ca acid acetic
0
nguyn cht l 16,7 C. Hng s nghim lnh ca acid nguyn cht l
3,9. Xc nh nng molan ca tp cht trong acid k thut.
S: a. 12g; 48g v 40g; b. 57,14g

Xc nh nng mol v nng molan ca dung dch cha 20g
CH3COOH trong 100g nc 250C. Bit nhit ny khi lng
3
ring ca dung dch 1,01 g/cm .
S: Cm = 3,33 molan, CM = 2,8M
Tnh nhit kt tinh, nhit si, p sut thm thu ca dung dch
0
cha 9g ng glucose (C6H12O6) trong 100g nc 25 C. Cho bit
nhit ny p sut hi ca nc l 23,76mmHg, khi lng ring
39
Chng 7
Hot trung bnh ca ion:
+
a a .a
Trong : = +
Ta c: a+ = +.m+ v a- = -.m-
IN HA HC
7.1. Khi nim v dung dch in ly

7.1.1. Dung dch cc cht in ly
Mt cht tan khi ha tan vo dung mi, to thnh dung dch m dung
dch c kh nng dn in gi l dung dch in ly.
7.1.2. S in ly
tng im si v gim im ng c ca dung dch in ly cao
hn so vi dung dch l tng hay dung dch khng in ly.
T = i.K.Cm
Trong :
i: l h s Vant Hoff
K: hng s
Cm: nng molan
p sut thm thu ca dung dch in ly cng cao hn p sut thm
thu ca dung dch l tng hay dung dch khng in ly.
in ly = i.C.R.T
Trong :
: p sut thm thu
C: nng mol/l
R hng s kh
T: nhit tuyt i
H s b chnh i l t s gia tng s tiu phn thc s c trong dung
dch v s tiu phn ban u:
Trong :
. .m
.m
m : molan trung bnh ca cc ion

: h s hot trung bnh ca cc ion
+, -: h s hat ca cc ion
Lc ion: I m
1
mi Zi2
hoc I C
1
Ci Zi2
Trong :
i: l k hiu ca tt c cc ion trong dung dch mi
Ci: nng thc ca cc ion
7.2. S chuyn vn in tch trong dung dch in ly
7.2.1. dn in ring
dn in ring () l dn in ca mt dung dch c th tch V =
3
1 cm , c t gia hai in cc phng song song c din tch nh nhau
v cch nhau 1 cm.
i 1 1
Trong :
: phn ly
=m+n
Vi m, n l h s ca phng trnh:
AmBn = mAn+ + nBm7.1.3. Hot , h s hot ca cc cht in ly
z+
zM+A- = +M
+ -A
Trong l in tr sut:
L
7.2.2.
1
1
S
R l
l
s
dn in ng lng ()
40
L dn in ca mt th tch tnh theo cm3 cha ng mt ng

lng gam cht in ly nm gia hai in cc phng song song cch nhau 1
cm.
.1000
CN
Trong :
: dn in ring
CN: nng ng lng
Ngi ta kho st mi tng quan gia theo C v
7.2.3.
7.3.2. Nhit ng hc ca pin v in cc

7.3.2.1. Cng ca pin
Xt phn ng: aA + bB = cC + dD
Ta c:
G = - Amax
Cng to c l: A = n.F.E
G = -n.F.E
7.3.2.2. nh hng ca nng n sc in ng v in cc phng trnh Nernst.
Sc in ng ph thuc vo nng cc cht c trong pin v nhit
ca pin.
Phng trnh Nernst:
c
= - A C
Mi quan h gia dn in v in ly
Ta c:
0,059 C .D
lg
n
A a .B b
Trong :
E 0 0 0 : sut in ng tiu chun

M:
Trong :
: dn in ng lng ca dung dch.
: dn in ng lng gii hn ca dung dch.
, : dn in ng lng gii hn ca cation v
anion hay cn gi l linh ion.
7.3. Pin v in cc
7.3.1. Th in cc
Trn ranh gii phn chia 2 pha gm mt tm kim lai dng lm in
cc (vt dn lai 1) v dung dch in phn (vt dn lai 2) xut hin mt
hiu in th gi l th in cc c ln c xc nh bng phng trnh
Nernst.
E E0
RT oxh
ln
nF
kh
Trong :
R: hng s kh
T: nhit tuyt i
F: hng s Faraday
n: s electron trao i
0 ,0 : th in cc tiu chun ca in cc dng (+) v m (-)

7.3.2.3. Phng php kho st mt phn ng
Ta c: G = - n.F.E
Nu E > 0 G < 0: phn ng xy ra theo chiu thun.
Nu E < 0 G > 0: phn ng xy ra theo chiu ngc li.
Nu E = 0 G = 0: phn ng cn bng.
7.3.2.4. H thc Luther
H thc ny dng xc nh th in cc cho mt cp oxi ha - kh
ca nguyn t c nhiu mc oxi ha khc nhau. V d, kim loi M c hai
h+
n+
cation M v M (h > n). H ny ng vi ba qu trnh in cc:
h+
M
+ he = M
(1)
G1 = -hFh
Mn+ + ne = M
(2)
G2 = -nFn
Mh+ + (h - n)e = Mn+
(3)
G3 = -(h - n)Fh/ n
V (3) = (1) - (2), nn:
G3 = G1 - G2
Hay:
(h - n)h/ n = hh - nn
7.3.3. Cc loi in cc
in cc loi 1: l mt h gm kim loi hoc kim c nhng vo
n+
ndung dch cha ion ca kim lai hoc kim . K hiu M / M hoc A / A:
n+
M + ne = M
41
Phng trnh Nernst:

0
Mn /M M
n
/M
RT
1
ln
nF aMn
in cc loi 2: l mt h gm kim loi c ph mt hp cht kh

tan (mui, oxit hay hydroxit) ca kim loi v nhng vo dung dch cha
nanion ca hp cht kh tan . K hiu A / MA/ M.
nMA + ne = M + A
Phng trnh Nernst :
0
MA/M,An MA/M,
An
RT
lnaAn
nF
7.4.
Bi tp mu
V d 1. Tnh nhit kt tinh ca dung dch cha 7,308g NaCl trong 250g
6
2
nc cho bit 291K p sut thm thu ca dung dch l 2,1079.10 N/m ,
3
khi lng ring ca dung dch l 1g/cm , nhit nng chy ca nc
3
nguyn cht l 333,48.10 J/kg.
Gii
Ta c:T = i.k.Cm
(1)
RTo2M
8,314.273 2.18
Vi: k d
1,86
1000 1000.333, 48.18
Trong :
7,308
Cm
0,5
58,5 0,25
(mol/kg)
i.CRT
Ta li c:
Nng ca dung dch:
7,308
1000 0,5 (mol/l)
58,5250 7,308
2,1079.106
i
1,74
CRT 1,013.105.0,082.291.0,5
C
Th vo cng thc (1), ta c:

T = i.k.Cm = 0,5 1,74 1,86 = 1,62
Nhit kt tinh ca dung dch in ly l:
0
T = 0 - 1,62 = -1,62 C
V d 2. h im kt tinh ca dung dch CH3COOH 0,1M l 0,1885 ,

hng s nghim lnh ca nc l 1,86. Tnh phn ly ca dung dch
CH3COOH 0,1M v 0,05M.
Gii
nng long th nng mol/l gn bng vi nng molan nn ta
c:
Trng hp dung dch c nng 0,1M:
T = i.k.Cm
M ta li c:
0,1885
1,0134
1,86 0,1
i 1 1,0134 1
0,0134
1
2 1
phn ly ca dung dch CH3COOH 0,1M l 1,34%.

Trng hp dung dch c nng 0,05M:
Ta c phng trnh phn ly:
+
CH3COOH = CH3COO + H
Hng s phn ly:
2
2 .C 0,0134 0,1
1,82.10 5
1
1 0,0134
i vi dung dch in ly yu, ta c: 1 1
K
1,82.10 5
0,019
C
0,05
Khi dung dch c nng 0,05M th phn ly ca dung dch l 1,9%.

V d 3. Dung dch cha 4,355 mol ng ma trong 5 lt dung dch 291K
c cng p sut thm thu vi dung dch cha 2 mol NaCl trong 4 lt dung
dch. Xc nh phn ly ca dung dch NaCl v h s Vant Hoff.
Gii
Dung dch ng l dung dch khng in ly:
4,355 0,082 291

20,78 (atm)
5
i vi dung dch NaCl ta c: iCRT
CRT
20,78
1,742
CRT 0,5 0,082 291
42
in ly:

Gii
Vi dung dch KCl ta c:
k = R. 457 = 1,2796 (cm-1)
Vi dung dch CaCl 2 ta c:
i 1 1,742 1
0,742
1
2 1
Vy in ly ca dung dch NaCl l 74,2%.

V d 4. Tnh p sut thm thu ca dung dch NaCl 0,15M 370C bit
phn ly ca dung dch l 95%.
Gii
Nng ca dung dch CaCl2 l:
iCRT
i 1
i 1) 1 0,95(2 1) 1 1,95
1
Ta c:
M:
m
0,555 2
CN
0,01
V
1 111
p sut thm thu ca dung dch l:
iCRT 1,95.0,15.0,082.310 7,43atm

V d 5. Tnh nng ca dung dch ng sacaroza c gi tr p sut
0
thm thu l 8,1134 atm 37 C.
Gii
Nng dung dch ng sacaroza l:
8,1134
CRT 8,1134 C
0,32 mol/l
RT 0,082.310
V d 6. Thit lp biu thc tnh sc in ng ca pin c nng sau:
Ag/ AgCl/ HCl (C1)// HCl (C2)/ AgCl/ Ag
Cho bit C1 > C2.
Gii
Cc m:
Ag + Cl (C1) = AgCl + e
Cc dng: AgCl + e
= Ag + Cl (C2)
Sc in ng ca pin c tnh nh sau:
E ( )
RT C1
ln
F C2
RT C1
ln
F
C2
V d 7. in tr ca dung dch KCl 0,02N 25 C trong mt bnh o dn

in o c l 457. Bit dn in ring ca dung dch l 0,0028
1
-1
.cm . Dng bnh ny o dn in ca dung dch CaCl2 cha 0,555g
CaCl2 trong 1 lt dung dch c gi tr l 1050. Tnh hng s bnh in cc v
dn in ng lng ca dung dch CaCl2.
k 1,2796
0,00122 ( 1 .cm-1)
R 1050
(N)
dn in ng lng ca dung dch CaCl2 c tnh theo cng

thc:
1000 1000 0,00122
122
C
0,01
(cm .
1 .lg-1)
V d 8. dn in ng lng gii hn ca axit propionic (C2H5COOH)

0
-1
-1
2
-5
25 C l 385,6 .lg .cm . Hng s phn ly ca acid ny l 2,34.10 .Tnh
dn in ng lng ca dung dch acid propionic 0,05M cng nhit
.
Gii
Dung dch acid propionic l mt cht in ly yu nn:
M:
2,34.10 5
0,0216
0,05
0,0216.385,6 8,34cm 2 . 1.dlg 1
Vy dn in ng lng ca dung dch l: = 8,34.cm2.-1.lg-1

V d 9. dn in ng lng ca NH4Cl trong dung dch v cng long
-1
-1
2
-1
-1
l 149,7 .lg .cm . Linh ion ca OH l 198 ca Cl l 76,3 .dlg
1
2
.cm . Tnh dn in gii hn ca dung dch NH4OH.
Gii
Ta c:

(NH Cl) ) Cl
4
43
(NH ) 149,7 76,6 73,4 (cm2.-1.lg-1)
CHCl
dn in ng lng gii hn ca NH4OH l:
(NH OH) ) ) 73,4 + 198 = 271,4cm2.1.dlg1
V d 10. in tr ca dung dch KNO3 0,01N l 423 . Hng s bnh in

-1
cc l 0,5 cm . Xc nh dn in ring, dn in ng lng v
phn ly ca dung dch, bit linh ion ca NO3- v K+ ln lt l 71,4 v 73,4
-1.lg-1.cm2.
Gii
dn in ring ca dung dch KNO3:
k 0,5
1,182.10-3 -1.cm-1
R 423
1000. 1000.1,182.10 3
118,2cm2 . 1.dlg1
C
0,01
2
(KNO ) ) ) 73,4 + 71,4 =144,8cm . .dlg
89

113,7
2+
Ta c:
3
V d 12. Tnh th in cc: Zn/ ZnCl 2 (0,005N) 250C cho bit dn in

-1
-1
2
ng lng ca dung dch l 89 .lg .cm , dn in ng lng
-1
-1
2
gii hn ca dung dch l 113,7 .dlg cm v in th tiu chun ca in
cc Zn l -0,76V.
Gii
phn ly ca dung dch ZnCl2 l:
Nng ca Zn :
2+
[Zn ] = 0,783 0,005 = 0,004 N = 0,002 M
Th in cc:
dn in ng lng:
CNaOH .VNaOH 8.1,56
0,125N
VHCl
100
l:

144,8
in ly
Nh vy in ly ca dung dch l 81,63%

V d 11. Xc nh nng ca dung dch HCl nu dng dung dch NaOH 8N
chun 100ml dung dch HCl bng phng php chun dn in th
th kt qu thu c l:
VNaOH (ml)
0,32
0,60
1,56
2,00
2,34
-1
-2
3,2
2,56
1,64
2,38
2,96
( .cm.10 )
Gii
Ta xc nh im tng ng ca php chun in th bng s
thay i t ngt ca dn in ring. T bng s liu th im tng
ng chnh l im c th tch NaOH bng 1,56ml.
Ta tnh c nng ca dung dch HCl:
0,059
lg[Zn2 ]
2
0,76
0.059
lg0,002 0,839 V
2
2+
V d 13. Cho pin Cd / Cd // CuSO4 / Cu c sc in ng l 0,745V. Hy

xc nh phn ly ca dung dch CuSO4 0,1N cho bit in th tiu chun
2+
ca in cc Cu l 0,34V, ca in cc Cd l -0,4V v nng ion Cd
trong dung dch l 0,05N.
Gii
Phn ng xy ra trong pin:
2+
2+
Cd + Cu
= Cd
+ Cu
Sc in ng ca pin nh sau:
E E0
0
0,059 Cd 2
lg
2
Cu 2
0
Trong :
E 0,34 0,4 0,74 (V)
Th vo cng thc trn ta c:
0,059 [Cu2 ]

lg
2
0,05
44
phn ly:
[Cu2 ] = 0,074 (N)

Cu 2
0,074
0,74
CuSO4 0,1
E E0
o Cal E
pH Quin
0,059
0,699 0,3338 0,0096
pH
6,027
0,059
V d 15. Cho pin, Cu/ CuCl2 (0,7M)// AgNO3 (1M)/ Ag. Cho bit phn ly
ca dung dch CuCl2 l 80% v dung dch AgNO3 l 85%, in th tiu chun
ca in cc Cu l 0,34V v in cc Ag l 0,8V. Tnh sc in ng ca
pin v tnh lng AgNO3 cn thm vo sc in ng ca pin tng thm
0,02V, cho th tnh bnh l 1lt.
Gii
2+
CuCl2 = Cu + 2Cl
2+
Nng ion Cu :
80
Cu 0,7 100
0,56
2
AgNO3 = Ag +
+
Nng ion Ag :
85
Ag 1
0,85 (M)
100
(V)
Thm vo sut in ng ca pin 0,02V
E = 0,483 (V)
0,059
0,56
lg
2
2
Ag
0,483 = 0,46 -
[Ag ] = 1,836 (M)
[AgNO3] =
nAgNO
1,836
2,16(M)
0,85
= CM.V = 2,16 x 1 = 2,16 (mol)
Vy s mol AgNO3 thm vo l: 2,16 1 = 1,16 (mol)
m AgNO = 1,16 x 170 = 197,2 (g)

3
V d 16. Vit cu trc pin trong cc m l in cc Hiro, cc dng l

in cc Calomen. Cho bit in cc Calomen nhng vo dung dch KCl
0,1M v pH ca dung dch l 1,0. Tnh sc in ng ca pin.
Gii
Pt, H2 /H+ //KCl 0,1M /Hg2Cl2/Hg, Pt
p dng cng thc:
(M)
pH
NO3
0,059
0,56
lg
0,463
2
0,85 2
E 0,46
V d 14. Cho pin

(Pt) Hg/ Hg2Cl2/ KCl 0,01N// H+ / Quinhydron.
0
C sc in ng 25 C l 0,0096V. Tnh pH ca dung dch bit in th
in cc Calomen l 0,3338V v th in cc tiu chun ca in cc
Quinhydron l 0,699V.
Gii
p dng cng thc tnh pH ca dung dch:
0,059 Cu 2
lg
2
2
Ag
0Cal = 0,268 (V)
M:
Ta c:
Sut in ng ca pin:
0
0
0
E = + - - = 0,8 - 0,34 = 0,46 (V)
E cal
1
0,059
M:
E cal
0,059
E = 0,059 +
cal 0,788
Cal
0,059
1
lg
0,847
2
0,12
(V)
E = 0,059 + 0,847 = 0,906 (V)
45
V d 17. Cho in th tiu chun ca in cc Cu l 0,34V, ca in cc Ag
l 0,799V. Chng minh phn ng sau khng xy ra:
2+
+
2Ag + Cu = 2Ag + Cu.
Gii
+
Cc m:
2Ag 2e = 2Ag
2+
Cc dng:
Cu + 2e = 2Cu
Vy pin c hnh thnh t phn ng trn l:
+
2+
Ag/ Ag // Cu / Cu
Sc in ng tiu chun ca pin tnh c:
E0 = 0,34 0,799 = - 0,459 (V)
E0 < 0 nn phn ng khng t xy ra.

V d 18. Vit cc phng trnh phn ng in cc v phn ng tng qut
xy ra trong cc pin sau:
a.
Zn / ZnSO4 // CuSO4 / Cu
b.
Cu / CuCl2 / AgCl / Ag
c.
(Pt) H2 / H2SO4 / Hg2SO4 / Hg (Pt)
d.
Cd/ CdSO4 / Hg2SO4 / Hg (Pt)
Gii
a.
Zn / ZnSO4 // CuSO4 / Cu
Cc m:
Zn - 2e = Zn2+
2+
Cc dng:
Cu + 2e = Cu
Zn + CuSO4 = ZnSO4 + Cu
b.
Cu / CuCl2 / AgCl / Ag
2+
Cc m:
Cu - 2e = Cu
Cc dng:
2AgCl + 2e = 2Ag + 2Cl
Cu + 2AgCl = 2Ag + CuCl2

c.
(Pt) H2 / H2SO4 / Hg2SO4 / Hg (Pt)
+
Cc m:
H2 - 2e = 2H
2Cc dng:
Hg2SO4 + 2e = 2Hg + SO4
H2 + Hg2SO4 = 2Hg + H2SO4

d.
Cd / CdSO4 / Hg2SO4 / Hg (Pt)
Cc m:
Cd - 2e = Cd2+
2Cc dng:
Hg2SO4 + 2e = 2Hg + SO4
Cd + Hg2SO4 = 2Hg + CdSO4

V d 19. Lp pin trong xy ra cc phn ng sau.
a.
Cd + CuSO4
= CdSO4 + Cu
b.
2AgBr + H2 = 2Ag + 2HBr
c.
H2
+ Cl 2
= 2HCl
3+
2+
2+
d.
Zn + 2Fe = Zn + 2Fe

Gii
Cd + CuSO4 = CdSO4 + Cu
2+
Cc m:
Cd - 2e = Cd
2+
Cc dng:
Cu + 2e = 2Cu
Cd/ CdSO4// CuSO4/ Cu

b.
2AgBr + H2 = 2Ag + 2HBr
+
Cc m:
H2 - 2e = 2H
Cc dng:
2AgBr + 2e = 2Ag + 2Br
Pt, H2 / HBr / AgBr / Ag

c.
H2 + Cl2 = 2HCl
+
Cc m:
H2 - 2e = 2H
Cc dng:
Cl 2 + 2e = 2Cl
Pt, H2/ HCl/ Cl2, Pt
d.
Zn + 2Fe3+ = Zn2+ + 2Fe2+
Cc m:
Zn - 2e = Zn2+
3+
2+
Cc dng:
2Fe + 2e = 2Fe
2+
3+
2+
Zn/ Zn // Fe , Fe / Pt
2+
2+
3+
V d 20. Cho phn ng ca pin l: Hg + 2Fe = 2Hg + 2Fe c hng
0
0
0
0
s cn bng 25 C l 0,018 v 35 C l 0,054. Tnh G v H ca phn
0
ng 25 C.
Gii
0
Coi H khng thay i trong khong t 25 - 35 C ta c:
a.
K T2
H 1
1

K T1
R T2 T1
0,054 H 0 1 1

ln
0,018 8,314 T2 T1
ln
H = 83834,58 (J)
0
G = -RTlnKp = -8,314 298 ln(0,018)
= 9953,36 (J)
V d 21. Cho pin: Zn / ZnCl 2 (0,5M) / AgCl / Ag.
a.
Vit phn ng in cc v phn ng trong pin.
b.
Tnh sc in ng tiu chun, bin thin th ng p tiu chun ca
pin.
c.
Tnh sc in ng v bin thin th ng p ca pin.
Cho bit in th tiu chun ca in cc Zn l -0,76V, ca in cc
Ag/AgCl/Cl l 0,2224V.
46
a.
b.
c.
Gii
Phn ng in cc v phn ng trong pin
2+
Cc m:
Zn - 2e = Zn
Cc dng: 2AgCl + 2e = 2Ag + 2Cl
Trong pin: Zn + 2AgCl = 2Ag + ZnCl 2
Sut in ng chun trong pin
M ta li c:
Ta c:
E 0 0 0 0,2224 0,76 0,9824 (V)
t ( ) t . 0,508.149 75,84cm2 . dlg-1
0,059
lg Zn2 Cl
2
E 0,9824
0,059
2
lg0,5
. 1 0,9913 (V)
2
Th ng p ca pin:
G = -nFE = -2 96500 0,9913 = -191321 (J)
+
V d 22. Hy xc nh nng ion H trong dung dch. Khi chun 10ml
hn hp HCl bng dung dch NaOH 0,1N th cc gi tr o c, c c
trn cu Wheatstone l:
VNaOH(ml)
0
5
8
9
10
11
12
13
(cm2.-1
540
490
468
466
464
462
475
490
.lg-1)
Gii
Ta xc nh im tng ng ca php chun in th bng s
thay i t ngt ca dn in ring.
T bng s liu th im tng ng chnh l im c th tch NaOH
bng 11ml. Ta tnh c nng ca dung dch HCl:
CHCl
CNaOH .VNaOH 0,1.11
0,11N
VHCl
10
t t 1 t 1 0,491 0,509
V d 24: Hng s phn ly ca NH4OH 313K l 2.10-5. Xc nh nng

ca ion OH trong cc dung dch sau:
a.
Nng ca NH4OH l 0,1N?
b.
Trong 1 lt dung dch cha 0,1 mol NH4OH v 0,1 mol NH4Cl. Coi
NH4Cl phn ly hon ton.
Gii
Ta c phng trnh phn ly:
+
NH4OH
NH4 + OH
a.
Trong dung dch NH4OH 0,1N
Th ng p chun:
0
0
G = -nFE = -2 96500 0,9824 = -189603,2 (J)
Sut in ng ca pin:
E E0
V d 23. Trong dung dch NH4Cl, s vn chuyn ca anion Cl l 0,491. Tm

linh cation bit dn in ng lng gii hn ca dung dch l
2
-1
-1
149cm . .dlg
Gii
Ta c biu thc lin h gia s ti ca cation vi dn in ng
lng gii hn nh sau:
[NH4 ].[OH ]
[OH ]2
[NH4 OH]
[NH4OH]
Ta tnh c:
[OH ] K.[NH4OH] 2.105.0.1 1,4.103 M

b.
Trong 1 lt dung dch cha 0,1 mol NH4OH v 0,1 mol NH4Cl.
[NH 4 ].[OH ]
[NH 4 OH]
Trong : [NH 4 ] = [OH ] + 0,1 [OH ] = 2.10 M

30
V d 25. Cho lng Ag d vo dung dch Mo(CN)6 0,1 M, 25 C c phn
ng xy ra nh sau:
Ag + Mo(CN)63- = Ag+ +
Mo(CN)64a.
Thnh lp pin m trong in cc xy ra phn ng trn.
b.
Tnh hng s cn bng ca phn ng
+
c.
Tnh nng ca Ag lc cn bng
0
3d.
Tnh sc in ng ca pin 25 C khi nng ca Mo(CN)6 v ca
4+
Mo(CN)6 bng nhau, nng Ag bng nng lc cn bng (cu
c).
-5
47
Bit

6
a.
b.
Theo th in cc chun ca Zn v Cd. Tnh cng ca phn ng trong

iu kin hon ton thun nghch p sut v nhit tiu chun cho bit
a 2 l 0,001 v a 2 l 0,125. (tra s tay ha l cc th in cc chun)
0
0Ag/Ag 0,799(V); Mo(CN)
0,868(V).
3
/Mo(CN)4
6
Gii
+
Cc m:
Ag
- 1e = Ag
3Cc dng:
Mo(CN)6
+
1e
Pin: Ag / Ag+ // Mo(CN)63-, Mo(CN)64- / Pt
Hng s cn bng
Sc in ng tiu chun:
Zn
4Mo(CN)6
E0 0,868 0,799 0,069(V)
12
3.
4.
lnK cb
nFE
1 96500 0,069
2,6875
RT
8,314 298
c.
Kcb = 14,695
+
Nng ca Ag
3Ag + Mo(CN)6
=
0,1
x
(0,1 - x)
Hng s cn bng:
K cb
d.
2.
Mo(CN)6
0
x
x
x
x
0,059 Mo CN 6 Ag
lg
3
n
Mo CN 6
cm2. dlg-1
0,059
lg0,09932 0,1282V
1
Bi tp t gii
Cho dng in khng i i qua bnh in phn vi in cc l Pt
cha dung dch H2SO4 long trong 1 gi c 336 ml hn hp kh H2 v
O2 thot ra. Tnh cng dng in.
S: I = 0,536 ampe
Xc nh hng s cn bng ca phn ng:
Cd + ZnSO4 = CdSO4 + Zn
8.
cm2. dlg-1
0
Khi o dn in ca 1000ml dung dch cha 0,1lg KCl 25 C

bng bnh o dn cho gi tr in tr l 3468,9 . Mt dung dch
ca mt cht khc c nng 0,1N cng c cho vo bnh o ni
trn, gi tr in tr o c l 4573,4 . Tnh dn in ng
lng ca cht .
S:
7.
-1
S: 62%
Tnh dn in ng lng gii hn ca dung dch acid acetic khi
0
dung dch c pha v cng long 25 C. Bit dn in ng
lng gii hn ca HCl, CH3COONa v ca NaCl ln lt l: 426,1;
91 v 126,5
6.
S: K= 1,6.10 ; A = 8,14.10 kJ.mol

Tnh bin thin entanpy ca pin khi phn ng trong pin xy ra thun
nghch trong dung dch nc: Zn + CuSO4 = ZnSO4 + Cu. Bit sc
in ng ca pin 273K l 1,0960V v 276K l 1,0961V.
S: H = -2,10.105KJ
Ha tan 1 mol KNO3 vo 1lit nc, nhit ng c ca dung dch
thp hn nhit ng c ca nc l 3,01 , hng s nghim lnh
ca nc l 1,86. Tnh in li biu kin ca KNO3 trong dung dch?
S: 390,6
Vy nng ca Ag+ = 0,09932 (M)

Sc in ng ca pin
E 0,069
1.
4-
x2
14,695 x 0,09932
0,1 x
E E0
7.5.
5.
+
Ag
Cd
97,51cm21dlg1
Cho lc ion ca dung dch NaCl l 0,24. Hy xc nh:

a.
Nng ca dung dch trn.
b.
Dung dch Na2SO4 phi c nng bao nhiu c cng lc
ion.
c.
Dung dch MgSO4 phi c nng bao nhiu c cng lc
ion.
S: a. C=0,24M; b. C=0,08M, C=0,06M
Tnh h s hot v hot ca dung dch Fe2(SO4)3 0,001M.
a 2 = 0,28 .0,002 = 0,56.10-4
Fe
aSO
2
4
= 0,57 .0,003 =1,7.10
-3
48
9.
Tnh nhit si ca dung dch CH3COOH 0,2M trong nc. Cho bit
-5
hng s phn ly K ca CH3COOH l 1,8.10 v hng s nghim si
ca nc l 0,513.
0
S: 100,104 C
49
Chng 8
A +
Phng trnh ng hc:
hoc
8.1.
1 dA
1 dB
1 dC
1 dD
v

a dt
b dt
c dt
d dt
8.1.2. Bc phn ng
Bc phn ng ca mt cht: chnh l s m nng ca cht trong
phng trnh ng hc.
Bc tng ca phn ng: l tng cc bc nng ca cc cht trong
phng trnh ng hc.
8.1.2.1. Phn ng bc 1
A
Phng trnh ng hc:
Thi gian bn hy:

8.1.2.2.
sn phm
C
ln Ao kt
C
A
ln2
t1/2
k
Phn ng bc 2
2A
Sn phm
1
1
Phng trnh ng hc:
0 kt
CA CA
1
Thi gian bn hy: t 1 2
kC 0A
Sn phm
1
b(a x)
ln
k.t
a b a(b x)
NG HA HC
ng hc
8.1.1. Xc nh thc nghim vn tc phn ng
Vn tc phn ng: l s bin thin nng ca cc cht trong mt
n v thi gian v mt n v th tch.
aA + bB = cC + dD
Vn tc ca phn ng:
8.1.2.3.
C0A C 0B x
1
ln
kt
C0B C0A C0B C 0A x
Phn ng bc 3
3A
Phng trnh ng hc:
1
2
C A
0 2
A
Sn phm
2kt
8.1.3. Xc nh bc phn ng
8.1.3.1. Phng php th
Gi nh bc ca phn ng (bc 0, 1, 2, 3 )
Nu phn ng xy ra theo mt bc gi nh, th ta thay th cc gi
tr thu c t qu trnh kho st theo vn tc theo thc nghim
t1 x1 vo phng trnh ng hc thu c k1
tn xn vo phng trnh ng hc thu c kn
Nu k 1, k 2, k n tng ng nhau th bc phn ng l bc gi nh.
8.1.3.2. Phng php da trn c im ca chu k bn hy
Ngi ta quan st c im ca T1/2 v nng v xem s tng
quan ca n l g.
8.1.3.3. Phng php xc nh theo vn tc u
n1A + n2B + n3C +...+ nn Z Sn phm
-
n
n
Vn tc phn ng: V k. A 1 B 2 ...
Tm n1: Cho [B], [C], [D]., [Z] d
Z n n
V k.A n1
Tm n2: Cho [A], [C], [D]., [Z] d
V k.B n 2
50
Tng t ta c n3, n4,, nn
N = n1 + n2 +..+ nn
8.1.4. nh hng ca nhit n tc phn ng
Vant Hoff khi nghin cu s nh hng nhit n vn tc phn
0
ng th ng cho rng c tng nhit ln 10 C th vn tc phn ng tng t
2 n 4 ln.
k T n.10
n
kT

V d 2. Trong 10 pht, phn ng gia hai cht xy ra ht 25% lng ban
u. Tnh chu k bn hy ca phn ng nu nng ban u hai cht trong
phn ng bc hai l nh nhau.
Gii
Nng ban u hai cht bng nhau, ta c:
1
1
o kt
CA CA
Hng s tc ca phn ng l:
Trong : l h s nhit .
8.1.5. Nng lng hot ha
ln
k 2 E a T2 T1
k1
R T1 .T2
Trong :
k1, k2: hng s tc phn ng nhit T1, T2.
Ea: nng lng hot ha
T1, T2: nhit (0K)
R: hng s kh l tng
8.2. Bi tp mu
V d 1. Lng cht phng x Poloni sau 14 ngy gim i 6,85% so vi ban
u. Xc nh hng s tc phng x v chu k bn hy ca Poloni. Cho
bit phn ng l bc 1.
Gii
V phn ng l bc 1 ta c phng trnh ng hc cho phn ng bc
1:
ln
C0A
kt
CA
Chu k bn hu ca phn ng l:
t 1/ 2
1
kC0A
V d 3. Chu k bn hy ca N2O5 l 5,7 gi. Tnh hng s tc phn ng

v thi gian cn thit phn ng ht 75% v 87% lng cht ban u nu
phn ng l bc 1.
Gii
V phn ng l bc 1 ta c:
ln2 0,693
0,1216 (gi-1)
t1/ 2
5,7
0
A
1
C
ln
0,00507 (ngy-1)
0
14 0,9315CA
ln
t 75%
ln 2
0,693
136,7 (ngy)
k
0,00507
C0A
0,25C0A
11,4 (gi)
0,1216
Thi gian phn ng ht 87% lng cht ban u l:
Chu k bn hy l:
t 1/ 2
30 (pht)
Thi gian phn ng ht 75% lng cht ban u l:
Hng s tc ca phn ng trn l:
1
1
o 10k
o
0,75C A C A
1
k
30CoA
ln
t 87%
C0A
0,13C0A
16,78 (gi)
0,1216
51
V d 4. Trong 10 pht hai phn ng bc mt v hai u phn ng ht 40%.

Tnh thi gian hai phn ng u ht 60% khi cho nng ban u ca
phn ng bc 2 l nh nhau.
Gii
i vi phn ng bc 1:
ln
k2
52000 1
1
)
0,00191 1,987 723 651
-1
k2 = 0,1046 (pht )
0
Thi gian (pht) phn ng ht 75% lng cht 450 C l:
C 0A
1
-1
ln
0,0511 (pht )
0
10
0,6C A
Thi gian (ph) phn ng ht 60% lng cht l:
i vi phn ng bc 2:
1
1
1
1
o kt
o 10k
o
CA CA
0,6C A C A
Hng s tc ca phn ng l:
1
1
1
o
o
6C A 10C A 15CoA
Thi gian (ph) phn ng ht 60% lng cht l:
V d 6. Cho phn ng:

CH3COCH3 = C2H4 + CO + H2
p sut tng bin i nh sau:
Thi gian (pht)
0
6,5
13
Ptng (N/m2)
41589,6
54386,6
65050,4
Xc nh bc phn ng v tnh gi tr hng s tc phn ng.
Gii
CH3COCH3 = C2H4 + CO + H2
P0
0
0
(P0 x)
x
x
Gi p sut ban u ca Aceton l P0.
p sut ti cc thi im t ca Aceton l P = PO - x
p sut tng cng ca h l PT = PO + 2x
V d 5. 378 C, chu k bn hy ca phn ng bc nht l 363 pht. Tnh

0
thi gian phn ng ht 75% lng ban u 450 C, bit nng lng
-1
hot ha ca phn ng l 52.000 cal.mol .
Gii
0
V phn ng l bc 1 nn ta c hng s tc ti nhit 378 C l:
k1
ln2 0,693
0,00191 (pht-1)
t1/ 2
363
0
Hng s tc ca phn ng 450 C c tnh theo phng trnh:
ln
k 2 E a 1 1
( )
k1
R T2 T1
19,9
74914,6
0
x
3Po PT
2
Ti t = 6,5 pht:
P6,5
3Po PT 3.41589,6 54386,6
35191,1N/ m2
2
2
Ti t = 13 pht:
P13
3Po PT 3.41589,6 65050,4
29859,2N/ m2
2
2
Ti t = 19,9 pht:
52
P19,9
3P P 3.41589,6 74914,6
o T
24927,1N/ m2
2
2

Thi gian phn ng ht 50% lng cht cng chnh l chu k bn hy
ca phn ng .
t1/ 2 t 50%
Gi s phn ng l bc 1 p dng phng trnh ng hc cho phn ng bc

1 ta c:
ln
CoA
kt vi CoA 41589,6
CA
ln
Ti t = 6,5 pht ta c
k1
ln
k3
41589,6
24927,1 0,0256phut 1
19,9
ta c:
o
A
C C
o
B
CoA CBo
1
0,025N
40
1
1
0,025N v CBo
0,05N
40
20
Thi gian (pht) phn ng ht 50% lng cht l:
t 1/2 t 50%
1
2 0,05 0,025 6,8
ln
2,380,05 0,025
0,05
V d 8. Nu phn ng bc 1 c nng lng hot ha l 25.000 cal/mol v

13
-1
trong phng trnh Arhenius c hng s k0 l 5.10 giy , nhit no
chu k bn hy ca phn ng l 1 pht v 30 ngy.
Gii
Khi chu k bn hy l 1 pht ta c hng s tc l:
k1 k 2 k3
0,0256phut 1
3
V d 7. Hng s tc phn ng x phng ha etylacetat bng xt 283K

-1
-1
l 2,38 l.lg .ph . Tnh thi gian cn thit x phng ha 50% lung
etylacetat nhit trn, nu trn 1lt dung dch etyl acetat 1/20N vi:
a.
1 lt dung dch xt 1/20N
b.
1 lt dung dch xt 1/10N.
Gii
a.
Khi trn 1lt dung dch etylacetat 1/20N vi 1 lt dung dch NaOH 1/20N
CoA CBo
CoA
Ta nhn thy ti cc thi im khc nhau c cc gi tr ca k l sp x nhau

nn ta kt lun phn ng l bc 1 v c hng s tc l:
Khi trn 1lt dung dch etylacetat 1/20N vi 1 lt dung dch NaOH 1/10N
ta c:
41589,6
35191,1 0,0257phut 1
6,5
41589,6
ln
29859,2 0,0255phut 1
Ti t = 13 pht ta c: k 2
13
Ti t = 19,9 pht ta c:
b.
1
1
16,8phut
o
kC A 2,38.0,025
ln2 0,693
0,01155 (giy-1)
t1/ 2
60
lnk
Ea
lnko
RT
Nhit cn thit l:
Ea
25000
349K
R(ln k o ln k) 1,987.(ln 5.1013 ln 0,01155)
Khi chu k bn hy l 30 ngy (2592000 giy) th hng s tc ca

phn ng l:
k1
ln 2
0,693
0,267.106
t1/ 2 2592000
lnk
-1
(pht )
Ea
lnko
RT
Nhit cn thit l:
53
T
Ea
25000
269K
R(ln k o ln k) 1,987.(ln 5.1013 ln 0, 267.10 6 )
V d 9. Nng lng hot ha ca phn ng l bao nhiu tc phn

ng tng ln 3 ln khi tng nhit ln 10 ti 300K v ti 1000K?
Gii
Ti 300K tc tng 3 ln th hng s tc ca phn ng cng tng
3 ln ta c:
ln
k 2 E a 1 1
( )
k1
R T2 T1
ln3
Ea
1
1
(
)
1,987 310 300
Ea = 20,3 (kcal/mol)
Ti 1000K:
ln3
Ea = 220 (kcal/ mol)

V d 10. Cho phn ng: A + B = AB, thu c vn tc theo nng u
cc cht l:
1,0
0,1
1,0
0
CA
1,0
1,0
0,1
Wo
0,025
0,0025
Hy vit phng trnh ng hc ca phn ng.
Gii
Phng trnh ng hc ca phn ng c dng:
W kC A C B
Da vo gi tr tc u ta xc nh gi tr ca
o
B
CA 29,7 18,1 11,6

Ti t = 60 pht th CA 29,7 26 3,7
o
A
W = 0,025(CA )(CB )
V d 11. ng hc phn ng bc mt hnh thnh axit c nghin cu
bng cch ly mu t hn hp phn ng theo tng chu k v nh phn
bng dung dch kim. Th tch dung dch kim dng nh phn cc thi
im khc nhau sau khi phn ng bt u thu c nh sau:
Thi gian (pht)
0
27
60
Th tch kim (ml)

0
18,1
26
29,7
Chng minh phn ng l bc mt v tnh hng s tc phn ng.
Gii
Ti thi im t = th th tch kim tiu tn chnh l lng ban u
ca A hay C oA 29, 7 .
Ti t = 27 pht th
Ea
1
1
(
)
1,987 1010 1000
C0B
Ta tnh c = 1, = 2 v k = 0,025
Vy phng trnh ng hc ca phn ng trn l:
0,00025
W01 =
k(C ) (C ) k1 1 0,025
W02 =
k(CoA ) (CBo ) k0,11 0,0025
W03 =
k(CoA ) (CBo ) k10,1 0,00025
Gi s phn ng l bc 1. p dng phng trnh ng hc cho phn

ng bc 1 ta c:
Ti t = 27 pht
1 C0
1
29,7
-1
k ln A
ln
0,0348 (pht )
t
C A 27
11,6
Ti t = 60 pht
1 C0
1
29,7
k ln A
ln
0,0347 (pht-1)
t
C A 60
3,7
V cc gi tr ca k l bng nhau nn ta kt lun phn ng l bc 1 v
hng s tc l: k = 0,03475 pht-1
V d 12. Dung dch este etylacetat c nng ban u 0,01N x phng ha
vi dung dch NaOH c nng 0,002N trong thi gian 23 pht t c
chuyn ha l 10%. Nu nng ban u gim i 10 ln th thi gian phn
ng s l bao nhiu nu mun t c chuyn ha l 10% nh trc.
Gii
CH3COOC2H5
+ NaOH
= CH3COONa
+ C2H5OH
0,01
0,002
0,001
0,001
0,009
0,001
54
y l phn ng bc 2 ta c:
kt
o
A
o
B
o
B
o
A
1
C (C x)
ln
o
(C C A ) C (C x)
o
B
Hng s tc phn ng (lit/ mol.phut) l:

Ea = 24,461 (kJ/mol)
V d 14: Ngi ta o tc u hnh thnh C i vi phn ng:
A + B = C v thu c kt qu sau:
3
-1
o
o
S TN
Wo.10 (M.pht )
(M)
(M)
CA
a.
b.
c.
Tnh Wo khi
a.
Gii
Phng trnh ng hc ca phn ng c dng:
W kC A C B
1
1
0,002 0,01 0,001
k
ln
3,194
23 0,01 0,002 0,010,002 0,001
Khi nng u gim i 10 ln th:
1
1
0,00020,001 0,0001
t
ln
230
3,194 0,001 0,0002 0,0010,0002 0,0001
Khi nng ban u gim i 10 ln t c mc chuyn ho
10% th cn 1 khong thi gian l 230 pht.
V d 13. Xc nh bng thc nghim hng s tc phn ng phn hy
N2O5 c kt qu:
0
Nhit ( C)
0
25
35
45
55
65
-15 -1
k.10 .s
0,0787
3,46
13,5
47,44
250
577,8
Xc nh nng lng hot ha ca phn ng.
Gii
-15
Khi T1 = 273K v T2 = 298K th hng s tc k1 = 0,0787.10 s v k2 =
-15
3,46.10 s:
k 2 E a 1
1
3, 46.1015
E a
1
1
( ) ln
)
15
k1
R T2 T1
0,0787.10
1,987 298 273
Ea = 24,463 (kJ/mol)
ln
Khi T1 = 308K v T2 = 318K th hng s tc :

k1= 13,5.1015s v k2= 19,8.1015s:
k 2 E a 1
1
47, 44.1015
E a
1
1
( ) ln
)
15
k1
R T2 T1
13,5.10
1,987 318 308
Ea = 24,460 (kJ/mol)
ln
Khi T1 = 328K v T2 = 338K th hng s tc :

15
15
k1 = 250.10 s v k2 = 487.10 s:
k 2 E a 1
1
577,8.1015
E a
1
1
( ) ln
)
15
k1
R T2 T1
250.10
1,987 338 328
Ea = 24,461 (kJ/mol)
ln
CB
1
0,1
0,1
2
0,2
0,2
3
0,1
0,2
Bc phn ng i vi A v B.
Hng s tc phn ng.
2,0
8,0
8,0
C oA = CBo =0,5M.
W01 =
k(C ) (C ) k0,1 0,1 2.103
W02 =
k(CoA ) (CBo ) k0,20,2 8.103
Da vo gi tr tc u ta xc nh gi tr ca
o
A
o
B
k(CoA ) (CBo ) k0,10,2 8.103

T 3 phng trnh trn ta tnh c = 0 v = 2
W03 =
b.
c.
-1
Hng s tc ca phn ng l: k = 0,2 M .pht

Khi
o
A
-1
o
=0,5M.
B
Ta c: Wo 0,2.0,5 .0,5 0,05M/ phut

V d 15. Phn ng trong pha kh gia NH3 v NO2 trong giai on u l
phn ng bc 2.
a.
Tnh nng lng hot ha ca phn ng.
b.
Tnh tha s k0 ca phng trnh Arrhenius.
Bit nhit 600K v 716K, hng s tc phn ng c gi tr tng ng
-1 -1
-1 -1
bng 0,385 M .s v 16 M .s .
Gii
a.
S dng phng trnh:
ln
k 2 E a 1 1
( )
k1
R T2 T1
Vy nng lng hot ha ca phn ng l:
55

Ti 270C ta c:
Ea
16
1
1
ln
) a 114778J / mol
0,385 8,314 716 600
Ea
lnko
b.
Tnh hng s k0: lnk
RT
114778
ln0,385
lnk o
8,314.600
ko 378,559.107 M1.s1
V d 16. Nghin cu phn ng 2I(k) + H2(k) = 2HI(k). Cho thy hng s tc
phn ng 418K l 1,12.10-5 M-2.s-1 v 737K l 18,54.10-5 M-2.s-1. Xc
nh nng lng hot ha v hng s tc phn ng 633,2K.
Gii
p dng phng trnh:
ln
k 2 E a 1 1
( )
k1
R T2 T1
-5
-5
Vi T1 = 418K, T2 = 737K v k1 = 1,12.10 , k2 = 18,54.10 ta c:

5
18,54.10
Ea
1
1
ln
)
5
1,12.10
8,314 737 418
Ea 22,522kJ/ mol
E a 1 1
k
Cng p dng phng trnh: ln 2
( )
k1
R T2 T1
-5
Vi T1= 418K, T2= 633,2K v k1 = 1,12.10 , Ea 22,522kJ/ mol
ta c:
ln
k2
22522
1
1
)
5
1,12.10
8,314 633,2 418
k 633,2K 10,114.10 5 M 2 s 1
0
V d 17. Trong mt phn ng bc nht tin hnh 27 C, nng cht u

gim i mt na sau 5000s. 370C nng gim i mt na sau 1000s.
Xc nh nng lng hot ha ca phn ng.
Gii
k1
ln 2 0,693
1,386.10 4 s 1
t1/ 2
5000
Ti 370C ta c:
ln 2 0,693
6,93.10 4 s 1
t1/ 2
1000
E a 1 1
k
p dng phng trnh: ln 2
( )
k1
R T2 T1
Ea 124,4 (kJ/ mol)
k2
8.3.
1.
Bi tp t gii
S ph thuc ca hng s tc phn ng phn hy PH3 vo nhit
c biu th bng phng trnh:
lgk
18963
2lgT 12,130.
T
Xc nh nng lng hot ha ca phn ng 800K.

S: Ea= 376,39 KJ
2.
Phn ng phn hy nhit mt hp cht A 378,50C l phn ng bc
nht. Thi gian phn ng 50% lng cht ban u nhit trn
bng 363 pht. Nng lng hot ha ca phn ng bng 217 KJ.mol
1
0
. Xc nh hng s tc ca phn ng 450 C.
-1
S: 0,1011 pht
3.
Xt phn ng:
2HgCl2 + K2C2O4 = 2KCl + 2CO2 + Hg2Cl2
C th o vn tc phn ng theo lng Calomen Hg2Cl2 gim. 1000C vn
tc u (mol/lit), HgCl2 /pht l:
Stt
Hg2Cl2 (mol/lit)
K2C2O4 (mol/lit)
dx/dt
1
0,0836
0,202
0,26
2
0,0836
0,404
1,04
3
0,0418
0,404
0,53
Xc nh bc ca phn ng.
0
-4
4.
Phn ng phn hy hp cht c hng s tc k1 10 C l 1,08.10
0
-4
0
v k2 60 C l 5,484.10 . Tnh hng s tc k 30 C.
5.
Phn ng phn hy phng x ca ng v l bc nht v c chu k
bn hy t1/2 l 15 pht. Sau bao lu 80% ng v b phn hy?
56
Phn ng phn hy kh A sau y l phn ng bc nht:

A(k) = 2B(k) + C(k)
Xut pht t kh A nguyn cht, p sut ca hn kh sau 10 pht l
176 mmHg v sau mt thi gian rt di l 270 mmHg. Th tch bnh phn
ng khng i, nhit c gi c nh. Tm:
a.
p sut ban u ca cht A.
b.
p sut ring phn ca cht A sau 10 pht.
c.
Chu k bn hy ca phn ng.
6.
57
Chng 9
HP PH V HA KEO
Vi:
V
3
(cm /g)
22400
Trong : x hay V c th xc nh bng thc nghim.

hp ph x l mt hm c hai thng s x = f(P,T). Gin hp ph
c biu din theo cc ng ng nhit (T = const) v ng p (P =
const). Thng thng ng ng nhit c s dng nhiu nht.
9.2. Phng trnh hp ph ng nhit Freunlich
ng hp ph ng nhit gn vi dng parapol, do Freunlich
ngh phng trnh thc nghim:
1/n
x = b.p
Trong :
x: hp ph.
p: p sut kh cn bng trn cht hp ph.
b v n: l cc hng s.
Hoc:
1
lgx lgb lgp
n
9.3. Phng trnh hp ph ng nhit Langmuir

Gi p l p sut kh, l phn b mt ti thi im no b phn t
kh chim, phn b mt cn trng s l 1 - .
Ta s c:
Nu t:
k 1.p
k 2 k 1.p
k
A 2
k1
x l hp ph mt thi im no .
xm l hp ph cc i.
p
A
1
p
x xm xm
9.1. Hp ph v hp ph
S hp ph y c nh gi bng lng kh bay hi (tnh bng
mol) b hp ph trong mt n v khi lng, x (mol/g). Ngoi ra, ngi ta
cn s dng i lng th tch iu kin tiu chun:
x
xm
9.4. Phng trnh hp ph BET (Brunauer- Emmett - Teller)
P
1
C 1 P
V(P0 P) Vm .C Vm .C P0
Vi:
P0: p sut hi bo ha
V: th tch kh hp ph p sut P
Vm: th tch kh b hp ph lp th nht (lp n phn t)
C: tha s nng lng.
th
P
V(P0 P)
theo P/P0 l mt ng thng, t c th xc
nh Vm v C. Bit Vm, ta c th tnh c b mt cht hp ph.
S0
Vm .N.Wm
V0
Trong :
23
N : s Avogadro (= 6,023.10 )
Wm : b mt chim bi cht b hp ph lp n phn t.
V0: th tch ca 1 mol kh iu kin chun (22.400 cm3/mol).
9.5. S hp ph trn ranh gii b mt pha lng - rn
Lng cht b hp ph x (mmol/g) b hp phn t trn b mt cht rn
trong dung dch c tnh bng cng thc:
(C0 C1 )V
100
m
Trong :
C0 v C1 l nng ban u v cn bng ca cht b hp ph (mol/l).
V l th tch trong xy ra s hp ph (l).
m l lng cht hp ph (g).
58
9.6. Bi tp mu

0
V d 1. Tnh lng ru etylic b hp ph 15 C trn b mt dung dch c

0
-3
nng 0,12M cho bit 15 C sc cng b mt ca nc l 73,49.10 N/m
-3
v ca dung dch trn l 63,3.10 N/m.
Gii
p dng cng thc:
dm.dd
RT
Th cc s liu vo cng thc ta c:
dm . dd
10,19.10 3
G
mol.m 2
RT
8,314.(15 273)
V d 2. Xc nh ngng keo t ca dung dch in ly K2Cr2O7 nng
0,01M i vi keo nhm. Bit rng keo t 1 lt keo phi thm vo mt
lng cht in ly l 0,0631 lt.
Gii
Ta c cng thc tnh ngng keo t nh sau:
C.V
=
1000
Trong :
C: Nng ca dung dch in ly (mol/l)
V: th tch ca dung dch cht in ly (ml)
: th tch ca dung dch keo (ml)
Th cc gi tr c c vo cng thc trn ta c:
C.V
0,01.0,0631
.1000
.1000 0,631.103 mol / lit
1000
V d 3. iu ch keo hydronol st (III) bng cch cho t t dung dch FeCl3

vo nc ang si. Hy vit cu to v k hiu keo .
Gii
Phng trnh phn ng iu ch ht keo:
FeCl3 + 3H2O = Fe(OH)3 + 3HCl
Cu to Mixen keo:
3+
- x+
{mFe(OH)3.nFe .(3n-x)Cl } .xCl .
V y l qu trnh thy phn khng hon ton nn trong dung dch
cn d FeCl3. Keo ny l keo dng.
V d 4. Vit cng thc v s cu to ca mixen keo c to thnh khi
cho Na2SO4 tc dng vi BaCl2 trong hai trng hp.
a.
Cho mt lng d Na2SO4.
Cho mt lng d BaCl2.

Cc cht in ly di y gy keo t nh th no i vi cc dung
dch keo ni trn: Al(OH)3; Na3PO4.
Gii
Phng trnh phn ng:
Na2SO4 + BaCl2 = 2NaCl + BaSO4
a.
Nu d Na2SO4 th mixen keo c dng:
2+
+
{mBaSO4.nSO4 .(2n-x)Na }.xNa
y l keo m
b.
Nu d BaCl2 th mixen keo c dng:
2+
{mBaSO4.nBa .(2n-x)Cl }.xCl
y l keo dng
c.
Cc cht gy s keo t:
2+
+
Vi ht keo {mBaSO4.nSO4 .(2n-x)Na }.xNa th cht gy keo t tt
nht l Al(OH)3 v y l keo m nn ion tri du vi n s quyt nh kh
3+
+
nng keo t. Ion Al c bc cao hn so vi ion Na .
2+
Vi ht keo {mBaSO4.nBa .(2n-x)Cl }.xCl th cht gy keo t tt nht
l Na3PO4 v y l keo dng nn ion tri du vi n s quyt nh kh
3nng keo t. Ion PO4 c bc cao hn so vi ion OH .
V d 5. Keo As2S3 thu c t phn ng sau vi lng d H2S:
2H3AsO3 + 3H2S = As2S3 + 6H2O
a.
Khi t h vo in trng, cc ht keo di chuyn v in cc no.
Gii thch.
b.
Vit cng thc ca mixen keo v cho bit du ca ht keo.
Gii
a.
Cng thc ca Mixen keo c dng:
2+
+
{mAs2S3.nS .(2n-x)H }.xH
b.
Khi t h vo in trng th cc ht keo s di chuyn v in cc
dng. V cc ht keo mang in tch m n s chuyn ng di tc
dng ca in trng.
V d 6. Keo AgI c iu ch t phn ng trao i:
KI + AgNO3 = AgI + KNO3, vi lng d KI.
Tip theo ngi ta dng dung dch K2SO4 v dung dch (CH3COO)2Ca
keo t dung dch keo thu c. Hi dung dch no trong hai dung dch trn
gy keo t mnh hn. V sao? (Cc dung dch trn c cng nng mol/l).
Gii
Trong hai dung dch trn th dung dch (CH3COO)2Ca s gy keo t
vi tc mnh hn. V keo c hnh thnh l keo m, n c cng thc
nh sau:
b.
c.
59
{mAgI.nI-.(n-x)K+}.xK+
M kh nng gy keo t t l thun vi bc ca in tch ion tri du.
2+
+
Dung dch (CH3COO)2Ca c ion Ca c bc ln hn ion K ca dung dch
K2SO4.
V d 7. Vit cng thc ca mixen keo Al(OH)3 vi cht n nh l AlCl3 v
keo Fe(OH)3 vi cht n nh l FeCl 3. Dung dch Na2SO4 l cht keo t tt
i vi keo no? V sao?.
Gii
Mixen keo: {mFe(OH)3.nFe3+.(3n-x)Cl-}.xCl -.
V
{mAl(OH)3.nAl3+.(3n-x)Cl-}.xCl-.
3+
3+
Dung dch Na2SO4 l cht keo t tt vi keo Fe(OH)3 v Fe v Al c
cng in tch nn kh nng keo t t l thun vi bn knh Ion. Bn knh
3+
3+
ca ion Fe ln hn Al nn n b keo t mnh hn.
-6
V d 8. Ngng keo t ca Al2(SO4)3 i vi keo As2S3 l = 96.10
3
3
kmol/m . Hi cn bao nhiu ml dung dch Al2(SO4)3 nng 0,01 kmol/m
3
keo t 0,1 m dung dch keo As2S3 ni trn.
Gii
Ta c cng thc tnh ngng keo t nh sau.
C.V
=
1000
Trong :
C: Nng ca dung dch in ly (mol/l)
V: th tch ca dung dch cht in ly (ml)
: th tch ca dung dch keo (ml)
Th cc gi tr c c vo cng thc trn ta c:
96.106

V d 10. Thi gian bn keo t ca keo AgI c nng ht bng 3,2.1011
ht.l -1 l 11,5 giy. Xc nh hng s tc keo t.
Gii
p dng phng trnh:
ko
1
1
2,72.10 9 l / hat.giay
11
3,2.10 .11,5
9.7. Bi tp t gii.
1.
Keo AgI c iu ch t phn ng trao i:
KI + AgNO3 = AgI + KNO3, vi lng d KI.
Tip theo ngi ta dng dung dch CaSO4 v dung dch CH3COONa
keo t dung dch keo thu c. Hi dung dch no trong hai dung dch
trn gy keo t mnh hn.V sao? (Cc dung dch trn c cng nng
mol/l).
2.
Vit cng thc v s cu to ca mixen keo c to thnh khi
cho K2SO4 tc dng vi Ba(NO3)2 trong hai trng hp:
a.
Cho mt lng d K2SO4.
b.
Cho mt lng d Ba(NO3)2.
3.
Vit phng trnh phn ng v cu to ca mixen keo c to thnh
khi cho KAuO2 tc dng vi K2CO3 trong HCHO.
11
4.
Thi gian bn keo t ca keo BaSO4 c nng ht bng 3,5.10
-1
ht.l l 10,5 giy. Xc nh hng s tc keo t.
0,01.V
V 96.102 ml
100
V d 9. Keo Fe(OH)3 iu ch bng cch thy phn khng hon ton st

(III) clorur, b keo t bng cc dung dch sau: Na2S, NaCl, BaCl2. Cht in ly
no c tc dng keo t mnh hn ?V sao?
Gii
Khi iu ch keo Fe(OH)3 iu ch bng cch thy phn khng hon
ton st (III) clorur th s to ra keo c in tch dng. Vi cng thc nh
sau:
{mFe(OH)3.nFe3+.(3n-x)Cl-}.xCl -.
2Trong 3 dung dch trn th bc ca ion tri du cao nht l S nn
dung dch s gy keo t mnh nht l dung dch Na2S.
60

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Bi tp ha l c s rt gn

Su tm v trnh by: Don Trng C

1.1. Nguyn l I nhit ng hc

1.1.3. p dng nguyn l I cho mt s qu trnh.

Su tm v trnh by: Don Trng C

Nhit phn ng nghch bng nhng tri du vi nhit phn ng thun.

Nhit phn ng bng tng nhit sinh ca cc cht to thnh tr i tng

Q m CdT hoc Q n CdT

nh hng ca nhit n nhit dung

Su tm v trnh by: Don Trng C

Bin thin ni nng l:

Bin thin ni nng ca qu trnh l:

Su tm v trnh by: Don Trng C

H = Qp = n.Cp. (T2 T1)

U = Q A = 67469 - 15120 = 52349 (J)

Suy ra: U = Qv = 1 28,786(546 - 273) = 7859 (J)

Su tm v trnh by: Don Trng C

A PdV PV2 V1 1.40 20 20l.atm

Tnh nhit lng Q:

Bin thin ni nng:

Su tm v trnh by: Don Trng C

Su tm v trnh by: Don Trng C

i vi qu trnh chuyn pha nh qu trnh nng chy, qu trnh ha

Du = khi qu trnh l thun nghch.

Nu dS = 0 hay d S < 0: Qu trnh t cn bng

Bin thin entropy nhit bt k c th tnh bng phng trnh:

Entropy c o bng n v cal.mol .K hay J.mol .K

2.1.4.2. Qu trnh ng nhit

2.1. Nguyn l II nhit ng hc

C Rp1 : nhit dung trng thi rn 1

Su tm v trnh by: Don Trng C

CRp 2 : nhit dung trng thi rn 2

S 0298 S 0298(sp) S 0298(tc)

Nu dG = 0 hay d2G > 0 : Qu trnh t cn bng

Nu dF = 0 hay d F > 0 : Qu trnh t cn bng

V d 2. Xc nh nhit lc cn bng nhit v bin thin entropy khi trn

Bin thin entropy ca h:

Su tm v trnh by: Don Trng C

V d 4. Xc nh bin thin entropy ca qu trnh chuyn 2g nc lng

Bin thin etropy ca qu trnh

Nhit lng cn cung cp

Bin thin entropy ca h:

Q p 75,24(373 298) 40629,6 46272,69(J)

A A1 A2 0 PV nRT2 1 8,314 373 3101,1J

Su tm v trnh by: Don Trng C

Cp = [4.Cp(H2) + Cp(Fe3O4)] [4.Cp(H2O) + 3.Cp(Fe)]

Tnh bin thin entropy ca qu trnh un nng 2 mol Nit (c xem

Tnh bin thin entropy ca phn ng:

Tnh G 298 khi to thnh 1 mol nc lng bit cc gi tr entropy tiu

ca phn ng phn hy nhit CaCO3

S o298 = 158,9 J/K; Ho298 = 178,30 kJ;

Su tm v trnh by: Don Trng C

Cho phn ng: CO(k) + H2O(k) = CO2(k) + H2(k), c nhng gi tr bin

Phn ng xy ra theo chiu no 300K v 1200K?

S: G 300 28,44 KJ; G1200 2590J

Tnh bin thin entropy ca qu trnh ng c benzen di p sut

Cho phn ng v cc s liu sau:

Su tm v trnh by: Don Trng C

Tnh hiu ng nhit ng p v ng tch ca phn ng 25 C

Su tm v trnh by: Don Trng C

Hng s cn bng tnh theo nng mol/l:

Mi quan h ca cc hng s cn bng:

Nu P > KP: phn ng xy ra theo chiu nghch

Nu cc phn ng xy ra trong cc h d th m cc cht trong pha