Bi ging mn C s l thuyt Ha hc

PHN I: NHIT NG HO HC

Mun xt mt phn ng ho hc c thc hin c hay khng cn bit:
- iu kin no th phn ng xy ra v xy ra n mc no?
- Phn ng xy ra nh th no? Nhanh hay chm? Nhng yu t no nh hng
n tc phn ng?
Khi tr li c c hai cu hi ny, ngi ta c th iu khin c phn ng,
tm c iu kin ti u thc hin phn ng, nhm t hiu qu cao nht.
Cu hi th nht l i tng ca nhit ng ho hc, cn cu hi th hai l i
tng ca ca ng ho hc.
Nhit ng hc l b phn ca vt l hc, nghin cu cc hin tng c v nhit,
cn nhit ng ho hc l b phn ca nhit ng hc nghin cu nhng quan h nng
lng trong cc qu trnh ho hc.


Bi ging mn C s l thuyt Ha hc

CHNG I: P DNG NGUYN L TH NHT
CA NHIT NG HC VO HO HC

I. MT S KHI NIM M U
1. Kh l tng:
- Cht kh c coi l l tng khi m khong cch gia cc phn t kh xa nhau,
c th b qua s tng tc gia chng v coi th tch ring ca cc phn t kh l
khng ng k (kh c p sut thp).
- Phng trnh trng thi ca kh l tng: nu c n mol kh p sut P, nhit T
v chim th tch V th: PV = nRT = RT
M
m
(1.1)
trong : m- khi lng ca kh, g
M: Khi lng mol ca kh, g
T Nhit tuyt i, K ( T = t
0
C +273)
R: Hng s kh l tng, ty theo n v ca P v V m c ga tr
khc nhau:
- Nu P (atm), V(dm
3
=l) R = 0,082 atm.l.K
-1
.mol
1

- Nu P (Pa=N/m
2
), V(m
3
) R = 8,314 J.K
-1
.mol
-1

1atm = 1,013. 10
5
Pa= 1,013. 10
5
N/m
2
= 760 mmHg
- Nu trong bnh c mt hn hp kh th mi kh gy nn mt p sut gi l p sut ring
phn ca kh v c k hiu l Pi .Tng tt c cc p sut ring phn bng p sut
chung P ca hn hp.Nu gi V l th tch chung ca hn hp kh ( bng dung tch bnh
ng th phng trnh kh kh l tng c dng:

V
RT n
P P
i
i

= = (1.2)

i
n : Tng s mol kh trong hn hp.
p sut ring phn Pi ca kh i trong hn hp c th tnh:

V
RT
n P
i i
= hoc Pi= NiP vi Ni =
i
i
n
n

(1.3)
2. H v mi trng
- H: H l i tng cn nghin cu cc tnh cht nhit ng hc. i km vi khi nim
h l khi nim mi trng xung quanh, l ton b phn cn li ca v tr bao quanh h.
H c phn cch vi mi trng xung quanh bng mt mt thc hay tng tng.
- C 4 loi h:
+ H c lp: l h khng trao i cht v nng lng vi mi trng
+ H m: l h trao i cht v nng lng vi mi trng.
Bi ging mn C s l thuyt Ha hc

+ H kn l h ch trao i nng lng vi mi trng
+ H khng trao i nhit vi mi trng c gi l h on nhit.
3.Quy c v du trong qu trnh trao i nng lng
Nng lng trao i gia h v mi trng c th l cng , nhit, nng lng in...
- H nhn nng lng: du (+)
- H nhng nng lng du ()
4.Trng thi ca h v cc thng s trng thi:
- Trng thi v m ca mt h c c trng bng nhng i lng xc nh nh: t
0
C, P,
V, C...Cc thng s ny c th o c, gi l cc thng s trng thi.
v d: gia s mol kh n, nhit T v p sut P ca mt h kh (gi s l kh l tng)
c mi quan h cht ch, c biu din bng phng trnh trng thi ca kh l tng
PV=nRT.
- C hai loi thng s trng thi: dung v cng
+ Thng s trng thi dung l nhng thng s trng thi t l vi lng cht, th d
th tch, khi lng.
+ Thng s trng thi cng khng t l vi lng cht, v d nhit p sut, nng
, nht.
5. Trng thi cn bng ca h
L trng thi ti cc thng s trng thi ca h khng i theo thi gian. VD phn ng
thun nghch CH
3
COOH + C
2
H
5
OH <=> CH
3
COOC
2
H
5
+ H
2
O t trng thi cn bng
khi nng ca 4 cht khng bin i .
6. Bin i thun nghch v bin i bt thun nghch
- Nu h chuyn t mt trng thi cn bng ny sang mt trng thi cn bng khc v
cng chm qua lin tip cc trng thi cn bng th s bin i c gi l thun
nghch.y l s bin i l tng khng c trong thc t.
- Khc vi s bin i thun nghch l s bin i bt thun nghch. l nhng bin i
c tin hnh vi vn tc ng k. Nhng bin i xy ra trong thc t u l bt thun
nghch.
7.Hm trng thi
- Mt hm F( P,V,T...) c gi l hm trng thi nu gi tr ca n ch ph thuc vo
cc thng s trng thi ca h m khng ph thuc vo cch bin i ca h.
- V d: n mol kh l tng:
+ trng thi 1 c c trng bng P
1
V
1
=nRT
1

+ trng thi 1 c c trng bng P
2
V
2
=nRT
2

PV l mt hm trng thi, n khng ph thuc vo cch bin i t trng thi 1
sang trng thi 2.
Bi ging mn C s l thuyt Ha hc

8.Cng v nhit: L hai hnh thc trao i nng lng.
Cng W (J, kJ)
Nhit Q (J, kJ)
Cng v nhit ni chung khng phi l nhng hm trng thi v gi tr ca chng ph
thuc vo cch bin i.
* Cng gin n ( cng chuyn dch)
W = - Pngoi.dV =-PndV (1.4)
W ph thuc vo Pn ( v h sinh cng nn c du -).
Nu qu trnh l hu hn => W =

2
1
dV P
n
(1.5)
Nu gin n trong chn khng Pn =0 W=0.
Nu gin n bt thun nghch: gin n chng li Pn

khng i:
P
n
= const (P
n
=P
kq
) W
btn
= -Pn(V
2
-V
1
) (1.6)
Nu gin n thun nghch: tc l P
n
=P
h
W
tn
=

2
1
V
V
n
dV P (1.7)
Nu kh l l tng v gin n ng nhit c :
P
n
= P
h
=
V
nRT
=>
1
2
ln
2
1
V
V
nRT
V
dV
nRT W
V
V
TN
= =


Vy W
TN
=- nRT ln
1
2
V
V
=- nRT ln
2
1
P
P
(1.8)

II. NGUYN L I P DNG VO HA HC
1. Khi nim ni nng (U)
Nng lng ca h gm 3 phn
- ng nng chuyn ng ca ton h
- Th nng ca h do h nm trong trng ngoi
- Ni nng ca h
Trong nhit ng ho hc nghin cu ch yu ni nng.
Ni nng ca h gm:
- ng nng chuyn ng ca cc phn t, nguyn t, ht nhn v electron (tinh
tin, quay..)
- Th nng tng tc (ht v y) ca cc phn t, nguyn t, ht nhn v electron.
Nh th ni nng (U) ca h l mt i lng dung , gi tr ca n ch ph thuc
vo trng thi vt l m khng ph thuc vo cch chuyn cht ti trng thi . N l
mt hm trng thi.
Bi ging mn C s l thuyt Ha hc

Ni nng ca h ph thuc vo bn cht, lng ca n, p sut. nhit ,th tch v
thnh phn.
i vi kh l tng ni nng ca h ch ph thuc vo nhit .
2. Pht biu nguyn l I ca nhit ng hc
Nguyn l I ca nhit ng hc v thc cht l nh lut bo ton nng lng:
Nng lng ca mt h c lp lun lun bo ton.
a.Tn ti mt hm trng thi U gi l ni nng. dU l mt vi phn ton phn.
b. S bin i ni nng U ca h kn chuyn t trng thi 1 sang trng thi 2 bng tng
i s ca tt c cc nng lng trao i vi mi trng trong qu trnh bin i ny (d
l bin i thun nghch hay bt thun nghch).
U = U
2
-U
1
= W
A
+ Q
A
=W
B
+ Q
B
=...=const
trong W l Q l cng v nhit lng m h trao i vi mi trng.
i vi mt bin i v cng nh
dU= Q W +
dU: vi phn ton phn
W v Q : khng phi l vi phn ton phn.
i vi mt bin i hu hn
Q W dU U + = =

2
1
(1.9)
Nu: + Trng thi u v cui nh nhau 0 = =

dU U --> W+Q=0
+ H c lp: W = Q = 0 --> U =0
3. Nhit ng tch, nhit ng p
a.Nhit ng tch.( V = const)
Xt 1 h kn, c T, V = const, h ch sinh cng c hc:
pdV W = v V = const 0 = = pdV W
Theo nguyn l I: dU= Q W +
Do : dU= Q v
v
const v
Q Q U = =

=
(1.10)
Qv l nhit ng tch, gi tr ca n ch ph thuc vo trng thi u v cui ca h.
b. Nhit ng p(P= const)
Xt h kn, thc hin c T, P =const, h ch sinh cng c hc:
W= ) (
1 2
2
1
V V P pdV =

U = U
2
-U
1
= W + Q

U
2
- U
1
= Qp-P(V
2
-V
1
) hay Qp = (U
2
+PV
2
) (U
1
+PV
1
)
Q
P
: Gi l nhit ng p
Bi ging mn C s l thuyt Ha hc

t H=U+PV
Ta c: Q
p
= H
2
-H
1
= H (1.11)
H c gi l entapi, n l hm trng thi v U v PV u l nhng hm trng thi.
III. NHIT PHN NG HO HC.
1. Nhit phn ng
L nhit lng thot ra hay thu vo khi phn ng xy ra theo ng h s t lng,
cht tham gia v sn phm cng mt nhit T.
c th so snh nhit ca cc phn ng cn ch r iu kin phn ng xy ra:
- Lng cc cht tham gia v sn phm to thnh theo h s t lng.
- Trng thi vt l ca cc cht
Vi mc ch ny ngi ta a ra khi nim trng thi chun. Trng thi chun ca
mt cht nguyn cht l trng thi l hc di p sut 101,325kPa(1atm) v nhit
kho st n bn nht.
V d: Cacbon tn ti hai dng th hnh l graphit v kim cng. 298K v di p
sut 101,325kPa, graphit l bin i th hnh bn nht do trng thi chun 298K ca
cacbon l graphit.
- Nu phn ng c thc hin P=const th nhit phn ng c gi l nhit phn
ng ng p Qp= H .
- Nu phn ng c c thc hin V=const th nhit phn ng c gi l
nhit phn ng ng tch Qv= U .
Phn ng ta nhit v phn ng thu nhit
- Phn ng ta nhit: l phn ng nhng nhit lng cho mi trng. Khi
P
Q H = <0 hoc
V
Q U = <0. V d phn ng ti vi
- Phn ng thu nhit: l phn ng nhn nhit lng t mi trng. Khi
P
Q H = >0 hoc
V
Q U = >0. V d phn ng nung vi..
Quan h gia nhit ng tch v nhit ng p:
( ) V p U pV U H
p
+ = + =
Qp= Qv+nRT (1.12)
Trong : n = s mol sn phm kh s mol cht kh tham gia phn ng.
R = 8.314 J/mol.K: hng s kh l tng
T: K
V d: C
6
H
6
(l) +
2
15
O
2
(k) = 6CO
2
(k) + 3H
2
O(l)
n= 6-7,5=-1,5.
C(r) + O
2
(k) = CO
2
(k)
n= 1- 1= 0
Bi ging mn C s l thuyt Ha hc

2. Nhit sinh chun ca mt cht:
L nhit ca phn ng to thnh 1 mol cht t cc n cht bn iu kin chun
(cht sn phm v cht phn ng phi l cc cht nguyn cht 1atm v gi P, T=const,
cc s liu nhit ng chun trong cc ti liu thng c xc nh nhit T=298
K).
K hiu
0
s T
H
,
(kJ.mol
-1
)
Nu T =298 =>
0
, 298 s
H
V d:
0
, 298 s
H (CO
2
)=-393,51(kJmol
-1
). N l nhit phn ng ca phn ng sau 25
0
C
khi atm p p
CO O
1
2 2
= =
Cgr + O
2
(k) = CO
2
(k).
C graphit l n cht bn nht ca cacbon 1 atm v 298K.
- T nh ngha trn ta suy ra nhit sinh chun ca n cht bn bng khng.
3. Nhit chy chun ca mt cht:
L nhit ca qu trnh t chy han ton 1 mol cht bng O
2
to thnh cc xit bn
nht ( vi ha tr cao nht ca cc nguyn t), khi cc cht trong phn ng u nguyn
cht P=1atm v gi T, P khng i (thng T=298K).

0
,c T
H (kJ.mol
-1
)
V d: ) (
4
0
, 298
CH H
c
=-890,34kJ.mol
-1
ng vi nhit ca phn ng sau 25
0
C v p=const
khi atm P P P
CO O CH
1
2 2 4
= = = .
CH
4
(k)+ 2O
2
(k) CO
2
(k) + 2H
2
O(l)
Tt c cc xit bn vi ha tr cao nht ca cc nguyn t u khng c nhit chy.
IV.NH LUT HESS V CC H QU
1.Pht biu: Hiu ng nhit ca mt phn ng ch ph thuc vo trng thi u v trng
thi cui ca cc cht tham gia v cc cht to thnh ch khng ph thuc vo cc giai
on trung gian, nu khng thc hin cng no khc ngoi cng gin n.

V d:
Cgr

+ O
2
(k) CO
2
(k)

Theo nh lut Hess:
2 1
H H H + = (1.13)
2.Cc h qu
CO(k) + 1/2 O
2
(k)
H
1
H
2
H
Bi ging mn C s l thuyt Ha hc

H qu 1: Hiu ng nhit ca phn ng thun bng hiu ng nhit ca phn ng nghch
nhng ngc du.:
n t
H H = (1.14)
H qu 2: Hiu ng nhit ca mt phn ng bng tng nhit sinh ca cc cht cui tr i
tng nhit sinh ca cc cht u.

= ) ( ) ( thamgia H m nph s H H
s s
(1.15)
Nu iu kin chun v T=298K th

= ) ( ) ( , , , thamgia H nphm s H H s s pu 298
0
298
0
298
0
(1.16)
T nh ngha ny suy ra: nhit sinh ca mt n cht bn vng iu kin chun
bng khng:
0
s T
H
,
(n cht) = 0.
V d: Tnh H
0
ca phn ng:
C
2
H
4
(k) + H
2
(k) --> C
2
H
6
298K?
Cho bit
0
298 s
H
,
ca cc cht (kJ.mol
-1
) nh sau:
C
2
H
4
(k): +52,30
C
2
H
6
(k): -84,68
Gii:
Ta c:
0
298
H =
0
298 s
H
,
(C
2
H
6
(k)) - [
0
298 s
H
,
(C
2
H
4
(k)) +
0
298 s
H
,
(H
2
(k))]
=-84,68-52,30-0
=-136,98kJ.mol
-1

H qu 3: Hiu ng nhit ca mt phn ng bng tng nhit chy ca cc cht u tr i
tng nhit chy ca cc cht cui.

= ) ( ) (

sp H tg H H
c c p
(1.17)
Nu iu kin chun v T=298K th

= ) ( ) ( , , , sp H tg H H c c p 298
0
298
0
298
0
(1.18)
3.Cc ng dng
* nh lut Hess v cc h qu ca n c mt ng dng rt ln trong Ho hc, n cho
php tnh hiu ng nhit ca nhiu phn ng trong thc t khng th o c.
V d1: khng th o c nhit ca phn ng Cgr + 1/2 O
2
(k) =CO(k) v khi t chy
Cgr ngoi CO (k) ra cn to thnh CO
2
(k) nhng nhit ca cc phn ng sau y o
c:
Cgr + O
2
(k) = CO
2
(k)
0
298
H =-393513,57 J.mol
-1

CO(k) + O
2
(k) = CO
2
(k)
0
298
H =-282989,02 J.mol
-1

tnh c nhit ca phn ng trn ta hnh dung s sau:
Bi ging mn C s l thuyt Ha hc

C
gr
O
2
(k)
1/2O
2
(k) +
+ CO
2
(k)
CO(k)
x=?

Trng thi u (Cgr+O
2
) v trng thi cui (CO
2
(k)) ca c hai cch bin i l nh nhau,
do theo nh lut Hess:
-393.513,57 = x - 282.989,02
x=-110507,81J.mol
-1

V d 2: Xc nh nng lng mng lui tinh th ca NaCl(r) bit
+ Nhit nguyn t ha Na(r)
Na(r) Na(h)
1
1
724 108

+ = mol J H . .
+ Nhit phn ly Cl
2
(k)
Cl
2
(k) 2Cl(k)
1
2
672 242

+ = mol J H . .
+ Nng lng ion ha Na(h)
Na(h) Na
+
(h) + e
1
3
528 489

+ = mol J H . .
+i lc i vi electron ca Cl(k)
Cl(k) + e Cl
-
(k)
1
4
192 368

= mol J H . .
+Nhit ca phn ng
Na(r) + 1/2 Cl
2
(k) NaCl
1
5
216 414

= mol J H . .
xc nh nng lng mng li tinh th NaCl ta dng chu trnh nhit ng Born
Haber:
Na(r) + 1/2 Cl
2
(k)
Na(h) + Cl(k)
NaCl(r)
Na
+
(h) + Cl
-
(k)
Trng
thi u
Trng
thi cui
1
H
3
H
4
H
5
H
x=?
1/2

Theo nh lut Hess ta c:
x H H H H H + + + + =
4 3 2 1 5
2 1/
x= ) / (
4 3 2 1 5
2 1 H H H H H + + +
x= -765.612J.mol
-1

V. S PH THUC HIU NG NHIT VO NHIT .NH LUT KIRCHHOFF
1. Nhit dung mol ca 1 cht
L nhit lng cn thit nng nhit ca 1 mol cht ln 1K v trong sut qu trnh
ny khng c s bin i trng thi(nng chy, si, bin i th hnh...)
Bi ging mn C s l thuyt Ha hc

- n v thng dng ca C l: J.K
-1
mol
-1

- Nhit dung mol ng p. Qu trnh c thc hin P=const.
dT
dH
T
H
C
p
P
=

= => dH=CpdT =>

=
2
1
2
1
dT C dH
P

==>

=
2
1
dT C H
P

-Nhit dung mol ng tch. Qu trnh c thc hin V=const.
dT
dU
T
U
C
v
v
=

= => dU=CvdT =>

=
2
1
dT C U
v

==>

=
2
1
dT C U
v

2.Nhit chuyn pha
-Chuyn pha: bay hi ,nng chy, ng c, thng hoa...
-
cf
H l nhit lng trao i vi mi trng khi 1 mol cht chuyn pha. P=const, khi
mt cht nguyn cht chuyn pha th trong sut qu trnh chuyn pha, nhit khng
thay i.
3. nh lut Kirchhoff
Xt 1 h kn, P=const.. Xt phn ng sau thc hin bng hai con ng:
n
1
A + n
2
B
n
1
A + n
2
B
n
3
C + n
4
D
n
3
C + n
4
D
1
H
a
H
2
H
b
H
T
1
T
2

Theo nh lut Hess ta c
b a
H H H H + + =
1 2



+ = + =
2
1
1
2
2 1 2 1
T
T
P P
T
T
P P a
dT C n C n dT C n C n H
B A B A
) ( ) (

+ =
2
1
4 3
T
T
P P b
dT C n C n H
D C
) (
T dT C n C n C n C n H H
B A D C
P P
T
T
P P
)] ( ) [(
2 1 4 3 1 2
2
1
+ + + =


=>

+ =
2
1
2 2
T
T
P T T
dT C H H => Cng thc nh lut Kirchhoff
Vi:

= ) ( ) ( tg C sp C C
P P P

Bi ging mn C s l thuyt Ha hc

iu kin chun(P=1atm) v T
1
=298 K c:

+ =
T
P T
dT C H H
298
0 0
298
0

Nu trong khong hp ca nhit => coi const C
P
=
0
th
) ( 298
0 0
298
0
+ = T C H H
P T

4.Mi quan h gia nng lng lin kt v nhit phn ng
C th quy uc nng lng lin kt (Elk) tng ng vi nng lng ph v lin kt hoc
hnh thnh lin kt.
y ta qui c E
lk
ng vi qu trnh ph v lin kt: nng lng lin kt l nng
lng ng vi qu trnh ph v lin kt do nng lng lin kt cng ln th lin kt
cng bn.
- Mt phn ng ho hc bt k v bn cht l ph v lin kt c v hnh thnh cc lin
kt mi do Hp c th c tnh qua Elk ca cc lin kt ho hc.
V d1: Ph v 1 mol thnh cc nguyn t c lp:
H
2
(k,cb) --> H(k,cb) + H (k,cb)
298K, p= 1atm => EH
-H
= +432kJ.mol
-1
=
0
298
H
Trong trng hp ny Elk coi nh hiu ng nhit ca qu trnh.
V d2: Xt phn ng N
2
(k) + 3H
2
(k) => NH
3
(k). Thc hin bng 2 con ng
N
2
(k) + 3H
2
(k)
2NH
3
(k)
H
2H(k) + 6H(k)
E
N-N
3E
H-H
-6E
N-H


H N H H N N
E E E H

+ = 6 3




Ti liu tham kho:

1. Nguyn nh Chi, C S L Thuyt Ha Hc, NXB GD, 2004.
2. Nguyn Hnh, , C S L Thuyt Ha Hc, Tp 2, NXB GD 1997.
3. L Mu Quyn, C S L Thuyt Ha Hc - Phn Bi Tp, NXB KHKT, 2000.