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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.
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Bi ging mn C s l thuyt Ha hc
m
RT
M
(1.1)
ni RT
V
n i
(1.2)
: Tng s mol kh trong hn hp.
n
RT
hoc Pi= NiP vi Ni = i
n i
V
(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.
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Bi ging mn C s l thuyt Ha hc
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Bi ging mn C s l thuyt Ha hc
= - Pngoi.dV =-PndV
(1.4)
Nu qu trnh l hu hn => W = Pn dV
1
(1.5)
(1.6)
Wtn= Pn dV
(1.7)
V1
V2
V
nRT
dV
=> WTN = nRT
= nRT ln 2
V
1
V
V1
V
Vy WTN =- nRT ln
V2
P
=- nRT ln 1
V1
P2
(1.8)
Ni nng ca h
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Bi ging mn C s l thuyt Ha hc
i vi mt bin i hu hn
2
U = dU = W + Q
(1.9)
Q = Q
(1.10)
v = const
W= pdV = P(V 2 V1 )
1
= U2-U1 = W + Q
Bi ging mn C s l thuyt Ha hc
H=U+PV
Ta c: Qp= H2-H1 = H
(1.11)
(1.12)
15
O2(k) = 6CO2(k) + 3H2O(l)
2
n= 6-7,5=-1,5.
Bi ging mn C s l thuyt Ha hc
-1
0
0
V d: H 298
, s (CO2)=-393,51(kJmol ). N l nhit phn ng ca phn ng sau 25 C
H T0,c (kJ.mol )
-1
0
V d: H 298
ng vi nhit ca phn ng sau 250C v p=const
,c (CH 4 ) =-890,34kJ.mol
V d:
Cgr
H 1
O2(k)
CO2(k)
H 2
H = H 1 + H 2
2.Cc h qu
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(1.13)
Bi ging mn C s l thuyt Ha hc
(1.14)
(1.15)
(1.16)
C2H4(k): +52,30
C2H6(k): -84,68
Gii:
Ta c:
0
H 298
0
0
0
= H 298
, s (C2H6(k)) - [ H 298, s (C2H4(k)) + H 298, s (H2(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.
H p = H c (tg ) H c (sp)
(1.17)
(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 O2(k) =CO(k) v khi t chy
Cgr ngoi CO (k) ra cn to thnh CO2(k) nhng nhit ca cc phn ng sau y o
c:
0
Cgr + O2(k) = CO2(k) H 298
=-393513,57 J.mol-1
0
=-282989,02 J.mol-1
CO(k) + O2(k) = CO2(k) H 298
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Bi ging mn C s l thuyt Ha hc
Cgr +
O2(k)
CO2(k)
x=?
CO(k) + 1/2O2(k)
Trng thi u (Cgr+O2) v trng thi cui (CO2(k)) ca c hai cch bin i l nh nhau,
do theo nh lut Hess:
-393.513,57 =
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)
H1 = +108.724 J .mol 1
Na(r) Na(h)
+ Nhit phn ly Cl2(k)
H 2 = +242.672 J .mol 1
Cl2(k) 2Cl(k)
H 3 = +489.528 J .mol 1
+i lc i vi electron ca Cl(k)
Cl(k) + e Cl-(k)
H 4 = 368.192 J .mol 1
+Nhit ca phn ng
Na(r) + 1/2 Cl2(k) NaCl H 5 = 414.216 J .mol 1
xc nh nng lng mng li tinh th NaCl ta dng chu trnh nhit ng Born
Haber:
Trng
thi u
1/2
Na(h) + Cl(k)
H5
NaCl(r)
Trng
thi cui
x=?
H3
H4
Na+(h) + Cl-(k)
x= H 5 (H1 + 1 / 2H 2 + H 3 + H 4 )
x= -765.612J.mol-1
V. S PH THUC HIU NG NHIT VO NHIT .NH LUT KIRCHHOFF
Bi ging mn C s l thuyt Ha hc
dH = CP dT
==> H = C P dT
1
dU
U
Cv=
=
T v dT
U = Cv dT
==> U = C v dT
1
n1A + n2B
n3C + n4D
T2
H b
Ha
H1
n1A + n2B
n3C + n4D
T1
T2
T2
T1
T2
T2
T1
T2
T1
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Bi ging mn C s l thuyt Ha hc
H = H
0
T
0
298
+ C P0 dT
298
3EH-H
2NH3(k)
-6EN-H
2H(k) + 6H(k)
H = E N N + 3 E H H 6 E N H
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Bi ging mn C s l thuyt Ha hc
CHNG II: NGUYN L II CA NHIT NG HC CHIU V GII HN
T DIN BIN CA QU TRNH
M U
Trong t nhin, cc qu trnh l hc v ho hc xy ra theo chiu hon ton xc nh.
- Nhit t truyn t vt nng sang vt lnh hn
- Kh t truyn t ni c p sut cao n ni c p sut thp
- Cc phn ng ho hc t xy ra, v d: Zn + HCl --> ZnCl2 + H2
Cn cc qu trnh ngc li th khng t xy ra c.
Nguyn l I cho php tnh nhit ca cc phn ng nhng khng cho php tin
on chiu v gii hn ca qu trnh
Nguyn l II cho php gii quyt cc vn ny.
I.NGUYN L II. HM ENTROPY
1.Nguyn l II (Tiu chun xt chiu ca qu trnh)
- Tn ti mt hm trng thi gi l entropi (S).
- nhit T khng i, trong s bin i v cng nh, h trao i vi mi trng mt
nhit lng Q th bin thin entropi ca qu trnh c xc nh:
Q
Nu l bin i thun nghch: dS = TN
T
QbTN
T
Tng qut
dS
T
2
* Ch :
V S l hm trng thi --> S ch ph thuc vo trng thi u v trng thi cui, tc
2
l:
S BTN = S TN =
1
QTN
T
2
S TN = S BTN >
1
Qbtn
T
==> QTn> QBTN : Nhit qu trnh thun nghch ln hn nhit qu trnh bt thun nghch.
+ xc nh Sbtn , trc ht hnh dung mt qu trnh thun nghch c cng trng
thi u v trng thi cui vi qu trnh bt thun nghch, sau tnh S theo cng thc:
2
S =
1
QTN
T
Bi ging mn C s l thuyt Ha hc
2. Nguyn l II p dng trong h c lp
i vi h c lp:
Qtn= 0 --> S = 0
Qbtn=0 --> S > 0
Nh vy i vi h c lp:
- Trong qu trnh thun nghch (cn bng), entropi ca h l khng i.
- Trong qu trnh bt thun nghch ngha l t xy ra, entropi ca h tng.
iu ny c ngha rng trong cc h c lp, entropy ca h tng cho ti khi t ti gi
tr cc i th h t ti trng thi cn bng.o li ta c th ni:
Trong h c lp:
- Nu dS >0 ( S tng)
h t din bin
2
- Nu dS=0, d S<0 (S max) h trng thi cn bng.
3. ngha hm entropi
a. Entropi l thc o hn n ca h
Xt 1 h c lp T=const, h gm 2 bnh c th tch bng nhau, ng 2 kh l tng
A v B c pA=pB u thp. Hai bnh c ni vi nhau bng mt dy dn c kho K.
M K--> 2 kh khuch tn vo nhau cho n khi c s phn b ng u trong ton b
th tch ca 2 bnh.
S khuch tn cc kh l tng vo nhau l qu trnh c T=const(Q=0) --> S > 0
(S2> S1) --> hn n ca trng thi cui (hn hp 2 kh) c trng bng S2 ln hn
hn n ca trng thi u ( mi kh 1 bnh ring bit) c trng bng S1.
Vy trong h c lp, qu trnh t xy ra theo chiu tng hn n ca h (tng
entropi, S > 0 ). Qu trnh ngc li: Mi kh t tch ra khi hn hp kh tr li trng
thi u khng th t xy ra.
* Kt lun:
- Entropi c trng cho hn n: hn n ca h cng ln th S cng ln.
- Nu s ht trong h cng ln--> hn n cng ln--> Sln
- Lin kt gia cc ht trong h cng yu --> hn n cng ln--> S ln. V d:
SH2O(r) ,SH2O(l)< SH2O (k) .
- S l hm trng thi v l i lng dung .
b. ngha thng k ca S
Trng thi ca mt tp hp bt k c th c c trng bng 2 cch:
- Bng gi tr ca cc tnh cht o c : T, P,C...--> c gi l cc thng s trng
thi v m.
- Nhng c trng nht thi ca cc phn t to nn h c gi l cc thng s vi
m.
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Bi ging mn C s l thuyt Ha hc
* S thng s trng thi vi m ng vi mt trng thi v m c gi l xc sut nhit
ng
Nu s phn t trong h tng th S tng--> tng. Gia S v c quan h vi nhau
thng qua h thc Bolzomann.
H thc Boltzmann (l c s ca nguyn l III)
S=kln
k: hng s Boltzmann
Nhn xt: Trong h c lp, qu trnh t din bin theo chiu tng xc sut nhit ng .
4.Bin thin entropi ca mt s qu trnh
a. Bin thin entropi ca qu trnh bin i trng thi ca cht nguyn cht
Trong sut qu trnh ny T=const ==> S ca mt mol cht nguyn cht trong qu
trnh bin i trng thi xy ra P=const l
2
S =
Q
T
H cf
Tcf
S =
QTN
T
QTN
v T=const
T
V2
V1
V2
V1
V2
P
= nR ln 1
V1
P2
S p =
1
Q p
Vy S p = nC p
1
dH
dT
=
= nC p
T
T
T
1
1
dT
T
Bi ging mn C s l thuyt Ha hc
2
S v =
Q v
dU
dT
=
= nC v
T
T
T
1
1
==> Vy S v = nC v
1
dT
T
T2
T1
S v = nC v ln
T2
T1
( = 1)
S = S T S T =0 = S T =
T =0
S = S T S T =0 =
nC
dT
T
S
H nc
H s
dT
dT
dT
+n
+ nC p ( l )
+n
+ nC P ( h )
T
TS
T
Tnc
T
Tnc
TS
Tnc
0K
nC p
p( r )
0
thng th P=1atm, T=298K, n=1mol ==> S 298
( J .K 1 .mol 1 )
( T, P =const)
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Bi ging mn C s l thuyt Ha hc
n < 0 ==> S nh ==> phn ng gim S
V d:
==> S 0
H mt
H
= S
T
T
Mi trng
H mt = H h = H
S mt =
H mt
H
=
T
T
<=> S
H
0
T
<=> H TS 0
<=> (H TS ) 0
<=> G 0
G = H T S 0
t cn bng khi G = 0
G c gi l : Nng lng Gibbs, Entanpi t do hay th ng p.
b. ngha vt l ca G
G = H TS = U +PV TS
dG = dU + pdV + VdP- TdS SdT
Nguyn l I => dU = Q + W , m dW = pdV + W ' ( W ' : cng hu ch)
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Bi ging mn C s l thuyt Ha hc
=> dG = Q PdV + W '+ VdP + PdV TdS SdT
dG = Q + W '+ VdP TdS SdT
U mt = U h = U
S =
U Mt
U
=
T
T
<=> S
U
0
T
<=> U TS 0
<=> (U TS ) 0 t U - TS = A => A l th ng tch ( nng lng Helmholtz).
<=> A 0
b. ngha A
A = U TS
dA = dU - TdS SdT ; dU = Q + W = Q PdV + W '
Q TdS
=>
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Bi ging mn C s l thuyt Ha hc
A = W ' max
VD:
-1
0
G 298
, s ( NH 3 ) =-16,65kJ.mol ng vi qu trnh
-1
0
G 298
, s ( HCl ) =-95,5kJ.mol ng vi qu trnh
3
1
H 2 (k ) + N 2 (k ) NH 3 (k )
2
2
1
1
H 2 (k ) + Cl 2 (k ) HCl(k )
2
2
G p = G s (sp) G s (tg )
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Bi ging mn C s l thuyt Ha hc
G >0; phn ng xy ra theo chiu nghch
- G T = H T TS T
0
0
0
G 298
= H 298
298.S 298
(G )
= S ,
T P
=>
nn
( G )
G = H + T
T P
( G )
G = H
T P
=> T
=>
G
H
= 2
T T p
T
H
T2
H
T
hoc l
T
T2
G
H
) = 2 dT
T
T
G 0
H 0
0
v
) = 2 dT -> ly tch phn t 298-->T v thng thng bit gi tr G 298
T
T
H T0 = f (T )
H T
G 0
)=
dT
C: d (
2
T
298
298 T
T
==>
T
0
G T0 G 298
H T0
= 2 dT
298
T
298 T
H T0 = f ( T ) = a + bT + .....
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Bi ging mn C s l thuyt Ha hc
=> G 0 = f (T )
2. nh hng ca p sut:
Xt h: bin i thun nghch, khng sinh cng hu ch, T=const.
T biu thc: dG = W '+ VdP SdT , W ' = 0 , T= const
G
=V
P T
P2
P1
nn c
=> dG = Vdp
P2
i vi cht rn v cht lng --> coi V=const khi P bin i ( tr min P ln) nn
: G T G T = V( P2 P1 )
P2
P1
G TP 2 = G TP1 + V( P2 P1 )
hay G = V( P2 P1 )
P2
G TP 2 G TP1 = nRT
P1
Vy: G = nRT ln
nRT
P
P
dP
= nRT ln 2
P
P1
P2
P1
hay G T = G T + nRT ln
P2
P1
P2
P1
G T = G + nRT ln P
0
T
P2
2
= nRT ln > 0
1
P1
G
G
G
) P , N dT +
dP +
T
P T , N
n1 T ,, P,, n
G
G
dn1 +
dn 2 + ... +
n1 T ,, P,, n j 2
n i
j 1
dn i
T , , P ,, n j i
ni T ,, P ,,n j i
t:
Bi ging mn C s l thuyt Ha hc
i Th ho ca cht i
cht i vo h trong iu kin P,T v thnh phn (s mol) ca cc cht khc l khng i.
i c tnh cho 1 mol cht.
dn
i
i:
do :
ni
)
ni
=> i ( T ) = i0( T , P ) + RT ln N i
-
iu kin chun:
G p0 = i0 (sp ) i0 (tg )
Bi ging mn C s l thuyt Ha hc
: Qu trnh t xy ra
STT
Du H
Du S
Du G
Phn ng t xy ra mi nhit
D on chiu
V d:
- phn ng: CaCO3(r) <=> CaO(r) + CO (k)
H p0 = +178,22kJ
H p0 = 99,12kJ
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Bi ging mn C s l thuyt Ha hc
Xt v mt nhit ng: G p = 0
* Vy trng thi cn bng ho hc: l trng thi ca phn ng thun nghch khi tc
phn ng thun bng tc phn ng nghch (hoc khi bin thin th ng p bng
khng).
* c im ca trng thi cn bng ho hc:
- L cn bng ng (phn ng vn xy ra theo 2 chiu ngc nhau nhng vt=vn).
-Ti trng thi cn bng thnh phn ca cc cht khng thay i: cht tham gia
phn ng mt i bao nhiu theo phn ng thun th li c sinh ra by nhiu theo phn
ng nghch).
- Trng thi cn bng ch tn ti khi cc iu kin thc hin phn ng (C, t0,p)
khng i.
II.PHNG TRNH NG NHIT VANT HOFF. HNG S CN BNG K
B (T )
= b
0
B (T )
+ RT ln P Bb :
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d D ( T ) = d D0 ( T ) + RT ln PDd
Bi ging mn C s l thuyt Ha hc
a
A(T )
= a
0
A(T )
+ RT ln P Aa
=>
G T = [(c C0 ( T ) + RT ln PCc ) + (d D0 ( T ) + RT ln PDd )] [(a A0 ( T ) + RT ln PAa ) + (b B0 ( T ) + RT ln PBb )]
PCc .PDd
G T = [(c (C) + d ( D) (a ( A) + b ( B )] + RT ln a b
PA .PB
0
T
0
T
PCc .PDd
G T = G + RT ln a b
PA .PB
0
T
0
T
0
T
bd
bd
=P
bd
=> G T = G T0 + RT ln P
(*)
PCc .PDd
- Ti trng thi cn bng==> G T = 0 => G = RT ln a b
PA .PB
0
T
PCc .PDd
t: a b
PA .PB
cb
cb
(**)
(***)
KP
G T , , G T0 (J)
Trong :
R=8,314J.K-1mol-1
P (atm)
Cc phng trnh (*) (**) v (***) c gi l cc dng khc nhau ca phng trnh
ng nhit Vant Hoff
2.Phng trnh hng s cn bng K:
a.Hng s cn bng Kp
PCc .PDd
K p = a b
PA .PB
cb
KP khng c n v.
Kp ch ph thuc vo bn cht phn ng v nhit .
i vi 1 phn ng xc nh, T=const --> Kp=const --> gi l hng s cn
bng ca phn ng.
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Bi ging mn C s l thuyt Ha hc
CCc .C Dd
* K C = a b
C A .C B
cb
n c .n d
* K n = Ca Db
n A .n B cb
n i RT
= Ci RT
V
(CC RT )c (C D RT )d
=
(C B RT )b (C A RT )a
CCc .C Dd
b
B
C .C
a
A
RT [(c + d )(b + a )] = K c .( RT ) n
n = s mol kh sn phm- s mol kh tham gia (da vo phng trnh phn ng)
Vy
K P = K c .( RT ) n
-Mt khc ta c:
Pi = N i .P =
ni
.P --> thay vo Kp ta c:
ni
K P = K N .Pcbn
KP
= K n .
P
ni
cb
P
= K n .
n
i
cb
*Nhn xt:
- Khi n = 0 (tng s mol kh 2 v phn ng bng nhau) --> Kp=KC=Kn=KN=K=f(T)
- i vi 1 phn ng cho th:
+ Kp,KC ch ph thuc vo nhit
+ KN ph thuc vo nhit , P chung ca h khi cn bng
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Bi ging mn C s l thuyt Ha hc
K' P =
K =
PSO3
1
PSO2 .PO22
PSO2 3
2
SO2
.PO2
= K P2
''
P
PSO2 .PO22
PSO3
= K P1
3
PCO
2
3
PCO
KP =
Gii:
K P = PCO2 =
740
760
==> K P = exp
0
1
bit G 298
,s (NH 3 ) = 16,65kJ .mol
Gii:
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1
1
PO22
Bi ging mn C s l thuyt Ha hc
0
0
1
G 298
= 2G 298
,s (NH 3 ) = ( 2)( 16,65) = +33,3kJ .mol
0
G 298
33,3.10 3
= exp
= 1,45.10 6
K P = exp
8,314.298
R.298
c. Xc nh theo phng php gin tip: Phn tch qu trnh theo 1 chu trnh kn
V d:
KP=?
O2(k)
Cgr
K1
CO2(k)
K2
CO(k)
1/2 O2(k)
G 0 = G10 + G 20
RT ln K P = ( RT ln K 1 ) + ( RT ln K 2 )
lnKP=lnK1+lnK2
==> K=K1.K2
P
KP
= 1 khi
h ang trng thi cn bng nu ta thay i mt trong cc thng s trng thi (P,T,C)
ca h --> G 0 => cn bng b ph v, qu trnh s tin hnh theo chiu G < 0 t
ti trng thi cn bng mi ng vi cc thng s mi (P,T,C).
- Xt v mt ng hc, khi phn ng t trng thi cn bng --> vt=vn => v=0. Khi h
t trng thi cn bng, ta thay i 1 trong cc thng s trng thi (P,C,T) => vt vn ==>
qu trnh tin hnh theo chiu v > 0 t trng thi cn bng mi ng vi cc thng
s mi.
==> gi l s chuyn dch cn bng.
nh ngha: S chuyn dch cn bng l s chuyn t trng thi cn bng ny sang trng
thi cn bng khc di nh hng ca cc tc ng bn ngoi (P,T,C) ln h.
2.nh hng ca nhit ti s chuyn dch cn bng. Phng trnh ng p Vant
Hoff
Xt phn ng: aA + bB <=> cC + dD
P=const
G T0
Ta c: ln K P =
RT
Mt khc:
GT0
ln K P
T
do : =>
H 0
= 2T
T
P
H T0
=
2
P RT
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Bi ging mn C s l thuyt Ha hc
ln K P =
RT 2
.T
R
T1
T2
=> ln
K PT
K PT
T2
dT
T1
H 0 1 1
=
R T1 T2
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Bi ging mn C s l thuyt Ha hc
Nu P tng => cn bng chuyn dch theo chiu P gim (gim s mol kh
n < 0 )
Nu P gim => cn bng chuyn dch theo chiu tng P (tng s mol kh
n > 0 )
4. nh hng ca nng
Xt phn ng: aA + bB <=> cC + dD
C c .C d
c K C = Ca Db = const T=const
C A .C B cb
- Nu tng CA, CB => cn bng chuyn dch theo chiu tng CC,CD ( gi KC=const) =>
cn bng chuyn dch theo chiu thun lm gim CA,CB
- Nu gim CA, CB => cn bng chuyn dch theo chiu gim CC,CD ( gi KC=const)
=> cn bng chuyn dch theo chiu nghch lm tng CA,CB
* Nhn xt: Kt qu ca s chuyn dch cn bng l chng li thay i bn ngoi.Nu
tng Ci th cn bng chuyn dch theo chiu lm gim Ci v ngc li.
5. Nguyn l chuyn dch cn bng Le Chatelier
Khi mt h ang trng thi cn bng, nu ta thay i 1 trong cc thng s trng
thi ca h ( T, P hoc C) th cn bng s chuyn dch theo chiu chng li s thay i
.
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[H 2 ][Cl2 ]
[HCl]2
ca cu t cn li.
Vy h c: R=3, q=1, ==> K= R-q=2
Nu gi thit ban u h ch c HCl ( hoc cho t l mol H2:Cl2 ban u) => q=2 => K=1
4.Bc t do ca h(C): L s ti thiu cc thng s trng thi cng (P,T,C) xc
nh trng thi cn bng ca 1 h ( l s thng s trng thi cng c th thay i
1cch c lp m khng lm bin i s pha ca h)
V d:
H2O(l) <=> H2O(k)
==> cn bng c 2 pha==> C=1 v
+ C th thay i 1 trong 2 thng s P hoc T m khng lm thay i s pha ca
h.
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C=R-q- +2
C= K - q + 2
=> Biu thc ton hc ca quy tc pha Gibbs
* Nhn xt:
+ Khi K tng, => C tng, tng v C gim.
+ Bc t do C 0 K + 2
+Nu trong iu kin ng nhit hoc ng p th: C =K - + 1 (Nu phng trnh
c n = 0 => P khng nh hng ti phn ng --> dng phng trnh ny)
+Nu h va ng nhit va ng p th C=K-
V d1: Xt h 1 cu t (R=K=1), v d nc nguyn cht
- Nu trng thi hi => =1 => C= K- +2= 1-1+2=2 => trng thi ca hi nc c
xc nh bi 2 thng s trng thi cng l T v P
- Nu hi nc nm cn bng vi nc lng th =2=> C=1-2+2=1 => trng thi ca h
gm H2O lng v hi c xc nh bi 1 trong 2 thng s l T hoc P ( v 1nhit
xc nh th P ca hi nc l xc nh)
V d2: Xt h gm: Mg(OH)2 (r) <=> MgO (r) + H2O(k)
=2 pha rn + 1 pha kh =3 pha
C=R-q+2=3-1-3+2=1
=> c php thay i 1 trong 2 thng s l T hoc P m khng lm thay i s pha ca
h hoc trng thi cn bng c xc nh bng 1 trong 2 thng s T hoc PH O(h )
2
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G ( ) = G ( )
V h c C=1 nn nu mt thng s bin i, v d, p sut bin i mt lng dP th
mun hai pha tn ti cn bng, nhit cng phi bin i mt lng dT. Khi th
ng p mol phi bin i:
G ( ) > G ( ) + dG ( )
G ( ) > G ( ) + dG ( )
Sao cho: G ( ) + dG ( ) = G ( ) + dG ( ) => dG ( ) = dG ( )
Thay vo cng thc: dG= VdP SdT ta c:
V ( ) dP S ( ) dT = V ( ) dP S ( ) dT
dT V ( ) V ( ) V
=>
=
=
S
dP S ( ) S ()
H
C S =
suy ra:
T
dT Tcf V
=
phng trnh Clapeyron
dP H cf
Trong H c tnh bng J th V tnh bng m3, T bng K v P bng Pa.
- Khi mt cht si th V =Vh- Vl >0 v H hh>0 (hh:ha hi), nn p sut bn
ngoi tng th nhit si tng theo.
- Khi nng chy H nc >0 v a s trng hp V = Vl-Vr >0, do P tng th
nhit nng chy tng. i vi nc Vl<Vr nn V <0 ngha l p sut tng
th nhit nng chy ca nc gim.
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RT
thay vo phng trnh Clayperon c:
P
H cf H cf
dP H cf
=
=
=
.P
dT Tcf .V Tcf .V Tcf2 .R
=>
dP H
=
dT
P RT 2
d ln P H
=
dT
RT 2
(v
dP
= d ln P ) nn c:
P
P2 H 1 1
=
P1
R T1 T2
(*)
P1,P2 : cng n v
R=8,314J.K-1.mol-1
H : J
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1.nh ngha: L h gm 2 hay nhiu cht trong cht ny c phn b trong cht kia
di dng nhng ht rt nh.
- Cht phn b c gi l cht phn tn, cht kia l mi trng phn tn. Cht phn tn
v mi trng phn tn c th 1 trong 3 trng thi: rn, lng hay hi.
Vd: ng tan trong nc => ng l cht phn tn, H2O l mi trng phn tn
- Da vo kch thc ca ht phn tn, chia lm 3 h phn tn:
a.H phn tn th: Kch thc ht t 10-7-10-4m
-c im: Khngbn,cht phn tn d tch ra khi mi trng phn tn.
-C 2 dng:
+ Huyn ph: cht phn tn l rn, pha phn tn l lng. v d: nc ph sa
+ Nh tng: cht phn tn l lng, mi trng phn tn cng l lng v d: sa c
ln nhng ht m l lng
b.Dung dch keo: (H keo): Kch thc ht t 10-7 10-9m
- c im: tng i bn
c. Dung dch thc (dung dch): Kch thc ht 10-10m (bng kch thc phn t hoc
ion), trong cht phn tn v mi trng phn tn c phn b vo nhau di dng
phn t hoc ion, gia chng khng cn b mt phn chia, to thnh 1 khi ng th gi
l dung dch thc
Cht phn tn c gi l cht tan, mi trng phn tn c gi l dung mi
-c im: H ny rt bn
2.Cc loi nng
-Nng % (C%): l t l % khi lng cht tan so vi khi lng dung dch (C%chnh l
lng cht tan c trong 100g(100kg) dung dch)
C% =
a
.100 %
a+b
a,b lng cht tan v lng dung mi, tnh bng g (kg)
-Nng mol/lit (CM): l s mol cht tan c trong 1 lit dung dch
-Nng ng lng (CN):S mol ng lng cht tan c trong 1 lt dung dch
-Nng molan ( ) l s mol cht tan c trong 1000gam dung mi
-Nng phn mol: N i =
ni
ni
II. ng lng ()
Trong cc phn ng ho hc, cc cht tc dng va vi nhau theo nhng s phn khi
lng tng ng gi l ng lng.
Chn ng lng ca H lm n v H=1
1.nh ngha nglng
- ng lng ca mt cht hoc ca 1 nguyn t l phn khi lng ca cht hoc
nguyn t tc dng va vi 1 ng lng ca H.
V khng phi mi cht u phn ng vi H => nh ngha c m rng nh sau:
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A
n
Vi nguyn t
c nhiu ho tr
khc nhau s c nhiu ng lng v ng lng ca chng gn vi 1 phn ng c th
m chng tham gia.
b.ng lng ca hp cht
=
M
n
Cch xc nh n
- i vi phn ng oxi ho kh: n l s e trao i ng vi 1 phn t cht (n l s
e m 1 phn t trao i trong phn ng)
- i vi phn ng trao i: n l s in tch (+) hoc (-) m 1 phn t cht trao
i trong phn ng
=
NaHSO4
+ H2O
(1)
V d:
H2SO4 + NaOH
H 2 SO4 (1) =
NaOH (1) =
M H 2 SO4
1
M NaOH
1
98
= 98
1
40
=
= 40
1
=
H2SO4 + 2NaOH
H 2 SO4 ( 2 ) =
M H 2 SO4
NaOH ( 2 ) =
M NaOH
1
Na2SO4
+ H2O
(2)
98
= 49
2
40
=
= 40
1
=
M
n
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M Na2 SO4
2
Al2 ( SO4 )3 =
M Al2 ( SO4 )3
CM=
6
CN
n
mA A
=
mB B
=>
mA mB
=> n ng lng cht A phn ng va vi n ng lng cht B ( S
=
A B
VA. C N =VB. C N
A
V d: trung ho 25ml NaOH cn 28ml dung dch axit 0,1N => tnh lng NaOH c
trong 1l dung dch ?
Gii
Gi x l nng ng lng mol ca NaOH
=> x.25=0,1.28
=>x=28.0,1/25
NaOH=40=> s g NaOH c trong 1 lt dung dch l
m=40.x=40.28.0,1/25=4,48g
III. ho tan
1.Qu trnh ho tan. Nhit ho tan ca mt cht
Qu trnh ho tan (khng phi l qu trnh trn ln) gm qu trnh
+ Qu trnh phn tn cht tan( di dng nguyn t, phn t,ion) vo trong khp
th tch dung mi.
+Qu trnh tng tc gia cc phn t ca dung mi vi cc phn t ca cht tan
=> to thnh dung dch (hp cht ho hc)
Hp cht ho hc to thnh gi l hp cht sonvat, nu dung mi l nc th gi l hp
cht hydrat.
=> Qu trnh ho tan c s ph v lin kt cng loi to lin kt khc loi v c th
biu din bng s :
H ht
+
dm
T+T +
dm
T_T
T_dm
H pt > 0
Trong :
H sv < 0
T cht tan
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dm dung mi
H pt nng lng phn tn ( cn tiu tn -> H pt > 0 )
H sv nng lng qu trnh sovat (Qu trnh l to nhit --> H sv < 0 )
Theo s trn ta c:
H ht = H pt + H sv
ha tan: Qu trnh ha tan: cht tan + dm <-> dung dch l mt qu trnh thun
nghch, khi t cn bng cht tan khng tan thm na to thnh dung dch bo ha.
- ha tan ca mt cht c tnh bng nng ca dung dch bo ha cht
iu kin cho v k hiu l s.
- S c th biu din bng mi cch biu din nng .
- ha tan s ca mt cht ph thuc vo:
+ Bn cht ca dung mi v cht tan.
+ Nhit
+ p sut: (nu cht tan l cht kh).
a. nh hng ca bn cht cht tan v dung mi n s
- Cc cht c cu to phn t tng t nhau d ha tan vo nhau, phn t dung mi
phn cc ln th ha tan tt cc cht phn cc v ngc li.
- VD: Dung mi l H2O l phn t phn cc ch ha tan cc cht m fn t phn
cc hoc hp cht ion nh HCl, NaCl..
H2O t ha tan I2 v I2 khng phn cc
Benzen khng phn cc benzen thc t khng tan trong H2O.
I2 tan tt trong benzen c mu tm.
C th ng dng tnh cht ny trong tch, chit hu c.
b. nh hng ca nhit ti tan
CT + Dm <=> Dd , H ht
-
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+ Khi nhit tng -> cn bng chuyn dch theo chiu thun tan
tng.
+ Khi nhit gim -> cn bng chuyn dch theo chiu nghch tan
gim.
Trong mt s trng hp c th iu ch dung dch qu bo ha c nng ln hn
ha tan s nhit T dung dch qu bo ha khng bn.
- Nu H ht <0 (ha tan a s cht kh)
+ Khi nhit tng -> cn bng chuyn dch theo chiu nghch tan
gim.
+ Khi nhit gim -> cn bng chuyn dch theo chiu thun tan
tng.
c. nh hng ca P (i vi cht kh). nh lut Henry
CT(kh) + dm <=> dd (*)
qu trnh ha tan cht kh lm gim n nn:
+ Khi P tng => ha tan s tng
+Khi P gim => ha tan s gim
T cn bng (*) thy rng: S tng P s dn n s chuyn dch cn bng sang phi. Nu
tng P ln n ln th ha tan ca cht kh cng tng ln n ln.
nh lut Henry: mt nhit khng i, khi lng cht kh ha tan trong 1 th
tch cht lng xc nh t l thun vi P ca n trn b mt cht lng.
m= k.P
trong : k- h s t l ph thuc vo bn cht ca cht kh, dung mi v
nhit -> gi l h s Henry.
P p sut ring phn ca cht kh trn mt cht lng.
Nu trn mt cht lng c 1 hn hp kh th s ca mi kh t l vi P ring phn ca tng
kh. nh lut Henry ch ng cho cht kh c s nh, P khng ln v kh khng tc dng
ha hc vi dung mi.
IV. Tnh cht ca dung dch.
- Ch xt dung dch: + long
+ cht tan khng bay hi
+ cht tan khng to dung dch rn vi dung mi.
VD: dd mui hoc dd ng khi un ch c H2O bay hi.
Dung dch l tng: l dung dch m ca n tun theo nh lut tng t nh
i vi kh l tng. Cc dung dch rt long c coi nh dung dch l tng.
ca cu t i trong dung dch l tng c tnh theo cng thc ging nh i vi
kh l tng: i ( T ) = i0 + RT ln Ni .
( T ,P)
1 = 10 + RT ln N1
0 l i0 h
Pi
= i
= const
Ni
RT
Ngha l
Pi
= k i = const
Ni
Pi
Ni
t0C xc nh.
=> Pi= ki.Ni
V N1= 1-N2
=>
P1,0 P1
P1,0
n2
P
P
= N 2 =>
= N2 =
P1,0
P1,0
n1 + n 2
Pht biu: gim tng i ca dung dch cha cht ho tan khng bay hi t l vi s
mol cht tan c trong 1 lng dung mi xc nh.
2. Nhit si v nhit ng c ca dung dch. nh lut Rault II
a.Nhit si ca dung dch
* Nhit si ca cht lng: L nhit p sut hi bo ha ca cht lng bng p
sut bn ngoi.
Xt cn bng L H
C=2+2-2 =2
Vy nhit si ca dung dch ngoi s ph thuc vo p sut bn ngai cn ph thuc
vo nng cht ha tan.
- p sut bn ngoi nh nhau, khi dung mi nguyn cht si th dung dch cha cht tan
khng bay hi s cha si v p sut hi bo ha ca dung dch lun lun nh hn p sut
hi bo ha ca dung mi nguyn cht cng 1 nhit . Vy dung dch cha cht tan
khng bay hi c nhit si cao hn dung mi nguyn cht.
- tng nhit si ca dung dch so vi dung mi nguyn cht t s c tnh theo cng
thc Rault 2:
t s = k s = k s
m
M
trong t s =ts,dd-ts,dm (ts,dd: nhit si dung dch, ts,dm: nhit si dung mi nguyn
cht, nng molan; ks: hng s nghim si (ch ph thuc vo bn cht dung mi).
- Khi dung dch si th hi bay ra l ca dung mi nn nng dung dch tng dn, do
nhit si ca dung dch tng dn, nhng khi t n dung dch bo ha th hi dung
mi bay ra lm cho cht ha tan kt tinh li, lc ny nng dung dch khng thay i v
nhit si ca dung dch khng bin i na. Vn dng quy tc pha ta c: C=2-3+2 =1.
Ngha l khi xut hin tinh th cht tan th nhit si ca dung dch ch cn ph thuc
vo p sut bn ngoi.
b. Nhit ng c ca dung dch cha cht tan khng bay hi
Nhit ng c ca cht lng l nhit c cn bng sau: R L
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m
M
trong t s =ts,dd-ts,dm ,ks: hng s nghim ng (ch ph thuc vo bn cht dung mi).
3. S thm thu v p sut thm thu:
a. S thm thu
L s khuch tn mt chiu ca cc phn t dung mi qua mng bn thm (mng bn
thm l mng ch cho cc phn t dung mi i qua m khng cho cc phn t cht ha tan
lt qua). Hin tng ny thy rt r khi hai bn ca mng bn thm cha dung dch c
nng khc nhau hoc 1 bn l dung dch cn bn kia l dung mi nguyn cht; khi
cc phn t dung mi s khuch tn t dung dch long hoc t dung mi nguyn cht
sang pha bn kia nhiu hn s khuch tn theo qu trnh ngc li, do lm tng th
tch ca dung dch pha bn kia.
b. p sut thm thu
Hin tng thm thu lm cho mc dung dch mt pha ca mng bn thm dng ln
cao. Chiu cao ca ct dung dch ny to nn mt p sut lm cho hin tng thm thu
ngng li. p sut c to ra bi ct dung dch ny c trng nh lng cho s thm
thu v c gi l p sut thm thu P. N c tnh theo cng thc:
PV=nRT=
m
RT
M
m
: s mol cht ha tan.
M
R: Hng s kh l tng.
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i = --------------------------------------
S phn t ho tan
S phn t trong dung dch bng s ion c to thnh cng vi s phn t cha b
phn li thnh ion.
II. in ly
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q. .N + N - .N
q. - + 1
=> i = -------------------------- = ----------------N
1
i 1
=
q 1
Da vo cng thc ny ta c th tnh c
I c th xc nh bng thc nghim t vic o gim nhit ng c hoc gim
Phi bo ha hoc t t s
'
t s' t d' P
i=
=
=
t s t d P
t d'
. Bit i tnh c v ngc li.
t d
8
= 0,372 =
40
1,821
= 0,82 hay 82%.
2 1
1. Hng s in ly
Trong dung dch cht in ly yu AB tn ti cn bng sau:
AB
A+ + B-
[A ][. B ]
Hng s in ly ca phn ng K =
+
[AB]
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K=
(C)2
C C
K=
2 .C
1
Ostwald
T cng thc ny nhn thy rng C cng nh th cng ln, c ngha l dung dch
cng long th in ly cng ln.
Khi long 1/C th i vi cht in ly yu nng v cng long th
c th coi qu trnh in ly l hon ton.
C th xc nh c cc C khc nhau nu bit K v ngc li
1/C
Nu < 0,05 th 1- 1 2.C = K
=
K
C
[H O ][OH ]
+
[H 2 O]
H2O
H2O
K H2O
[H O ] = 10
+
M.
3. Hng s in ly axit-baz
a. Hng s in ly ca axit Ka
Trong dung dch ca axit yu HA tn ti cn bng ng sau:
HA + H2O A- + H3O+
Ka
[HA]
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Ka l hng s in ly ca axit trong nc, c trng cho mnh ca axit. Ka cng cao
th axit cng mnh. Ka ph thuc vo bn cht ca axit v ph thuc vo nhit .
- Axit mnh : khng dng Ka v coi 1 .
- Axit yu ( 0 < < 1 ) c hng s cn bng Ka.
b. Hng s in ly ca baz Kb
Trong dung dch ca baz yu B tn ti cn bng ng sau
B + H2O BH+ + OH-
[BH ][. OH ]
K =
+
[B]
[B].[H 3O + ]
Ka =
[A]
[
A].[OH ]
Kb =
[B]
[
B].[H3O+ ] [A].[OH ]
.
= [H3O+ ][. OH ] = KH O =1014 25 C
Ka .Kb =
[A]
[B]
o
[H O ] > 10
[H O ] < 10
+
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[
[
][ ]
] [ ] [ ] [
H 3 O + . OH = K H2O
H 3 O + = OH + A = OH + C a
] [HK O ] + C [H O ] C [H O ] K
+
=> H3O =
+ 2
H2O
H2O
=0
=> [H 3 O ] =
+
Ca + Ca2 + 4 K H2O
2
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][ ]
[ ][ ][ ][
H3O+ . OH = KH2O
OH = H3O+ + Na+ = H3O+ + Cb
O
] KH
[OH ] + C
OH =
OH C b . OH K H2O = 0
][
[
]
][ ]
] [ ] [
[ ]
H 3 O + OH = K H 2 O
H 3O + . A
K =
[HA ]
=> ta c h: a
+
= A + OH
H 3O
[HA ] = C A
a
Ca
<100 th c th b qua s in ly ca nc, do
Ka
ch cn xt s in ly ca axit yu
HA + H2O
B Ca
cb Ca- x
Ka =
x2
Ca x
A- + H3O+
0
0
x
x
Gii ra tm c x pH
* Nu Ca.Ka 10-12 v
Ca
> 10 0
Ka
x2
Ka =
Ca
x = Ka .Ca tnh pH
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CH3COOH + H2O
[H O ] =
+
CH3COO- + H3O+
4. Tnh pH ca baz yu 1 bc
Xt cn bng trong dung dch baz yu B (A l axit lin hp ca B)
B + H2O A + OHH3O+ + OH2H2O
L lun tng t nh trng hp axit yu thy rng tm c [OH ] phi gii
phng bc 3 . i n cc php gn ng:
* Nu Cb.Kb 10-12 v 0,1 <
Cb
< 100
Kb
B + H2O
b Cb
cb Cb-x
A + OH- t [OH-] = x
0
0
x
x
x2
Kb =
Cb x
gii ra tm c [OH-]
* Nu Cb.Kb 10-12 v
C
K
baz yu x<< Cb Cb - x Cb
x = [OH ] = Cb .Kb =
-
> 100
Cb .KH2O
Ka
M3+.H2O + 2H2O
Ka =
MOH2+ + H3O+
3+
t x= [H3O+]
x2
Ka =
= 2.103 x pH
0,1 x
V d 2: Cho dung dch K2CO3 0,2M, bit rng Ka2(H2CO3) = 5,6.10-11. Tnh pH ca
dung dch, b qua nc in ly th 2 ca CO32-.
K2CO3
2K+ + CO32CO32- + HOH
HCO3- + OHCO32- l baz lin hp ca HCO3 14
14
Kb(CO32-) = 10 = 10 11 = 1,78 .10 4
Ka.Kb = 10-14
5, 6 . 10
Ka
-4
-12
nn b qua s in ly ca nc
Cb
0,2
=
> 100
K b 1,78 .10 4
[ ]
4
4
OH = Kb .Cb = 1,78.10 .0,2 pH = 14+ lg 1,78.10 .0,2 = 11,7
[NH3 ][ H 3 O + ]
[NH 4+ ]
v K a ca NO2 l: K a
2
[ H O + ][NO2 ]
= 3
[ HNO2 ]
=> K a .K a = [ H3 O + ]2 => [ H3 O + ] = K a . K a
1
=> K a =
2
10 14
= 5.10 4 ; [ H3 O + ] = 6,3.10 10.5.10 4 = 5,6.10 7 M
11
2.10
=> pH =6,25.
6.Tnh pH ca dung dch axit nhiu bc:
- i vi axit nhiu bc nh H2S, H2SO3, H3PO4 s in ly theo nhiu nc, nc u
tin mnh nht cn cc nc sau yu dn.
V d: Nh s in ly ca axit H2S
H2S + H2O
HS- + H3O+ Ka1 = 10-7
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HS- + H2O
Do nc 2 yu hn nhiu so vi nc 1 nn c th b qua s in ly ca nc 2 v a v
bi ton tnh pH ca axit 1 bc.
VI. Cn bng trong dung dch cht in ly t tan
Ks
4
K s, AgI
[ ] []
Ag+ + Is
s + 0,1
AgI
Vy s = 1,5.10-15M
s 1,22.108
=
= 8,1.106 ln
ho tan gim i
15
s' 1,5.10
3. iu kin to thnh kt ta v ho tan kt ta
* iu kin to thnh kt ta:
Mun to thnh kt ta cht in ly t tan th tch s nng ca cc ion ca chng
trong dung dch vi s m thch hp phi ln hn tch s ho tan.
V d: Trn 2 th tch bng nhau ca dung dch AgNO3 10-2M vi NaI 2.10-2 M. C
to thnh kt ca AgI hay khng?
[ ]
102
Ag =
= 5.103 M
2
+
[I ] = 2.102
= 102 M
[ ][ ]
3
2
5
16
Vy Ag . I = 5.10 .10 = 5.10 > Ks ,AgI = 1,5.10 vy to thnh kt ta
b. iu kin ho tan kt ta
V d: Ho tan FeS bng dung dch HCl
FeS (r)
S2- + Fe2+
(1)
+
HCl
= H + Cl
(2)
2+
S + 2H = H2S
(3)
2Do (3) nn nng ca ion S gim xung lm [Fe2+].[S2-] < TFeS v lm cho cn
bng dch chuyn theo chiu thun.
Nh vy ho tan mt cht in ly t tan th phi thm vo dung dch mt cht no
c kh nng kt hp vi mt trong cc ion ca cht in ly, lm cho tch s nng
ca cc ion < tch s tan.
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Chng VII: ng ho hc
Nhit ng ho hc nghin cu phn trc ch mi cho php xt on chiu hng
t din bin ca mt phn ng ho hc v ch kho st h trng thi cn bng, nn
khng h cho bit mt tn hiu no v tc , ngha l s bin i cc tham s ca h theo
thi gian.
V d: Phn ng gia H2(K) + 1/2 O2(K) = H2O(l) c Go298 = -237,2 kJ/mol, Go298 ca
phn ng rt m, c ngha l v mt nhit ng hc phn ng c th xy ra mt cch hon
ton T= 298K v P = 1atm (K= 1041), song thc t cho thy phn ng hu nh khng
xy ra iu kin cho, bi v tc ca phn ng cc k nh, do iu kin
thng ngi ta tng phn ng ny khng xy ra.
ng ho hc l mn khoa hc nghin cu v tc v c ch ca cc qu trnh
ho hc.
I.khi nim v vn tc phn ng
1. nh ngha vn tc phn ng
Vn tc trung bnh ca phn ng: c o bng bin thin nng ca mt
trong cc cht tham gia phn ng hay to thnh sau phn ng trong mt n v thi gian.
Xt phn ng: aA + bB cC + dD
Gi s thi im t1 nng ca cc cht l CA1, CB1, CC1, CD1, thi im t2 th
nng tng ng l CA2, CB2, CC2, CD2. Khi vn tc trung bnh ca phn ng l:
C A 2 C A1
VA,tb =
t 2 t1
Vtb =
, VB,tb =
C B 2 C B1
t 2 t1
, VC,tb =
C C 2 C C1
t 2 t1
C
t
1 dC A
1 dC B
1 dC C
1 dC D
=
=
=
a dt
b dt
c dt
d dt
2.Cc yu t nh hng ln vn tc
-
Nng cc cht.
Nhit
Cht xc tc.
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, VD,tb =
C D 2 C D1
t 2 t1
1.Ni dung:
Gi s xt phn ng A(K) + B(K) AB(K). phn ng xy ra th A v B phi va chm
vi nhau.
C 2 loi va chm:
+ Va chm gy phn ng: gi l va chm c hiu qu(s va chm ny nh).
+ Va chm khng gy phn ng: gi l va chm khng hiu qu(s va chm ny ln).
gy va chm c hiu qu => cc phn t phi c nng lng ln hn nng lng
trung bnh ca h => gi l cc phn t hot ng => vn tc phn ng t l vi tn s va
chm gia cc phn t hot ng.
2.Phn b Boltzman:
C kh l tng A vi tng s mol l N, trong c s phn t hot ng l N* th:
E
A
N*
= e RT => Biu thc nh lut phn b Boltzman.
N
Bc ca p (a) l 1+1=2.
* Ch : nu phn ng n gin ch xy ra theo 1 giai on th n=a, m=b (a, b l cc
h s t lng trong phng trnh phn ng) => Bc phn ng (m+n) =(b+a).
IV. nh hng ca nhit ln vn tc phn ng
- l h s nhit cho bit vn tc tng ln bao nhiu ln khi nhit tng thm
10 C.
Tng qut:
nhit t1 vn tc ca phn ng l v1, nhit t2 vn tc ca phn ng l v2, ta c:
o
V2 =
t 2 t1
10
V1
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A
lnk = + ln => k = .e T
T
+ ln
T2
1
1
K2
= A
ln
A
K1
T 2 T1
lnK 1 =
+ ln
T1
lnK 2 =
Ei
RT
( E A + EB )
E Ai
RT
RT
C B e
EA
RT
vi l h s t l.
t EA + EB = Ea
gi l nng lng hot ha ca phn ng. Ea l nng lng cn thit
a mt mol cc cht tham gia phn ng c nng lng trung bnh tr thnh hot
ng.
=> v = C AC B e
Ea
RT
(b)
Ea
RT
=> lnk =
Ea
A
+ ln => lnk = + ln
T
RT
A=-Ea/R
* ngha ca Ea:
hiu r ngha ca Ea ta xt gin nng lng ca phn ng:
I2(K) + H2(K) 2HI(K)
E
K
H2I2
Ea
Ea
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1. nh ngha:
Cht xc tc l cht lm tng vn tc phn ng, nhng n khng b bin i v tiu tn
do phn ng xy ra.
Nu cht xc tc v cc cht tham gia phn ng trong cng mt pha th c gi l xc
tc ng th.
NO
V d:
2SO2(K) + O2(K) 2SO3(K)
Nu cht xc tc khc pha vi cc cht tham gia phn ng th c xc tc d th.
V2O5(r)
V d:
2SO2(K) + O2(K) 2SO3(K)
Xc tc men ng vai tr quan trng i vi qu trnh qu trnh trao i cht: Phn
ln cc phn ng sinh ho xy ra trong c th u di tc dng ca cc enzim
2. c im ca xc tc:
- C tnh chn lc cao: Mt xc tc ch c th c tc dng i vi mt phn ng hay
mt loi phn ng (cho v d)
- Cht xc tc c tc dng lm gim nng lng hot ho ca phn ng
- Cht xc tc lm xc tc cho phn ng thun th cng lm xc tc cho phn ng
nghch, nn cht xc tc lm cho phn ng nhanh chng t ti trng thi cn bng, ch
khng lm chuyn dch cn bng v n lm tng tc phn ng thun v phn ng
nghch vi s ln bng nhau
- i vi xc tc ng th: tc dng ca xc tc t l vi nng ca cht xc tc
3. Gii thch c ch ca xc tc
a. i vi xc tc ng th:
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A+B
Ea1
AB
II
Tin trnh phn ng
lnk1 =
v2 k2
=
=e
v1 k1
Ea Ea *
RT
S ln vn tc tng ln khi c xc tc
b. i vi xc tc d th
C ch ca mt phn ng xc tc d th rt phc tp, cho n nay cha c mt thuyt
duy nht v xc tc d th. Mt phn ng xc tc d th xy ra gm nhiu giai on vt l
v ho hc ni tip nhau
- Giai on u: Xy ra s hp ph ca cc cht tham gia ln cc tm hot tnh ca
cht xc tc
- Giai on 2: Di tc dng ca cc lc ho hc trn b mt xc tc to ra cc hp
cht b mt, dn ti thc hin phn ng trn b mt xc tc
VI. Cc phng trnh ng hc ca phn ng ha hc
d[ A]
d[ A]
= k[ A] hay
= kdt
dt
[ A]
[ A]
= kt
[ A]0
4
Th 228
88 Ra + 2 He
d[ A]
d[ B ]
=
= k[ A][ B]
dt
dt
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d[ A]
d[ A]
d[ A]
= k[ A] 2 hay
= k dt . Ly tch phn 2 v
= k dt
2
dt
[ A]
[ A] 2
=>
1
= kt + const
[ A]
khi t =0 th
1
= const . T :
[ A]0
1
1
1 1
1
= kt k = (
)
[ A] [ A]0
t [ A] [ A]0
1
k[ A]0
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1. Phn ng oxy ho kh
V d: Xt phn ng oxy ho kh thng thng xy ra trong dung dch khi nhng thanh
Zn vo dd CuSO4
Zn + CuSO4 = ZnSO4 + Cu
Zn + Cu2+ Zn2+ + Cu
Ho = -230 KJ
2e
Cu2+ trc tip n thanh Zn nhn e
Zn-2e =Zn2+
Qu trnh xi ha
Qu trnh kh
Cu2+ +2e = Cu
c im ca phn ng xi ha kh:
- e trc tip t cht kh sang cht xi ha.
- Nng lng phn ng xi ha kh gii phng di dng nhit.
Trong phn ng oxy ho kh ny cht kh v cht oxy ho c tip xc vi nhau, cc
electron s c chuyn trc tip t cht kh sang cht oxy ho v nng lng ca phn ng
ho hc c to ra di dng nhit. Nhng nu ta thc hin qu trnh oxy ho Zn v qu
trnh kh Cu2+ 2 ni ring bit v cho e chuyn t Zn sang Cu2+ bng 1 dy dn in, c
ngha l to nn mt dng e nht nh th nng lng ca phn ng ny c chuyn thnh
in nng, lm xut hin trong dy dn 1 dng in ngc chiu vi dng electron. cng
l qu trnh xy ra trong mi pin.
2. Nguyn tc bin ha nng thnh in nng
-
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1. in cc kim loi:
+
+
+
+
Nu thm mui cha ion Mn+ vo dung dch trn th cn bng chuyn dch theo chiu nghch
v s c mt s ion Mn+ t dung dch chuyn vo thanh kim loi v cn bng trn vn c
thit lp.
Khi cn bng, gia b mt kimloi- dung dch xut hin 1 hiu s in th gi l th
in cc kim loi. Th in cc kim loi ph thuc vo: bn cht cu KL v dung mi, nng
ion kim loi M v nhit .
Nu xt cng 1 nhit , cng 1 dung mi, th in cc kim loi c trng cho bn cht
kim loi: nu th in cc c gi tr cng (-) th kim loi hat ng cng mnh v ngc li.
2. in cc tr nhng trong dung dch cha cp oxy ho kh
-
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H2
2H3O+ +2e
H2 + 2H2O
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Trong :
G 0
G
0
nu iu kin chun => E =
E=
n.F
nF
Vi phn ng (*) c G T = G T0 + RT ln
[ Sn 4+ ][ Fe 2+ ]2
[ Sn 2+ ][ Fe 3+ ]2
Chia c 2 v cho 2F c:
G T
G o T RT [ Sn 4+ ][ Fe 2+ ]2
=
ln
2.F
2F
2F [ Sn 2+ ][ Fe 3+ ]2
[
[
][
][
RT Sn 2 + Fe 3+
E=E +
ln
2F
Sn 4 + Fe 2+
o
]
]
2
2
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C E = E 0 +
RT [ A]a [ B ]b
ln
nF [C]c [ D]d
V. Th in cc (th kh)
1. Cp xi ha kh:
V d: Trong dung dch tn ti Cu2+ nhng trong phn ng th Cu2+ + 2e = Cu
gi Cu2+/Cu l 1 cp xi ha kh.
* nh ngha: Cp xi ha kh l mt cp gm cht xi ha v cht kh, chng c th bin
i ln ra nhau trong qu trnh phn ng.
- K hiu cp xi ha kh l cht xi ha/cht kh hoc cht xi ha, cht kh.
- Vi cch quy c ny phn ng in cc bao gi cng l qu trnh kh
xi ha + ne = Kh
- Cp xi ha kh chun: L cp xi ha kh khi [xi ha] =[kh] = 1M ( nu l cht kh P=
1atm).
2. Th kh
Quy c qu trnh in cc l qu trnh kh dng: Oxh + ne -> Kh
Th o c gi l th kh ca cp oxiha kh. K hiu l ox
Kh
yu.
Nu ox
yu.
Th kh ca 1 cp oxiha kh chun gi l th kh chun 0 ox Kh
* Cch xc nh th kh chun ca mt cp oxiha kh:
Vic xc nh gi tr tuyt i th kh ca cc in cc l khng th lm c, nhng nu
quy c th kh ca mt in cc no lm chun v bng cch so snh s xc nh c
th kh ca cc in cc khc
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0
o c E0= 0,34 (V) = Cu
2+
Cu
0
Fe
Fe3+ + 3e Fe
= 0,77( V ) = 10
3+
Fe 2 +
= 0,44( V ) = 20
2+
Fe
=?
0
Fe 3 +
Fe
G 0
G10 +n1e
G 20
+n2e
0
1
( G = nE 0 F = n 0 F )
0
0
2
=> n 0 F = n1 10 F n 2 20 F
=> 0 =
n1 10 + n 2 20
n
C th v d trn:
G 0
3+
Fe
G10
+3e
+1e
Fe
+2e G 0
2
Fe2+
G 0 = G10 + G 20
=>
0 =
1 10 + 2 20 0,77 + 2(0,44)
=
= 0,036(v)
3
3
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3. Cc yu t nh hng n th in cc
T v d trn vi phn ng: 2Fe3+ + Sn2+ 2Fe2+ + Sn4+
[
[
][
][
RT Sn 2 + Fe 3+
ln
C E = E +
2F
Sn 4 + Fe 2+
o
]
]
2
2
M E = + v E 0 = 0 + 0 nn c:
+ = 0+ 0 +
=> + =
= 0
[
[
Fe 3+
RT
(ln
2F
Fe 2+
[
[
RT [Sn
+
ln
2F [Sn
]
]
]
]
Fe 3+
RT
+
ln
2F
Fe 2+
4+
2+
]
]
[Sn ])
[Sn ]
4+
- ln
2+
2
2
Tng qut:
C phn ng in cc: axh + ne bKh
=> i = 0 i +
RT [Oxh]
ln
nF
[Kh]b
25 C: i =
0
0,059 [Oxh]
+
lg
n
[Kh]b
=0 +
0,059
lg([H + ]4 . pO2 )
4
* i vi in cc tr trong dung dch xi ha kh: Nu trong phn ng kh c mt H+, OH=> pH thay i => pH lm thay i th kh.
VD1: Sn2+
+ 2e Sn4+
=0 +
[
[
0,059 Sn 4+
lg
2
Sn 2+
]
]
0,059 [ MnO4 ][ H + ]8
lg
= 0 +
5
[ Mn 2 + ]
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ox / kh >ox / kh
1
th phn ng xy ra theo
Ch :
Trong trng hp tng qut xt chiu ca phn ng oxy ho kh th phi tnh th
kh ca cc cp oxy ho kh trong iu kin phn ng ri mi so snh v rt ra kt
lun
Theo cng thc Nernest th kh ca mt cp oxy ho kh ph thuc vo nng cc
dng oxy ho, dng kh, ph thuc vo nhit v pH ca mi trng, nn khi
thay i mt cc thng s trn th th kh ca cc cp s thay i v c th dn n
lm thay i chiu ca phn ng oxy ho kh.
Di y xt mt vi v d v chiu ca phn ng oxy ho kh.
V d 1: Cho bit cn bng sau 25oC trong dung dch nc:
2Cr2+ + Cd2+
3+
/Cr 2 +
3+
/Cr 2 +
= 0,41V
Cr 3 + /Cr 2 + = o Cr 3 + /Cr 2 + +
2+
[
[
2+
]
]
0,059 Cr 3+
0,1
lg
= 0,41 + 0,059lg
= 0,351V
2+
1
0,01
Cr
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0,059
0,059
lg0,01 = 0,459V
lg Cd 2 + = 0,4 +
2
2
Cd 2 + /Cd = o Cd 2 + /Cd +
o Cu2+/Cu+ = 0,153V
Sn4+ + 2e Sn2+;
iu kin chun do
2+
Cu+ + Sn4+
Sn4+ /Sn2+ =
4+
2+
Sn /Sn
[ ]
[ ]
[Cu ]
+ 0,059lg
[Cu ]
0,059 Sn4+
lg 2+
+
2
Sn
2+
+
hay
nghch.
2. Trng thi cn bng ca phn ng oxy ho kh
Phn ng oxy ho kh t n trng bng khi GT = n.ET .F = 0 ET = 0 hay ox = kh.
Hng s cn bng ca phn ng xi ha kh:
G 0 = RT ln K
mt khc G 0 = nFE 0
=> RT ln K = nFE 0
lnK =
n.E o .F
(phn ng trong dung dch th K=Kp=KC).
RT
n.E o
T = 298K lgK =
0,059
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2Fe3+ + Sn2+
2Fe2+ + Sn4+ ;
4+
/Sn 2 +
= 0,15V
2.(0,77 0,15)
= 21 K= 1021
0,059
1. nh ngha:
in phn l qu trnh oxy ho v qu trnh kh xy ra trn b mt in cc khi cho dng
in mt chiu i qu dung dch cht in ly hoc cht in ly nng chy.
V d: in phn dung dch CuCl2
Khi cho dng in mt chiu i qua dung dch CuCl2 th di tc dng ca in trng
cc cation Cu2+ i v cc m, cn anion Cl- i v cc dng. Ti cc in cc s xy ra hin
tng phng in.
Catt (-): Cu2+ + 2e Cu
Ant (+): 2Cl- -2e Cl2
Cu2+ + 2Cl- Cu+ Cl2
y chnh l phn ng oxy ho kh xy ra khi in phn dung dch CuCl2. Phn ng ny
khng t xy ra c, m n ch xy ra c di tc ng ca ngun in mt chiu bn
ngoi. Do qu trnh in phn l qu trnh bin i in nng thnh ho nng.
2. S phn cc:
Khi in phn trng thi in ca in cc (th v mt in tch ca lp in tch kp)
b thay i. Th ca in cc s khc vi th ca n lc cn bng (khi cha c dng in).
Hin tng ny c gi l s phn cc.
Tu thuc vo tnh cht ca qu trnh lm thay i th ca in cc c 3 loi phn cc
khc nhau:
a. S phn cc v nng :
Khi in phn nng ca cc ion catt v ant b thay i. ant do kim loi b ho
tan, nng ca ion tng ln, cn catt xy ra s kh nn nng ca ion gim i, dn
n th ca in cc gim. Nu mt dng in cng ln th s bin i nng ca cc
ion cng ln, do s phn cc cng ln. Cn khuy mnh gim s phn cc.
b. S phn cc ho hc:
Khi in phn cc sn phm thot ra cc in cc dn ti s to thnh 1 pin c chiu
ngc vi chiu dng in
c. S phn cc in ho:
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Cl- -e 1/2Cl2
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Na2SO4
Catt
SO42- ,H2O
2Na+ + SO42-
H2O , 2Na+
2H2O + 2e = H2 + 2OH-
Catt
H2O , Cu2+
Ant (Cu)
SO42- ,H2O
Cu2+ + SO42-
Cu2+ + 2e = Cu
Cu to thnh bm vo catt
Cu - 2e = Cu2+
Ant tan dn
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