11/7/2017

TRNG I HC BCH KHOA H NI

VIN KHOA HC V K THUT VT LIU

NHIT NG HC

Ging vin: TS. Trn V Dim Ngc.

B mn: Vt liu Kim loi mu v Compozit
Email: ngoc.tranvudiem@hust.edu.vn

Chng 1: M u

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1.1. Gii thiu v Nhit ng hc

nh ngha

S chuyn ha nng lng gy ra bi cc qu trnh vt l v ha hc khc

nhau, s ph thuc ca chng vo iu kin tin hnh cc qu trnh (nghin
cu v c nhit).
L hm s c bn v ni nng v entrop S

Mun xt 1 phn ng ha hc c thc hin c hay khng:

- iu kin no th phn ng xy ra v xy ra n mc no.
-Phn ng xy ra nh th no? Nhanh hay chm? Cc yu t nh hng n
tc phn ng

1.2. Phng trnh trng thi kh l tng

Kh l tng

Cc lc tng tc, lc lin kt gia cc phn t (lc Van der Waals) hon
ton bng khng.
Th tch ring ca cc phn t kh l khng ng k

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1.2. Phng trnh trng thi kh l tng.

Kh l tng

Cht kh c coi l kh l tng nu tha mn cc gi thit sau:

+ Lc tng tc phn t ch ng k khi va chm
+ Mi phn t c coi nh mt cht im.
+ Cc phn t lun chuyn ng tnh tin hn lon, chng va chm vi nhau v
vi thnh bnh gy ra p sut. S va chm tun theo quy lutva chm n hi

1.2. Phng trnh trng thi kh l tng.

Thng s trng thi:

L cc i lng vt l dng m t cc trng thi khc nhau ca mt h

nhit ng
Thng s trng thi nhit ng: p sut P, th tch V v nhit T

Khi thay i cc thng s nhit ng th h s chuyn t trng thi ny sang

trng thi khc v ngi ta ni h thc hin mt qu trnh (qu trnh nhit
ng)

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1.2. Phng trnh trng thi kh l tng.

Phng trnh trng thi KLT

m l khi lng kh, MA l khi lng mol,

N l s phn t kh, V th tch kh, n l s mol
NA = 6,023.1023 ht s A-v-ga-r.
R: hng s kh; = 8,3143 J/mol.K ; 1,987 [cal/mol.K]; = 0,082[l.at/mol.K]

1.3. H v mi trng

H v m: Nhit ng hc ch nghin cu nhng h v m gm mt

s lng ln cc tiu phn (phn t, nguyn t, ion).

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1.3. H v mi trng

H c lp, h ng v h m

H m: l h trao i c vt cht v nng lng vi mi trng xung quanh.

H kn: h ch trao i nng lng vi mi trng xung quanh m khng trao
i vt cht.
H c lp: h khng tng tc vi mi trng xung quanh

1.3. H v mi trng

H ng th, d th

H ng th v d th, ng nht v khng ng nht

H ng th l h c tnh cht l ha hc ging nhau mi thi im ca h

(khng c s phn chia h thnh nhng phn c tnh cht ha l khc nhau).

H d th: l h c b mt phn chia thnh nhng phn c tnh cht ha l k

hc nhau

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Chng 2: Cc nh lut ca nhit ng hc

2.1. nh lut th nht ca NH

2.1.1. Quan h gia nhit v cng

Cng l i lng c trng cho phn nng lng trao i gia cc h

tng tc vi nhau m kt qu l lm thay i mc chuyn ng nh
hng ca mt h no .

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2.1. nh lut th nht ca NH

2.1.1. Quan h gia nhit v cng

Nhit lng l s o phn nng lng trao i gia cc h tng tc m kt

qu l lm thay i mc chuyn ng hn lon ca phn t trong cc h .

C: nhit dung ring

2.1. nh lut th nht ca NH

2.1.1. Quan h gia nhit v cng

Ging nhau: o phn nng lng trao i gia cc h sau qu trnh tng tc
Khc nhau:
- Cng lin quan n chuyn ng c hng, c trt t ca h.
- Nhit lin quan n chuyn ng hn lon ca tng phn t trong h

Qui c v du ca nhit v cng

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2.1. nh lut th nht ca NH

2.1.2. Ni nng v nh lut th 1

Ni nng:

Vi kh l tng, th nng tng tc phn t c b qua, v vy, ni nng ca

h kh l tng ng nng chuyn ng nhit ca cc phn t trong h.

2.1. nh lut th nht ca NH

2.1.2. Ni nng v nh lut th 1

nh lut 1:

Trong mt qu trnh bin i trng thi, bin thin ni nng ca h bng tng
cng v nhit lng m h nhn c trong qu trnh

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2.1. nh lut th nht ca NH

2.1.3. Cc qu trnh ng tch, ng p v enthalpy H

Qu trnh ng tch V = 0 A=0

Qu trnh ng p Pngoai = Pkhi = P

Qp : Nhit ng p

Enthalpy H:
t H = U + PV Qp = H2 H1 = H

2.1. nh lut th nht ca NH

2.1.3. Cc qu trnh ng tch, ng p v enthalpy H

Enthalpy H

Qp dH T2
Cp H n.Cp.dT
dT dT T1

T2
Cv v U n.Cv.dT
Q dU
dT dT T1

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2.1. nh lut th nht ca NH

2.1.3. Cc qu trnh ng tch, ng p v enthalpy H

Enthalpy H

Phn ng ta nhit Phn ng thu nhit

Cht ban u
Sn phm

Cht bn u
Sn phm

H = (H)sn phm - (H)cht u

2.1. nh lut th nht ca NH

2.1.3. Cc qu trnh ng tch, ng p v enthalpy H

Enthalpy H
nh lut Hess

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2.1. nh lut th nht ca NH

2.1.3. Cc qu trnh ng tch, ng p v enthalpy H

Enthalpy H

aA + bB = cC + dD ; Hp

Hp = [aHc (A) + bHc (B)] - [cHc (C) + dHc (D)]

Phng trnh Kirchhoff

T2
H H (c.CpC d.CPD ) (a.CpA b.CpB )dT
0
T2
0
T1
T1

2.1. nh lut th nht ca NH

2.1.3. Cc qu trnh ng tch, ng p v enthalpy H

Enthalpy H

3H2 (k) + N2(k) = H2 (k) + N2H4(k) H01 = 95,4 kJ

N2H4(k) + H2(k) = 2NH3(k) H02= -187,6 kJ

3H2(k) + N2(k) = 2NH3 (k) H03 = -92,2kJ

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2.1. nh lut th nht ca NH

Nhng hn ch

L I cha cho bit chiu din bin ca qtrnh truyn nhit.

Cha nu c s khc nhau trong qu trnh chuyn ha gia nhit lng
Q v cng A .
Cha cp n cht lng ca nhit

2.2. nh lut hai ca NH

2.2.1. Entropy S

Entropi l i lng c trng cho mi trng thi ca h.

Biu din t do, xo trn, mt trt t ca cc phn t (nguyn t) trong
h ang xt.

- Du = : qu trnh thun nghch

- Du > : qu trnh qu trnh khng thun nghch

Bin thin Entropi ca phn ng ha hc

So= So(sn phm) - So(ban u)

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2.2. nh lut hai ca NH

2.2.1. Entropy S

2.2. nh lut hai ca NH

2.2.2. S kt hp nh lut 1 v 2

L 1

L 2

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2.2. nh lut hai ca NH

2.2.2. S kt hp nh lut 1 v 2

Phng trnh c bn ca NH

G : th ng nhit, ng p (Nng lng t do Gibbs)

G < 0 : phn ng xy ra
G > 0 phn ng xy ra theo chiu nghch
G = phn ng t cn bng

2.2. nh lut hai ca NH

2.2.2. S kt hp nh lut 1 v 2

Phng trnh c bn ca NH

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2.2. nh lut hai ca NH

2.2.3. Pht biu nh lut 2

- Pht biu ca Clausius: Nhit khng th t ng truyn vt lnh hn

sang vt nng hn
- Pht biu ca Thompson: Mt ng c khng th sinh cng, nu c
ch trao i nhit vi ngun nhit duy nht.

2.3. nh lut 3:

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 ph
n ca h )

C Q Q [cal/] hay [J/]

dT 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.

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2.3. nh lut 3:
Nhit dung mol ca 1 cht
L lng nhit cn thit nng nhit ca 1 mol cht ln 1K v trong sut qu tr
nh ny c s bin i trng thi (nng chy, si, bin i th hnh)
n v: J.K-1.mol-1

Nhit dung mol ng p: P = const

Nhit dung mol ng tch: V= const

2.3. nh lut 3:
2.3.2. Enthapy H

Nhit phn ng: l lng nhit ta ra hay thu vo khi phn ng xy ra ng theo
t l cht tham gia phn ng v sn phm phn ng theo T

- Nu P = const: nhit phn ng ng p Qp = H.

- Nu V = const : nhit phn ng ng tch QV = U
- Phn ng ta nhit : H = Qp < 0 hoc U = Qv <0
- Phn ng thu nhit: H = Qp > 0 U = Qv > 0

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2.3. nh lut 3:

2.3.2. Enthapy H

Hiu ng nhit tiu chun : H0T = H0298

- P= 1 atm

- T = const, (25 oC hoc 298 oK )

- Cht u v sn phm trng thi chun v cng nhit .

2.3. nh lut 3:
2.3.2. Enthapy H

nh lut Hess:

Trong cng mt iu kin , hiu ng nhit ca mt phn ng bng tng hiu

ng nhit ca cc phn ng trung gian.

H1 H1 = HB -HA
A B
H1 = HB HC+HC-HA
H2 H3
H1 = H3 + H2
C

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2.3. nh lut 3:
2.3.2. Enthapy H
nh lut Lavoiser La Place

2.3. nh lut 3:

Entropy S ca 1 cht kt tinh hon ton nhit 0oK = 0

L hm trng thi khi tnh ton entapy tuyt i

Cng thc Gibbs-Helmholtz

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Chng 3: Quy tc pha, gin pha

3.1. Quy tc pha

Pha:

+ Tp hp cc phn ng th ging nhau trong h

+ Gii hn vi nhng phn khc bi b mt phn cch

Cht hp phn:

+ Nhng cht ho hc trong h

+ C th tch ra, tn ti dng c lp ngoi h.

S cu t:

S cht hp phn ti thiu cn thit xc nh thnh phn mt pha bt k ca h.

S cu t = S cht hp phn - S phng trnh ho hc lin quan gia cc cht

hp phn

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3.1. Quy tc pha

S bc t do: C = K +2 -F

Thng s ti a c th tu thay i m vn khng lm thay i

s pha trong h, khng lm bin mt hoc xut hin pha mi.

K: S cu t c lp

F: S pha trng thi cn bng nhit ng (To, P, V)

3.2. Gin h 1 cu t

S bc t do: C = K +2 -F

K = 1 ; C = 3 -F

Gin trng thi ca C Gin trng thi ca nc

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3.2. Gin h 1 cu t

H mt cu t khng c s bin i thnh phn nn gin pha ca n ch

c mt trc, trn nh du nhit chy (kt tinh) v cc nhit bin
i th hnh.

- Lp phng tm mt A1, Fe, trong khong nhit

911 1392 C.
o

- Lp phng tm khi A2, Fe Tphong n 911oC,

Fe trong khong nhit t 13921539oC

3.3. Gin h 2 cu t

S bc t do: C = K +2 F; K = 2 ; C = 4 -F

H bc hai trng hp to thnh tecti n gin (a),

Cu t A c hai dng th hnh, nhit chuyn ho gia chng ng vi im P (b),
Cu t B c hai dng th hnh, nhit ca chng ng vi im R v im I (c)

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3.3. Gin h 2 cu t

S bc t do: C = K +2 F; K = 2 ; C = 4 -F

H bc hai trng hp to thnh dung dch rn v hn

3.3. Gin h 2 cu t

S bc t do: C = K +2 F; K = 2 ; C = 4 -F

ng aeb c gi l ng lng
- Arr/ B c gi l ng rn.
+Vng nm pha trn ng lng, h ch gm
mt pha l dung dch lng A B (LA-B) ;
+ Vng nm pha di ng rn, h bao gm
2 pha rn : rn A v rn B (RA, RB) ;
- E l im eutecti
Gin (T-x) ca
h hai cu t cn bng lng - rn

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3.3. Gin h 2 cu t

S bc t do: C = K +2 F; K = 2 ; C = 4 -F

- ae1 l ng kt tinh cht rn A,

- e1de2l ng kt tinh cht rn D,
- e2b l ng kt tinh cht rn B,
-e1 v e2 im eutecti ca h: A- D v h
D B.

H 2 cu t to hp cht ha hc bn

3.3. Gin h 2 cu t Gin trng thi Fe-C

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3.4. Gin h 3 cu t

S bc t do: C = K +2 F; K = 3 ; C = 5 -F

3.4. Gin h 3 cu t

S bc t do: C = K +2 F; K = 3 ; C = 5 -F

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3.4. Gin h 3 cu t

S bc t do: C = K +2 F; K = 3 ; C = 5 -F

H bc 3 tng tc thun nghch

Chng 4 :Kh nng v mc bin i cn bng ca

phn ng ha hc

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4.1. Cn bng ha

v1A1 v2 A2 ....v1, A1, v2, A2, ....

v . 0
i i
(4.1)

i i0(T)RTlnPi (12.2) (4.2)

v 0v TRTlnP0
i i i
0
i i

lnP
(T) i i
0 (4.3)
i i
RT

ln p ln p lnk (12.4)
i i i
i
p
(4.4)

4.1. Cn bng ha
, ,
PAV1,1 .PAV22 V
lnP lnP ....lnPA2 lnPA2 ....ln V1 V2 Pi i lnKp (4.5)
V1,
A1,
V2,
V2
A2,
V2
PA1 .PA2
, ,
PAV1,1 .PAV2,2 (4.2)- tch p sut ring phn
(PiVi ) Kp kp - hng s cn bng phn ng
PAV11 .PAV22

i ioTRTlnCi KC CiVi (4.6)

hay i i0Tlnxi KX x Vi
i (4.7)

Ci l nng m/l, cn xi l nng phn mol.

Kc v Kx l hng s cn bng biu din nng mol/l v phn mol.

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4.2 Phng php Temkin-Svatroman GT0

d lnKp H0
d RlnKp H0 d GT0 H0
dT RT2 2 dT T T2
dT T

GT0 RTlnKp
(4.2)
GT0
T
GT0 T H0
0 298 T2 dT
G298
d

298

T T
GT0 H298
0
TS298
0
T dT2 CpdT (4.8)

298T 298

4.2 Phng php Temkin-Svatroman GT0

T T
G H TS T 2 CpdT
0
T
0
298
dT
0
298
(4.8)
298T 298

Cp a0 a1.103T a2.106T2 a2.105T2

GT0 H298
0
TS298
0
Ta0M0 a1M1 a2M2 a2M2
0
ai Mi
2
GT0 H298
TS298
0 (4.9)
io

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4.3 Tnh GT0 theo nhit ng quy c

GT H0
0 0

T / H298

0
H00 GT0 HT0 TST0
/ GT H298
0 0 T
T

/ GT H298 HT H298 ST0

0 0 0 0
GT H0 HT H0 ST0
0 0 0 0

T T T T

s.phamban.u f / u GY H0 GT H0
0 0 0 0

T T T
GT0 H00 GT0 H00

GT0 H00 T
T T T

H0 GT
0 0

GT0 H298
0
T/ T T
H00 / H298

0
RlnKp
0
T T
/ H298
0
GT
T T

4.4 Mc bin i cn bng

nh ngha- l phn trm mol hay l % khi lng cht tham gia phn ng b
tiu hao to thnh sn phm, khi t cn bng.
c th nguyn l phn mol hay % mol.

- l ch tiu nh gi hiu sut ca phn ng ha hc

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4.4 Mc bin i cn bng

Phn ng tng qut:
bBk + dDL + eEE + = cCk + sSL + tTR +.. (4.10)
Trong :
b, d, e, r, s, t.- cc h s hp thc ca phn ng ho hc
B, D, E, R, S, T.- cc cht tham gia v sn phm phn ng
K, L, R..- trng thi kh, lng, rn

kcb e b .bC.pdS.Sd
t c c s s
aT p C
aE pB.B.pD.D
(4.11)

kcb k{a .k{p.k

ai - hot ca cu t L, R
L,R
pi- p sut ring phn cu t kh;K
ka - hng s cn bng cu t R, L;
Kp cu t kh;
K - hng s cn bng hot vit cho cu t kh

4.4 Mc bin i cn bng

m

kp kn p
ni
(4.12)

xi ni Pi
ni P
Pi xi P Kp Kx Pm m
P
K K
xi ni Kx Kn m p n ni
ni
(4.13)

ni
m

Kcb Ka Kn K P
ni
(4.14)

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4.4 Mc bin i cn bng

cCr + bBk = sSk + Dr

FeOr + COk = Fer + CO2(k)
Lc u b 0
Khi cn bng b-b. s.

kn ss
; m s b

bb b

ni s bbntro

K s b
s
p
bb bs b ntro

Bi tp

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Bi tp

Tnh th ng p GT0 ca phn ng: 2CH4 = C2H2 + 3 H2 1000oK v 1500oK

theo th ng p rt gn trong bng GT0 74280 cal/ mol

Chng 5: Gin Elligham

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T
GTo H298
o
CPdT
298

GTo Ho I.T a.lnT b.T C

2

2 2T

GTo AB.T.lgT C.T GTo AB.T

Gin Ellingham cho php ta xc nh c ngay nhng kim

loi no to nn cc hp cht bn vng so vi kim loi khc

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Gin Ellingham i vi cc xit kim loi

G v T ca phn ng
MeR + O2=MeO2R

GTo R.T.lnPO2 RTln 1 RTlnPO2

PO2

1/10

G Ellingham i vi cc clorua kim loi:

2x/yMe + Cl2=2/yMexCly
Kp=1/PCl2

GTo R.T.lnPO2 RTln 1 RTlnPO2

PO2

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G Ellingham i vi cacbit sunfua kim loi:

G Ellingham i vi cc sunfua kim loi:

ng dng ca gin Elligham:

Xc nh hng s cn bng ca phn ng oxi ha KL:

Xc nh s bin i pha
Nghin cu cc phn ng chy carbon:
Phn ng hon nguyn oxit KL bng kh CO
Biu din th cn bng trong h thng KL-O2-C (M-O-C)

1/10

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ng dng ca gin Elligham:

Xc nh hng s cn bng ca phn ng oxi ha KL:

GTo Ho T.STo RT.lnKP RT.lnPO2 (cb,T)

Xc nh s bin i pha

1/10

ng dng ca gin Elligham:

Nghin cu cc phn ng chy carbon:

Cgr + O2 =CO2 (1) G1o 942000,2.T (cal)

2Cgr + O2 =2CO (2) G2o 5340041,9.T (cal)

2(1)-(2)=(3) 2CO+O2=2CO2 (3) 2G1o G2o G3o 135000
41,5.T (cal)
(2)-(1)=(4) Cgr +CO2 =2CO Q (phn ng Ben-Budoa)

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ng dng ca gin Elligham:

Phn ng hon nguyn oxit KL bng kh CO

Xt cn bng 2CO+O2=2CO2 (3) G3o 135000 41,5.T (cal)

PCO2
RT.ln 2 2 2RT PCO RT.lnPO2cb
PCO2PO2 PCO2 cbC

Me + O2=MeO2(5)

Me + 2CO=Me+CO2(6)

ng dng ca gin Elligham:

Biu din th cn bng trong h thng KL-O2-C (M-O-C)

=> Bin thin ca ng ng p O2 theo lg(Pco2/Pco)

CD: Go 116003,57.T (cal) RT.lg PCO2
CO cb
P
PCO2
AB: G3 54505,8.T (cal) RT.lg
o
PCO cb

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ng dng ca gin Elligham:

Chng 6: NH qu trnh phn l oxit v hp cht KL

6.1 i lc ha hc:
i lc ha hc ca KL vi O2 hay cc kim khc (Cl, S,) c t
rng bi kh nng kt hp O2 tao ra xit hay bn vng ca l
in kt Me-O

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Chng 6: NH qu trnh phn l oxit v hp cht KL

6.2. p sut phn ly:

MexOy v Me pha ngng t (R,L)

C=K-+2 = 2-3+2=1Po2=f(T)

Chng 6: NH qu trnh phn l oxit v hp cht KL

6.2 iu kin phn ly oxit hay xi ha KL:

2/yMexOy 2x/yMe + O2

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