Nguyen ly 1 Nhiet dong hoc.

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Nguyen ly 2 Chieu huong va gioi han cua qua trinh.ppt
 Bi ging

HA L
(PHYSICAL CHEMISTRY)
 CHNG 1
NGUYN L 1 CA NHIT NG HC
MC TIU CA NHIT NG HC
Nhit ng hc kho st s lin h gia cng
v nhit.
Nhit ha hc nghin cu nhng bin i Vt
l v Ha hc ca vt cht v phng din trao
i nng lng.
Gii quyt:
- Ha cht trn li phn ng ha hc?
- Phn ng thu nhit hay ta nhit?
- Phn ng trn vn hay ch mt phn v thnh phn ha
cht th no khi phn ng c th xem l ngng li, thnh
phn y c th thay i c trong iu kin th nghim
no?
MT S KHI NIM C BN
H thng (system) l bt c phn no ca v tr c
gii hn thng thy c trong phm vi ha hc ang
c kho st v phng din trao i nng lng.
Phn cn li hp thnh mi trng (surrounding) ngoi
i vi h thng.
- H m l h c kh nng trao i va cht va nng
lng vi mi trng ngoi, th tch ca h c th thay
i.

- H kn l h khng trao i cht nhng c kh nng

trao i nng lng vi mi trng ngoi, th tch ca
h c th thay i.

- H c lp l h khng trao i cht v nng lng vi

mi trng bn ngoi v c th tch khng i.
 MT S KHI NIM C BN
Trng thi: tp hp tt c cc tnh cht v m ca
h
Thng s trng thi: th tch (V), p sut (P), nhit
(T), nng (C), ni nng (U)
Thng s dung l thng s t l vi lng cht
nh: th tch, khi lng, nng lng C tnh
cht cng.
Thng s cng khng ph thuc lng cht
nh: nhit , p sut, nng , nht...
Hm trng thi l hm ca cc thng s trng
thi Y = f(T, P, n,)
MT S KHI NIM C BN
Trng thi ca h
V d : 1 lt dd HCl 0,1 M; 250C.
Cc thng s trng thi c lin h vi nhau
bng phng trnh trng thi
V d : Kh l tng PV = nRT P = nRT/V
Dung dch m = V.d
 MT S KHI NIM C BN
Trong qu trnh bin i trng thi, bin thin ca
hm trng thi ch ph thuc vo trng thi u v
cui ch khng ph thuc vo ng i.
A B

C
MT S KHI NIM C BN
- Mt bin thin hu hn t trng thi 1 n
trng thi 2:
1(Z1) 2 (Z2) Z = Z2 Z1
- Mt bin thin v cng b: dZ hay Z
- Trong mt chu trnh: Z =0
2
Z dZ Z
1
2 Z1 Z

1
Z dZ dZ 0
1
MT S KHI NIM C BN
TRNG THI CHUN
p sut chun 1 atm.
Nhit tu , thng chn 250C
Cht rn, lng - dng nguyn cht, bn
1atm, nhit T .
Kh kh nguyn cht, bn nht hoc thng
gp, Pkh = 1atm
Dung dch C = 1 mol/l
NI NNG (U)
U = Etnh tin + Equay+ Edao ng+ Eht,y + Enhn
MT S KHI NIM C BN
Khng xc nh chnh xc ni nng U.
Theo nhit ng hc, trong qu trnh bin i
trng thi ch cn xc nh U.
Ni nng ph thuc vo: bn cht, lng cht,
nhit , p sut, th tch
Ni nng ca kh l tng ch ph thuc vo
nhit U=f(T)
Ni nng l hm trng thi, l thng s dung .
MT S KHI NIM C BN
QU TRNH l con ng m h chuyn t
trng thi ny sang trng thi khc c s bin
i t nht mt thng s trng thi
MT S KHI NIM C BN
Qu trnh ng tch V=0
Qu trnh ng p P=0
Qu trnh ng nhit T= 0
Qu trnh on nhit l qu trnh khng trao
i nhit nhng c th trao i cng.
Qu trnh vi phn l qu trnh cc thng s
trng thi bin i v cng nh.
MT S KHI NIM C BN
Pha
L tp hp nhng phn ng th ca h

Ging nhau v thnh phn ha hc v tnh

cht ha l.

c phn cch vi cc pha khc bi b

mt phn chia pha.

H 1 pha: h ng th

H nhiu pha: h d th
 NHIT V CNG

- Nng lng l thc o vn ng ca vt

cht. ng vi nhng hnh thi vn ng khc
nhau ca vt cht chng ta c nhng hnh thi
nng lng khc nhau.

- Hai dng th hin ca nng lng ha hc l:

NHIT (Q) v CNG (W)
NHIT V CNG
- Nhit l thc o s chuyn
ng nhit hn lon ca cc
tiu phn.

- Cng l thc o s chuyn

ng c trt t c hng ca
cc tiu phn trong trng lc.
 NHIT V CNG
Qui c v du ca nhit v cng
- Nu h ta nhit th nhit c tr s m, q < 0
- Nu h thu nhit th nhit c tr s dng, q > 0
- Nu cng cung cp vo h thng c tr s dng, W > 0
- Nu cng phng thch t h thng c tr s m, W < 0
NHIT
Thang nhit Celsius (0C) k hiu t
Thang nhit Kelvin (K) k hiu T
T(K) = t (0C) + 273,15
NHIT DUNG (C) l nhit lng cn dng
nng nhit mt cht ln mt .
(khng c phn ng ho hc,khng c bin i
pha,khng c s thay i thnh phn ca h )

Q Q
C
Q Q

C
dT dt
dT dt
 Q
C
dT

Nhit dung ring (t nhit) [cal/g.] hay [J/g.]

Nhit dung mol [cal/mol.] hay [J/mol.]

Nhit dung mol ng p Cp ; Cp=a1+b1.T+ c1.T2
Nhit dung mol ng tch Cv; Cv=a2+b2.T+ c2.T2..
Cp v Cv l hm trng thi.
Nhit dung [cal/] hay [J/]
CNG
Cng dn n A=Png.dV
2
A P
1
ng .dV

Cng in A=E.dq

Cng b mt A=.dS
 NGUYN L 1 NHIT NG HC
BIU THC TON HC

Nu qi v wi l nhit v cng trao i gia h vi mi

trng ngoi theo ng qu trnh i th qi v wi ring r
thay i theo ng qu trnh nhng tng s qi + wi lun
lun l mt hng s khng ty thuc ng qu trnh m
ch ty thuc vo trng thi u v trng thi cui ca h
m thi U = Q + A
Do quy c v du nn biu thc nguyn l 1 c vit li
nh sau: U = Q - A
NHIT NG CA MT S QU TRNH

a. Qu trnh ng tch
V= hng s, dV=0
QV = U
b. Qu trnh ng p
P = hng s, dP=0
Qp = H

Nu h l kh l tng th pV=nRT
Wp = nRT
Up = Qp nRT
NHIT NG CA MT S QU TRNH

Qu trnh gin n ng nhit KLT

nh lut Joule: ni nng ca kh l tng ch ph
thuc vo nhit
UT = 0
 NH LUT HESS
Trong qu trnh ng p hay ng tch, nhit
phn ng ch ph thuc vo trng thi u v
trng thi cui m khng ph thuc vo trng
thi trung gian ca qu trnh
QV = U v Qp = H
i vi cc qu trnh ca kh l tng:
H = U + RTn hay Qp = Qv + nRT
H = U + PV ( enthalpy) hm trng thi
 NH LUT HESS

H qu nh lut Hess

Hnghch = - Hthun

Hphn ng = Hs(sp) Hs(tc)

Hphn ng = Hc(tc) Hc(sp)

Hs : nhit sinh, nhit to thnh

Hc : nhit chy, thiu nhit
NH LUT HESS
 Phng trnh Kirchhoff

aA + bB cC +dD
T2

H H (c.CpC d.CPD ) (a.CpA b.CpB )dT

0
T2
0
T1
T1

Phng trnh Kirchhoff , khi Cp f(T)

T2

H 0T2 H 0T1 Cp .dT H 0T1 Cp (T2 T1 )

T1

H thay i theo nhit khng nhiu.

 Bi ging

HA L
(PHYSICAL CHEMISTRY)
 CHNG 2

NGUYN L 2
CHIU HNG V GiI HN CA QU TRNH
1. S bin i t nhin
- L mt bin i xy ra mt cch t nhin m khng cn tc
ng ca yu t bn ngoi.
- Mt bin i t nhin khng nht thit phi xy ra nhanh.
- Chiu ca bin i t nhin c th ph thuc vo nhit .
Xt v mt nng lng cc qu trnh ha hc c xu hng t
din ra khi c s gim enthalpy.
1. S bin i t nhin

- Tuy nhin, mt s qu trnh vn din ra khi enthalpy bng

0 hoc ln hn 0.

- Do , ch da vo s bin i ni nng (hay Enthalpy

H) th khng th tin on c chiu phn ng.
tin on chnh xc chiu hng ca phn ng ta cn
phi xem xt mt yu t na l MT TRT T ca
h (c th hin qua gi tr ENTROPY k hiu l S)
Qu trnh thun nghch
- L qu trnh c th tin hnh
theo hai chiu ngc nhau, cc
trng thi trung gian ging
nhau, khng gy nn bin i g
trong h cng nh mi trng.

- S thay i l rt nh qu
trnh thun nghch.
 Qu trnh bt thun nghch

- Qu trnh bt thun nghch khng th thc hin qu

trnh ngc li khi h thng thay i.

- Tt c cc qu trnh t pht u l bt thun nghch.

- Tt c cc qu trnh xy ra thc t l bt thun nghch.

2. Entropy
Entropi (S) l thc o hn lon ca trng
thi ca h thng. Cc bin i xy ra t nhin
th i km vi s tng entropy.
Entropy l mt hm trng thi
Cho 1 h thng: S = Scui - Su
Nu S > 0 h thng mt trt t hn
S < 0 h thng trt t hn
 Tnh cht ca entropi
- Mi cht c gi tr antropi ring ca mnh, phn t
cng phc tp th antropi cng ln.

- Antropi ca mi cht 00K u bng 0.

- Antropi ca cc cht tng theo s tng ca nhit .

- Antropi l mt hm trng thi, do s tng antropi

ca qu trnh tnh theo cng thc:
 Entropy tiu chun

S0
298
L gi tr Entropy ca 1 mol cht o iu
kin iu kin tiu chun c p sut 1 atm
(760 mm Hg), v nhit bng 250C
(298.15K)
n v tnh ca S0298 l cal/mol.K hoc
J/mol.K
 S bin i entropy
Nhn chung, entropy tng
khi:
+Kh c to ra t dng
lng v rn
+ Dung dch hoc cht ha
tan c to ra t cht rn
+ S lng phn t kh
tng
+ S lng phn t tng
Mt s quy tc dnh gi s bin thin ca entropy
(S) trong cc qu trnh ha hc

- So tng (So > 0) khi cc cht chuyn t trng thi

rn sang lng hay kh.
V d: H2O (r) H2O (l) So > 0
- So tng (So > 0) khi mt cht rn hay lng ha tan
vo nc hay dung mi.
- So gim (So < 0) khi mt cht kh ha tan vo
nc hay dung mi.
- So tng khi M (khi lng phn t) tng.
V d: So(O2) < So(O3)
 Mt s quy tc dnh gi s bin thin ca entropy
(S) trong cc qu trnh ha hc

- So gim cht rn mng lin kt cng ha tr, So tng

khi lin kt c mt phn tnh kim loi.
V d: So C(diamond, 2.44) < So C(graphite, 5.69)
- So tng t l vi yu v mm ca lin kt gia
cc nguyn t.
- So tng theo phc tp ca phn t.
3. Nguyn l II
Trong iu kin nng lng khng i, h c
khuynh hng chuyn t trng thi c
mt trt t thp sang trng thi c mt
trt t cao hn.
- Nu h l c lp v qu trnh l thun nghch

- Nu h l c lp v qu trnh l bt thun nghch

Entropy l tiu chun xt chiu trong h c lp

Nu: dS > 0 Qu trnh t xy ra

dS = 0 Qu trnh t cn bng

Nu xt chiu h khng c lp, ta c th c lp

h bng cch ghp thm mi trng vo h

S(tng cng) = S(h) + S(mi trng)

Entropy h c lp chiu hng ca qu trnh
H c lp = h kho st + ngun nhit bn ngoi
Sh c lp = (Sh kho st + Sngun nhit) 0

Nu qu trnh din ra l thun nghch (cn bng) th

entropy ca h c lp l khng i
S(h c lp) = 0

Trong h c lp din ra qu trnh khng thun

nghch th nhng qu trnh ny lm cho entropy ca
h c lp tng ln
S(h c lp) > 0
 Entropy mt s qu trnh
- Nu qu trnh thun nghch (TN):

- mt nhit xc nh:

- Khi h chuyn t TT1 sang TT2:

- Nu qu trnh l bt thun
nghch (BTN) hay t xy ra
Entropy mt s qu trnh thun nghch
- Qu trnh ng p: S = Cpln(T2/T1)

- Qu trnh ng tch: S = Cvln(T2/T1)

- Qu trnh ng nhit: S = QTN/T

Nu l kh l tng:
ST = nR.ln(V2/V1) = nR.ln(P1/P2)
V V2 > V1 nn S > 0, ngha l qu trnh t xy ra.
 nh hng ca mi trng
V d:
Phn ng: 2Mg (r) + O2 (k) 2MgO (r)
c So = -217 J.K-1.mol-1 < 0
Tuy nhin phn ng vn xy ra v:
Ho << 0 (Ho = -1202 kJ.mol-1).
Ta c:
S(tng cng) = S(h thng) - H/ T
= -217 J.K-1.mol-1+ 1202.103 J.mol-1/298 K
= 3.81.103 J.K-1.mol-1 > 0
4. Nng lng t do G
S(tng cng) = S(h) - H/T
Hay: -T.S(tng cng) = H T.S(h)
Biu din khi nim bin i ca entropy tng bng
mt i lng gi l nng lng t do Gibbs:
G = -TS(tng cng)
Ta c: G = H - TS
Nh vy, thay v xem xt s bin i ca entropy
tng cng cu c h thng v mi trng xung
quanh, nay ta ch xt s bin i ca nng lng t
do G ca bn thn h thng d on mt bin
i c xy ra t nhin hay khng.
Nng lng t do tiu chun
L bin thin nng lng t do ca qu trnh to thnh 1
mol cht iu kin tiu chun (250C, 1 atm) xut pht t
cc n cht bn. Go298

- n v ca G0 l Kcal/mol hoc KJ/mol

- Cc n cht bn iu kin tiu chun c G0 = 0
- Gi tr G0 ca cc cht c xc nh bng thc nghim.
- C th tra cu cc i lng G0 trong cc s tay ha hc.

Nng lng t do ca phn ng ha hc

G = Gsn phm - Gtc cht
Nng lng t do tiu chun
- Nng lng t do tiu chun Go chnh l thc o bn
tng i ca mt hp cht so vi cc nguyn t to thnh
n.
- Nu Go < 0 ti mt nhit xc nh th c ngha l cc
nguyn t c khuynh hng t nhin to thnh hp cht ti
nhit tc ti iu kin chun hp cht ny l bn hn
cc nguyn t to thnh nn n.
- Cn nu Go > 0 th iu ngc li s xy ra, hp cht c
khuynh hng t nhin l phn hy tr li thnh cc nguyn
t.
Nng lng t do tiu chun
Ta c: G = Go + RTlnK
Ti cn bng: 0 = Go + RT lnK
hay Gor= RT lnK
V d: Tnh Kp ti 25oC cho cn bng sau
N2O4 (k) 2 NO2 (k)
Ta c: Go = 2 Go (NO2,k) - Go(N2O4,k)
= 2 51.31 97.89 kJ.mol-1
= +4.73 kJ.mol-1
M lnKp = -Go / RT
= -(4.73 kJ.mol-1/ 2.4780 kJ.mol-1) = -1.91
Suy ra Kp = 0.15
Chuyn i n v o lng
Chuyn i n v o lng
1 J = 1 N.m= 1 Pa.m3 = 1 kg. m2. s-2
1 erg = 10-7 J
1 cal = 4,184 J
1 eV = 1,6021892 x 10-19 J
L.atm = 101,325 J
cm-1 = 1,986477 x 10-23 J
1 Pa = 1 N.m-2 = 1 kg. m-1. s-1
1 bar = 105 Pa
1 atm = 101,325 Pa
1 atm = 760 torr
1 psi = 6897, 7572 Pa
R = 8,31441 J.K-1mol-1 = 1,987 cal. K-1mol-1 = 0,0831441 L.bar. K-
1.mol-1 = 0,0820568 L.atm.K-1.mol-1