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TRNG I HC S PHM
-----
BI GING MN
NHIT NG HA HC
Nng, 2009
1
V d: s truyn nhit t ngun nng sang ngun lnh l mt bin i bt thun nghch hay
t nhin v bin i ngc li, tc s truyn nhit t ngun lnh sang ngun nng khng
th thc hin mt cch t nhin. S ri t do di tc dng ca trng trng cng l mt
bin i t nhin hay bt thun nghch.
S ng c ca nc 0oC, 1atm l mt bin i thun nghch v bin i ngc li ng
vi nc nng chy 0oC, 1atm cng c th thc hin c.
- Bin i ng tch: l bin i c thc hin trong iu kin th tch ca h khng thay
i.
V d: mt phn ng ha hc c thc hin trong ng hn kn.
- Bin i ng p: l bin i c thc hin trong iu kin p sut khng i.
V d: phn ng c thc hin trong bnh cu n thng vi kh quyn bn ngoi.
- Bin i ng nhit: l bin i c thc hin trong iu kin nhit khng i.
V d: phn ng c thc hin trong mt bnh cu nh c t trong bnh iu nhit(*)
gi nhit xc nh.
- Bin i on nhit: l bin i c thc hin trong iu kin khng c s trao i nhit
lng gia h vi mi trng ngoi.
V d: phn ng c thc hin trong bnh Dewar y kn, c bao quanh bi cc lp
cch nhit tht dy.
4. Hm s trng thi
Mt i lng c gi l hm s trng thi ca h nu bin thin ca i lng ch ph
thuc vo trng thi u v trng thi cui ca h m khng ph thuc vo cch tin hnh
qu trnh (nh thun nghch hay bt thun nghch).
Ni chung, tt c cc thng s trng thi ca h nh nhit T, p sut p, th tch V.... u
l nhng hm s trng thi ca h v nhng thng s ch c trng cho trng thi ang
xt ca h. Khi h chuyn t trng thi u sang trng thi cui, bin thin ca nhng
thng s trng thi ca h ch ph thuc vo nhng trng thi , khng ph thuc vo cc
trng thi trung gian m h tri qua.
5
a. Nhit
Nhit lng q cn dng em m gam ha cht tng ln mt khong nhit tng i
nh t T1 n T2 l:
q = mc(T2 - T1)
Vi c l nhit dung ring) ca ha cht, l lng nhit cn em mt gam ha cht
tng ln mt , c xem nh khng i trong khong nhit trn.
Thng ngi ta o nhit lng q p sut khng i hoc th tch khng i, lc t
nhit c s l t nhit ng p
Nu m = M, phn t gam (khi lng mol phn t tnh bng gam), th c t nhit mol ng
p
hoc t nhit mol ng tch
, l lng nhit cn em mt mol ha cht tng ln
mt iu kin p sut khng i hoc th tch khng i.
Mcp =
McV =
ng vi mt mol ha cht, ta c:
=>
Tr s t nhit mol ng p
iu kin
Vi n mol ha cht:
b. Cng
Ta thit lp biu thc tnh cng gin p ca h.
- Trng hp p sut ngoi khng i:
tng ng l:
Ngoi ra ngi ta cng chng minh c rng cng gin n thun nghch l cng cc i
(v tr s tuyt i) cn cng cn cung cp nn p h mt cch thun nghch l cng cc
tiu (v tr s tuyt i). Ngha l cng trng thi u, trng thi cui nh nhau, nu h gin
n thun nghch th cng to c tr s m hn so vi cng gin n bt thun nghch.
Nu h b nn p thun nghch th cng cn cung cp t dng hn so vi bin i nn p
bt thun nghch.
Do xt theo du i s th
II. NGUYN L TH NHT NHIT NG HC. NI NNG U V ENTANPI H
1. Nguyn l th nht nhit ng hc v ni nng U
Xem mt h bin i t trng thi (1) n
trng thi (2) theo nhiu ng bin i khc
nhau. Gi q1, W1; q2, W2; ...; qi, Wi l nhit
v cng trao i gia h vi mi trng
ngoi theo cc ng bin i 1, 2, ..., i.
Nguyn l th nht nhit ng hc c pht biu nh sau:
Nu qi v Wi l nhit v cng trao i gia h vi mi trng ngoi theo ng
bin i i th qi v Wi ring r thay i theo ng bin i nhng tng s qi+Wi
lun lun l mt hng s khng ty thuc ng bin i m ch ty thuc vo
trng thi u v trng thi cui ca h m thi.
Q1 + W1 = q2 + W2 = .... = qi + Wi = const (hng s)
V phng tin ton hc, biu thc trn ch rng ta c th tm c mt hm s nng lng
U ca h nghim ng iu kin:
Ghi ch:
- Nguyn l th nht nhit ng hc ch xc nh bin i ni nng
tnh c tr s tuyt i ca ni nng U.
ch khng th
- Nu h bin i t trng thi (1) n trng thi (2) theo cc cch bin i thun nghch
u ging nhau. Cn q, W tri li
hay bt thun nghch, th trong cc cch bin i y
c tr s khc nhau ty theo cch bin i.
- Xem mt h bin i t trng thi (1) n trng thi (2) theo hai ng bin i khc
nhau: mt thun nghch v mt bt thun nghch ta c:
11
Ngha l nhit trao i cch bt thun nghch nh hn cch thun nghch theo i s.
[Nhit m h nhn trong qu thun nghch ln hn so vi trong qu trnh bt thun nghch
cn nhit m h ta ra trong qu trnh thun nghch nh hn so vi trong qu trnh bt
thun nghch ].
- Trong trng hp trng thi u v trng thi cui ging nhau, tc h thc hin mt chu
trnh bin i kn, ta c:
bng lng
bng lng nhit
b. Bin i ng p.
Vi mt bin i xc nh:
Vi kh l tng:
pV = nRT
13
T: H = U + pV => H = U + nRT
M:
Vi n mol ha cht:
T:
(Tng qut q khng phi l hm s trng thi, nhng iu kin ng
p, qp l hm s trng thi).
M:
Vi n mol ha cht:
14
vi
ca kh l tng
Vi kh l tng:
15
( T const
(1.22)
Chia hai v cho
=>
16
m kh l tng:
(1.23)
17
BI TP CHNG 1
Cu hi.
1. Thit lp biu thc ton hc ca nguyn l 1?
2. Thit lp cng thc tnh cng v nhit cho qu trnh dn n ng nhit ca kh l
tng?
3. Thit lp cng thc tnh cng v nhit cho qu trnh dn n ng p v ng tch ca
kh l tng?
4. nh lut Hecx v cc h qu.
5. Thit lp mi quan h gia nhit dung ng p v nhit dung ng tch?
6. Khi nim entanpi. Mi quan h gia Qv v Qp?
7. S ph thuc ca hiu ng nhit vo nhit . Phng trnh Kichp ?
8. Thit lp quy tc tnh hiu ng nhit ca phn ng da vo sinh nhit v thiu nhit?
9. Thit lp phng trnh on nhit cho kh l tng
Bi tp
Cu 1. Tnh U v H cho cc qu trnh sau y:
a. Mt mol nc ng c 0oC v 1 atm
b. Mt mol nc si 100oC v 1 atm
Bit rng: nhit ng c v nhit bay hi ca 1 mol nc tng ng bng -6,01 kJ v
40,79 kJ; th tch mol ca nc lng v nc bng 0,0180 lit v 0,0195 lit. Chp nhn
hi l l tng.
( R = 0,082 atm.l/K.mol ; p =1 atm = 101300 Pa ; 1atm.l = 101,3 J = 0,101kJ)
Cu 2. Nhit trung ho NaOH v dung dch NH3 bng axit HCl tng ng l -55,9 v 51,34 kJ/mol. Xc nh nhit in ly ca amoniac.
Cu 3. Hiu ng nhit ca phn ng Na vi H2O (d) l H01=-183,8 kJ/mol; ca phn
ng Na2O vi H2O (d) l H02= -237,9 kJ/mol. Bit: Hos,H2O = -285,8 kJ/mol.
Hy tnh H0298 ca phn ng:
2 Na + 1/2 O2 = Na2O
Cu 4. Nhit hnh thnh ca Fe2O3 (R) bng -821,3 kJ/mol; ca Al2O3 bng -1675 kJ/mol.
Tnh hiu ng nhit ca s kh 1 mol Fe2O3 bng nhm kim loi.
Cu 5. Nhit trung ho axit HNO3 bng xt l 55,9 kJ. Cng lng dung dch xt trn
c dng trung ho axit CHCl2COOH th hiu ng nhit nhn c bng -62,05 kJ.
Nu cho 1 ng lng NaOH vo dung dch cha 1 ng lng HNO3 v 1 ng
lng CHCl2COOH th to ra 58,4 kJ. Xc nh s ng lng gam HNO3 phn ng
vi NaOH.
Cu 6. Nhit hnh thnh kh amoniac 298 K bng -46,2kJ/mol. Nhit dung mol ca H2,
N2, NH3 trong khong nhit 250-450 K c cho di y:
18
-393,51
-285,84
-1487
Cu 16. Tnh Ho298,s ca CH4(k), bit rng nng lng lin kt H-H trong H2 l
436kJ/mol, nng lng lin kt trung bnh C-H trong CH4 l 410kJ/mol v nhit nguyn t
ho Ho298,a ca Cgr l:
Cgr --> C (k) , Ho298,s = 718,4 kJ/mol. Cc gi tr trn ly iu kin chun v 25oC.
Cu 17. Tnh nhit lng cn thit nng nhit ca 0,5mol nc t -50oC n 500oC
P = 1 atm. Bit rng nhit nng chy ca nc 273K l 6004J/mol; nhit bay hi ca
nc 373K l 40660 J/mol; cc gi tr nhit dung (J/mol.K ) l: CoP,R = 35,56; CoP,L =
75,3 v CoP,H = 30,2 + 10-2T.
20
22
l:
l:
ca h l:
23
24
2. S = S(T,p)
dS =
[Coi nh ch c cng gin p]
dS =
Vi trng hp kh l tng:
- Vi bin i ng p p0:
Nu t nhit mol ng p
25
Ghi ch:
- p dng cc cng thc trn phi ch n cc iu kin thc hin bin i.
- Tuy iu kin thit lp cc cng thc trn l h kh l tng nhng cng c th p
dng tnh bin i entropi cho ha cht trong iu kin thch hp khong nhit
khng ln lm.
3. Cch tnh bin i entropi trong s thay i trng thi
a. Qu trnh nng chy:
Gi
nhit nng chy ca ha cht
l nhit ti c s cn bng pha gia
dng rn v dng lng ca ha cht di p sut 1 atm.
nhit nng chy mol ca ha cht, l nhit lng cn cung cp mt mol ha cht
(A) t dng rn thnh dng lng nhit nng chy
, p sut 1atm.
cng l nhit lng phng thch khi mt mol ha cht ng c t dng lng
,
, 1atm).
Gi TS: nhit si (oK) ca ha cht (A), l nhit ti c s cn bng pha gia dng
lng v dng hi ca ha cht di p sut 1atm.
26
S:
Nu chn
27
V t nhit mol ng p
theo thng s
28
nhit ToK.
Da vo cch tnh , c th tnh c entropi mol ca ha cht mt nhit xc nh
(nhit ti ha cht cha b phn hy).
Sau y l tr s entropi mol iu kin chun thc (298 K, 1atm) ca mt s ha cht
Ha cht
Ha cht
298 K
J/mol.K
cal/mol.K
Ag(r)
42,55
10,17
AgCl(r)
96,20
Al(r)
0
298 K
J/mol.K
cal/mol.K
H2O(k)
188,70
45,11
23,00
H2O(l)
69,96
16,72
28,30
6,77
HCl(k)
186,70
44,62
Al2O3(r)
51,00
12,19
HNO3(l)
155,60
37,19
C(r,graphit)
5,69
1,36
H2SO4(l)
157,00
37,50
CO(k)
197,90
47,30
CH3COOH(l)
160,00
38,20
CO2(k)
213,60
51,06
Hg(l)
76,10
18,20
CH4(k)
186,20
44,50
Hg(k)
175,00
41,80
CH3Cl(k)
234,20
55,97
K(r)
64,18
15,34
CH3OH(l)
126,80
30,30
KCl(r)
82,59
19,74
CO(NH2)2(r,ure) 104,60
25,00
K2SO4(r)
176,00
42,00
C2H2(k)
200,80
48,00
N2(k)
191,50
45,77
C2H4(k)
219,80
52,54
NH3(k)
192,50
46,01
C2H6(k)
229,50
54,85
NH4Cl(r)
94,60
22,60
29
C2H5OH(l)
161,00
38,40
NO(k)
210,60
50,34
Ca(r)
41,40
9,89
NO2(k)
240,50
57,47
CaCO3(r)
92,90
22,20
N2O(k)
220,00
52,58
CaCl2(r)
114,00
27,20
N2O4(k)
304,00
72,70
CaO(r)
40,00
9,50
Na(r)
51,00
12,20
Ca(OH)2(r)
76,10
18,20
Na2CO3(r)
136,00
32,50
CaSO4(r)
107,00
25,50
NaHCO3(r)
102,00
24,40
CaSO4.2H2O(r)
194,00
46,36
NaCl(r)
72,38
17,30
Cl2(k)
223,00
53,29
NaOH(r)
64,18
15,34
Fe(r)
27,00
6,50
Na2SO4(r)
149,40
35,70
Fe2O3(r)
90,00
21,50
O2(k)
205,00
49,00
H2(k)
130,60
31,21
PbO(r)
67,80
16,20
S(r)
31,90
7,62
SO2(k)
248,50
59,40
C(r,kim cng)
2,40
0,57
SO3(k)
256,20
61,24
ln hn.
Vi phn ng:
mA + nB -> pC + qD
2.26
V d 1:
V d 2:
T (2.17) =>
31
Nu
32
CHNG 3. TH NHIT NG TH HA HC
IU KIN CN BNG V DIN BIN CA QU TRNH
I. HM NNG LNG T DO G (TH NG NHIT NG P, HM GIBBS)
1. Hm s nng lng t do v bin i
Trn nguyn tc nu tnh c ca h v ca mi trng ngoi km theo mt
bin i th ta c th xc nh bin i c xy ra t nhin (bt thun nghch) hay khng.
Tuy nhin, s xc nh ca mi trng ngoi khng phi lc no cng d dng do
ngi ta tm cch da trn chnh h kho st kt lun.
Mt h c khuynh hng bin i t nhin (bt thun nghch) khi tha mn hai iu
kin sau y:
- iu kin v
hay
: mt bin i c khuynh hng xy ra nu ta nhit
(
, ty iu kin th nghim ng p hay ng tch).
- iu kin v
(
).
. Tuy nhin,
Vy iu kin u i mt bin i p, T khng i l
c trng hp
(thu nhit) hoc
(gim entropi ca h), bin i cng c th
xy ra c, nu yu t cn li ln p hn (tc
trong trng hp bin i thu nhit
v
trong trng hp c s gim entropi ca h).
Mt hm s trng thi c chn gp hai iu kin trn li, l hm s nng
lng t do G, c nh ngha nh sau:
3.1
33
Vi mt bin i xc nh:
3.3
Vi mt bin i xc nh:
3.5
Tm li:
2. Vi phn ca hm th ng nhit ng p G
T biu thc G = H - TS
=> dG = dH - TdS - SdT (2.36)
m H = U + pV
=> dH = dU + pdV + Vdp
Vi kh l tng:
35
(2.39)
3.8
[Cng thc trn p dng cho kh l tng, nhng c th p dng cho ha cht vi iu kin
nhit T, ha cht trng thi kh v coi nh l kh l tng].
Nu p1 = 1 atm
Vi 1 mol:
3.9
36
3.10
37
=>
3.11
3.12
bt c nhit no iu
y l h thc Gibbs - Helmholtz, h thc ny gip tnh
kin ng p, khi bit mt nhit xc nh v bit
ca qu trnh.
4. Nng lng t do mol chun
trong mt bin i, ngi ta cng chn trng thi chun
c th tnh bin thin
nh trng hp entalpi. Trng thi chun ca mt ha cht l dng bn nht ca ha cht
25oC, 1atm. V d trng thi chun thc ca carbon (25oC, 1atm) l carbon graphit
(than ch), ch khng phi l carbon kim cng.
Ngi ta qui c, nng lng t do ca n cht trng thi chun bng khng.
Da vo qui c ny, ngi ta xc nh c nng lng t do mol chun ca cc hp
cht. Nng lng t do mol chun c biu din bng k hiu
V d:
38
M:
Tnh c
[Cn c vo tr s entalpi mol chun v entropi mol chun ca cc cht]
Th T = 298 K
Tnh c
Di y l tr s nng lng t do mol chun ca mt s cht
Ha cht
Ha cht
298 K
298 K
Ag(r)
KJ/mol
0,00
Kcal/mol
0,00
H2O(k)
KJ/mol
- 228,60
Kcal/mol
- 54,64
AgCl(r)
- 109,70
- 26,22
H2O(l)
- 237,20
- 56,69
Al(r)
0,00
0,00
HCl(k)
- 95,27
- 22,77
Al2O3(r)
- 1576,40 - 376,77
HNO3(l)
- 79,91
- 19,10
C(r,graphit)
0,00
0,00
H2SO4(l)
- 689,90
- 164,90
CO(k)
- 137,30
- 32,81
CH3COOH(l)
- 392,50
- 93,80
CO2(k)
- 394,40
- 94,26
Hg(l)
0,00
0,00
CH4(k)
- 50,79
- 12,14
Hg(k)
+ 31,80
+ 7,59
CH3Cl(k)
- 58,60
- 14,00
K(r)
0,00
0,00
CH3OH(l)
- 166,20
- 39,73
KCl(r)
- 408,30
- 97,59
CO(NH2)2(r)
- 197,20
- 47,12
K2SO4(r)
- 1316,40 - 314,62
CO(NH2)2(aq)
- 203,80
- 48,72
N2(k)
0,00
0,00
C2H2(k)
+ 209,00 + 50,00
NH3(k)
- 16,70
- 3,98
39
C2H4(k)
+ 68,12
+ 16,28
NH4Cl(r)
- 203,90
- 48,73
C2H6(k)
- 32,90
- 7,86
NO(k)
+ 86,69
+ 20,72
C2H5OH(l)
- 174,80
- 41,77
NO2(k)
+ 51,84
+ 12,39
C8H18(l)
+ 17,30
+ 4,14
N2O(k)
+ 103,60 + 24,76
Ca(r)
0,00
0,00
N2O4(k)
+ 98,28
+ 23,49
CaCO3(r)
- 1128,80 - 269,78
Na(r)
0,00
0,00
CaCl2(r)
- 750,20
- 179,30
Na2CO3(r)
- 1048,00 - 250,40
CaO(r)
- 604,20
- 144,40
NaHCO3(r)
- 851,90
- 203,60
Ca(OH)2(r)
- 896,76
- 214,33
NaOH(r)
- 382,00
- 91,40
CaSO4(r)
- 1320,30 - 315,56
NaCl(r)
- 384,00
- 94,79
Na2SO4(r)
- 1266,80 - 302,78
CaSO4.2H2O(r)
- 1795,70 - 429,19
O2(k)
0,00
0,00
Cl2(k)
0,00
0,00
PbO(r)
- 189,30
- 45,25
Fe(r)
0,00
0,00
S(r)
0,00
0,00
Fe2O3(r)
- 741,00
- 177,10
SO2(k)
- 300,40
- 71,79
H2(k)
0,00
0,00
SO3(k)
- 370,40
- 88,52
ri p dng bng tr s
40
ca cc ha cht tnh
. T tr s
tnh c c th
kt lun phn ng c xy ra c iu kin chun thc (250C, 1atm) hay khng.
Vi phn ng:
mA + nB -> pC + qD
3.13
V d 1:
Vi phn ng
NO(k) + 1/2 O2(k) -> NO2(k)
Cch 1: Tnh
ca phn ng da vo
ca cc cht
41
Cch 2: Tnh
ca phn ng da vo
V d 2: Tnh
ca phn ng
ca cc cht.
ca phn ng cn c vo tr s
42
ca cc cht.
trc ri tnh
sau:
43
3.14
[ Dng du - v c
S chuyn s xy ra t nhin nu
Vy vt cht chuyn t trng thi c cao n trng thi c thp tng t nh dng
in di chuyn t cc c in th cao n cc c in th thp, do m t ha th c
gn cho .
ng v mt phn ng ha hc, ha th cn do tim nng ca cu t cho phn ng ha
hc, v bin i ha hc iu kin ng nhit v ng p xy ra t nhin, i km theo vi
s gim nng lng t do v ha th th c ng gp vo nng lng t do.
44
3. Biu thc ca ha th
a. Kh l tng nguyn cht
Trong trng hp ny, ha th chnh l nng lng t do mol ca cu t i nguyn cht.
Nu ly
bng atm, ta c:
3.16
(2.49)
3.18
Vi:
3.19
45
a).
u ng trong tt c mi bin i.
b).
u ng trong tt c mi bin i.
Cu 2. Tnh q,
p sut 1atm.
46
a) NO(k) +
f) Ca(r) +
ca bin i trn.
a) Ca(r) +
c) NO(k) +
Cho bit:
Cu 8. a) Tnh
Cu 9. Gii thch du ca
Cu 10. Tnh q,
nhit bc hi ca
48
Cu 11. Tnh
cho bin i:
49
Cu 13. D on du ca
a) Ca(r) v Mg(r)
b) H2O(k) v H2S(k)
c) PCl3(k) v PCl5(k)
d) Cl2(k) v F2(k)
50
e) Br2(l) v I2(r)
Cu 16. a) Th hnh (a hnh) l g?
Cc d kin v hai cht th hnh ca phosphor sau:
51
(effusion) ca
cng nh ch to bom nguyn t.
chim
c vn tc r r ln hn hi
=0. iu ny c ng khng?
b) Tnh trong mt bin i ng nhit v bt thun nghch c trng thi u v trng thi
cui ging nh cu (a)
52
c) Tnh
xy ra vi
nh th no?
bn hn Ciclohexan dng tu
p sut 1atm
54
55
Chng 4
CN BNG HA HC
Phn ng
c gi l phn ng cn bng hay thun nghch
khi n xy ra theo hai chiu ngc nhau trong cng mt iu kin. Do , phn ng cn
bng xy ra khng hon ton, ngha l sau phn ng khng nhng thu c sn phm (C,
D) m cn c c cc tc cht (A, B).
V d: Vi phn ng ester ha gia acid acetic
CH3-COOH + CH3-CH2-OH
vi ru etilic
CH3-COO-CH2-CH3 + H2O
Nu ly 1mol
cho tc dng vi 1mol
th sau khi phn ng t
mc cn bng (coi nh phn ng xong), ta thu c 2/3 mol ester
mol ru
Phn ng cn bng
c gi l t trng thi cn bng khi
trong cng mt n v thi gian nu c bao nhiu phn t tc cht (A, B) mt i do tham
gia phn ng thun to sn phm (C, D) th cng c by nhiu phn t tc cht (A, B)
c to tr li t phn ng nghch, lc vn tc phn ng thun v vn tc phn ng
nghch bng nhau, lc ny nng cc cht trong phn ng khng thay i na.
Cn bng ha hc c gi l cn bng ng v thc ra lun lun c phn ng thun
v nghch xy ra nhng do lng cc cht trong h phn ng khng thay i khi phn ng
t trng thi cn bng nn phn ng c coi nh xong. Hn na, c th lm thay i
trng thi cn bng ca phn ng bng cch thay i cc yu t nh nng cc cht, nhit
, p sut.
I. NH LUT TC DNG KHI LNG
nh lut ny do Gulberg, Waage (Na Uy) a ra nm 1864, nhm xc nh trng
thi cn bng ca mt phn ng cn bng.
1. Trng hp cn bng gia cc kh c th xem nh kh l tng
a. Hng s cn bng KC
56
Xt phn ng cn bng:
Gi
ln lt l hng s vn tc ca phn ng thun v nghch. Gi s phn
ng thun cng nh phn ng nghch u thuc loi n gin (ngha l phn ng ch xy ra
trong mt giai on, bc phn ng ring phn ca mi tc cht bng h s t lng nguyn
ti gin ng trc mi tc cht trong phn ng).
Vn tc phn ng thun l:
v1 = k1[A][B]
Vn tc phn ng nghch l:
v-1 = k - 1[C][D]
Gi s lc bt u phn ng, ch c A, B hin din. Vn tc phn ng thun lc
u rt ln, vn tc phn ng nghch
bng khng. Phn ng cng xy ra lu, nng
cc tc cht A, B cng gim
, nng cc sn phm C, D cng tng
.
Nh vy, gim dn theo thi gian, cn
tng dn theo thi gian. Sau mt thi
gian vn tc phn ng thun v1 s bng vn tc phn ng nghch
, lc ny phn ng t
trng thi cn bng, phn ng c coi nh xong.
v1 = v- 1
=> k1[A][B] = k_ 1[C][D]
=>
V
l cc hng s vn tc phn ng, ch ty thuc nhit (v ty thuc bn cht
ca phn ng), cho nn ng vi mt nhit xc nh (v mt phn ng xc nh), ta c:
57
pC + qD
b. Hng s cn bng KP
Hng s cn bng ny lin h n p sut ring phn ca ha cht th kh lc cn
bng (lc t trng thi cn bng).
[p sut ring phn ca mi cu t ca hn hp c th tch chung l V l p sut m
cu t y c khi n ng ring mt mnh v cng chim th tch V ca hn hp cng
nhit ].
58
Xt phn ng:
Gi PA, PB, PC, PD ln lt l p sut ring phn ca cc kh A, B, C, D c th xem
, ln lt l s mol ca A, B, C, D hin din
nh kh l tng lc cn bng
trong th tch V ca h phn ng (bnh phn ng) lc cn bng nhit T (oK).
T ta c:
Thay [A], [B], [C], [D] vo biu thc ca hng s cn bng KC:
(4-3)
Hng s cn bng ny lin h n phn s mol (phn mol, phn mol) ca cc cht
trong phn ng.
[Phn s mol (phn mol hay phn mol) x ca cu t i trong hn hp gm nhiu cu
t l t s gia s mol ca i vi tng s mol ca cc cu t c trong hn hp.
Xt phn ng:
Gi P l p sut ca hn hp kh lc cn bng; xA, xB, xC, xC ln lt l phn s mol
ca A, B, C, D lc cn bng.
Vi
Th
ca phn ng:
60
Ch thch:
- Ngi ta ch rng trong biu thc ca cc hng s cn bng lin h n kh nu trn, ta
khng ch n cc cht lng v cht rn.
V d:
- Vi phn ng:
CaCO3(r)
CaO(r) + CO2(k)
NH4Cl(r)
HCl(k) + NH3(k)
HCl(k) + NH3(k)
NH4Cl(r)
Th hng s cn bng l Kp =
- Hng s cn bng K cng ln, phn ng cng thin v chiu thun, hng s cn bng K
cng nh phn ng cng thin v chiu nghch
61
- Vi phn ng:
pC(dd) + pD(dd)
62
Vi
ca phn ng
pC(k) + qD(k)
Trong
(4-13)
Khi phn ng t trng thi cn bng p sut P, nhit T th:
63
pC(dd) + qD(dd)
trng thi chun thch hp, ngi ta cng chng minh c h thc:
64
C+D
vn gi nguyn tr s c
(khng i) th
phi tng, nn phn ng cn bng s di i
theo chiu lm gim A, to ra thm C, D cho n khi no cc nng mi t c tr s
nh th no cho:
65
C+D
(4-16)
Vi
* Nu
T:
67
* Nu
T:
* P tng
hn).
* P gim
hn).
V d:
khi p sut gim, phn ng s thin v chiu to sn phm.
3. nh hng ca nhit
Trong mt phn ng cn bng, khi tng nhit mc cn bng s di i theo chiu
chng li s tng nhit tc l chiu lm nhit h xung, chiu thu nhit. Tri li, khi
h nhit mc cn bng s di i theo chiu lm nhit tng ln, chiu ta nhit.
V d: vi phn ng:
, nn phn ng ta nhit theo chiu to SO3
vy khi h nhit th cn bng s di i theo chiu to ra thm SO3. Tuy nhin, trn
thc t, ta khng th h qu thp nhit v lc by gi, vn tc phn ng s qu nh, phn
ng xy ra rt chm, khng c li v phng din thi gian.
* Cch tnh nhit phn ng
ca phn ng cn bng:
68
H = Ea1 - Ea - 1 > 0
iu kin ng p, ta c:
Theo Arrhnius:
k1 = A1e-Ea1/RT
k_1 = A_1e-Ea-1/RT
Trng hp ny
69
Vi
gim ngha l khi T tng, ph hp vi s kin
cn bng di i theo chiu thu nhit khi nhit tng.
70
pC(k) + qD(k)
71
BI TP CHNG 4
Cu 1. Cho phn ng cn bng:
H2(k) + I2(k)
2HI(k)
Cu 4. Vi phn ng:
2CH3I(k) -> CH3-CH3 (k) + I2(k)
biu thc vn tc phn ng l:
v = k [ CH3-I ]
a) Hy cho bit biu thc vn tc ca phn ng nghch.
b) Tnh gi tr
CH3-CH3(k) + I2(k)
300oC.
CH3I(k)
CH3 - CH3(k)
73
I2(k)
20,5
- 84,67
62,24
254,6
229,5
260,58
(KJ/mol)
(J/K. mol)
Coi
R = 8,315 J/mol.K.
ca cc phn ng sau:
2NO(k) + Cl2(k)
b) Zn(r) + CO2(k)
ZnO(r) + CO(k)
c) MgSO4(r)
MgO(r) + SO3(k)
N2(k) + O2(k)
d) 2NO(k)
e) CoO(r) + H2(k)
f) NOBr(k)
Co(r) + H2O(k)
NO(k) +
g) 2SO2(k) + O2(k)
h) SO2(k) +
O2(k)
i) N2(k) + 3H2(k)
j) BaCO3(r)
Br2(k)
2SO3(k)
SO3(k)
2NH3(k)
BaO(r) + CO2(k)
74
2SO3(k)
b) CO(k) + H2O(k)
H2(k) + CO2(k)
c) COCl2(k)
CO(k) + Cl2(k)
d) N2(k) + 3H2(k)
e) 2NO2(k)
2NH3(k)
N2O4(k)
Cu 7. Xem qu trnh:
Cl2(k)
2Cl(k)
B(k) + C(k)
300oC, Kp = 11,5atm
500oC, Kp = 33 atm
a) Phn ng trn thu nhit hay ta nhit?
b) Gi s phn ng trn xy ra trong mt giai on th nng lng kch ng Ea ca phn
ng c tr s ti thiu bng bao nhiu?
Ly
75
H2(k) + CO2(k)
H2O(k) + CO(k)
Cu 10. S nhit phn carbamat amonium c biu din bng phng trnh:
a) Tr s
CO(k) + Cl2(k)
76
e) Tnh h s phn ly
l t s gia s
c lc u)
phn t
a) Tnh
ln lt l 20,72 v
ca phn ng:
Kt lun.
b) Tnh
Tnh t s
. Kt lun.
c) Khi cho acid nitric long tc dng vi kim loi ng ngoi kh tri th nhn thy hin
tng g? Da vo kt qu trn gii thch.
CO(k)
- 26,42
(Kcal.mol- 1)
77
CO2(k)
- 94,05
Pb(r)
0
PbO(r)
- 52,40
- 32,81
- 94,26
- 45,25
6,95
8,76
6,34
11,07
-1
298 K
p
(Kcal.mol )
(cal.K- 1.mol- 1)
a) Tnh
PbO(r) + CO(k)
Pb(r) + CO2(k)
c) Tnh
b)
Gi s
CO(k) + H2O(k)
ng c th tch
Tnh:
a)
b) p sut tng qut lc cn bng.
c) S mol ca mi loi ha cht sau khi cn bng t c.
d)
79
c) 2SO3(k)
2SO2(k) + O2(k)
80
K-L
K-R
L- K
L-L
L-R
R-K
R-L
R-R
-Sa
10-5 - 10-7
<10-7
Khng bn
Bn
82
Gelatin
NaCl tan trong nc
Thp
Rn
Rn
Rn
Nc ng
Soda
Lng
Lng
Rn
Kh
Lng
Lng
H2 tan trong Pd
Rn
Kh
Rn
83
Nu tip tc thm ng vo dung dch, ta thy ng tip tc tan ra, dung dch by
gi s cha mt lng ng nhiu hn ban u. Nhng nu tip tc thm ng n mt
lc no ta thy ng khng th ha tan thm c na mt nhit xc nh, lc
ny ta c dung dch nc ng bo ha v lc ny lng ng c trong dung dch bng
tan ca n. Tng qut ta hiu nh sau:
- Dung dch cha bo ha l dung dch m cht tan c th tip tc tan thm.
- Dung dch bo ha l dung dch m cht tan khng th tan thm c na mt nhit
xc nh.
- tan l lng cht tan c vo dung dch to ra mt dung dch bo ha mt nhit
xc nh.
Nu nng nhit dung dch ln cao hn, ng s tip tc ha tan . Khi lm ngui
dung dch v nhit ban u t0C th lng ng d so vi tan nhit t0C s kt
tinh tch ra khi dung dch v c s hnh thnh tr li dung dch bo ha. Trong mt s
trng hp, qu trnh kt tinh c th xy ra lp tc hoc s xy ra khi ta thm vo vi
tinh th ca cht tan, hoc lc dung dch. Dung dch cha mt lng cht tan vt qu so
vi tan c gi l dung dch qu bo ha, Sir l dung dch nc ng qu bo ha
m chng ta thng gp.
2. Thnh phn ca dung dch
Do thnh phn ca dung dch c th thay i nn mi quan h v lng ca cc cht
trong dung dch phi c xc nh r rng v c nhiu cch khc nhau xc nh mi
quan h .
a). Nng phn trm khi lng (%)
S gam cht tan trong 100 gam dung dch.
V d 5.1. Dung dch NaOH 20% ngha l c 100g dung dch th c 20g NaOH tan trong
.
b). Phn mol
84
85
87
Ty qu trnh no chim u th m gi tr
qu trnh ha tan thu nhit hoc ta nhit.
phi ln v c du (+) do
cng rt
vi cc phn t H2O.
Tuy nhin y cha th gii thch c ti sao NaCl tan tt trong nc. Theo
nguyn l II ca nhit ng lc hc mt qu trnh xy ra t nhin l mt qu trnh tin n
88
mt trng thi xo trn cao hn. Do NaCl tan tt v tuy phi cung cp mt nng lng
nh nhng trng thi dung dch t xo trn ln hn rt nhiu so vi ban u, kt qu l
c s hnh thnh dung dch NaCl khi ha tan NaCl vo nc. Cc kt qu thu c y
hon ton ph hp vi qui lut kinh nghim v tan l <Cc cht c cng tnh phn cc
th ha tan tt vo nhau>.
Bng 5.3. Yu t nng lng ca qu trnh hnh thnh dung dch
t cc cht tan v dung mi khc nhau
Bn cht ca cc cht
DH1
DH2
DH3
(+)
ln
(+)
nh
(+)
ln
(+)
ln
(-)
ln
(-)
nh
(+)
nh
(+)
nh
(-)
nh
nh
(+)
ln
(+)
nh
(-)
nh
ln
(+)
Kt qu
nh
(+)
ln
Mi lin h gia p sut v nng kh tan trong dung dch c th hin qua
phng trnh:
P = kC.
Vi P l p sut ring phn ca kh tan trn b mt dung dch.
C l nng ca kh tan trong dung dch
k l hng s c trng ca mi loi dung dch.
y l phng trnh ton hc ca nh lut Henry, n th hin ni dung sau: <lng
kh tan trong dung dch t l vi p sut ring phn ca n>.
iu quan trng cn phi ch l nh lut Henry ch ng trong trng hp kh tan
khng phn ng vi dung mi, v d: ng vi trng hp kh O2 tan trong nc, nhng
khng ng vi trng hp HCl tan trong nc v y xy ra s phn ly ca HCl.
K = 32 l.atm/mol.
Khi m np, CO2 trong dung dch thot ra v t n trng thi cn bng vi p sut
ca
atm,
91
do
92
93
94
Trong trng hp cht tan bay hi, thng gp i vi cc dung dch lng-lng l
tng, phng trnh m rng ca dnh lut Raoult c dng.
Vi:
Hnh 5.5. S ph thuc ca p sut hi ca dung dch cha cht tan bay hi theo
phn mol ca dung mi v cht tan trong trng hp l tng v c xy ra sai lch
1: p sut hi dung dch. 2: p sut ring phn ca B. 3: p sut ring phn ca A.
i vi cc dung dch m tng tc gia cht tan- cht tan, dung mi-dung mi,
cht tan- dung mi c cng bn cht th tnh cht ca dung dch cng gn vi tnh cht ca
dung dch l tng. Trong trng hp ny cht tan ch lm nhim v pha long dung mi
v ngc li.
V d 5.8. Dung dch benzen-toluen chng c cng bn cht l khng phn cc.
Entanpy ha tan coi nh bng 0, dung dch ny rt gn dung dch l tng v c th xem l
dung dch l tng.
Trong mt s trng hp dung mi c th c nhng i lc c bit i vi cht tan,
v d nh to c lin kt hydro i vi cht tan, lc ny kh nng ha hi ca cht tan
cng nh dung mi trong dung dch u gim v do p sut hi ca dung dch nh hn
so vi tnh ton bng phng trnh Raoult, ta c s sai lch m, v d: dung dch aceton
trong nc c sai lch m v xy ra lin kt hydro gia aceton v nc.
phn cc, chng tng tc vi nhau rt yu. Entanpy ha tan c gi tr (+)xy ra s sai lch
dng.
Bng 5.4. Bng tm tt tnh cht ca cc loi dung dch khc nhau
Gii:
Khi ha tan vo nc, 1 mol Na2SO4 phn ly cho 2 mol Na+ v 1 mol SO42-, do s tiu
phn tan trong dung dch tng ln 3 ln nn cng s ng vi s mol l:
98
Nhit si (C)
100,0
76,5
ks0C.Kg/mol
0,51
5,03
Nhit
0
-22,99
kd0C.Kg/mol
1,86
3,00
61,2
80,1
46,2
34,5
208,0
3,63
2,53
2,34
2,02
5,95
-63,5
5,5
-111,5
-116,2
179,8
4,70
5,12
3,83
1,79
40
99
V d 5.12. Mt dung dch c iu ch bng cch ha tan 18,00g Gluc trong 150,00g
nc. Dung dch c nhit si l 100,340C. xc nh phn t lng ca Gluc, bit hng
s nghim si ca nc l 0,510C.Kg/mol.
Gii:
c). h nhit ng c
Ngi ta nh ngha nhit ng c ca mt cht lng l nhit m lc p
sut hi ca pha lng bng vi p sut hi ca pha rn, c th i vi nc tinh cht c
nhit ng c l 00C (chnh xc l 0,00990C) ng vi p sut hi bo ha ca nc
v nc lng l 0,006atm. Vic ha tan cht tan vo nc s lm cho dung dch c nhit
ng c thp hn nc tinh cht, bi v s hin din ca cht tan trong nc s lm cho
p sut hi ca nc trong dung dch thp hn p sut hi ca nc , do ti nhit
ny dung dch khng th ng c v khng c s bng nhau ca p sut hi gia pha lng
v pha rn. Nu ta h nhit , p sut hi ca pha rn gim nhanh hn pha lng, kt qu s
dn n s cn bng p sut hi ca 2 pha lng v rn v lc ny dung dch s ng c.
Do cht tan lm h nhit ng c ca nc, nn cc cht nh NaCl, CaCl2
thng c ri trn va h hoc ng trnh s ng bng trong ma ng cc nc
Chu u, d nhin vi iu kin nhit bn ngoi khng qu thp.
100
101
. Khi lng
V d 5.13b. Ha tan 0,546g thyroxin (mt loi hocmon ng vt) vo 15,0g benzen. Dung
dch thu c c h nhit ng c l 0,2400C. xc nh phn t lng ca thyroxin.
Gii:
Khi 2 cht lng tip xc nhau qua mng bn thm, c s chuyn cc phn t dung
mi t dung mi tinh cht sang dung dch v ngc li. Do trong dung dch c xy ra s
tng tc gia cc phn t cht tan v dung mi nn tc chuyn cc phn t dung mi
t dung dch vo dung mi tinh cht s nh hn tc ca qu trnh ngc li. Kt qu l
s phn t dung mi s chuyn vo dung dch nhiu hn, lm tng th tch dung dch. S
gia tng th tch dung dch, s to nn mt p sut c tc ng lm tng vn tc ca qu
trnh chuyn cc phn t dung mi t dung dch tr li dung mi tinh cht. Khi vn tc ca
hai qu trnh ny bng nhau, h t cn bng v th tch dung dch khng gia tng c
na. T iu ny cho thy p sut thm thu cng ph thuc vo nng cht tan trong
dung dch. i vi cc dung dch long mi lin h c biu din bng phng trnh:
dng quan trng ca s thm thu l to ra my lc mu cho nhng bnh nhn b bnh
thn. Mu c cho chy qua mt ng lm bng cellophane, ng vai tr mng bn thm,
ng c t trong dung dch ra (dialyzing). Dung dch ny cha cc ion cng nh cha
cc cht tan c nng bng nng ca chng trong mu, do s thm thu cc cht thy
s thm qua mng i vo dung dch v do mu c lc sch. Dung dch c p sut
thm thu nh nhau gi l dung dch ng trng. Cc cht lng bm vo mu phi ng
trng vi cht lng trong mu.
Nu t bo c ngm vo dung dch u trng, ngha l dung dch c p sut thm
thu ln hn cht lng trong t bo, th t bo s b co li do s mt nc. Ngc li, nu t
bo c ngm vo dung dch nhc trng, tc dung dch c p sut thm thu nh hn
cht lng ca t bo, t bo s b trng phng v v ra do s thm nhp ca nc. Khi
p tht, c bng mui, chng ta to ra mt dung dch u trng so vi dung dch trong
t bo vi khun do xy ra qu trnh loi nc khi cc t bo ca vi khun lm vi khun
b co rt li v cht, nn chng ta c th dng mui bo qun tht, c...
By gi nu chng ta cho nc tinh cht tip xc vi dung dch nc mui thng
qua mt mng bn thm v tc ng ln dung dch nc mui mt p sut ln hn p sut
thm thu ca dung dch nc mui th s xy ra qu trnh thm thu ngc ngha l nc
s chuyn t dung dch vo nc tinh cht. ng dng ny c ngha thc tin ln. Cc
my kh mui xch tay ng dng nguyn tc trn cho php lc c 5 lt nc t nc
bin trong 1 gi, ngha l c th cu sng 25 ngi.
BI TP CHNG 5
Bi 1.
Hng s phn b ca SO2 gia nc v CHCl3 bng 0,953. Hi phi cn bao nhiu
nc vo 1 lt dung dch SO2 trong CHCl3 tch c 25% SO2.
Bi 2.
200C; CH3OH (Me) v C2H5OH (E) c p sut hi = 96 v 44 mmHg. Xc nh
thnh phn hi trn dung dch c hnh thnh t nhng th tch bng nhau ca 2 ru.
Cho bit: khi lng ring ca 2 ru ldMe = 0,7915 v dE = 0,7894
Bi 3.
Hng s phn b ru etylic (C2H5OH) gia CCl4 v H2O bng 0,0244. Tnh nng
ru ca mi lp, nu 0,1 mol C2H5OH ru phn b gia 300ml H2O v 500ml CCl4.
104
Bi 4.
tan ca I2 trong H2O 250C l 0,34 g/l. H s phn b I2 gia CS2 v H2O l
590. Tm lng I2 cn li trong 100ml dung dch I2 trong nc sau khi lc dung dch ny
vi 100ml dung dch CS2.
Bi 5.
Thm vo 500ml dung dch I2 trong te cha 1,7272 g I2 mt th tch 200 ml dung
dch I2 trong glyxerin cha 2,0726 g I2. Xc nh nng mol/lit cc dung dch I2 cn bng
, bit hng s phn b ca I2 gia glyxerin v te l 0,2.
105
l hai hp phn ca h,
- Trong dung dch mui n trong nc th mui n (NaCl) v nc (H2O) l hai hp phn
ca h nhng cc ion
ion
cng nh
c. Cu t (Cu t c lp)
Cu t hay cu t c lp l s hp phn ti thiu m qua c th xc nh c thnh
phn ca c h [ hay t cc hp phn t nht ny c th bit c cc hp phn khc ca c
h ].
V d:
- Dung dch nc ng th s cu t l 2 v cn phi c nc v ng mi to c dung
dch ny.
- Mt bnh cha hn hp hai kh
l h gm hai hp phn nhng l h c mt
cu t v trong h c phn ng ha hc xy ra gia hai hp phn trn, thnh phn ca
chng khng c lp m ph thuc nhau.
hoc
ca h trn.
nn ch cn bit c
) th c
107
th c 4 cu t v c mt
(6-1)
V d:
- Xem h:
NH4Cl(r)
NH3(k) + HCl(k)
PNH3 = PHCl
=> S cu t cn l: 3 - 2 = 1
- Nu ch nung nng CaCO3 lc u, ta cng ch c mt biu thc lin h
nn s cu t ca h vn l 2. H thc
(n: s mol) khng c tnh v CaO(r) v
CO2(k) hai pha khc nhau. Tht vy, nhit xc nh, PCO2 c tr s xc nh m
khng ph thuc vo iu kin
trong 3 ha cht hin din.
CaCO3(r)
CaO(r) + CO2(k)
A v B ca h nu
th cu t i s di chuyn mt cch bt thun nghch t A n B.
Ngha l vt cht di chuyn mt cch t nhin t vng c ha th cao n vng c ha th
thp tng t nh dng in di chuyn t vng c in th cao n vng c in th thp.
Do , mi cu t trong cc pha cn bng nhau th ha th ca cu t ny trong cc pha
phi bng nhau ].
3. Qui tc pha
Qui tc pha do nh bc hc M Gibbs a ra nm 1876, n biu din s lin h
gia s pha (F), s cu t (C) v bc t do (f) ca mt h.
Gi X l tng s thng s trng thi ca h.
Y l s phng trnh lin h gia cc thng s trng thi.
Th s bc t do f ca h l:
f=X-Y
. S thng s trng thi nhit F pha l F.
. S thng s trng thi p sut F pha l F.
. S thng s trng thi v thnh phn ca C cu t F pha l CF.
Vy tng s thng s X ca h l:
X = F + F + CF = 2F + CF.
S phng trnh lin h cc thng s trng thi trn gm:
- iu kin cn bng nhit :
110
- iu kin tng thnh phn cc cht trong mt pha phi bng 100% => c F phng trnh
(v mi pha c 1 phng trnh).
Nh vy, tng s phng trnh Y l:
Y = (F - 1) + (F - 1) + C(F - 1) + F
Y = 3F + CF - C - 2
Bc t do f l:
f=X-Y
f = 2F + CF - (3F + CF - C - 2)
T :
f=CF + 2
(6-2)
(6-3)
111
(6-4)
kh tch ra khi c cn hay chng ct nhm kt tinh n hay ly n ra khi h. Phng php
trn cng gp kh khn khi nghin cu hp kim, thy tinh, dung dch... Do , c mt
phng php khc cho php xc nh bn cht v thnh phn ca cc pha c trong h m
khng cn tch n ra. Phng php ny c gi l phng php phn tch ha l.
Phng php phn tch ha l nghin cu s ph thuc cc tnh cht vt l ca h
vo nhng thng s trng thi ca h nh nhit T, p sut P, thnh phn x. Ta c hm
s:
(6-5)
113
(6-6)
(6-7)
t:
=> T, P ng bin.
114
- Nu th tch cht lng nh hn th tch cht rn (cht ny khi nng chy c s co th tch
hay gim th tch), th:
115
V d: Nc c p sut hi bo ha bng
17,5 mmHg 20oC
760 mmHg (1atm) 100oC
2 atm 120oC
4 atm 143oC
(6-8)
(6-9)
Vi s si (s bc hi):
(6-11)
Vi s thng hoa:
(6-12)
117
(tung gc l
Tnh
ca clorur tert-butil.
Gii:
Phng trnh Clapeyron - Clausius ly tch phn ch p dng c trong khong nhit
nh v tht ra
ph thuc vo nhit T.
=> f = 3 - F
i vi h 1 cu t th s pha F nhiu nht c th
V
l 3.
=> S bc t do trn : f = 3 - F = 3 - 2 = 1.
Ngha l trn cc ng ny ch c th thay i t do 1 thng s nhit (hoc p
sut), thng s kia thay i tng ng theo, v h vn cn cn bng tn ti hai pha. Cn
im ba (0), s pha F = 3
=> S bc t do: f = 3 - F = 3 - 3 = 0
=> Ti y khng th thay i thng s nhit hay p sut c m ch c mt tr s xc
nh (0,0098oC; 4,58mmHg) nc tn ti ng thi 3 pha.
dc cc ng OA, OB, OC c th c gii thch khi da vo phng trnh
Clapeyron:
Cn c vo du ca
bin v cn c vo ln ca
120
tinh th H2O.
tinh th NaCl.
tinh th
122
123
124