Bai Tap Hoa Ly Full PDF

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
1
Chng 1 Bin thin ni nng khi dn n ng nhit (T = const) kh l tng l
bng khng nn:
V2 P
NGUYN L I NHIT NG HC Q T A T nRTln nRTln 1
V1 P2
Trong :
P1: p sut trng thi u.
1.1. Nguyn l I nhit ng hc P2: p sut trng thi cui.
1.1.1. Nhit v cng 1.1.3.5. Nhit chuyn pha
Nhit v cng l hai hnh thc truyn nng lng ca h. Cng k cp
hiu l A v nhit k hiu l Q. Q
Quy c du Cng A Nhit Q T
H sinh >0 <0 Trong :
H nhn <0 >0 cp: nhit chuyn pha (cal hoc J)
1.1.2. Nguyn l I nhit ng hc nc = -, hh = -ngt
Biu thc ca nguyn l I nhit ng hc: Ghi ch:
U = Q - A R l hng s kh l tng v c cc gi tr sau:
Khi p dng cho mt qu trnh v cng nh: R = 1,987 cal/mol.K = 8,314 J/mol.K
dU = Q - A R = 0,082 lit.atm/mol.K
dng tch phn nguyn l I c th c vit: 1 cal = 4,18 J; 1 l.atm = 101,3 J = 24,2 cal
V2 1.2. nh lut Hess
U Q PdV 1.2.1. Ni dung nh lut
V1
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
1.1.3. p dng nguyn l I cho mt s qu trnh.
trung gian.
1.1.3.1. Qu trnh ng tch: V = const, dV = 0.
Biu thc ca nh lut Hess:
V2
QV = U v Qp = H
A v PdV 0 Trong :
V1 U: nhit phn ng ng tch.
T ta c: QV = U H: nhit phn ng ng p.
1.1.3.2. Qu trnh ng p: P = const, dP = 0. Khi qu trnh xy ra iu kin tiu chun ta c nhit phn ng tiu
Ap = P.(V2 - V1) = P.V chun: H0298, U0298.
Do : Qp = U + PV = (U + PV) = H i vi cc qu trnh xy ra khi c mt cc cht kh (c xem l kh
1.1.3.3. Qu trnh ng p ca kh l tng l tng), ta c:
T phng trnh trng thi kh l tng: PV = nRT H = U + RTn
Ta c: Ap = PV = nRT Vi n l bin thin s mol kh ca qu trnh.
Up = Qp nRT 1.2.2. Cc h qu ca nh lut Hess
1.1.3.4. Qu trnh dn n ng nhit ca kh l tng Nhit phn ng nghch bng nhng tri du vi nhit phn ng thun.
Hnghch = - Hthun
2
Nhit phn ng bng tng nhit sinh ca cc cht to thnh tr i tng Sau khi ly tch phn ta c:
nhit sinh ca cc cht tham gia phn ng. T
s s
H phn ng = H sp - H tc H T H 0 C p dT
Nhit phn ng bng tng nhit chy ca cc cht tham gia phn ng 0
tr i tng nhit chy ca cc cht to thnh. Nu ly tch phn t T1 n T2 ta c:
H phn ng = Hchtc - Hchsp T2
Ghi ch: Nhit to thnh tiu chun (H0298, tt), nhit t chy tiu H T2 H T1 C p dT
chun (H0298,c ) c cho sn trong s tay ha l. T1
1.3. Nhit dung 1.4. Bi tp mu
1.3.1. nh ngha 0
V d 1: Tnh bin thin ni nng khi lm bay hi 10g nc 20 C. Chp
Q H nhn hi nc nh kh l tng v b qua th tch nc lng. Nhit ha hi
Nhit dung ng p: Cp 0
ca nc 20 C bng 2451,824 J/g.
dP P T P Gii
Q U Nhit lng cn cung cp lm ha hi 10g nc l:
Nhit dung ng tch: C v Q = m. = 10. 2451,824 = 24518,24 (J)
dT V T V Cng sinh ra ca qu trnh ha hi l:
Mi lin h: Cp - Cv = R A = P.V = P(Vh - Vl) = PVh
Nhit lng Q c tnh: 10
T2 T2 = nRT 8,314 293 1353,33 (J)
Q m CdT hoc Q n CdT 18
Bin thin ni nng l:
T1 T1
U = Q A = 23165 (J)
1.3.2. nh hng ca nhit n nhit dung 0
V d 2: Cho 450g hi nc ngng t 100 C di p sut khng i 1
S ph thuc vo nhit ca nhit dung c biu din bng cc atm. Nhit ha hi ca nc nhit ny bng 539 cal/g. Tnh A, Q v U
cng thc thc nghim di dng cc hm s: ca qu trnh.
2
Cp = a0 + a1.T + a2.T Gii
-2
Hoc Cp = a0 + a1.T + a-2.T Nhit lng ta ra khi ngng t l:
Trong : a0, a1, a2, a-2 l cc h s thc nghim c th tra gi tr ca
Q = m.ng. t = 450. (- 539) = - 242550 (cal)
chng trong s tay ha l.
Cng ca qu trnh:
1.2.2. nh lut Kirchhoff
A = P.V = P. (Vl - Vh) = - P.Vh = - nRT
Hiu ng nhit ca phn ng ph thuc vo nhit c biu din
bi nh lut Kirchhoff: 450
= 1,987 373 18529(cal)
H 18
C p Bin thin ni nng ca qu trnh l:
T P U = Q A = - 224021 (cal)
U V d 3: Cho phn ng xy ra p sut khng i:
Hoc C v 2H2 + CO = CH3OH(k)
T V
3
nhit to thnh tiu chun 298K ca CO v CH3OH(k) bng -110,5 v - H = Qp = n.Cp. (T2 T1)
201,2 kJ/mol. Nhit dung mol ng p ca cc cht l mt hm ca nhit :
-3 PV PV
Cp (H2) = 27,28 + 3,26.10 T
-3
(J/mol.K) n.C p 2 1
Cp (CO) = 28,41 + 4,1.10 T
-3
(J/mol.K) nR nR
Cp (CH3OH)k = 15,28 + 105,2.10 T (J/mol.K)
0
Tnh H ca phn ng 298 v 500K? 100
0,082 273
37,1
Nhit phn ng 298K l:
Gii
1 0,2.10 3 44
0
0,082 1
H 298 = - 201,2 - (-110,5) = - 90,7 (KJ)
Bin thin nhit dung:
Cp = Cp(CH3OH) Cp(CO) 2Cp(H2) J
= - 67,69 + 94,58. 10-3T (J/K) A = PV = P(V2 V1)
Nhit phn ng 500K l : 100
500 0,082 273
0 3
1 0,2.10 44 8,314 15120 J
H 500 H 0298 C p dT 1 0,082
298
500

67,69 94,58.10
3 U = Q A = 67469 - 15120 = 52349 (J)
90,7.103 T dT c.
5
un nng ng tch (V = const) ti p sut bng 2,026.10 Pa (2 atm)
298 A=0
= - 96750,42 (J) C v = Cp - R = 37,1 - 8,314 = 28,786 (J/mol.K)
0
V d 4: Cho 100g kh CO2 (c xem nh l kh l tng) 0 C v U = Qv = n.Cv.(T2 T1)
5
1,013.10 Pa. Xc nh Q, A, U v H trong cc qu trnh sau. Bit Cp =
37,1 J/mol.K.
P2 P1
3
Ta c:
a. Dn n ng nhit ti th tch 0,2 m .
3
T2 T1
b. Dn ng p ti 0,2 m .
c. un nng ng tch ti khi p sut bng 2,026.105 Pa. P 2
T2 2 T1 273 546K
Gii P1 1
3
a. Dn n ng nhit (T = const) ti th tch 0,2m .
Suy ra: U = Qv = 1 28,786(546 - 273) = 7859 (J)
V PV2 H = U + PV = 7859 (J)
Q T A T nRTln 2 nRTln
V1 nRT 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
100 1 0,2.103 thc hin cc qu trnh sau y:
8,314 273.ln 7061 (J) a. Dn n thun nghch ng p p sut 1atm t 20dm3 n 40dm3.
44 100
0,082 273 b. Bin i thun nghch ng tch t trng thi (1atm; 40dm3) n
3
44 (0,5atm; 40dm ).
0
U = 0 c. Nn thun nghch ng nhit t 0,5 atm n 1 atm 25 C.
3
b. Dn n ng p (P = const) ti 0,2m . Gii
a. Dn n thun nghch ng p (P = const).
4
Tnh cng A: V d 6: Tnh nhit to thnh ca etan bit:
0
V2 Cgr + O2 = CO2 H 298 = -393,5 KJ
A PdV PV2 V1 1.40 20 20l.atm H2 + 1/2O2 = H2O(l)
0
H 298 = -285 KJ
0
V1 2C2H6 + 7O2 = 4 CO2 + H2O(l) H 298 = -3119,6 KJ
Gii
8,314
20 2028 (J) Cgr + O2 = CO2 (1)
0,082 H2 + 1/2O2 = H2O(l) (2)
Tnh nhit lng Q: 2C2H6 + 7O2 = 4CO2 + 6H2O(l) (3)
T Nhit to thnh C2H6 l:
2
P V PV
Q p C p dT C p .T2 T1 C p 2 1 0
2C + 3H2 = C2H6
0 0 0
(4)
T1 R R 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)
3,5R
40 20 70 (l.atm) V d 7. Tnh Q, A, U ca qu trnh nn ng nhit, thun nghch 3 mol kh
0
R He t 1atm n 5 atm 400 K.
Gii
8,314 Nhit v cng ca qu trnh:
70 7097 (J)
0,082 P1 1
Bin thin ni nng: Q T A T nRTln 3 8,314 400ln 16057(J)
U = Q A = 5069 (J)
P2 5
Bin thin entapy U = 0
0 0
H = Qp = 7097 (J) V d 8. Cho phn ng: 1/2N2 + 1/2O2 = NO. 25 C, 1atm c H 298 =
b. Dn n thun nghch ng tch (V = const). 90,37 kJ. Xc nh nhit phn ng 558K, bit nhit dung mol ng p ca
-1 -1
A=0 1 mol N2, O2 v NO ln lt l 29,12; 29,36 v 29,86 J.mol .K .
Nhit lng: Gii
T Hiu ng nhit ca phn ng 558K l:
2
P V PV
Q v C v dT C v .T2 T1 C v 2 1 558
T1 R R H 0558 H 0298 Cp dT
298
2,5R
400,5 1 50 (l.atm) Trong :
-1
R Cp = 29,86 1/2(29,12) 1/2(29,36) = 0,62 (J.K )
0 -3
8,314 H 558 = 90,37 + 0,62.(558 - 298).10 = 90,5312 (KJ)
50 5069 (J) 1.5. Bi tp t gii
0,082 1. Xc nh bin thin ni nng khi lm ha hi 20g etanol ti nhit
U = Qv = - 5069 (J) si, bit nhit ha hi ring ca etanol bng 857,7 J/g v th tch hi
3
c. Nn ng nhit (T = const) U = 0 ti nhit si bng 607 cm /g (b qua th tch pha lng).
S: 2,54 kJ
P1 0,5 2. Tnh H v U cho cc qu trnh sau y:
Q T A T nRTln 1 8,314 298 ln 1717 (J)
P2 1 a. Mt mol nc ng c 00C v 1 atm;
5
b. Mt mol nc si 1000C v 1 atm. 0
H 298,tt (kcal/mol) 0 0 -11,04
Bit rng nhit ng c v nhit ha hi ca 1 mol nc bng -6,01 V nhit dung ca cc cht:
kJ v 40,79 kJ, th tch mol ca nc v nc lng bng 0,0195 v CP (N2) = 6,65 + 10-3T (cal.mol-1.K-1)
-3 -1 -1
0,0180 lit. Chp nhn hi nc l kh l tng. CP (H2) = 6,85 + 0,28.10 T (cal.mol .K )
-3 -1 -1
S: a. H = U = -6,01 kJ CP (NH3) = 5,92 + 9,96.10 T (cal.mol .K )
0 0
b. H = 37,7 kJ; U = 40,79 kJ Xc nh hm s H T = f(T) v tnh H 1000 ca phn ng?
3. Nhit sinh ca H2O(l) v ca CO2 ln lt l -285,8 v -393,5 kJ/mol S: H T = -18,22 15,36.10-3T + 8.10-6T2 (Kcal)
0
0
25 C, 1 atm. Cng iu kin ny nhit t chy ca CH4 bng - H0 = -25,58 Kcal
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)
6
Chng 2 T2
dT
Nu qu trnh ng tch: S C v
T1
T
NGUYN L II NHIT NG HC
2.1.4.2. Qu trnh ng nhit
Trong qu trnh thun nghch ng nhit, ta c th p dng:
QT
2.1. Nguyn l II nhit ng hc S
2.1.1. nh ngha entropy
T
Trong qu trnh thun nghch, bin thin entropy khi chuyn h t i vi qu trnh chuyn pha nh qu trnh nng chy, qu trnh ha
trng thi 1 sang trng thi 2 c xc nh bng phng trnh: hi
Q HT
dS S
T T T
Q nc hh
S nc hay Shh
hay S TN Tnc Thh
T
-1 -1 -1
Entropy c o bng n v cal.mol .K hay J.mol .K
-1
V2
2.1.2. Biu thc ton ca nguyn l II
i vi kh l tng: Q T nRTln
V1
Q
dS QT V P
T Ta c: S nRln 2 nRln 1
T V1 P2
Du = khi qu trnh l thun nghch.
Bin thin entropy nhit bt k c th tnh bng phng trnh:
Du > khi qu trnh l bt thun nghch. Tchph Tnc
2.1.3. Tiu chun xt chiu trong h c lp dT chph dT nc
Trong h c lp (on nhit) S T C Rp1 C Rp 2
0 T Tchph Tchph T Tnc
Nu dS > 0 : Qu trnh t xy ra
2 Thh
Nu dS = 0 hay d S < 0: Qu trnh t cn bng dT hh T k dT
C lp Cp
T Thh Thh
2.1.4. Bin thin entropy ca mt s qu trnh thun nghch
2.1.4.1. Qu trnh ng p hoc ng tch
Tnc T
T2
dT
S C dT
T1
T hoc ST C p
T2
T T
dT Trong :
Nu qu trnh ng p: S C p
T1
T C Rp1 : nhit dung trng thi rn 1
7
T2
CRp 2 : nhit dung trng thi rn 2 S n C p
dT 16.103 5
1,987.ln
373
775cal/K
Bin thin entropy tiu chun ca cc phn ng c xc nh bng T1
T 32 2 273
phng trnh: b. i vi qu trnh ng tch
S 0298 S 0298(sp) S 0298(tc) T2
dT 16.103 3 373
2.2. Th nhit ng S n C v 1,987.ln 465cal/K
Cc th nhit ng bao gm: ni nng, entapy, nng lng t do v T1
T 32 2 273
th ng p. V d 2. Xc nh nhit lc cn bng nhit v bin thin entropy khi trn
0 0
Nng lng t do F v th ng p G c nh ngha bi cc 1g nc 0 C vi 10g nc 100 C. Cho bit nhit nng chy ca
phng trnh sau: bng 334,4 J/g v nhit dung ring ca nc bng 4,18 J/g.K.
F = U - TS Gii
G = H - TS Gi T (K) l nhit ca h sau khi trn. Gi s h l c lp.
Ti mt nhit xc nh, bin thin th ng p v ng tch c Ta c phng trnh:
biu din bng phng trnh sau: Nhit lng ta ra = Nhit lng thu vo
F = U - TS - Qta = Qthu hay Q3 = Q1 + Q2
G = H - TS - 10.4,18.(T - 373) = 334,4 + 1.4,18.(T - 273)
V G = Gcui - Gu T = 356,64 (K)
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 Bin thin entropy ca h:
Nu dG < 0 : Qu trnh t xy ra S = S1 + S2 + S3
Nu dG = 0 hay d2G > 0 : Qu trnh t cn bng nc 334,4
2.2.2. Xt chiu trong h ng nhit, ng tch Vi: S1 1,225(J/K)
Trong h ng nhit, ng tch
Tnc 273
356,64
Nu dF < 0 : Qu trnh t xy ra
S 2 1.
dT
1,117(J/K)
2
Nu dF = 0 hay d F > 0 : Qu trnh t cn bng 4,18
273
T
2.3. Bi tp mu 356,64
V d 1. Tnh bin thin entropy khi un nng thun nghch 16 kg O2 t 273K dT
S 3 10. 4,18 1,875(J/K)
n 373K trong cc iu kin sau: T
373
a. ng p
b. ng tch S = 0,467 (J/K)
Xem O2 l kh l tng v nhit dung mol Cv = 3R/2. V d 3. Tnh bin thin entropy ca qu trnh nn ng nhit, thun nghch.
Gii a. 1 mol oxy t P1 = 0,001atm n P2 = 0,01atm.
a. i vi qu trnh ng p b. 1 mol mtan t P1 = 0,1 atm n P2 = 1 atm.
Cp = Cv + R = 5R/2 Trong hai trng hp trn kh c xem l l tng.
Gii
8
P1 V2
a. S nRln 1,987.ln0,1 4,575(cal/K) S1 nR.ln 13,32(cal/K)
P2 V1
P V
b. S nRln 1 1,987.ln0,1 4,575(cal/K) S 2 nR.ln 2' 7,46(cal/K)
P2 V1
V d 4. Xc nh bin thin entropy ca qu trnh chuyn 2g nc lng Vy S = 20,78 (cal/K)
00C thnh hi 1200C di p sut 1 atm. Bit nhit ha hi ca nc 0
V d 6. Tnh U, H v S ca qu trnh chuyn 1 mol H2O lng 25 C v
0 -3 0
100 C l 2,255 (kJ/g), nhit dung mol ca hi nc Cp,h = 30,13 + 11,3.10 T 1 atm thnh hi nc 100 C, 1 atm. Cho bit nhit dung mol ca nc
(J/mol.K) v nhit dung ca nc lng l Cp,l = 75, 30 J/mol K. lng l 75,24 J/mol.K v nhit ha hi ca nc l 40629,6 J/mol.
Gii Gii
Bin thin etropy ca qu trnh Nhit lng cn cung cp

S = S1 + S2 + S3 373
2 373
dT Q p Q1 Q 2 75,24dT hh
Vi S1 75,3 2,61(J/K) 298
18 273 T
Q p 75,24(373 298) 40629,6 46272,69(J)
2 2255 Cng ca qu trnh
S2 12,09(J/K)
373
2 393 dT A A1 A2 0 PV nRT2 1 8,314 373 3101,1J
18 373

S1 30,13 11,3.10-3 T
T
0,2(J/K) Ni nng
U = Q A = 43171,5 (J)
S = 14,9 (J/K) H = Qp = 4627,6 (J)
3
V d 5. Mt bnh kn hai ngn, ngn th nht c th tch 0,1 m cha oxi, Bin thin entropy ca qu trnh
3
ngn th hai c th tch 0,4 m cha Nit. Hai ngn u cng mt iu 373
kin nhit l 170C v p sut 1,013.105 N/m2. Tnh bin thin entropy khi dT hh
cho hai kh khuch tn vo nhau.
S S1 S 2 Cp
298
T Thh
Gii
3
Khi hai kh khuch tn vo nhau, th tch ca hn hp V2 = 0,5 m 373 40629,6
75,24ln 125,8 J/K
Bin thin entropy ca h: 298 373
S =S1 + S2 V d 7. Cho phn ng c cc s liu sau:
Vi S1: bin thin entropy ca kh Oxy khi khuch tn 3Fe(r) + 4H2O(h) = Fe3O4(r) + 4H2(k)
S2: bin thin entropy ca kh Nit khi khuch tn
0
H 298 t.t 0 -57,8 -267 0
(Kcal/mol)
9
S0298 6,49 45,1 3,5 32,21 2. Tnh bin thin entropy ca qu trnh un nng 2 mol Nit (c xem
(cal/mol.K) l l tng) t 300K n 600K di p sut kh quyn trong 2 trng
-3
Cp(Fe) = 4,13 + 6,38.10 .T (cal/mol.K) hp:
-3
Cp(H2Oh) = 2,7 + 1.10 .T (cal/mol.K) a. ng p
-3
Cp(Fe3O4) = 39,92 + 18,86.10 .T (cal/mol.K) b. ng tch
-3
Cp(H2) = 6,95 - 0,2.10 .T (cal/mol.K) Bit rng nhit dung Cp ca Nit trong khong nhit 300 - 600K
0 -3
a. Tnh hiu ng nhit ng p v ng tch 25 C v 1atm? c cho bng phng trnh: Cp = 27 + 6.10 T (J/mol.K).
b. Tnh hiu ng nhit ng p v ng tch 1000K? S: 41 J/K; 29,5 J/K
c. Xt chiu phn ng 250C v 1atm? 3. Tnh bin thin entopy ca qu trnh trn 10g nc 00C vi 50g
Gii nc lng 400C trong h c lp. Cho bit nhit nng chy ca nc
Phn ng: 3Fe(r) + 4H2O(h) = Fe3O4(r) + 4H2(k) bng 334,4 J/g, nhit dung ring ca nc lng bng 4,18 J/g.
a. Tnh H0298 = -267 - 4.(-57,8) = - 35,8 Kcal.
Tnh U0298 = H0298 - nR.T vi n = 4 - 4 = 0 4. Tnh bin thin entropy ca phn ng:
Do U0298 = H0298 = -35,8 Kcal 4 Fe + 3O2 = 2Fe2O3.
0
1000 Cho bit S 298 ca Fe, O2 v Fe2O3 tng ng bng 27,3; 205 v 87,4
0 0 J/mol.K.
b. Tnh H = H +
1000 298
Cp.dT
298 5. Hy d on du ca S trong cc phn ng sau:
Cp = [4.Cp(H2) + Cp(Fe3O4)] [4.Cp(H2O) + 3.Cp(Fe)] a. CaCO3(r) = CaO(r) + CO2(r)
b. NH3(k) + HCl(k) = NH4Cl(r)
Cp = 44,53 - 5,08.10-3.T c. BaO(r) + CO2(k) = BaCO3(r)
Ta c:
1000
S: a. S > 0; b. S < 0; c. S < 0
3 0
0
6. Tnh G 298 khi to thnh 1 mol nc lng bit cc gi tr entropy tiu
H 1000 = -35800 + (44,53 5,08.10 .T)dT
chun ca H2, O2 v H2O ln lt bng 130; 684; v 69,91 J/mol.K v
298
0
= - 6854,37 (cal) nhit to thnh nc lng 25 C l -285,83 KJ/mol.
U01000 = H01000 - nRT vi n = 4 - 4 = 0 S: G 0298 = -237,154 kJ
0 0
U 1000 = H 1000 = - 6854,37 (cal)
c. Xt chiu phn ng ktc t cng thc: 7. Tnh S0298, H0298 v G 0
298
ca phn ng phn hy nhit CaCO3
0 0 0
G 298 = H 298 T.S 298. bit:
Trong : CaCO3 = CaO + CO2
0 0
S 298 = (4x32,21 + 35) (4x45,1 + 3x6,49) S 298 (J/mol.K) 92,9 38,1 213,7
= - 36,03 (cal) -1206,90 -635,10 -393,50
0 H 0tt,298 ( KJ/mol)
G 298 = -35800 + 298x36,03 = - 25063,06 (cal)
0
V: G 298 < 0 nn phn ng t din bin.
2.4. Bi tp t gii S: S o298 = 158,9 J/K; Ho298 = 178,30 kJ;
1. 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 + Go298 = 130,90 kJ
-3
3,32.10 T cal/mol.
S: 6,65 cal/mol.K
10
8. Cho phn ng: CO(k) + H2O(k) = CO2(k) + H2(k), c nhng gi tr bin 12. Tnh bin thin entropy ca qu trnh ng c benzen di p sut
thin entanpy v bin thin entropy tiu chun 300K v 1200K nh 1atm trong 2 trng hp:
0
sau: a. ng c thun nghch 5 C bit nhit ng c ca benzen l
0 0 -2370 cal/mol.
H300 41,16 KJ/mol H1200 32,93 KJ/mol b.
0
ng c bt thun nghch -5 C.
0 0
S300 42,40 J/K S1200 29,60 J/K Bit nhit dung ca Benzen lng v rn ln lt l 30,3 v 29,3
cal/mol.K.
Phn ng xy ra theo chiu no 300K v 1200K?
0 0 S: a. S = 0 cal/K ; b. S = 0,31 cal/K
S: G 300 28,44 KJ; G1200 2590J 13. Cho phn ng v cc s liu sau:
9. Cho phn ng: CH4(k) + H2O(k) = CO(k) + 3H2(k). FeO(r) + CO(k) = CO2(k) + Fe(r)
Cho bit nhit to thnh chun ca CH4(k), H2O(h) v CO(k) ln lt l -
0
74,8; -241,8; -110,5 KJ/mol. Entropy tiu chun ca CH4(k), H2O(h) v CO(k) H 298 t.t -63,7 -26,42 -94,052 0
0 0
ln lt l 186,2; 188,7 v 197,6 J/mol.K. (Trong tnh ton gi s H v S (Kcal/mol)
0
khng ph thuc nhit ). S 298 1,36 47,3 51,06 6,49
0
a. Tnh G v xt chiu ca phn ng 373K. (cal/mol.K)
b. Ti nhit no th phn ng t xy ra. Cp(Fe) = 4,13 + 6,38.10-3.T (cal/mol.K)
0 5
S: a. G = 1,26.10 J/mol; b. T> 961K Cp(CO) = 6,34 + 1,84. 10-3.T (cal/mol.K)
-3
10. Cho phn ng v cc s liu sau: Cp(FeO) = 12,62 + 1,50.10 .T (cal/mol.K)
-3
COCl2(k) = Cl2(k) + CO(k) 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?
H0298 t.t (Kcal/mol) - 53,3 0 -26,42
S0298 (cal/mol.K) 69,13 53,28 47,3 b. Tnh 0hiu ng nhit ng p v ng tch ca phn ng
Cp(CO) = 6,96 (cal /mol.K) 1000 K?
Cp(COCl2) = 14,51 (cal /mol.K) c. Xt chiu phn ng iu kin tiu chun.
Cp(Cl2) = 8,11 (cal /mol.K) d. Xt chiu phn ng 1000K xem entropy khng thay i theo
a. Tnh hiu ng nhit ng p v ng tch ca phn ng nhit .
0 0
250C? S: a. H 298 = U 298 = -3932 cal
0 0
b. Xt chiu phn ng 250C? b. H 1000 = U 1000 = -4567 cal
c. Tnh hiu ng nhit ng p ca phn ng 1000K? 14. Cho phn ng v cc s liu sau:
0 0
S: a. H = 26,88 Kcal, U = 26287,87 cal C(r) + CO2(k) = 2CO(k)
0 0
b. S = 31,45 cal/K, G = 17507,9 cal
0
c. H = 26486,88 cal
0 0
11. Tnh nhit lng cn thit lm nng chy 90 gam nc 0 C S 298 (cal/mol.K) 1,36 51,06 47,3
0 0
v sau nng nhit ln 25 C. Cho bit nhit nng chy ca nc 298 (Kcal/mol) 0 -94,052 -26,42
00C l 1434,6 cal/mol, nhit dung ca nc lng ph thuc vo Cp(CO) = 6,96 (cal /mol.K)
nhit theo hm s: Cp = 7,20 + 2,7.10-3T (cal.mol -1.K-1). Cp(Cgr) = 2,07 (cal /mol.K)
S: Q = 8169,4 cal Cp(CO2) = 8,88 (cal /mol.K)
11
0
a. Tnh hiu ng nhit ng p v ng tch ca phn ng 25 C
v 1atm.
0
b. Xt chiu phn ng 25 C v 1atm.
c. 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: GT G0T RTln P
Vi G0T RTlnKP
CN BNG HA HC
PCc .PDd
p
PAa .PBb
3.1. Hng s cn bng Trong : PA, PB, PC, PD l p sut ring phn ti thi im bt k

3.1.1. Cc loi hng s cn bng G T RTln KPP
Phn ng: aA(k) + bB(k) cC(k) + dD(k)
Hng s cn bng tnh theo p sut : Nu P > KP: phn ng xy ra theo chiu nghch
P c .P d
Nu P < KP: phn ng xy ra theo chiu thun
K P Ca Db
Nu P = KP: phn ng t cn bng
PA .PB cb P
n
Hng s cn bng tnh theo nng mol/l: Ch : P C (RT) n

x .P n
n
ni
C c .C d
K C Ca Db

C A .C B cb 3.2. Cn bng trong h d th
Hng s cn bng tnh theo phn mol: 3.2.1. Biu din hng s cn bng
Nu cc phn ng xy ra trong cc h d th m cc cht trong pha
x c .x d rn hoc pha lng khng to thnh dung dch th biu thc nh ngha hng
K x Ca Db
s cn bng khng c mt cc cht rn v cht lng.
x A .x B cb V d: Fe2O3(r) + 3CO(k) = 2Fe(r) + 3CO2(k)
Hng s cn bng tnh theo s mol: 3
PCO
c
n .n d Hng s cn bng: K P 2
C D 3
K n a

b
PCO
n .n cb
A B 3.2.2. p sut phn ly
Mi quan h ca cc hng s cn bng: p sut hi do s phn ly ca mt cht to thnh l c trng cho
n cht mi nhit c gi l p sut phn ly.
n P
K P K C .RT K x .P n K n . V d: CaCO3(r) = CaO(r) + CO2(k)
n i cb p sut phn ly: PCO K P
2
n l bin thin s mol kh ca h.
3.2.3. phn ly
n = (c + d) (a + b) phn ly l lng cht phn ly so vi lng cht ban u:
Nu n = 0 ta c Kp = KC = Kx = Kn
3.1.2. Phng trnh ng nhit Vant Hoff n

Xt phn ng: aA(k) + bB(k) cC(k) + dD(k) no
n: lng cht phn ly
13
no: lng cht ban u 250 1000 0 0
3.3. Cc yu t nh hng n hng s cn bng 28 18
3.3.1. nh hng ca nhit n hng s cn bng x x x x
T phng trnh ng p Vant Hoff
dlnK P H x x
250 1000
dT RT 2 ( x) ( x)
Trong khong nhit nh t T1 n T2, xem H khng i. Ly tch 28 18
phn 2 v, ta c: V n = 0, ta c hng s cn bng:
K pT2 H 1 1 n CO 2 .n H 2 x2
ln KP Kn 4,12
K pT1 R T2 T1 n CO .n H 2O 250 1000
x . x
dlnKP 28 18
Nu phn ng thu nhit, H > 0 0 : nh vy khi nhit Gii phng trnh ta c: x = 8,55 (mol)
dT Vy khi lng H2 sinh ra: m = 17,1 (g)
tng, gi tr Kp cng tng, phn ng dch chuyn theo chiu thun. 0
V d 2. 200 C hng s cn bng Kp ca phn ng dehydro ha ru
dlnKP Isopropylic trong pha kh:
Nu phn ng ta nhit, H < 0, 0 : nh vy khi nhit CH3CHOHCH3(k) H3CCOCH3(k) + H2
dT 4 0
tng, gi tr Kp s gim, phn ng dch chuyn theo chiu nghch. 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).
3.3.2. nh hng ca p sut Gii
n
Ti nhit khng i ta c: K p K x .P const Gi a l s mol ban u ca CH3CHOHCH3.
n x l s mol CH3CHOHCH3 phn ly, ta c:
Nu n > 0: Khi tng p sut P, gi tr P cng tng, do Kx gim,
cn bng s dch chuyn theo chiu nghch. CH3CHOHCH3(k) H3CCOCH3(k) + H2
Nu n < 0: Khi tng p sut P, gi tr Pn gim, do Kx tng, cn
a 0 0
bng dch chuyn theo chiu thun.
x x x
Nu n = 0: th Kp = Kx = const. Khi p sut chung P khng nh
hng g n cn bng phn ng.
(a x) x x
3.4. Bi tp mu
V d 1. Hng s cn bng ca phn ng: Tng s mol cc cht lc cn bng: ni a x
CO(k) + H2O(h) CO2(k) + H2(k) 800K l 4,12. n
P x.x P
un hn hp cha 20% CO v 80% H2O (% khi lng) n 800K. K P K n . . vi n = 1
Xc nh lng hydro sinh ra nu dng 1 kg nc. n i cb a x a x
Gii
Gi x l s mol ca H2O tham gia phn ng. 0,97.x 2
0,692
CO + H2O CO2 + H2 a2 x 2
x = 0,764a
14
x c. Phi thm bao nhiu mol Cl2 vo 1mol PCl5 phn ly ca PCl5
Vy phn ly: 0,764 8 atm l 10%.
a Gii
0
V d 3. un nng ti 445 C mt bnh kn cha 8 mol I2 v 5,3 mol H2 th to a. Tnh phn ly ca PCl 5
ra 9,5 mol HI lc cn bng. Xc nh lng HI thu c khi xut pht t 8 Gi a l s mol PCl 5 ban u
mol I2 v 3 mol H2. l phn ly ca PCl 5, ta c:
Gii
PCl5(k) PCl3(k) + Cl 2(k)
Gi x l s mol H2 tham gia phn ng:
H2 + I2 2HI Ban u a 0 0
Ban u 5,3 8 0 Phn ng a a a
Phn ng x x 2x
Cn bng a(1-) a a
Cn bng (5,3 x) (8 x) 2x n
P 2 2
Theo bi: 2x = 9,5 x = 4,75 (mol) a P
Ta c KP K n
Hng s cn bng: ni
a1 a1
n 2HI 4x 2 Vi n = 1, ni = a(1+)
Kn 50,49
n H 2 .n I 2 5,3 x 8 x P. 2 1
2

Hn hp 8 mol I2 v 3 mol H2. 1 3
H2 + I2 2HI 2 2
3P = 1 -
Ban u 3 8 0 1
Phn ng y y 2y
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: Vi P = 8 atm 0,2
4y 2 b. p sut no phn ly l 10%
Kn 50,49
3 y 8 y P. 2 1
Ta c
y = 2,87 1 2 3
S mol HI to thnh: nHI = 5,74 (mol)
V d 4. Hng s cn bng ca phn ng:
0,1 2.P 1
2

PCl 3(k) + Cl2(k) PCl5(k) 1 0,1 3
-1
500K l KP = 3 atm . P = 33 atm
a. Tnh phn ly ca PCl5 1atm v 8 atm. c. Lng Cl 2 cn thm vo
b. p sut no, phn ly l 10%. Gi b l s mol Cl 2 cn thm vo:
15
PCl5(k) PCl3(k) + Cl2(k) 2 2 n
KP
2x .2x P

Ban u 1 0 b 0,48 x . 1 4x n i cb
4
Phn ng 0,1 0,1 0,1
KP
0,402 4 1 1 81,2 -1
(atm )
Cn bng 0,9 0,1 (b + 0,1)
0,279 . 0,196 4 1,279
n V d 6. Cho Fe d tc dng vi hi nc theo phn ng:
P 3Fe + 4H2O(h) = Fe3O4(r) + 4H2
Ta c: K P K n 0
200 C nu p sut ban u ca hi nc l 1,315 atm, th khi cn
n
i bng p sut ring phn ca hydro l 1,255 atm. Xc nh lng hydro to
0,1. b 0,1 8 1 thnh khi cho hi nc 3atm vo bnh 2 lit cha st d nhit .
Gii
0,9 b 1,1 3 Gi x l s mol H2O tham gia phn ng:
b = 0,5 (mol) 3Fe + 4H2O(h) Fe3O4(r) + 4H2
V d 5. C th iu ch Cl2 bng phn ng
4HCl(k) + O2 = 2H2O(h) + 2Cl2 1,315 0
0
Xc nh HSCB KP ca phn ng 386 C, bit rng nhit v p x x
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. (1,315 - x) x
Gii Theo bi ta c: x = 1,255 (atm)
Gi x l s mol O2 tham gia phn ng. Hng s cn bng:
Tng s mol lc cn bng: ni 1,48 x ; n = -1 PH4 2 1,255
4
Theo bi ta c: 2x = 0,402 x = 0,201 (mol) KP 1,91.10 5

PH4 2O 1,315 1,255
4HCl(k) + O2 2H2O(k) + 2Cl2(k)
Gi x l p sut ring phn ca H2 lc cn bng:
1 0,48 0 0 3Fe + 4H2O(h) Fe3O4(r) + 4H2
4x x 2x 2x
(1 - 4x) (0,48 - x) 2x 2x 3 0
n
x x
P
Hng s cn bng: K P K n .
(3 x) x
i cb
n V nhit khng i nn hng s cn bng cng khng i:
PH4 2 x
4
5
KP 1,91.10
PH4 2O 3 x
16
x = 2,863 (atm) CO + 2H2 = CH3OH(k) (1)

S mol kh H2 sinh ra: CO + 2H2 = CH3OH(l) (2)
P.V 2,863 2 1
PV nRT n 0,148 (mol) Ta c: K P(2)
RT 0,082 473 PCO .PH22
Khi lng kh H2 sinh ra: m H2 2 0,148 0,296(g) PCH3OH
K P(1) PCH3OH .K P(2)
V d 7. p sut tng cng do phn ng nhit phn PCO .PH22
2FeSO4(r) = Fe2O3(r) + SO2(k) + SO3(k)
0
nhit 929K l 0,9 atm. Mt khc: G (2) RTlnK P(2)
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 G0(2)
SO2 vi p sut u l 0,6 atm 929K. K P(2) exp
RT
Gii
a. Hng s cn bng:
29,1.10 3
K p PSO .PSO 0,45 0,45 0,2025 (atm2) exp 126168 (atm-3)
2 3
8,314 298
b. p sut tng cng:
Gi x l s mol ca SO3 sinh ra: 16200 -2
2FeSO4 Fe2O3(r) + SO2 + SO3 Suy ra: K P(1) 126168 20177 (atm )
1,013.105
V d 9. Hng s cn bng 1000K ca phn ng:
0,6 0 -21
2H2O(h) = 2H2 + O2 l KP = 7,76.10 atm.
x x -18
p sut phn ly ca FeO nhit l 3,1.10 atm. Hy xc nh HSCB
KP 1000K ca phn ng
(0,6 + x) x FeO(r) + H2 = Fe(r) + H2O(h)
V nhit khng i nn hng s cn bng cng khng i: Gii
K p PSO2 .PSO3 x.0,6 x 0,2025 2H2O(h) = 2H2 + O2 (1)
2FeO(r) = 2Fe(r) + O2 (2)
x2 + 0,6x - 0,2025 = 0
FeO(r) + H2 = Fe(r) + H2O(h) (3)
x = 0,24 (atm)
Ta c: 2p. (3) = p. (2) - p. (1)
p sut ca hn hp:
G0(3) = G0(2) - G0(1)
P PSO2 PSO3 0,24 084 1,08 (atm)
2RTlnKP(3) RTlnKP(2) RTlnKP(1)
V d 8. Tnh HSCB KP 250C ca phn ng
CO + 2H2 = CH3OH(k) 2lnK P(3) lnK P(2) lnK P(1)
bit rng nng lng t do chun Go i vi phn ng
CO + 2H2 = CH3OH(l)
K P(2)
0 K 2P(3)
bng -29,1 KJ/mol v p sut hi ca metanol 25 C bng 16200 Pa. K P(1)
Gii -21
M: Kp(1) = 7,76.10 (atm)
17
Kp(2) = 3,1.10-18 (atm) Gi x l s mol COF2 tham gia phn ng:
K P(2) 3,1.10 18 2COF2(k) CO2 + CF4(k)
Suy ra: K P(3) 19,99
K P(1) 7,76.10 21 a
x x x
V d 10. Cho phn ng:
CuSO4.3H2O(r) = CuSO4(r) + 3H2O(h) 2 2
0 -6 3
bit hng s cn bng KP 25 C l 10 atm . Tnh lng hi nc ti thiu (a x)
o
phi thm vo bnh 2 lt 25 C chuyn hon ton 0,01 mol CuSO4 thnh x x
CuSO4.3H2O. 2 2
Gii Tng s mol lc cn bng:
Gi x l mol H2O thm vo:
ni a
CuSO4.3H2O(r) CuSO4(r) + 3H2O(h) x
Ban u 0,01 x
n V
Ta c: CF4 CF4
2 200 x 4a
Phn ng 0,01 0,03 n i Vi a 500 5
Cn bng 0,00 (x - 0,03) V n = 0, hng s cn bng:
Tng s mol ti thi im cn bng: 2
x
4a2
n i x 0,03 (mol) nCO2 .n CF4 2
Hng s cn bng: KP K n 2
2 25 4
n 3
nCOF2
a x a2
P 1 RT 1
Kp Kn 25
n 3
10 6
i x 0,03 o o
V b. Kp tng 10% khi tng 1 C ln cn 1000 C.
o
Hng s cn bng KP 1001 C:
2 1
Kp = 4 + 0,04 = 4,04
0,082 298 x 0,03 10 2 K p(T2 ) 0
H 1000 1 1
2 Ta c: ln
x 3,08.10 (mol) K p(T1 ) R
o
V d 11. Cho kh COF2 qua xc tc 1000 C s xy ra phn ng
T2 T1
2COF2(k) CO2 + CF4(k) K p(T2 )
Rln 4,04
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 0
K p(T1 ) 1,987ln 4
H1000 32065 (cal)
hp thu. 1 1 1 1
a. Tnh HSCB KP ca phn ng.
b.
o o o o
Bit KP tng 1% khi tng 1 C ln cn 1000 C, tnh H , S v G
o T2 T1 1274 1273
o
ca phn ng 1000 C. 0
G 1000 RTlnK 1,987 1273 ln4 3507 (cal)
p(1000)
Gii 0 0 0
a. Tnh HSCB KP ca phn ng Ta li c: G 1000 = H 1000 - TS 1000
18
0 0 CO CO2 Pb PbO
0 H1000 G1000 32065 3507 0
S 27,94 (cal/K) H 298,tt -110,43 -393,13 0 -219,03
1000
T 1273 (KJ/mol)
0
V d 12. 1000K hng s cn bng ca phn ng: G 298 -137,14 -394,00 0 -189,14
C(gr) + CO2(k) 2CO(k) (KJ/mol)
l Kp =1,85 atm v hiu ng trung bnh l 41130 cal. Xc nh thnh phn Cp,298 29,05 36,61 26,50 46,27
pha kh cn bng ti 1000K v 1200K bit p sut tng cng l 1atm. (J/mol.K)
0
Gii Chp nhn nhit dung khng thay i trong khong nhit 25 -127 C.
0 0 0
1000K: gi xCO v x CO l phn mol ca cc kh cn bng: a. Tnh G , H , Kp 25 C ca phn ng:
2
PbO(r) + CO(k) = Pb(r) + CO2(k)
Ta c, hng s cn bng: K Kx .n vi n = 2 1 =1 b.
0
Biu th = f(T) di dng mt hm ca nhit .
2
x CO
c. Tnh Kp 1270C.
Suy ra: K Gii
x CO 2 a. Tnh G0, H0, Kp 250C ca phn ng:
M: x CO x CO 1 xCO2 1 xCO H0298 = -393,13 + 0 + 110,43 + 219,03 = -63,67 (KJ)
2
G0298 = -394 + 0 + 137,14 + 198,14 = -67,72 (KJ)
2
x CO Hng s cn bng:
K G 0298
1 x CO 67,72.10 3
lnK P 27,33
2
Vy x CO K.xCO K 0 (1)
RT 8,314 298
11
Kp = 7,4.10 (atm)
2
Vi Kp = 1,85 atm 1,85.xCO 1,85 0
x CO b.
0
Biu th di dng mt hm ca T.
Gii phng trnh ta c: xCO= 0,72 v x CO = 0,28. Cp,298 = 36,61 + 26,50 29,05 46,27
2
= - 12,21 (J/K)
K , 2 1 1
ln
K ,1 R 2 1 0 0298 (12,21) d
298
K ,1200 41130 1 1 298
ln 63670
1,85 1,987 1200 1000 (12,21)d 63670 12,21( 298)

Ta tnh c:
KP,1200 = 58,28 atm 60031,42 12,21 (J)
0
Thay vo phng trnh (1) c: c. Tnh Kp 127 C
x 2CO 58,28.xCO 58,28 0 P,T2 1 1
ln
Gii phng trnh ta c: xCO = 0,98 x CO = 0,02 P,T1 R 2 1
2
V d 13. Cho cc d kin sau:
19
K p, T2 63670 1 1 T
ln 6,55 d. H0T H0298 C p dT 7546 11,05(T 298)
K p, T1 8,314 400 298
298
,400 e 6,55 7,4.1011 1,055.109 (atm) Vy H0T 11,05T 4253,1 (cal)
V d 14. Cho phn ng v cc s liu tng ng sau: 0
Ckc (r) + 2H2(k) = CH4(k) H1000 11,05 1000 4253,1 15303,1 (cal)
= - 15,3031 (Kcal)
0
H 298 0,453 0 -7,093 3.5. Bi tp t gii
(Kcal/mol) 1.
0
Ti 50 C v p sut 0,344 atm, phn ly ca N2O4 thnh NO2 l
0
S 298 0,568 31,21 44,50 63%. Xc nh KP v KC.
(cal/mol.K) S: Kp = 0,867 (atm); KC= 0,034 (mol/l)
Cp 2,18 6,52 4,170 2. 630C hng s cn bng KP ca phn ng:
(cal/mol. K)
0 N2O4 2NO2 l 1,27. Xc nh thnh phn hn hp cn bng
a. Hy xc nh G 298 v Kp298 ca phn ng trn. khi:
0
b. 25 C khi trn 0,55 mol kh CH4 vi 0,1 mol kh H2 trong bnh cha a. p sut chung bng 1atm.
Ckc rn (d), th phn ng xy ra theo chiu no nu p sut tng b. p sut chung bng 10 atm.
cng gi khng i 1 atm? Gii thch. S: a. 65,8% NO2; 34,2% N2O4
c. Kh H2 c nn vo bnh c cha Ckc rn d iu kin p sut 1 b. 29,8% NO2; 70,2% N2O4
atm v nhit 298K. Hy xc nh p sut ring phn ca CH4 khi 3. un 746g I2 vi 16,2g H2 trong mt bnh kn c th tch 1000 lit n
cn bng nhit p sut trn. 0
420 C th cn bng thu c 721g HI. Nu thm vo hn hp u
0
d. Thit lp phng trnh H = f(T) (phng trnh ch c s v T) v tnh 1000g I2 v 5g H2 th lng HI to thnh l bao nhiu?
0 0
H 1000 K. S: 1582 g
Gii 4. Xc nh hng s cn bng Kp ca phn ng sau 700K
0
a. H 298(p) = -7,093 0,453 = -7,546 (Kcal) SO2 + 1/2O2 = SO3
0
S 298(p) = 44,50 0,568 2x31,21 = -18,488 (cal) Bit rng 500K hng s cn bng Kp = 2,138.105 atm -1/2 v hiu
0
G 298 = -7546 + 298x18,488 = -2036,576 (cal) ng nhit trung bnh trong khong nhit 500 700K l -23400 cal.
-1
KP298 = 31,169 (atm ) S: 2,6.10+2 atm-1/2
n 1 5. 1000K hng s cn bng ca phn ng:
P 0,55 1
b. p n 35,75(atm 1 ) 2SO3(k) + O2(k) 2SO3(k)
n 2
0,1 0,1 0,55 C hng s cn bng KP = 3,5 atm-1. Tnh p sut ring phn lc cn
i
bng ca SO2 v SO3 nu p sut chung ca h bng 1 atm v p sut cn
p > Kp suy ra phn ng xy ra theo chiu nghch. bng ca O2 l 0,1 atm.
PCH 4
c. Kp 31,169 PCH 4 31,169P H2 2 S: PSO 2 0,75 atm , PSO 0,15 atm
PH2 2
3
0 0
6. Tnh G v hng s cn bng Kp 25 C ca phn ng sau:
2
Ta c PCH 4 PH 2 1 31,169P H2 PH 2 1 0 NO + O3 NO2 + O2 .
Cho bit cc s liu sau:
Ta c PH2 0,164(atm),PCH4 0,836(atm) NO2 O2 NO O3
20
H 0298, tt (KJ/mol) 33,81 0 90,25 142,12 ab a b 2 abPK P

0
S.
S 298 (J/mol.K) 240,35 240,82 210,25 237,42 2 4 P.K P 1
34 12. Cho phn ng: CO + Cl2 COCl2
S: Kp= 5.10 C phng trnh m t s ph thuc ca Kp vo nhit T l:
0 0
7. 298K phn ng: NO + 1/2O2 = NO2, c G = -34,82 (KJ) v H lgKp(atm) = 5020/T 1,75lgT 1,158.
= -56,34 (KJ). Xc nh hng s cn bng ca phn ng 298K v
598K.
a. Tm phng trnh m t s ph thuc nhit : G0T = f(T) v
S: Kp= 1,3.106 2980K v Kp= 12 5980K H0T = g(T).
8. nhit T v p sut P xc nh, mt hn hp kh cn bng gm 3 b. Tnh G0, H0, S0 v hng s cn bng KP, KC 700K.
mol N2, 1 mol H2 v 1 mol NH3. c. Hn hp phn ng sau s xy ra theo chiu no 1atm v
a. Xc nh hng s cn bng Kx ca phn ng. 700K:
3H2(k) + N2(k) 2NH3(k) 2 mol CO; 5 mol Cl2 v mol 3 COCl2.
b. Cn bng s dch chuyn theo chiu no, khi thm 0,1 mol N2 0,4 mol CO; 1,6 mol Cl2 v 8 mol COCl2.
vo hn hp cn bng T v P khng i. 13. C th iu ch Cl 2 bng phn ng:
S: a. Kx= 8,33; b. Kx = 8,39
9. Hng s cn bng ca phn ng: 4HCl(k) + O2 2H2O(h) + 2Cl2
0
Xc nh HSCB KP ca phn ng 386 C, bit rng nhit v
PCl3(k) + Cl 2(k) PCl5 (k) 500K l KP = 3 atm-1. p sut 1 atm, khi cho 1 mol HCl tc dng vi 0,5 mol O2 th khi cn bng s
a. Tnh phn ly ca PCl5 2 atm v 20 atm.
c 0,4 mol Cl 2.
b. p sut no, phn ly l 15%. S: Kp = 69,3 atm-1
S: a. 44,7%; 13%; b. 14,48 atm 0
14. 40 C, hng s cn bng ca phn ng:
10. Cho phn ng thy phn este axetat etyl.
LiCl.3NH3(r) LiCl.NH3(r) + 2NH3(k)
CH3COOC2H5 + H2O CH3COOH + C2H5OH 2
l Kp = 9 atm , nhit ny phi thm bao nhiu mol NH3 vo mt bnh c
Nu ban u s mol ca este bng s mol nc th khi cn bng c th tch 5 lit cha 0,1mol LiCl.NH3(r) tt c LiCl.NH3(r) chuyn thnh
1/3 lng este b thy phn. LiCl.3NH3(r).
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.
21
Chng 4
CN BNG PHA
4.1. 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: Hnh 4.2. Gin pha h ba cu t
c=k-f +n Ba nh ca tam gic l ba im h ca cc cu t nguyn cht A, B
Trong : v C.
k: s cu t Ba cnh ca tam gic biu din ba h hai cu t tng ng l AB, AC
f: s pha v BC.
n: s thng s bn ngoi tc ng ln h
4.3. Gin pha v cc qui tc cn bng pha Mi im trong tam gic biu din h 3 cu t.
4.3.1. Biu din thnh phn ca h 2 cu t Cch biu din im P(40%A, 40%B, 20%C) trn gin tam gic
Thnh phn ca cc cu t trn gin pha thng dng l phn mol u ABC.
xi hay phn trm khi lng yi. Trong h hai cu t, dng mt on thng Trn cnh AC, ta v ng thng i qua im 40% v song song vi
c chia thnh 100% nh sau: 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).
Hnh 4.1. Gin pha h hai cu t 4.4. Cc qui tc ca gin pha
Trn trc to ch cn biu din cho mt cu t v thnh phn ca 4.4.1. Qui tc lin tc
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:
22
Hnh 4.5. Minh ha quy tc n by

p dng quy tc n by, ta c:
g M HN

g N HM
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
Hnh 4.3. Gin nhit - thi gian ca cht nguyn cht. tm vt l ca a gic c nh l cc im biu din ca n h con.
Cc ng hoc cc mt trn gin pha biu din s ph thuc V d: H H gm ba h con l H1, H2 v H3. vi khi lng tng ng
gia cc thng s nhit ng ca h s lin tc nu trong h khng xy ra l:
s bin i cht, s thay i s pha hoc dng cc pha. g = g1 + g2 + g3
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 4.6. Minh ha quy tc khi tm

Nh vy, H phi nm khi tm vt l ca tam gic H1H2H3. u tin
Hnh 4.4. Minh ha quy tc ng thng lin hip ta xc nh im biu din ca h K, tha mn iu kin:
V d: h H = h M + h N. Th im biu din cc h H, M v N nm H K = h H1 + h H2
thng hng.
4.4.3. Qui tc n by g1 H2K
v .
Nu c ba im h lin hp M, H v N th lng tng i ca chng g2 H1K
c tnh theo qui tc n by nh sau:
Tip theo ta xc nh im H tha mn iu kin sau:
H H = h K + h H3
23
gK g1 g2 HH3 dT T.V
v
g3 g3 KH p dng phng trnh:
dP
4.5. nh hng ca p sut n nhit chuyn pha Vi: V = Vlng Vrn
Phng trnh Clausius Claypeyron I: = 1,001 1,098 = - 0,097 (ml/g)
dT T.V Hoc: V = 18.(- 0,097) = -1,746 (ml/mol)

dP dT 273 1,746
0,0081 (K/atm)
Trong : dP 1434,6 41,3
T: nhit chuyn pha (K)
Nh vy, c tng p sut ln 1 atm th nhit nng chy ca nc
: nhit chuyn pha (cal/mol hoc J/mol) gim 0,0081K. Mt cch gn ng, 4atm, nhit nng chy ca nc
V = V2 V1: bin thin th tch (ml) l:
Nu V c tnh bng ml, c tnh bng cal v 1cal = 41,3 T = 273 + (-0,0081) x (4 - 1)
ml.atm, nn phng trnh Clausius Claypeyron tr thnh: = 272,9757K = - 0,0243 C
0
dT T.V 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
dP 41,3. atm).
4.6. nh hng ca nhit n p sut hi bo ha Gii
Phng trnh Clausius Claypeyron II Nhit ha hi: = 538,1x18 = 9685,8 (cal/mol)
dlnP P2 1 1
p dng cng thc: ln
dT RT2 P1 R T2 T1
Ly tch phn 2 v, ta c:
2 9685,8 1 1
P 1 1 ln
ln 2 1 1,987 T 100 273
P1 R T2 T1 T tnh c: T = 394K = 1210C
Trong : V d 3. Tnh nhit nng chy ca 1 mol diphenylamin nu 1kg diphenylamin
T: nhit (K) -5 3 -7
nng chy lm tng th tch ln 9,58.10 m cho bit dT/dP = 2,67.10
P: p sut (atm) 2 0
K.m /N. Nhit nng chy ca diphenylamin l 54 C, khi lng mol ca
: nhit ha hi (cal/mol hoc J/mol) cht ny l 169.
R: l hng s kh Gii
4.7. Bi tp mu
0
V d 1. 0 C nhit nng chy ca nc l 1434,6 cal/mol. Th tch
dT T.V
p dng cng thc:
ring ca nc v nc lng ln lt l 1,098 v 1,001 ml/g. Xc nh h dP
s nh hng ca p sut n nhit nng chy ca nc v tnh nhit
nng chy ca nc 4 atm.
Gii
24
mAo = 20% 200 = 40 (g)

T.V
273 54 169 9,58.105 Phn trm ca cht C trong lp th 1:
1000 19,83.103 (J/mol)
%C = 100 - 50 - 20 = 30 (%)
dT 2,67.107 Vy im biu din ca lp 1: I1 (50%A, 20%B, 30%C)
Khi lng lp th 2:
dP m = 200 60 = 140 (g)
V d 4. p sut hi bo ha ca axit xyanhydric HCN ph thuc vo nhit Khi lng ca cht A trong lp th 1:
theo phng trnh: mA1 = 50% 60 = 30 (g)
1237 Khi lng ca cht A trong lp th 2:
lgP(mmHg) 7,04 mA2 = 40 - 30 = 10 (g)
T Khi lng ca cht B trong lp th 2:
Xc nh nhit si v nhit ha hi ca n iu kin thng. mB2 = 80% 140 = 112 (g)
Gii Khi lng ca cht C trong lp th 2
Nhit si ca axit HCN p sut 760 mmHg: mC2 = 140 - 122 = 17 (g)
1237 im biu in lp 2: I2 (7,15%A, 80%B,12,85%C)
Ta c: lg(760) 7,04 V d 6. Khi lng ring ca phenol dng rn v dng lng ln lt l 1,072
T v 1,056 g/ml, nhit nng chy ca phenol l 24,93 cal/g, nhit kt tinh
T = 297,4K 0
ca n 1 atm l 41 C. Tnh nhit nng chy ca phenol 500 atm.
0
Vy nhit si ca axit HCN l 24,4 C. Gii
Ly o hm hai v phng trnh theo T, ta c:
dT T.V
dlgP 1237 p dng phng trnh:
2 dP
dT T 1 1
dlgP Vi: V 0,014 (mol/g)
M: 1,056 1,072
dT 4,575.T2
dT 314 0,014
1237 Ta c: 4,26.10 3 (K/atm)
Suy ra: 2
2 = 5659 (cal/mol) dP 24,93 41,3
4,575.T T Nh vy, c tng p sut ln 1 atm th nhit nng chy ca phenol
-3
V d 5. Trn 200g hn hp gm 3 cht A, B, C cha 20% A, khi cn bng tng 4,26.10 K. Mt cch gn ng, 500atm, nhit nng chy ca
hn hp chia lm hai lp. phenol l:
-3
Lp th nht c khi lng 60g v bao gm 50% A v 20% B. T = 314 + 4,26.10 (500 - 1)
0
Lp th hai cha 80%B. = 316,13K = 43,13 C
Hy xc nh im biu din ca ba cu t A, B, C trn gin tam V d 7. p sut thng, nhit si ca nc v cloroform ln lt l
0 0
gic u trong hai lp trn. 100 C v 60 C, nhit ha hi tng ng l 12,0 v 7,0 kcal/mol. Tnh nhit
Gii m 2 cht lng trn c cng p sut?
c gi t v hnh Gii
Khi lng ca cht A trong hn hp ban u: Gi T l nhit m ti 2 cht lng c cng p sut:
25
8. Tnh p sut cn thit nhit si ca nc t c 1200C. Cho
1 1 1 1 bit nhit ha hi ca nc l 539 cal/g.
Ta c: 1 2
T1 T T2 T S: P = 2 atm
0 9. Cho gin pha ca h 3 cu t (hnh di). Xc nh thnh phn
Vi: 1 = 12 (Kcal/mol), T1 = 273 + 100 = 373 K
0 ca A, B, C khi im h chung l im P v hy kt lun v thnh
2 = 7 (Kcal/mol), T2 = 273 + 60 = 333 K phn ca A, B khi im h dch chuyn theo ng thng ni t nh
Th cc gi tr vo phng trnh trn, ta c: C vi im I.
1 1 1 1
12 7
373 T 333 T
Suy ra: T = 448,40K
4.8. Bi tp t gii
0
1. Xc nh nhit ha hi ca H2O 4 atm nu 100 C nhit ha hi
ca nc bng 2254,757 J/g.
2. 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
3. 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. S: %A = 40%, %B = 40%, %C = 20%
0
4. Ti 127 C HgI2 b chuyn dng th hnh t dng sang dng vng. 10. Nc nguyn cht c th tn ti 9 dng pha khc nhau (kh, lng v
3 -1 7 dng rn). Tnh s pha ti a ca nc c th ng thi nm cn
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. bng vi nhau.
-6
S: -1,73.10 K/Pa
5. 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
6. 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
7. 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
26
Chng 5 x i (dd)
Hng s cn bng: K
x i (kh)
DUNG DCH V CN BNG
lnKp
DUNG DCH - HI
Do ta c:
i
T 2
RT
Ly tch phn phng trnh, ta c:
5.1. Cch biu din thnh phn ca dung dch
1 1
- Nng phn trm khi lng (%):
lnx i 0
gi i R T T
C %,i 100(%) 0
Vi: T l nhit ngng t (nhit si)
g 1 g 2 ... g n 5.3. S ha tan ca cht lng trong cht lng v cn bng dung dch -
n hi
- Nng mol/lit: CM 5.3.1. H dung dch l tng tan ln v hn
V 5.3.1.1. p sut hi - nh lut Raoul
n' p sut hi bo ha ca mi cu t bt k t l thun vi phn phn
- Nng ng lng gam (lg/l): CN t ca n trong dung dch.
V Pi k R .x li
n ct Khi dung dch ch c cu t i (dung dch i nguyn cht): xi = 1 v kR =
- Nng molan (Cm): Cm 1000
m dm Pi0
ni Pi Pi0 .x il
- Nng phn mol: x i
i vi dung dch thc, nh lut Raoult ch c th p dng cho dung
ni 0 l
- CN = z.CM (z: s in tch trao i trong phn ng) mi ca dung dch v cng long: P1 P1 .x 1
5.2. S ha tan ca kh trong cht lng 5.3.1.2. Gin p sut - thnh phn (P - x)
5.2.1. nh hng ca p sut n tan ca cc kh trong cht lng p dng nh lut Raoult cho dung dch l tng ca hai cu t (A - B):
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

PA PA0 .xlA PA0 . 1 x lB (1)
0 l
xi = kH.Pi PB P .xB B (2)
Trong : p sut tng ca h l:
kH l hng s Henry P = PA + PB
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
PA0 . 1 x Bl PB0 .x lB
lng, phng trnh Sreder
Xt cn bng:
A
P PB0 PA0 .x lB
0
(3)
Nu ta biu din cc phng trnh (1), (2) v (3) ln th p sut - thnh
i (kh) = i (dung dch c nng xi) + Hha tan
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 Hnh 5.2. Gin (x-x) ca h hai cu t A-B
Xt h dung dch l tng ca hai cu t A v B nm cn bng vi 5.3.2. H dung dch thc tan ln v hn
pha hi ca chng. 5.3.2.1. p sut hi
Theo nh lut Raoult ta c: Dung dch sai lch dng c p sut hi trn dung dch ln hn p
sut hi tnh theo nh lut Raoult.
xh 0 l l
B PB x B . x B (nh lut Konovalop I) Dung dch sai lch m c p sut hi trn dung dch nh hn p sut
0 hi tnh theo nh lut Raoult.
xh
A PA x A
l x lA 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
P0
Trong B v c gi l h s tch hay h s chng ct sut hi tng cng (P - x) th pha lng v pha hi cn bng c cng thnh
PA0 phn.
5.3.1.4. Gin thnh phn hi thnh phn lng x lgB x hB
T nh lut Konovalop I, ta bin i rt ra biu thc:
5.3.3. H hai cht lng hon ton khng tan ln
xh .x l .x l 5.3.3.1. Tnh cht
B B B Thnh phn ca pha hi cng ch ph thuc vo nhit m khng
x h x h x l .x l (1 x l ) .x l ph thuc vo thnh phn ca hn hp lng.
A B A B B B x hB PB PB0
l f(T)
.x x hA PA PA0
xh B (4) Nhit si ca hn hp cng khng ph thuc vo thnh phn, n
B
1 1.x l nh hn nhit si ca mi cu t v ch ph thuc vo p sut bn
B ngoi.
Biu din phng trnh (4) ln th (x - x) ta c cc ng trn hnh 5.2.
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
PH0 2 O 18 m H 2O
g H 2O
PA0 MA M: x H 2O 18 0,997
m H 2O m gly
Trong : PH02O v
0
P
A ln lt l p sut hi ca nc v ca cht
A. 18 92
5.3.3.3. nh lut phn b Suy ra: m gly 0,014mH2O
nhit v p sut khng i, t s nng ca mt cht tan trong Nng phn trm ca dung dch glycerin
hai dung mi khng tan ln l mt hng s khng ph thuc vo lng
tng i ca cht tan v dung mi.
m gly
C% 100
C Y/A m gly m H 2O
K
C Y/B 0,014m H 2 O
CY/A, CY/B: l nng ca cht tan Y trong dung mi A v trong dung 100 1,38 (%)
mi B.
0,014m H 2O m H 2 O
0
K: h s phn b V d 2. 123,3 C bromobenzen (1) v clorobenzen (2) c p sut hi bo
5.4. Bi tp mu ha tng ng bng 400 v 762 mmHg. Hai cu t ny to vi nhau mt
0
V d 1: Tnh p sut hi ca dung dch ng (C12H22O11) 5% 100 C v dung dch xem nh l tng. Xc nh:
0
nng % ca dung dch glycerin trong nc c p sut hi bng p a. Thnh phn dung dch 123,3 C di p sut kh quyn 760mmHg.
sut hi ca dung dch ng 5%. b. T s mol ca clorobenzen v bromobenzen trong pha hi trn dung
Gii dch c thnh phn 10% mol clorobenzen.
Gii
p sut hi ca dung dch ng: P PH02O .xH2O Hai cu t ny to vi nhau mt dung dch l tng nn:
95
P P1 P2 P10 .x1l P20 .x l2 P20 P10 P20 x1l
0
18 a. Thnh phn hn hp 123,3 C di p sut kh quyn 760mmHg
P 760 758 (mmHg)
95 5 l P P20 760 762
x 0
1 0
0,00552
18 342 P1 P2 400 762
Dung dch glycerin:
x l2 1 x 1l 0,9948
P 758
P PH02O .xH2O x H 2O 0
0,997 Vy thnh phn ca Bromobenzen l: 0,00552
P 760 thnh phn ca Clorobenzen l: 0,9948
H2O
b. 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. 100
300C p sut hi ca benzen bng 120,2 mmHg, ca toluen bng 36,7 S mol etanol: nE 2,1739(mol)
mmHg. Xc nh: 46
a. p sut hi ring phn ca tng cu t. 100
b. p sut hi ca dung dch. S mol metanol: nM 3,125(mol)
Nu dung dch c hnh thnh t s trn 100g benzen v 100g toluen. 32
Gii 2,1739
Phn ca etanol: x E 0,41
a. p sut hi ring phn ca tng cu t 2,1739 3,125
Phn mol ca benzen:
3,125
100 Phn ca metanol: x M 0,59
2,1739 3,125
nB 78
xB 0,54 b. PE PE0 xlE 44,5 0,41 18,245(mmHg)
n B n T 100 100
PM PM0 xM
l
88,7 0,59 52,333(mmHg)
78 92
Phn mol ca toluen: P = 18,245 + 52,333 = 70,578 (mmHg)
c. Phn mol ca metanol trong pha hi:
100
88,7
nT 92 l 0,59
xT 0,46 h .xM 44,5
nB nT 100 100 xM 0,7415
1 ( 1)x lM 88,7
78 92 1 1 0,59
p sut hi ca Benzen: 44,5
V d 5. Hn hp SnCl4 (1) v CCl 4 (2) tun theo qui lut ca dung dch l
PB PB0 .x B 120,2 0,54 64,908 (mmHg) tng. 90oC p sut hi bo ha ca SnCl4 v CCl4 ln lt l 362 mmHg
p sut hi ca Toluen: v 1112 mmHg. Di p sut chun 760mmHg, SnCl 4 si 1140C v CCl4
o
PT PT0 .x T 36,7 0,46 16,882 (mmHg) si 77 C:
a. Xy dng gin thnh phn - p sut ca cc cu t v xc nh
b. Xc nh p sut hi ca dung dch trn gin p sut P1, P2 v P ca hn hp c phn mol ca CCl 4 l
P PB PT 64,90816,882 81,79 (mmHg) 0,7.
0
o
V d 4. Etanol v metanol to thnh dung dch xem nh l tng. 20 C b. Xc nh thnh phn hn hp SnCl 4 - CCl 4 si 90 C di p sut
p sut hi bo ha ca etanol v metanol ln lt l 44,5 v 88,7 mmHg. 760mmHg.
a. Tnh thnh phn mol cc cht trong dung dch cha 100g etanol v c. Xc nh thnh phn hi ti 900C.
100g metanol. Gii
b. Xc nh cc p sut ring phn v p sut tng ca dung dch. a. Xy dng gin thnh phn - p sut
c. Tnh phn mol ca metanol trong pha hi nm cn bng vi dung dch
trn.
Gii
a. Phn mol mi cht
30
Gii
P a. 250C:
(mmHg) 0 l 0 l
1112 Ta c: PA PA .x A v PB PB .x B
Theo bi ta c: PA = PB
3
PA0 .xlA PB0 .xlB
779,1
362 PA0 x Bl 0,75
2
3
PB0 x lA 0,25
0
b. 100 C:
1 108,6 P2 1 1
p dng cng thc: ln
x 0,7 P1 R T2 T1
SnCl4 CCl4 i vi cht A:
Hnh 5.3. Gin p sut - thnh phn P - x
p sut ca SnCl 4:
PA0 373 A 1 1
Ta c: ln (1)
PSnCl 4 0
PSnCl
. 1 0,7 362 0,3 108,6 (mmHg) PA0 298 R T2 T1
4
p sut ca CCl 4: Tng t i vi cht B:
PCCl 4 0
PCCl .x CCl 4 1112 0,7 779,1 (mmHg) PB0373 B 1 1
4 ln (2)
p sut ca hn hp: PB0298 R T2 T1
P = 108,6 + 779,1 = 887,7 (mmHg)
Ly phng trnh (1) (2), ta c:
b. Xc nh thnh phn hn hp SnCl 4 - CCl 4
PA0 373 PB0298 1
1 1
0 0 0 0 0
Ta c: Pt P1 x1 P2 x 2 P2 P1 P2 x1
ln 0 0 A
PB373 PA 298 R B T2 T1
Pt P20 760 1112
x1 0 0,47
P1 P20 362 1112 PA0 373 PB0298
1 7000 5000 298 373
Vy thnh phn ca SnCl 4 l 0,47 ln 0
PB373 PA0 298 1,987 298 373
Thnh phn ca CCl4 l 0,53
c. Xc nh thnh phn hi
1 PA0 373
x h2 P02 x l2 1112 0,53 0,507
3,464 3 PB0373
x 1h P01 x 1l 362 0,47
0
V d 6. Mt dung dch l tng ca A v B cha 25% mol A. 25 C, hi PA0 373
cn bng ca n cha 50% mol A. Nhit ha hi ca A v B ln lt l 5 v 1,52
7 Kcal/mol. Tnh t s p sut hi bo ha ca A v B khi nguyn cht PB0373
0 0
25 C v 100 C.
31
V d 7. 800C p sut hi bo ha ca A nguyn cht v B nguyn cht 2. 500C, dung dch l tng bao gm 1 mol cht A v 2 mol cht B c
ln lt l 100 v 600 mmHg. p sut tng cng l 250 mmHg. Thm 1 mol cht A vo dung dch
a. Hy v th p sut - thnh phn (P - x) ca dung dch l tng A - trn th p sut tng cng l 300 mmHg. Hy xc nh p sut hi bo
0
B. ha ca A v B nguyn cht 50 C.
b. Tm thnh phn ca A v B sao cho ti p sut ca A v B bng S: 450 v 150mmHg
nhau. 3. Xem dung dch ca CCl4 v SnCl4 l dung dch l tng. Tnh thnh
0
Gii phn ca dung dch si 100 C di p sut 760 mmHg v tnh
0
a. Gin P - x (hnh 5.4) 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.
PA PA0 .xlA 100x lA (1)
S: 0,274 v 0,522
0
PA PB0 .xBl 600x lB (2) 4. Xt dung dch toluen benzen cha 70% khi lng benzen 30 C.
Hy xc nh:

Pt PB0 PA0 PB0 x lA 600 500 x lA (3) 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
5. 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
6. 50 C p sut hi ca n - hecxan v n - pentan ln lt l 400 v
Hnh 5.4. Gin p sut - thnh phn P - x 1200 mmHg.
b. Thnh phn cu t A v B. a. Tnh p sut hi ca dung dch cha 50% (khi lng) ca n-
Ta c: PA = PB pentan.

100.xlA 600 1 x lA b.
c.
Xc nh phn mol ca n - hecxan trong pha hi.
Xc nh thnh phn ca hai cu t trn trong pha lng p
xlA 0,.857 v x Bl 0,143 sut hi ca chng bng nhau.
5.5. Bi tp t gii 7. Tnh p sut hi bo ha ca dung dch 5g ng glucose (C6H12O6)
0
1. 250C p sut hi bo ha ca nc nguyn cht l 23,7 mmHg. trong 180g nc 20 C. Bit rng nhit ny p sut hi bo ha
Tnh p sut hi trn dung dch cha 10% glyxerin trong nc nhit ca nc 17,5 mmHg.
.
S: 23,2 mmHg
32
8. 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.
9. 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 Hnh 6.1. Gii thch tng im si v h im kt tinh
6.1.2. tng im si v h im kt tinh
ng OC m t p sut hi trn dung mi rn nguyn cht. R.T02 .M
K
ng OA m t p sut hi trn dung mi lng nguyn cht. 1000
ng OB m t nh hng ca p sut bn ngoi n nhit nng Trong :
chy ca dung mi nguyn cht. R: hng s kh
tng im si v h im kt tinh ca cc dung dch cht tan T0: nhit chuyn pha
khng bay hi t l thun vi nng ca dung dch. M: phn t lng
T = K. Cm : nhit chuyn pha
Vi: 6.1.3. p sut thm thu
Cm: Nng molan ca dung dch. p sut thm thu ca dung dch c nng xc nh l p sut ph
K: Hng s nghim si Ks hay hng s nghim ng K 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
6.2. 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.
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
6.2.3. 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
Hnh 6.2. Gin (T-x) ca h hai cu t, cn bng lng rn. mt hn hp gm nhng tinh th rt nh, rt mn ca hai pha rn A v rn B
6.2.2. Kho st qu trnh a nhit nguyn cht kt tinh xen k vo nhau.
Ti nhit T2: H Q2 = lng l2 + rn r2 6.2.4. Php phn tch nhit
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:
T K .Cm
Hnh 6.4. Minh ha php phn tch nhit T
Lp 6 h c cng khi lng vi thnh phn ca cu t B thay i t
1,5
Cm 0,806 (mol/1000g)
0% n 100%. Lm nng chy tng h ri h dn nhit , quan st s thay K 1,86
i nhit theo thi gian v v cc ng ngui lnh (T - t). tng im si:
6.3. H hai cu t khng to dung dch rn, khi kt tinh to thnh hp
cht ha hc bn TS KS .Cm 0,513 0,806 0,414(0C)
Nhit si ca dung dch:
0
Tdd = 100 + 0,414 = 100,414 ( C)
b. p sut hi ca dung dch
1000
P P0 .x 23,76 18 23,42 (mmHg)
1000
0,806
18
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
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.
P 17,54 17,22
Ta c: x 0,018
ng ae1 l ng kt tinh ca cht rn A. P0 17,54
ng e1de2 l ng kt tinh ca cht rn D.
ng e2b l ng kt tinh ca cht rn B.
36
m ct b. 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
M x 60 0,018 (1) lng rn A v rn B kt tinh v lng lng eutecti cn li.
m ct m H2O Gii
a. S pha v bc t do ca h
60 18 Vng I: f = 1, c = k f + 1 = 2
Gi s m ct m H O 100 (g) (2) Vng II: f = 2, c = k f + 1 = 1
2
Ti im eutecti: f = 3, c = k f + 1 = 0.
m H 2O 100 m ct b. Khi lng ca pha rn v pha lng
T (1) v (2), ta c: mct = 5,75 (g) m l HR c 0,2 4

m 100 mr He 0,25 5
Th tch ca dung dch: V dd 99 (ml)
d 1,01 Ta c : ml + mr = 90 g
Nng ca dung dch: ml = 40 g; mr = 50 g
Khi lng ca rn A v rn B
5,75
m RA R C R B 0,8
n 4
CM 60 1000 0,968 (mol/l) m RB R C R A 0,2
V 99
p sut thm thu: Ta c RA + RB = 50 g
= CRT = 0,968x0,082x(273 + 40) = 24,84 (atm) RA = 40 g
V d 3. Gin kt tinh (T-x) ca h hai cu t A - B c cho trong hnh RB = 10 g
sau. 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.
a. 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) HR B 0,3 3

m Rc He 0,4 4
ml(e) + mRc = 110
Gii h ta c: ml(e) = 62,86 (g)
6.5. Bi tp t gii
1. 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
a. 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
b. Nhit bt u kt tinh: 600 C
Ta c h pt:
m Rc He 0,4 8
c. Khi im h Q trng vi im H. Hy xc nh khi lng ca
m le HR c 0,15 3 pha lng v pha rn.
mRc + mle = 110 d. Khi h Q kt tinh hon ton, hy xc nh lng eutectic thu
Gii h ta c: mRc = 80 (g), mle = 30 (g) Khi lng c.
S: c. mr = 85,7g; ml = 114,3g ; d. me = 94,11g
rn A v rn B.
2. V gin pha ca h Sb - Pb da vo cc d kin thc nghim sau:
Ta c h pt:
Thnh phn hn hp lng
m RA R C R B 0,15 3 Nhit bt u
(% khi lng) 0
Sb Pb
Kt tinh ( C)
m RB R C R A 0,85 17
100 0 632
mRa + mRb = 80 80 20 580
Gii h ta c: mRb = 68 (g); mRa = 12 (g). 60 40 520
38
40 60 433 ca dung dch l 1g/cm3, hng s nghim lnh v hng s nghim si

20 80 300 ca nc tng ng 1,86 v 0,513.
10 90 273 S: Tkt = -0,930C; Ts = 100,260C; = 11,2 atm
0 0
0 100 326 6. Benzen ng c 5,42 C v si 81,1 C. Nhit ha hi ti im si
a. Xc nh thnh phn eutecti. bng 399J/g. Dung dch cha 12,8g naphtalen trong 1kg benzen ng
0
b. Xc nh khi lng Sb tch ra nu 10kg hn hp lng cha c 4,91 C.
40% Pb c lm ngui ti 4330C. a. Xc nh nhit si ca dung dch ny.
S: a. 87%Pb v 13%Sb; b. mSb = 5kg 0
b. Tnh p sut hi ca benzen trn dung dch 81,1 C.
3. Gin kt tinh ca h A - B c dng nh hnh di. Lm lnh 100g c. Tnh nhit nng chy ring ca benzen.
h Q. Khi im h nm H. C A v B kt tinh mt phn. im rn 0
S: a. 81,36 C; b. 754.1mmHg; c. 128,24 J/g
chung nm ti R. 7.
0
Acid acetic k thut ng c 16,4 C. Bng im ca acid acetic
a. Xc nh lng A v B kt tinh v lng lng eutecti cn li. 0
nguyn cht l 16,7 C. Hng s nghim lnh ca acid nguyn cht l
b. Tnh lng eutecti ti a thu c. 3,9. Xc nh nng molan ca tp cht trong acid k thut.
c. Phi trn A v B vi thnh phn nh th no thu c hn
hp A v B ng thi kt tinh.
S: a. 12g; 48g v 40g; b. 57,14g

4. 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
5. 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 1
Hot trung bnh ca ion:
a a .a

+ -
Trong : = +
IN HA HC
Ta c: a+ = +.m+ v a- = -.m-
1
m
. .m
7.1. Khi nim v dung dch in ly a .m
7.1.1. Dung dch cc cht in ly 1
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.
Trong :
.
7.1.2. S in ly m : molan trung bnh ca cc ion

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.
: h s hot trung bnh ca cc ion
T = i.K.Cm +, -: h s hat ca cc ion
Trong : 1 1
i: l h s Vant Hoff Lc ion: I m mi Zi2 hoc I C Ci Zi2
K: hng s 2 2
Cm: nng molan Trong :
p sut thm thu ca dung dch in ly cng cao hn p sut thm i: l k hiu ca tt c cc ion trong dung dch mi
thu ca dung dch l tng hay dung dch khng in ly. Ci: nng thc ca cc ion
in ly = i.C.R.T 7.2. S chuyn vn in tch trong dung dch in ly
Trong : 7.2.1. dn in ring
: p sut thm thu dn in ring () l dn in ca mt dung dch c th tch V =
3
C: nng mol/l 1 cm , c t gia hai in cc phng song song c din tch nh nhau
R hng s kh v cch nhau 1 cm.
T: nhit tuyt i
H s b chnh i l t s gia tng s tiu phn thc s c trong dung 1
dch v s tiu phn ban u:
i 1 1

Trong : Trong l in tr sut:
: phn ly 1 1 S
=m+n L
Vi m, n l h s ca phng trnh: R l l
AmBn = mAn+ + nBm- s
7.1.3. Hot , h s hot ca cc cht in ly 7.2.2. dn in ng lng ()
z+ z-
M+A- = +M + -A
40
L dn in ca mt th tch tnh theo cm3 cha ng mt ng 7.3.2. Nhit ng hc ca pin v in cc
lng gam cht in ly nm gia hai in cc phng song song cch nhau 1 7.3.2.1. Cng ca pin
cm. Xt phn ng: aA + bB = cC + dD
.1000 Ta c: G = - Amax
Cng to c l: A = n.F.E
CN G = -n.F.E
Trong : 7.3.2.2. nh hng ca nng n sc in ng v in cc -
: dn in ring phng trnh Nernst.
CN: nng ng lng Sc in ng ph thuc vo nng cc cht c trong pin v nhit
ca pin.
Ngi ta kho st mi tng quan gia theo C v C Phng trnh Nernst:
0,059 C .D
c d
= - A C E E0 lg
7.2.3. Mi quan h gia dn in v in ly n A a .B b
Trong :
Ta c:
E 0 0 0 : sut in ng tiu chun
M: 0 ,0 : th in cc tiu chun ca in cc dng (+) v m (-)
Trong : 7.3.2.3. Phng php kho st mt phn ng
: dn in ng lng ca dung dch. Ta c: G = - n.F.E
: dn in ng lng gii hn ca dung dch. 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.
, : dn in ng lng gii hn ca cation v
Nu E = 0 G = 0: phn ng cn bng.
anion hay cn gi l linh ion. 7.3.2.4. H thc Luther
7.3. Pin v in cc H thc ny dng xc nh th in cc cho mt cp oxi ha - kh
7.3.1. Th in cc ca nguyn t c nhiu mc oxi ha khc nhau. V d, kim loi M c hai
h+ n+
Trn ranh gii phn chia 2 pha gm mt tm kim lai dng lm in cation M v M (h > n). H ny ng vi ba qu trnh in cc:
cc (vt dn lai 1) v dung dch in phn (vt dn lai 2) xut hin mt M
h+
+ he = M (1) G1 = -hFh
hiu in th gi l th in cc c ln c xc nh bng phng trnh Mn+ + ne = M (2) G2 = -nFn
Nernst. Mh+ + (h - n)e = Mn+ (3) G3 = -(h - n)Fh/ n
RT oxh V (3) = (1) - (2), nn:
0 ln
nF kh G3 = G1 - G2
Trong : Hay: (h - n)h/ n = hh - nn
R: hng s kh 7.3.3. Cc loi in cc
T: nhit tuyt i in cc loi 1: l mt h gm kim loi hoc kim c nhng vo
n+ n-
F: hng s Faraday dung dch cha ion ca kim lai hoc kim . K hiu M / M hoc A / A:
n+
n: s electron trao i M + ne = M
41
Phng trnh Nernst: V d 2. h im kt tinh ca dung dch CH3COOH 0,1M l 0,1885 ,
0 RT 1 hng s nghim lnh ca nc l 1,86. Tnh phn ly ca dung dch
Mn /M M n
/M
ln CH3COOH 0,1M v 0,05M.
nF aMn Gii
in cc loi 2: l mt h gm kim loi c ph mt hp cht kh nng long th nng mol/l gn bng vi nng molan nn ta
tan (mui, oxit hay hydroxit) ca kim loi v nhng vo dung dch cha c:
n-
anion ca hp cht kh tan . K hiu A / MA/ M. Trng hp dung dch c nng 0,1M:
n-
MA + ne = M + A 0,1885
Phng trnh Nernst : T = i.k.Cm i 1,0134
RT 1,86 0,1
0
MA/M,An MA/M,An
lnaAn i 1 1,0134 1
nF M ta li c: 0,0134
7.4. Bi tp mu 1 2 1
V d 1. Tnh nhit kt tinh ca dung dch cha 7,308g NaCl trong 250g phn ly ca dung dch CH3COOH 0,1M l 1,34%.
6 2
nc cho bit 291K p sut thm thu ca dung dch l 2,1079.10 N/m , Trng hp dung dch c nng 0,05M:
3
khi lng ring ca dung dch l 1g/cm , nhit nng chy ca nc Ta c phng trnh phn ly:
3 - +
nguyn cht l 333,48.10 J/kg. CH3COOH = CH3COO + H
Gii Hng s phn ly:
Ta c:T = i.k.Cm (1) 2
2 .C 0,0134 0,1
RTo2M 8,314.273 2.18 K 1,82.10 5
Vi: k d 1,86 1 1 0,0134
1000 1000.333, 48.18 i vi dung dch in ly yu, ta c: 1 1
7,308
Trong : Cm 0,5 (mol/kg) K 1,82.10 5
58,5 0,25 0,019
C 0,05
Ta li c: i.CRT Khi dung dch c nng 0,05M th phn ly ca dung dch l 1,9%.
Nng ca dung dch: V d 3. Dung dch cha 4,355 mol ng ma trong 5 lt dung dch 291K
7,308 c cng p sut thm thu vi dung dch cha 2 mol NaCl trong 4 lt dung
C 1000 0,5 (mol/l) dch. Xc nh phn ly ca dung dch NaCl v h s Vant Hoff.
58,5250 7,308 Gii
2,1079.106 Dung dch ng l dung dch khng in ly:
i 1,74 4,355 0,082 291
CRT 1,013.105.0,082.291.0,5 CRT 20,78 (atm)
Th vo cng thc (1), ta c: 5
T = i.k.Cm = 0,5 1,74 1,86 = 1,62
i vi dung dch NaCl ta c: iCRT
Nhit kt tinh ca dung dch in ly l:
0
T = 0 - 1,62 = -1,62 C 20,78
i 1,742
CRT 0,5 0,082 291
42
i 1 1,742 1 Gii
in ly: 0,742 Vi dung dch KCl ta c:
1 2 1 k = R. 457 = 1,2796 (cm-1)
Vy in ly ca dung dch NaCl l 74,2%. Vi dung dch CaCl 2 ta c:
V d 4. Tnh p sut thm thu ca dung dch NaCl 0,15M 370C bit k 1,2796
phn ly ca dung dch l 95%. 0,00122 ( 1 .cm-1)
Gii R 1050
Ta c: iCRT Nng ca dung dch CaCl2 l:
i 1 m
M: i 1) 1 0,95(2 1) 1 1,95 0,555 2
1 CN 0,01 (N)
p sut thm thu ca dung dch l: V 1 111
dn in ng lng ca dung dch CaCl2 c tnh theo cng
iCRT 1,95.0,15.0,082.310 7,43atm thc:
V d 5. Tnh nng ca dung dch ng sacaroza c gi tr p sut
0 1000 1000 0,00122
thm thu l 8,1134 atm 37 C. 122 2
(cm . 1 .lg-1)
Gii C 0,01
Nng dung dch ng sacaroza l: V d 8. dn in ng lng gii hn ca axit propionic (C2H5COOH)
8,1134 0 -1 -1 2 -5
25 C l 385,6 .lg .cm . Hng s phn ly ca acid ny l 2,34.10 .Tnh
CRT 8,1134 C 0,32 mol/l dn in ng lng ca dung dch acid propionic 0,05M cng nhit
RT 0,082.310 .
V d 6. Thit lp biu thc tnh sc in ng ca pin c nng sau: Gii
Ag/ AgCl/ HCl (C1)// HCl (C2)/ AgCl/ Ag Dung dch acid propionic l mt cht in ly yu nn:
Cho bit C1 > C2.
Gii K 2,34.10 5
Cc m:
-
Ag + Cl (C1) = AgCl + e 0,0216
Cc dng: AgCl + e
-
= Ag + Cl (C2) C 0,05
Sc in ng ca pin c tnh nh sau:
RT C1
M: 0,0216.385,6 8,34cm 2 . 1.dlg 1
E ( ) ln
F C2 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
RT C1 -1 -1 2 -1 - -1 -
E ln l 149,7 .lg .cm . Linh ion ca OH l 198 ca Cl l 76,3 .dlg
1 2
F C2 .cm . Tnh dn in gii hn ca dung dch NH4OH.
0 Gii
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
Ta c:
.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 (NH Cl) ) Cl
4

)

dn in ng lng ca dung dch CaCl2.
43
(NH ) 149,7 76,6 73,4 (cm2.-1.lg-1) CNaOH .VNaOH 8.1,56

4 CHCl 0,125N
dn in ng lng gii hn ca NH4OH l: VHCl 100
V d 12. Tnh th in cc: Zn/ ZnCl 2 (0,005N) 250C cho bit dn in
(NH OH) ) ) 73,4 + 198 = 271,4cm2.1.dlg1
4
-1 -1 2
ng lng ca dung dch l 89 .lg .cm , dn in ng lng

-1 -1 2
V d 10. in tr ca dung dch KNO3 0,01N l 423 . Hng s bnh in gii hn ca dung dch l 113,7 .dlg cm v in th tiu chun ca in
-1
cc l 0,5 cm . Xc nh dn in ring, dn in ng lng v cc Zn l -0,76V.
phn ly ca dung dch, bit linh ion ca NO3- v K+ ln lt l 71,4 v 73,4 Gii
-1.lg-1.cm2. phn ly ca dung dch ZnCl2 l:
Gii 89
dn in ring ca dung dch KNO3:
113,7
k 0,5
1,182.10-3 -1.cm-1 Nng ca Zn :
2+
R 423 2+
[Zn ] = 0,783 0,005 = 0,004 N = 0,002 M
dn in ng lng: Th in cc:
1000. 1000.1,182.10 3 0,059
118,2cm2 . 1.dlg1 lg[Zn2 ]
C 0,01 2
Ta c: 0.059
2 1 1 0,76 lg0,002 0,839 V
(KNO ) ) ) 73,4 + 71,4 =144,8cm . .dlg
3
2
2+
in ly l: 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
ca in cc Cu l 0,34V, ca in cc Cd l -0,4V v nng ion Cd
2+

144,8 trong dung dch l 0,05N.
Gii
Nh vy in ly ca dung dch l 81,63% Phn ng xy ra trong pin:
V d 11. Xc nh nng ca dung dch HCl nu dng dung dch NaOH 8N 2+ 2+
Cd + Cu = Cd + Cu
chun 100ml dung dch HCl bng phng php chun dn in th
Sc in ng ca pin nh sau:
th kt qu thu c l:
VNaOH (ml) 0,32 0,60 1,56 2,00 2,34
E E0 lg

0,059 Cd 2
-1
( .cm.10 )
-2
3,2 2,56
Gii
1,64 2,38 2,96 2
Cu 2
0 0 0
Ta xc nh im tng ng ca php chun in th bng s Trong : E 0,34 0,4 0,74 (V)
thay i t ngt ca dn in ring. T bng s liu th im tng Th vo cng thc trn ta c:
ng chnh l im c th tch NaOH bng 1,56ml.
Ta tnh c nng ca dung dch HCl:
0,059 [Cu2 ]
lg
2 0,05
44
[Cu2 ] = 0,074 (N) E E0

0,059 Cu 2
lg

Cu 2 0,074 2 Ag
2

phn ly: 0,74 0,059 0,56
CuSO4 0,1 E 0,46 lg 0,463 (V)
V d 14. Cho pin 2 0,85 2
(Pt) Hg/ Hg2Cl2/ KCl 0,01N// H+ / Quinhydron. Thm vo sut in ng ca pin 0,02V
0
C sc in ng 25 C l 0,0096V. Tnh pH ca dung dch bit in th E = 0,483 (V)
in cc Calomen l 0,3338V v th in cc tiu chun ca in cc 0,059 0,56
Quinhydron l 0,699V. 0,483 = 0,46 - lg 2
Gii 2 Ag
p dng cng thc tnh pH ca dung dch: +
[Ag ] = 1,836 (M)
o Cal E
pH Quin 1,836
0,059 [AgNO3] = 2,16(M)
0,85
0,699 0,3338 0,0096
pH 6,027 nAgNO = CM.V = 2,16 x 1 = 2,16 (mol)
0,059 3
V d 15. Cho pin, Cu/ CuCl2 (0,7M)// AgNO3 (1M)/ Ag. Cho bit phn ly Vy s mol AgNO3 thm vo l: 2,16 1 = 1,16 (mol)
ca dung dch CuCl2 l 80% v dung dch AgNO3 l 85%, in th tiu chun m AgNO = 1,16 x 170 = 197,2 (g)
3
ca in cc Cu l 0,34V v in cc Ag l 0,8V. Tnh sc in ng ca V d 16. Vit cu trc pin trong cc m l in cc Hiro, cc dng l
pin v tnh lng AgNO3 cn thm vo sc in ng ca pin tng thm in cc Calomen. Cho bit in cc Calomen nhng vo dung dch KCl
0,02V, cho th tnh bnh l 1lt. 0,1M v pH ca dung dch l 1,0. Tnh sc in ng ca pin.
Gii Gii
2+ -
CuCl2 = Cu + 2Cl Pt, H2 /H+ //KCl 0,1M /Hg2Cl2/Hg, Pt
Nng ion Cu :
2+
Cu 0,7 100
2 80
0,56 (M)
p dng cng thc:
pH
E cal
AgNO3 = Ag +
+
NO3
- 0,059
M: 0Cal = 0,268 (V)
85
Nng ion Ag :
+

Ag 1
100
0,85 (M)
Ta c:
E cal
1
Sut in ng ca pin:
0,059
0 0 0
E = + - - = 0,8 - 0,34 = 0,46 (V) E = 0,059 + Cal
0,059 1
M: cal 0,788 lg 0,847 (V)
2 0,12
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 Gii
l 0,799V. Chng minh phn ng sau khng xy ra: a. Cd + CuSO4 = CdSO4 + Cu
2+ + 2+
2Ag + Cu = 2Ag + Cu. Cc m: Cd - 2e = Cd
2+
Gii Cc dng: Cu + 2e = 2Cu
+
Cc m: 2Ag 2e = 2Ag Cd/ CdSO4// CuSO4/ Cu
2+
Cc dng: Cu + 2e = 2Cu b. 2AgBr + H2 = 2Ag + 2HBr
+
Vy pin c hnh thnh t phn ng trn l: Cc m: H2 - 2e = 2H
+ 2+ -
Ag/ Ag // Cu / Cu Cc dng: 2AgBr + 2e = 2Ag + 2Br
Sc in ng tiu chun ca pin tnh c: Pt, H2 / HBr / AgBr / Ag
E0 = 0,34 0,799 = - 0,459 (V) c. H2 + Cl2 = 2HCl
E0 < 0 nn phn ng khng t xy ra. Cc m: H2 - 2e = 2H
+
V d 18. Vit cc phng trnh phn ng in cc v phn ng tng qut Cc dng: Cl 2 + 2e = 2Cl-
xy ra trong cc pin sau: Pt, H2/ HCl/ Cl2, Pt
a. Zn / ZnSO4 // CuSO4 / Cu d. Zn + 2Fe3+ = Zn2+ + 2Fe2+
b. Cu / CuCl2 / AgCl / Ag Cc m: Zn - 2e = Zn2+
3+ 2+
c. (Pt) H2 / H2SO4 / Hg2SO4 / Hg (Pt) Cc dng: 2Fe + 2e = 2Fe
d. Cd/ CdSO4 / Hg2SO4 / Hg (Pt) 2+ 3+
Zn/ Zn // Fe , Fe / Pt2+
Gii 2+ 2+ 3+
V d 20. Cho phn ng ca pin l: Hg + 2Fe = 2Hg + 2Fe c hng
a. Zn / ZnSO4 // CuSO4 / Cu 0 0 0 0
s cn bng 25 C l 0,018 v 35 C l 0,054. Tnh G v H ca phn
Cc m: Zn - 2e = Zn2+ 0
ng 25 C.
2+
Cc dng: Cu + 2e = Cu Gii
Zn + CuSO4 = ZnSO4 + Cu 0
Coi H khng thay i trong khong t 25 - 35 C ta c:
b. Cu / CuCl2 / AgCl / Ag
Cc m: Cu - 2e = Cu
2+ K T2
H 1 1
- ln
Cc dng: 2AgCl + 2e = 2Ag + 2Cl K T1 R T2 T1
Cu + 2AgCl = 2Ag + CuCl2
c. (Pt) H2 / H2SO4 / Hg2SO4 / Hg (Pt) 0,054 H 0 1 1
Cc m: H2 - 2e = 2H
+
ln
Cc dng: Hg2SO4 + 2e = 2Hg + SO4
2- 0,018 8,314 T2 T1
0
H2 + Hg2SO4 = 2Hg + H2SO4 H = 83834,58 (J)
d. Cd / CdSO4 / Hg2SO4 / Hg (Pt) G = -RTlnKp = -8,314 298 ln(0,018)
0
Cc m: Cd - 2e = Cd2+ = 9953,36 (J)

2-
Cc dng: Hg2SO4 + 2e = 2Hg + SO4 V d 21. Cho pin: Zn / ZnCl 2 (0,5M) / AgCl / Ag.
Cd + Hg2SO4 = 2Hg + CdSO4 a. Vit phn ng in cc v phn ng trong pin.
V d 19. Lp pin trong xy ra cc phn ng sau. b. Tnh sc in ng tiu chun, bin thin th ng p tiu chun ca
a. Cd + CuSO4 = CdSO4 + Cu pin.
b. 2AgBr + H2 = 2Ag + 2HBr c. Tnh sc in ng v bin thin th ng p ca pin.
c. H2 + Cl 2 = 2HCl Cho bit in th tiu chun ca in cc Zn l -0,76V, ca in cc
3+ 2+ 2+ -
d. Zn + 2Fe = Zn + 2Fe Ag/AgCl/Cl l 0,2224V.
46
Gii
a. Phn ng in cc v phn ng trong pin t
Cc m: Zn - 2e = Zn
2+

-
Cc dng: 2AgCl + 2e = 2Ag + 2Cl
Trong pin: Zn + 2AgCl = 2Ag + ZnCl 2
M ta li c: t t 1 t 1 0,491 0,509
b. Sut in ng chun trong pin Ta c:
E 0 0 0 0,2224 0,76 0,9824 (V) t ( ) t . 0,508.149 75,84cm2 . dlg-1
Th ng p chun: V d 24: Hng s phn ly ca NH4OH 313K l 2.10-5. Xc nh nng
-
0 0
G = -nFE = -2 96500 0,9824 = -189603,2 (J) ca ion OH trong cc dung dch sau:
c. Sut in ng ca pin: a. Nng ca NH4OH l 0,1N?
b. Trong 1 lt dung dch cha 0,1 mol NH4OH v 0,1 mol NH4Cl. Coi
0,059
E E0
2

lg Zn2 Cl
2
NH4Cl phn ly hon ton.
Gii
Ta c phng trnh phn ly:
0,059
lg0,5
. 1 0,9913 (V)
2 + -
E 0,9824 NH4OH NH4 + OH
2 a. Trong dung dch NH4OH 0,1N
Th ng p ca pin: [NH4 ].[OH ] [OH ]2
G = -nFE = -2 96500 0,9913 = -191321 (J) K
+
V d 22. Hy xc nh nng ion H trong dung dch. Khi chun 10ml [NH4 OH] [NH4OH]
hn hp HCl bng dung dch NaOH 0,1N th cc gi tr o c, c c Ta tnh c:
trn cu Wheatstone l:
VNaOH(ml) 0 5 8 9 10 11 12 13 [OH ] K.[NH4OH] 2.105.0.1 1,4.103 M
(cm2.-1 b. Trong 1 lt dung dch cha 0,1 mol NH4OH v 0,1 mol NH4Cl.
540 490 468 466 464 462 475 490
.lg-1)
[NH 4 ].[OH ]
Gii K
Ta xc nh im tng ng ca php chun in th bng s [NH 4 OH]
thay i t ngt ca dn in ring.
Trong : [NH 4 ] = [OH ] + 0,1 [OH ] = 2.10 M
-5
T bng s liu th im tng ng chnh l im c th tch NaOH
3- 0
bng 11ml. Ta tnh c nng ca dung dch HCl: V d 25. Cho lng Ag d vo dung dch Mo(CN)6 0,1 M, 25 C c phn
CNaOH .VNaOH 0,1.11 ng xy ra nh sau:
CHCl 0,11N Ag + Mo(CN)63- = Ag+ + Mo(CN)64-
VHCl 10 a. Thnh lp pin m trong in cc xy ra phn ng trn.
-
V d 23. Trong dung dch NH4Cl, s vn chuyn ca anion Cl l 0,491. Tm b. Tnh hng s cn bng ca phn ng
+
linh cation bit dn in ng lng gii hn ca dung dch l c. Tnh nng ca Ag lc cn bng
0 3-
2 -1
149cm . .dlg
-1 d. Tnh sc in ng ca pin 25 C khi nng ca Mo(CN)6 v ca
4- +
Gii Mo(CN)6 bng nhau, nng Ag bng nng lc cn bng (cu
Ta c biu thc lin h gia s ti ca cation vi dn in ng c).
lng gii hn nh sau:
47
Theo th in cc chun ca Zn v Cd. Tnh cng ca phn ng trong
Bit 0Ag/Ag 0,799(V); Mo(CN)
0
3
/Mo(CN)4
0,868(V). iu kin hon ton thun nghch p sut v nhit tiu chun cho bit
6 6
Gii
+
a 2 l 0,001 v a 2 l 0,125. (tra s tay ha l cc th in cc chun)
Zn Cd
a. Cc m: Ag - 1e = Ag 12 7 -1
3- 4- S: K= 1,6.10 ; A = 8,14.10 kJ.mol
Cc dng: Mo(CN)6 + 1e = Mo(CN)6
Pin: Ag / Ag+ // Mo(CN)63-, Mo(CN)64- / Pt 3. Tnh bin thin entanpy ca pin khi phn ng trong pin xy ra thun
b. Hng s cn bng nghch trong dung dch nc: Zn + CuSO4 = ZnSO4 + Cu. Bit sc
Sc in ng tiu chun: in ng ca pin 273K l 1,0960V v 276K l 1,0961V.
S: H = -2,10.105KJ
E0 0,868 0,799 0,069(V) 4. Ha tan 1 mol KNO3 vo 1lit nc, nhit ng c ca dung dch
0 thp hn nhit ng c ca nc l 3,01 , hng s nghim lnh
nFE 1 96500 0,069
lnK cb 2,6875 ca nc l 1,86. Tnh in li biu kin ca KNO3 trong dung dch?
RT 8,314 298
S: 62%
Kcb = 14,695
c. Nng ca Ag
+ 5. Tnh dn in ng lng gii hn ca dung dch acid acetic khi
0
3- + 4- dung dch c pha v cng long 25 C. Bit dn in ng
Ag + Mo(CN)6 = Ag + Mo(CN)6
lng gii hn ca HCl, CH3COONa v ca NaCl ln lt l: 426,1;
0,1 0
x x x 91 v 126,5 cm2. dlg-1
(0,1 - x) x x
Hng s cn bng: S: 390,6 cm2. dlg-1
0
x2 6. Khi o dn in ca 1000ml dung dch cha 0,1lg KCl 25 C
K cb 14,695 x 0,09932 bng bnh o dn cho gi tr in tr l 3468,9 . Mt dung dch
0,1 x ca mt cht khc c nng 0,1N cng c cho vo bnh o ni
Vy nng ca Ag+ = 0,09932 (M) trn, gi tr in tr o c l 4573,4 . Tnh dn in ng
d. Sc in ng ca pin lng ca cht .
E E0 lg

0,059 Mo CN 6 Ag
4
S: 97,51cm21dlg1
n 3
Mo CN 6 7. Cho lc ion ca dung dch NaCl l 0,24. Hy xc nh:
a. Nng ca dung dch trn.
0,059 b.
E 0,069 lg0,09932 0,1282V Dung dch Na2SO4 phi c nng bao nhiu c cng lc
1 ion.
7.5. Bi tp t gii c. Dung dch MgSO4 phi c nng bao nhiu c cng lc
ion.
1. Cho dng in khng i i qua bnh in phn vi in cc l Pt S: a. C=0,24M; b. C=0,08M, C=0,06M
cha dung dch H2SO4 long trong 1 gi c 336 ml hn hp kh H2 v
O2 thot ra. Tnh cng dng in. 8. Tnh h s hot v hot ca dung dch Fe2(SO4)3 0,001M.
S: I = 0,536 ampe a 2 = 0,28 .0,002 = 0,56.10-4
Fe
2. Xc nh hng s cn bng ca phn ng:
Cd + ZnSO4 = CdSO4 + Zn aSO 2 = 0,57 .0,003 =1,7.10
-3
4
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 + B
Sn phm
Phng trnh ng hc:
NG HA HC 1 b(a x)
ln k.t
a b a(b x)
hoc
1
ln

C0A C 0B x
kt

8.1. ng hc
8.1.1. Xc nh thc nghim vn tc phn ng
C0B C0A C0B C 0A x
Vn tc phn ng: l s bin thin nng ca cc cht trong mt 8.1.2.3. Phn ng bc 3
n v thi gian v mt n v th tch. 3A
Sn phm
aA + bB = cC + dD Phng trnh ng hc:
Vn tc ca phn ng: 1 1
1 dA 1 dB 1 dC 1 dD 2kt
v C A 2
C
0 2
A
a dt b dt c dt d dt 8.1.3. Xc nh bc phn ng
8.1.2. Bc phn ng 8.1.3.1. Phng php th
Bc phn ng ca mt cht: chnh l s m nng ca cht trong Gi nh bc ca phn ng (bc 0, 1, 2, 3 )
phng trnh ng hc. Nu phn ng xy ra theo mt bc gi nh, th ta thay th cc gi
Bc tng ca phn ng: l tng cc bc nng ca cc cht trong tr thu c t qu trnh kho st theo vn tc theo thc nghim
phng trnh ng hc. t1 x1 vo phng trnh ng hc thu c k1
-
8.1.2.1. Phn ng bc 1 t2 x2 vo phng trnh ng hc thu c k2
-
A
sn phm - t3 x3 vo phng trnh ng hc thu c k3
C
Phng trnh ng hc: ln Ao kt - tn xn vo phng trnh ng hc thu c kn
C Nu k 1, k 2, k n tng ng nhau th bc phn ng l bc gi nh.
A 8.1.3.2. Phng php da trn c im ca chu k bn hy
ln2 Ngi ta quan st c im ca T1/2 v nng v xem s tng
Thi gian bn hy: t1/2 quan ca n l g.
k
8.1.3.3. Phng php xc nh theo vn tc u
8.1.2.2. Phn ng bc 2
n1A + n2B + n3C +...+ nn Z Sn phm
2A
Sn phm n n
1 1

Vn tc phn ng: V k. A 1 B 2 ... Z n n
Phng trnh ng hc: 0 kt Tm n1: Cho [B], [C], [D]., [Z] d
CA CA V k.A n1

1 Tm n2: Cho [A], [C], [D]., [Z] d
Thi gian bn hy: t 1 2
kC 0A V k.B n 2
50
Tng t ta c n3, n4,, nn V d 2. Trong 10 pht, phn ng gia hai cht xy ra ht 25% lng ban
N = n1 + n2 +..+ nn u. Tnh chu k bn hy ca phn ng nu nng ban u hai cht trong
8.1.4. nh hng ca nhit n tc phn ng phn ng bc hai l nh nhau.
Vant Hoff khi nghin cu s nh hng nhit n vn tc phn Gii
0
ng th ng cho rng c tng nhit ln 10 C th vn tc phn ng tng t Nng ban u hai cht bng nhau, ta c:
2 n 4 ln. 1 1
k T n.10 o kt
n CA CA
kT Hng s tc ca phn ng l:
Trong : l h s nhit . 1 1
8.1.5. Nng lng hot ha o
o 10k
0,75C A C A
k 2 E a T2 T1 1
ln
k1 R T1 .T2 k
30CoA
Trong : Chu k bn hu ca phn ng l:
k1, k2: hng s tc phn ng nhit T1, T2.
Ea: nng lng hot ha 1
t 1/ 2 30 (pht)
T1, T2: nhit (0K) kC0A
R: hng s kh l tng
V d 3. Chu k bn hy ca N2O5 l 5,7 gi. Tnh hng s tc phn ng
8.2. Bi tp mu v thi gian cn thit phn ng ht 75% v 87% lng cht ban u nu
V d 1. Lng cht phng x Poloni sau 14 ngy gim i 6,85% so vi ban phn ng l bc 1.
u. Xc nh hng s tc phng x v chu k bn hy ca Poloni. Cho Gii
bit phn ng l bc 1. V phn ng l bc 1 ta c:
Gii
V phn ng l bc 1 ta c phng trnh ng hc cho phn ng bc
ln2 0,693
k 0,1216 (gi-1)
1: t1/ 2 5,7
C0A Thi gian phn ng ht 75% lng cht ban u l:
ln kt
CA C0A
ln
Hng s tc ca phn ng trn l: 0,25C0A
1 C 0 t 75% 11,4 (gi)
k ln 0,00507 (ngy-1)
A 0,1216
0
14 0,9315CA Thi gian phn ng ht 87% lng cht ban u l:
Chu k bn hy l: C0A
ln 2 0,693 ln
t 1/ 2 136,7 (ngy) 0,13C0A
k 0,00507 t 87% 16,78 (gi)
0,1216
51
V d 4. Trong 10 pht hai phn ng bc mt v hai u phn ng ht 40%. k2 52000 1 1
Tnh thi gian hai phn ng u ht 60% khi cho nng ban u ca ln ( )
phn ng bc 2 l nh nhau. 0,00191 1,987 723 651
-1
Gii k2 = 0,1046 (pht )
i vi phn ng bc 1: 0
Thi gian (pht) phn ng ht 75% lng cht 450 C l:
1 C 0A -1
k ln 0
0,0511 (pht )
10 0,6C A
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 19,9
i vi phn ng bc 2: Ptng (N/m2) 41589,6 54386,6 65050,4 74914,6
1 1 1 1 Xc nh bc phn ng v tnh gi tr hng s tc phn ng.
o kt o
o 10k
CA CA 0,6C A C A Gii
Hng s tc ca phn ng l: CH3COCH3 = C2H4 + CO + H2
1 1 1 P0 0 0 0
k (P0 x) x x x
6C A 10C A 15CoA
o o
Gi p sut ban u ca Aceton l P0.
Thi gian (ph) phn ng ht 60% lng cht l: p sut ti cc thi im t ca Aceton l P = PO - x
p sut tng cng ca h l PT = PO + 2x
3Po PT
P
0
V d 5. 378 C, chu k bn hy ca phn ng bc nht l 363 pht. Tnh 2
0
thi gian phn ng ht 75% lng ban u 450 C, bit nng lng Ti t = 6,5 pht:
-1
hot ha ca phn ng l 52.000 cal.mol . 3Po PT 3.41589,6 54386,6
Gii P6,5 35191,1N/ m2
0
V phn ng l bc 1 nn ta c hng s tc ti nhit 378 C l: 2 2
ln2 0,693 Ti t = 13 pht:
k1 0,00191 (pht-1) 3Po PT 3.41589,6 65050,4
t1/ 2 363 P13 29859,2N/ m2
0
Hng s tc ca phn ng 450 C c tnh theo phng trnh: 2 2
k 2 E a 1 1 Ti t = 19,9 pht:
ln ( )
k1 R T2 T1
52
3P P 3.41589,6 74914,6 Thi gian phn ng ht 50% lng cht cng chnh l chu k bn hy
P19,9 o T 24927,1N/ m2 ca phn ng .
2 2 1 1
Gi s phn ng l bc 1 p dng phng trnh ng hc cho phn ng bc t1/ 2 t 50% o
16,8phut
1 ta c: kC A 2,38.0,025
CoA b. Khi trn 1lt dung dch etylacetat 1/20N vi 1 lt dung dch NaOH 1/10N
ln kt vi CoA 41589,6 ta c: CoA CBo
CA
41589,6 1 1
ln CoA 0,025N v CBo 0,05N
35191,1 0,0257phut 1 40 20
Ti t = 6,5 pht ta c k1 Thi gian (pht) phn ng ht 50% lng cht l:
6,5
t 1/2 t 50%
1
ln
2 0,05 0,025 6,8
41589,6
ln 2,380,05 0,025 0,05
Ti t = 13 pht ta c: k 2
29859,2 0,0255phut 1
V d 8. Nu phn ng bc 1 c nng lng hot ha l 25.000 cal/mol v
13 13 -1
trong phng trnh Arhenius c hng s k0 l 5.10 giy , nhit no
41589,6 chu k bn hy ca phn ng l 1 pht v 30 ngy.
ln Gii
24927,1 0,0256phut 1 Khi chu k bn hy l 1 pht ta c hng s tc l:
Ti t = 19,9 pht ta c: k3
19,9 ln2 0,693
Ta nhn thy ti cc thi im khc nhau c cc gi tr ca k l sp x nhau k 0,01155 (giy-1)
nn ta kt lun phn ng l bc 1 v c hng s tc l:
t1/ 2 60
k1 k 2 k3 Ea
k 0,0256phut 1 lnk lnko
3 RT
V d 7. Hng s tc phn ng x phng ha etylacetat bng xt 283K Nhit cn thit l:
-1 -1
l 2,38 l.lg .ph . Tnh thi gian cn thit x phng ha 50% lung Ea 25000
etylacetat nhit trn, nu trn 1lt dung dch etyl acetat 1/20N vi: T 349K
a. 1 lt dung dch xt 1/20N R(ln k o ln k) 1,987.(ln 5.1013 ln 0,01155)
b. 1 lt dung dch xt 1/10N. Khi chu k bn hy l 30 ngy (2592000 giy) th hng s tc ca
Gii phn ng l:
a. Khi trn 1lt dung dch etylacetat 1/20N vi 1 lt dung dch NaOH 1/20N ln 2 0,693
o o k1 0,267.106 -1
(pht )
ta c: C C
A B t1/ 2 2592000
1 Ea
CoA CBo 0,025N lnk lnko
40 RT
Nhit cn thit l:
53
Ea 25000 Ta tnh c = 1, = 2 v k = 0,025

T 269K Vy phng trnh ng hc ca phn ng trn l:
R(ln k o ln k) 1,987.(ln 5.1013 ln 0, 267.10 6 ) o o
V d 9. Nng lng hot ha ca phn ng l bao nhiu tc phn W = 0,025(CA )(CB )
ng tng ln 3 ln khi tng nhit ln 10 ti 300K v ti 1000K? V d 11. ng hc phn ng bc mt hnh thnh axit c nghin cu
Gii bng cch ly mu t hn hp phn ng theo tng chu k v nh phn
Ti 300K tc tng 3 ln th hng s tc ca phn ng cng tng bng dung dch kim. Th tch dung dch kim dng nh phn cc thi
3 ln ta c: im khc nhau sau khi phn ng bt u thu c nh sau:
k 2 E a 1 1 Thi gian (pht) 0 27 60
ln ( ) Th tch kim (ml) 0 18,1 26 29,7
k1 R T2 T1 Chng minh phn ng l bc mt v tnh hng s tc phn ng.
Ea 1 1 Gii
ln3 ( ) Ti thi im t = th th tch kim tiu tn chnh l lng ban u
1,987 310 300 ca A hay C oA 29, 7 .
Ea = 20,3 (kcal/mol)
Ti 1000K: Ti t = 27 pht th CA 29,7 18,1 11,6
Ea 1 1 Ti t = 60 pht th CA 29,7 26 3,7
ln3 ( )
1,987 1010 1000 Gi s phn ng l bc 1. p dng phng trnh ng hc cho phn
Ea = 220 (kcal/ mol) ng bc 1 ta c:
V d 10. Cho phn ng: A + B = AB, thu c vn tc theo nng u Ti t = 27 pht
cc cht l: 1 C0 1 29,7 -1
1,0 0,1 1,0 k ln A ln 0,0348 (pht )
0 t C A 27 11,6
CA
1,0 1,0 0,1 Ti t = 60 pht
C0B 1 C0 1 29,7
Wo 0,025 0,0025 0,00025
k ln A ln 0,0347 (pht-1)
t C A 60 3,7
Hy vit phng trnh ng hc ca phn ng.
V cc gi tr ca k l bng nhau nn ta kt lun phn ng l bc 1 v
Gii
hng s tc l: k = 0,03475 pht-1
Phng trnh ng hc ca phn ng c dng:
V d 12. Dung dch este etylacetat c nng ban u 0,01N x phng ha
W kC A C B vi dung dch NaOH c nng 0,002N trong thi gian 23 pht t c
Da vo gi tr tc u ta xc nh gi tr ca v . chuyn ha l 10%. Nu nng ban u gim i 10 ln th thi gian phn
o o ng s l bao nhiu nu mun t c chuyn ha l 10% nh trc.
W01 = k(C ) (C ) k1 1 0,025
A B Gii
CH3COOC2H5 + NaOH = CH3COONa + C2H5OH
W02 = k(CoA ) (CBo ) k0,11 0,0025 0,01 0,002
W03 = k(CoA ) (CBo ) k10,1 0,00025 0,001 0,001
0,009 0,001
54
y l phn ng bc 2 ta c: Ea = 24,461 (kJ/mol)
1 o
C (C x)o V d 14: Ngi ta o tc u hnh thnh C i vi phn ng:
A B
kt o o
ln o o
A + B = C v thu c kt qu sau:
(C C A ) C (C x) S TN o o
3 -1
Wo.10 (M.pht )
B B A
(M) CA (M) CB
Hng s tc phn ng (lit/ mol.phut) l:
1 0,1 0,1 2,0
1 1 0,002 0,01 0,001 2 0,2 0,2 8,0
k ln 3,194
23 0,01 0,002 0,010,002 0,001 3 0,1 0,2 8,0
Khi nng u gim i 10 ln th: a. Bc phn ng i vi A v B.
1 1 0,00020,001 0,0001 b. Hng s tc phn ng.
t ln 230
3,194 0,001 0,0002 0,0010,0002 0,0001 c. Tnh Wo khi C oA = CBo =0,5M.
Khi nng ban u gim i 10 ln t c mc chuyn ho Gii
10% th cn 1 khong thi gian l 230 pht. a. Phng trnh ng hc ca phn ng c dng:
V d 13. Xc nh bng thc nghim hng s tc phn ng phn hy W kC A C B
N2O5 c kt qu:
0
Nhit ( C) 0 25 35 45 55 65
Da vo gi tr tc u ta xc nh gi tr ca v .
-15 -1
k.10 .s 0,0787 3,46 13,5 47,44 250 577,8 W01 = k(C ) (C ) k0,1 0,1 2.103
o
A
o
B

Xc nh nng lng hot ha ca phn ng.

Gii W02 = k(CoA ) (CBo ) k0,20,2 8.103
-15
Khi T1 = 273K v T2 = 298K th hng s tc k1 = 0,0787.10 s v k2 =
-15
3,46.10 s:
k(CoA ) (CBo ) k0,10,2 8.103
W03 =
k 2 E a 1 1 3, 46.1015 E a 1 1 T 3 phng trnh trn ta tnh c = 0 v = 2

ln ( ) ln 15
( ) b. Hng s tc ca phn ng l: k = 0,2 M .pht
-1 -1
k1 R T2 T1 0,0787.10 1,987 298 273 o o

Ea = 24,463 (kJ/mol)
c. Khi C A
= C
B
=0,5M.
o 2
Khi T1 = 308K v T2 = 318K th hng s tc : Ta c: Wo 0,2.0,5 .0,5 0,05M/ phut
k1= 13,5.1015s v k2= 19,8.1015s: V d 15. Phn ng trong pha kh gia NH3 v NO2 trong giai on u l
k 2 E a 1 1 47, 44.1015 E a 1 1 phn ng bc 2.
ln ( ) ln 15
( ) a. Tnh nng lng hot ha ca phn ng.
k1 R T2 T1 13,5.10 1,987 318 308
b. Tnh tha s k0 ca phng trnh Arrhenius.
Ea = 24,460 (kJ/mol) Bit nhit 600K v 716K, hng s tc phn ng c gi tr tng ng
Khi T1 = 328K v T2 = 338K th hng s tc : -1 -1 -1 -1
bng 0,385 M .s v 16 M .s .
15 15
k1 = 250.10 s v k2 = 487.10 s: Gii
k 2 E a 1 1 577,8.1015 E a 1 1 k 2 E a 1 1
ln ( ) ln 15
( ) a. S dng phng trnh: ln ( )
k1 R T2 T1 250.10 1,987 338 328 k1 R T2 T1
Ea = 24,461 (kJ/mol)
Vy nng lng hot ha ca phn ng l:
55
16 Ea 1 1 Ti 270C ta c:
ln ( ) a 114778J / mol ln 2 0,693
0,385 8,314 716 600 k1 1,386.10 4 s 1
t1/ 2 5000
Ea Ti 370C ta c:
b. Tnh hng s k0: lnk lnko
RT ln 2 0,693
114778 k2 6,93.10 4 s 1
ln0,385 lnk o t1/ 2 1000
8,314.600 k E a 1 1
p dng phng trnh: ln 2 ( )
ko 378,559.107 M1.s1 k1 R T2 T1
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 Ea 124,4 (kJ/ mol)
nh nng lng hot ha v hng s tc phn ng 633,2K. 8.3. Bi tp t gii
Gii 1. S ph thuc ca hng s tc phn ng phn hy PH3 vo nhit
k 2 E a 1 1 c biu th bng phng trnh:
p dng phng trnh: ln ( ) 18963
k1 R T2 T1 lgk 2lgT 12,130.
-5 -5
Vi T1 = 418K, T2 = 737K v k1 = 1,12.10 , k2 = 18,54.10 ta c: T
5 Xc nh nng lng hot ha ca phn ng 800K.
18,54.10 Ea 1 1 S: Ea= 376,39 KJ
ln ( )
1,12.10 5
8,314 737 418 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
Ea 22,522kJ/ mol bng 363 pht. Nng lng hot ha ca phn ng bng 217 KJ.mol
-
1 0
k E a 1 1 . Xc nh hng s tc ca phn ng 450 C.
Cng p dng phng trnh: ln 2 ( ) S: 0,1011 pht
-1
k1 R T2 T1 3. Xt phn ng:
2HgCl2 + K2C2O4 = 2KCl + 2CO2 + Hg2Cl2
Vi T1= 418K, T2= 633,2K v k1 = 1,12.10 , Ea 22,522kJ/ mol
-5
C th o vn tc phn ng theo lng Calomen Hg2Cl2 gim. 1000C vn
ta c: tc u (mol/lit), HgCl2 /pht l:
k2 22522 1 1 Stt Hg2Cl2 (mol/lit) K2C2O4 (mol/lit) dx/dt
ln 5
( ) 1 0,0836 0,202 0,26
1,12.10 8,314 633,2 418 2 0,0836 0,404 1,04
k 633,2K 10,114.10 5 M 2 s 1 3 0,0418 0,404 0,53
0
V d 17. Trong mt phn ng bc nht tin hnh 27 C, nng cht u Xc nh bc ca phn ng.
0 -4
gim i mt na sau 5000s. 370C nng gim i mt na sau 1000s. 4. Phn ng phn hy hp cht c hng s tc k1 10 C l 1,08.10
0 -4 0
Xc nh nng lng hot ha ca phn ng. 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
Gii
bn hy t1/2 l 15 pht. Sau bao lu 80% ng v b phn hy?
56
6. 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.
57
Chng 9 x

xm
HP PH V HA KEO Vi: x l hp ph mt thi im no .
xm l hp ph cc i.
p A 1
p
9.1. Hp ph v hp ph x xm xm
S hp ph y c nh gi bng lng kh bay hi (tnh bng 9.4. Phng trnh hp ph BET (Brunauer- Emmett - Teller)
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: P 1 C 1 P

V 3
V(P0 P) Vm .C Vm .C P0
x (cm /g)
Vi:
22400
Trong : x hay V c th xc nh bng thc nghim. P0: p sut hi bo ha
hp ph x l mt hm c hai thng s x = f(P,T). Gin hp ph V: th tch kh hp ph p sut P
c biu din theo cc ng ng nhit (T = const) v ng p (P = Vm: th tch kh b hp ph lp th nht (lp n phn t)
const). Thng thng ng ng nhit c s dng nhiu nht. C: tha s nng lng.
9.2. Phng trnh hp ph ng nhit Freunlich P
th theo P/P0 l mt ng thng, t c th xc
ng hp ph ng nhit gn vi dng parapol, do Freunlich V(P0 P)
ngh phng trnh thc nghim:
1/n nh Vm v C. Bit Vm, ta c th tnh c b mt cht hp ph.
x = b.p
Trong : Vm .N.Wm
x: hp ph. S0
V0
p: p sut kh cn bng trn cht hp ph.
b v n: l cc hng s. Trong :
23
N : s Avogadro (= 6,023.10 )
1 Wm : b mt chim bi cht b hp ph lp n phn t.
Hoc: lgx lgb lgp V0: th tch ca 1 mol kh iu kin chun (22.400 cm3/mol).
n
9.3. Phng trnh hp ph ng nhit Langmuir 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
Gi p l p sut kh, l phn b mt ti thi im no b phn t
trong dung dch c tnh bng cng thc:
kh chim, phn b mt cn trng s l 1 - .
k 1.p (C0 C1 )V
Ta s c: x 100
k 2 k 1.p m
Trong :
k C0 v C1 l nng ban u v cn bng ca cht b hp ph (mol/l).
Nu t: A 2 V l th tch trong xy ra s hp ph (l).
k1
m l lng cht hp ph (g).
58
9.6. Bi tp mu b. Cho mt lng d BaCl2.

0 c. Cc cht in ly di y gy keo t nh th no i vi cc dung
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 dch keo ni trn: Al(OH)3; Na3PO4.
-3
v ca dung dch trn l 63,3.10 N/m. Gii
Gii Phng trnh phn ng:
Na2SO4 + BaCl2 = 2NaCl + BaSO4
dm.dd a. Nu d Na2SO4 th mixen keo c dng:
p dng cng thc: G 2- + +
RT {mBaSO4.nSO4 .(2n-x)Na }.xNa
Th cc s liu vo cng thc ta c: y l keo m
b. Nu d BaCl2 th mixen keo c dng:
dm . dd 10,19.10 3 2+
{mBaSO4.nBa .(2n-x)Cl }.xCl
- -
G mol.m 2
RT 8,314.(15 273) y l keo dng
V d 2. Xc nh ngng keo t ca dung dch in ly K2Cr2O7 nng c. Cc cht gy s keo t:
2- + +
Vi ht keo {mBaSO4.nSO4 .(2n-x)Na }.xNa th cht gy keo t tt
0,01M i vi keo nhm. Bit rng keo t 1 lt keo phi thm vo mt
nht l Al(OH)3 v y l keo m nn ion tri du vi n s quyt nh kh
lng cht in ly l 0,0631 lt. 3+ +
nng keo t. Ion Al c bc cao hn so vi ion Na .
Gii 2+ - -
Vi ht keo {mBaSO4.nBa .(2n-x)Cl }.xCl th cht gy keo t tt nht
Ta c cng thc tnh ngng keo t nh sau:
l Na3PO4 v y l keo dng nn ion tri du vi n s quyt nh kh
C.V 3- -
= 1000 nng 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:
Trong : 2H3AsO3 + 3H2S = As2S3 + 6H2O
C: Nng ca dung dch in ly (mol/l)
a. Khi t h vo in trng, cc ht keo di chuyn v in cc no.
V: th tch ca dung dch cht in ly (ml)
Gii thch.
: th tch ca dung dch keo (ml) b. Vit cng thc ca mixen keo v cho bit du ca ht keo.
Th cc gi tr c c vo cng thc trn ta c: Gii
C.V 0,01.0,0631 a. Cng thc ca Mixen keo c dng:
.1000 .1000 0,631.103 mol / lit 2- +
{mAs2S3.nS .(2n-x)H }.xH
+
1000 b. Khi t h vo in trng th cc ht keo s di chuyn v in cc

V d 3. iu ch keo hydronol st (III) bng cch cho t t dung dch FeCl3 dng. V cc ht keo mang in tch m n s chuyn ng di tc
vo nc ang si. Hy vit cu to v k hiu keo . dng ca in trng.
Gii V d 6. Keo AgI c iu ch t phn ng trao i:
Phng trnh phn ng iu ch ht keo: KI + AgNO3 = AgI + KNO3, vi lng d KI.
FeCl3 + 3H2O = Fe(OH)3 + 3HCl Tip theo ngi ta dng dung dch K2SO4 v dung dch (CH3COO)2Ca
Cu to Mixen keo: keo t dung dch keo thu c. Hi dung dch no trong hai dung dch trn
3+ - x+ -
{mFe(OH)3.nFe .(3n-x)Cl } .xCl . gy keo t mnh hn. V sao? (Cc dung dch trn c cng nng mol/l).
V y l qu trnh thy phn khng hon ton nn trong dung dch Gii
cn d FeCl3. Keo ny l keo dng. Trong hai dung dch trn th dung dch (CH3COO)2Ca s gy keo t
V d 4. Vit cng thc v s cu to ca mixen keo c to thnh khi vi tc mnh hn. V keo c hnh thnh l keo m, n c cng thc
cho Na2SO4 tc dng vi BaCl2 trong hai trng hp. nh sau:
a. Cho mt lng d Na2SO4.
59
{mAgI.nI-.(n-x)K+}.xK+ V d 10. Thi gian bn keo t ca keo AgI c nng ht bng 3,2.1011
M kh nng gy keo t t l thun vi bc ca in tch ion tri du. ht.l -1 l 11,5 giy. Xc nh hng s tc keo t.
2+ +
Dung dch (CH3COO)2Ca c ion Ca c bc ln hn ion K ca dung dch Gii
K2SO4. 1
V d 7. Vit cng thc ca mixen keo Al(OH)3 vi cht n nh l AlCl3 v p dng phng trnh: ko
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?.
1 1
Gii k 11
2,72.10 9 l / hat.giay
Mixen keo: {mFe(OH)3.nFe3+.(3n-x)Cl-}.xCl -. 3,2.10 .11,5
V {mAl(OH)3.nAl3+.(3n-x)Cl-}.xCl-. 9.7. Bi tp t gii.
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 1. Keo AgI c iu ch t phn ng trao i:
3+ 3+
ca ion Fe ln hn Al nn n b keo t mnh hn. KI + AgNO3 = AgI + KNO3, vi lng d KI.
-6 Tip theo ngi ta dng dung dch CaSO4 v dung dch CH3COONa
V d 8. Ngng keo t ca Al2(SO4)3 i vi keo As2S3 l = 96.10
3 3 keo t dung dch keo thu c. Hi dung dch no trong hai dung dch
kmol/m . Hi cn bao nhiu ml dung dch Al2(SO4)3 nng 0,01 kmol/m
3 trn gy keo t mnh hn.V sao? (Cc dung dch trn c cng nng
keo t 0,1 m dung dch keo As2S3 ni trn.
mol/l).
Gii
Ta c cng thc tnh ngng keo t nh sau. 2. Vit cng thc v s cu to ca mixen keo c to thnh khi
C.V cho K2SO4 tc dng vi Ba(NO3)2 trong hai trng hp:
= 1000 a. Cho mt lng d K2SO4.

b. Cho mt lng d Ba(NO3)2.
Trong :
C: Nng ca dung dch in ly (mol/l) 3. Vit phng trnh phn ng v cu to ca mixen keo c to thnh
V: th tch ca dung dch cht in ly (ml) khi cho KAuO2 tc dng vi K2CO3 trong HCHO.
11
: th tch ca dung dch keo (ml) 4. Thi gian bn keo t ca keo BaSO4 c nng ht bng 3,5.10
-1
Th cc gi tr c c vo cng thc trn ta c: ht.l l 10,5 giy. Xc nh hng s tc keo t.
0,01.V
96.106 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 -.
2-
Trong 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

Chng 1: Nguyn l I nhit ng hc..2

Bin thin etropy ca qu trnh Nhit lng cn cung cp

Hng s cn bng tnh theo nng mol/l: Ch : P C (RT) n

PCl5(k) PCl3(k) + Cl2(k) 2 2 n

Theo bi ta c: 2x = 0,402 x = 0,201 (mol) KP 1,91.10 5

x = 2,863 (atm) CO + 2H2 = CH3OH(k) (1)

H 0298, tt (KJ/mol) 33,81 0 90,25 142,12 ab a b 2 abPK P

4.1. Mt s khi nim c bn

Hnh 4.5. Minh ha quy tc n by

Hnh 4.6. Minh ha quy tc khi tm

dT T.V V d 2. Tnh nhit si ca nc 2 atm, bit nhit ha hi ca n l

mAo = 20% 200 = 40 (g)

Hnh 5.1. Gin p sut hi (P - x) ca dung dch 2 cu t l tng

CN BNG GIA DUNG DCH

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

Hai im e1 v e2 tng ng l cc im eutecti ca h A - D v h D

m ct b. Lm lnh 90g h Q, khi im h nm ti H, c A v B kt tinh mt

a. Tnh s pha v bc t do ca h ti cc vng I, II, III v ti im

40 60 433 ca dung dch l 1g/cm3, hng s nghim lnh v hng s nghim si

S: a. 12g; 48g v 40g; b. 57,14g

7.1.2. S in ly m : molan trung bnh ca cc ion

(NH ) 149,7 76,6 73,4 (cm2.-1.lg-1) CNaOH .VNaOH 8.1,56

[Cu2 ] = 0,074 (N) E E0

Cc m: Cd - 2e = Cd2+ = 9953,36 (J)

Ea 25000 Ta tnh c = 1, = 2 v k = 0,025

Xc nh nng lng hot ha ca phn ng.

k 2 E a 1 1 3, 46.1015 E a 1 1 T 3 phng trnh trn ta tnh c = 0 v = 2

k1 R T2 T1 0,0787.10 1,987 298 273 o o

9.6. Bi tp mu b. Cho mt lng d BaCl2.

1000 b. Khi t h vo in trng th cc ht keo s di chuyn v in cc

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