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I HC S PHM
NGUYN VN NG
Bi ging
HA I CNG 2
NNG - 2011
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I HC S PHM
NGUYN VN NG
Bi ging
HA I CNG 2
(L THUYT CC QU
TRNH HO HC)
NNG - 2011
MC LC
Chng 1 C s nhit ng lc hc
1.1.Mt s khi nim c bn1
1.2.Cng dn n ca kh...2
1.3.Nguyn l th nht ca nhit ng hc v mt s i lng nhit ng...3
1.4.Hiu ng nhit ca qu trnh ho hc, nhit ho hc.7
1.5.Nguyn l 2, 3 ca nhit ng hc12
Bi tp..23
Chng 2 Cn bng ho hc, cn bng pha
2.1.Khi nim v cn bng ho hc.26
2.2.Hng s cn bng...26
2.3.Phng php xc nh hng s cn bng...28
2.4.Quan h gia bin thin th ng nhit, ng p v hng s cn bng..28
2.5.Cc yu t nh hng n cn bng ho hc. Nguyn l Le Chtelier.29
2.6.Cn bng pha..30
Bi tp...34
Chng 3 ng ho hc
3.1.Mt s khi nim....35
3.2.nh hng ca nng cc cht n tc phn ng..36
3.3.Xc nh hng s tc v bc phn ng...37
3.4.nh hng ca nhit n tc phn ng....39
3.5.Thuyt va chm hot ng v thuyt phc cht hot ng.....41
3.6.nh hng ca cht xc tc n tc phn ng..42
3.7.Phn ng dy chuyn..44
3.8.Phn ng quang ho....45
Bi tp...46
Chng 4 Dung dch
4.1.Khi nim v dung dch 49
4.2.S hnh thnh cc loi dung dch....50
4.3.S ho tan51
4.4.Tnh cht ca dung dch long khng in ly, khng bay hi.....52
4.5.Dung dch cht in ly....55
4.6.Axit, baz....59
4.7.Dung dch m....63
94
4.8.S thu phn...64
4.9.Phn ng trung ho.65
4.10.Dung dch cht in ly t tan.....66
4.11.S to phc trong dung dch.67
4.12.Dung dch keo.......68
Bi tp.......70
Chng 5 Phn ng oxy ho kh. Phn ng ho hc v dng in
5.1.Phn ng oxy ho kh .72
5.2.Th in cc75
5.3.Cc qu trnh in ho.....81
5.4.n mn kim loi, cc phng php chng n mn kim loi.......87
5.5.Mt s ngun in ho thng dng : pin, accu....87
Bi tp....89
Ti liu tham kho.92
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CHNG 1
C S CA NHIT NG HC
y l chng khi u ca hc phn l thuyt cc qu trnh ha hc.

Qu trnh ha hc l g ? L s chuyn ha t cht ny sang cht khc. V l thuyt gia cc
qu trnh l c s d on s chuyn ha . Tc l phi tr li c cc vn :
1. Khi trn ln 2 hay nhiu cht xc nh, th gia chng c xy ra phn ng hay
khng ? Nu xy ra th xy ra theo chiu hng no v iu kin phn ng xy ra.
2. Xy ra n mc no ? V yu t no tc dng ln chng mc .
3. Nu phn ng xy ra th khi no xy ra ? Nhng yu t no nh hng n tc
phn ng ?
Khi tr li c 3 cu hi ny, ta c th iu khin c phn ng, tm c iu
kin ti u thc hin phn ng - nhm t hiu qu cao nht.
Hai cu hi u (cu 1 v 2) l i tng ca nhit ng hc ha hc, cn cu th ba
chnh l i tng ca ng ho hc.
Trong chng ny, chng ta phi tr li c cu hi th nht.
1.1.MT S KHI NIM C BN :

1.1.1.H nhit ng (gi tt l h ):
L mt vt hoc nhm vt ang c em ra nghin cu v phng din vt cht v
nng lng. Phn cn li ca h l mi trng ngoi. Vy:
H + mi trng ngoi = v tr
Th d : Mt ng nghim cha dung dch HCl tc dng vi Zn l h v mi trng
ngoi l phn cn li ca h k c ng nghim.
Ph thuc vo s trao i vi mi trng ngoi cn c :
- H m (h) : l h c th trao i vi mi trng ngoi c v cht v nng lng.
Nh th d v ng nghim cha HCl v Zn trn l h m : H trao i cht (H2) v nng
lng (nhit) vi mi trng ngoi.
- H kn : l h ch c th trao i nng lng vi mi trng ngoi m khng trao i
cht. Th d : l cc phn ng xy ra trong bnh kn.
- H c lp l h khng trao i c nng lng v vt cht vi mi trng ngoi. V
tr l mt h c lp.
1.1.2.Trng thi, thng s trng thi:
Mi h c mt trng thi xc nh nh cc thng s (bin s) c xc nh - gi l
thng s trng thi. Cc thng s c th l khi lng vt (khi lng Zn th d trn), c
th l p sut, th tch, thnh phn ca h, nhit ...
Th d nh kh l tng xc nh trng thi ca h ta cn bit mt s thng s nh
p, V, n, T nhng ch cn 3 trong s 4 thng s ta c th bit c thng s th 4 nh phng
trnh trng thi kh.
Mt h c gi l cn bng nhit ng hc khi h khng trao i vi bt c g vi
mi trng bn ngoi v nhng bin s trng thi ch c mt gi tr duy nht mi thi im
v khng ph thuc vo thi gian
1.1.3.Bin i (cn gi l qu trnh) : Bin i l s thay i trng thi nhit ng ca
h. Bin i c xc nh khi ch bit trng thi u v trng thi cui. ng bin i ch
c xc nh khi bit c trng thi u, trng thi cui v c cc trng thi trung gian m
h tri qua.
- Bin i h : L bin i m trng thi u v trng thi cui khc nhau.
1 HA I CNG 2
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- Bin i kn : Khi trng thi u v cui ging nhau - cn gi l mt chu trnh.
- Bin i ng tch (dV = 0) : Bin i thc hin trong iu kin th tch khng i.
- Bin i ng p (dp = 0) : Bin i thc hin trong iu kin p sut khng i.
- Bin i ng nhit (dT = 0) : Bin i thc hin trong iu kin nhit khng i.
- Bin i on nhit (Q = 0) : Bin i thc hin trong iu kin nhit lng khng
i.
- Bin i thun nghch : L bin i m cc trng thi trung gian m h tri qua c
xem l cn bng (xy ra theo hai chiu ngc nhau). Mun vy cc trng thi trung gian phi
xy ra v cng chm. Mun bit c bin i c thun nghch hay khng ta xem bin i
ngc li c th xy ra c hay khng khi thay i rt t iu kin thc nghim. V d nh
s chuyn pha l bin i thun nghch
Cn bin i bt thun nghch l bin i khng th xy ra khi ch thay i cc thng
s trng thi mt lng v cng nh - ta gi bin i bt thun nghch l qu trnh t din
bin hay cn gi l qu trnh t xy ra. Th d : S ri t do l bt thun nghch...
1.2.CNG GIN N CA KH :
Gi s ta c h bn : Trong mt xy lanh cha kh (l tng) pn dl
c chn bi mt piston (xem lc ma st gia piston v xy lanh bng
khng) v chu tc dng ca mt lc bn ngoi F. Khi kh gin n (nh
cung cp nhit chng hn) a piston ln mt on v cng nh dl th
h s sinh ra mt nguyn t cng A = -Fdl (du (-) do h phng thch pk
F
cng). Vi F l lc bn ngoi tc dng ln piston. M p n = .
s
Vi p n : p sut bn ngoi ; s : tit din ca piston. Th F = p ns vo biu thc trn
A = -pnsdl = -pndV
Khi h bin i t trng thi u (V1) sang trng thi cui (V2) th :
2 2
A = A p n dV (1)
1 1
- Nu s bin i l bt thun nghch : lc y p n p k v thng p n = p kq= const

th cng dn n l cng bt thun nghch :
2
Abtn = - p kq dV = -pkq (V2 - V1) hay Abtn = -pkq V (2)
1
Vi pkq l p sut kh quyn.

- Nu s bin i l thun nghch th p sut ca kh nm trong xy lanh mi
lc u khng khc vi p sut bn ngoi pn. Tc pn = pkh. V nu xem kh l l tng th
2 2 2
nRT dV
p kh = . T : Atn = A - p khi dV - nRT
V V
1 1 1
V2
Nu bin i ng nhit (dT=0) Atn = -nRTln (3)
V1
T (2) v (3) ta thy khi c cng trng thi u v cui : At/n Abtn v lun lun c Atn
l cc i.
2 HA I CNG 2
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Nh vy ta cng thy cng khng phi l hm trng thi v n khng nhng ph thuc
vo trng thi u, trng thi cui m cn ph thuc vo qu trnh bin i na. (Nu cng l
hm trng thi th cng ch ph thuc vo trng thi u v trng thi cui m y ta thy
vi bin i thun nghch v bt thun nghch th cng A khc nhau)
1.3.NGUYN L TH NHT CA NHIT NG HC V MT S I LNG

NHIT NG :
1.3.1.Nguyn l 1 v ni nng :
Nguyn l 1 chnh l nh lut bo ton nng lng, n c nhiu cch pht biu:
Nng lng khng th t sinh ra v cng khng th t bin mt. Mt cch pht biu
khc: Nng lng ca mt h c lp lun c bo ton.
Th d : Nu h m hay kn th khi nng lng ca h b mt mt lng l E th mi
trng ngoi s nhn c E di dng no nh nhit, cng,...
cng thc ha nguyn l 1, ta c th pht biu : C mt h bin i t trng thi
u (1) sang trng thi cui (2) theo nhiu ng bin i a, b, c, d... v nu gi nhit (nhit
lng) v cng trao i vi mi trng ngoi trong mi ng bin i l Qa, Aa, Qb, Ab, ...
Qi, Ai. Th Qi, Ai thay i ph thuc vo ng bin i, nhng tng i s Qi + Ai lun lun
l mt hng s.
Qi + Ai = Qa + Aa = .... = hng s.
Hng s l U : c gi l bin thin ni nng ca h
Vy U = Q + A (4) Hoc vit di dng vi phn : dU = Q + A (5)
Ni nng l g ? L nng lng bn trong ca h - l nhng nng lng no ?
Ta bit nng lng ca h c 3 phn :
- ng nng : S chuyn ng ca c h, thng thng trong phn ng ha hc th h
ng yn.
- Th nng : Nng lng ca h do trng ngoi v thng thng trong phn ng ha
hc th trng ngoi cng khng i.
- Ni nng : Nh vy ni nng l nng lng ton phn tr ng nng v th nng ca
c h. N chnh l nng lng do s chuyn ng ca phn t, nguyn t, electron, ht nhn
(cc chuyn ng tnh tin, quay) v th nng tng tc (lc ht, y) ca cc phn t,
nguyn t... trong h.
Thng thng ta khng kho st n ni nng U m ta ch cn bit n bin thin ni
nng U ca h.
hiu r hn biu thc (4) ta c th a ra mt th d :
Gi s ta c mt h kn cha kh l tng trong mt xy lanh c piston chn, lc
y ni nng ca h l U1. By gi nu ta cung cp mt nhit lng Q vo th h s nhn lng
nhit ny ni nng bin i t U1 U2 v phng thch mt cng A nng piston ln. V v
theo nguyn l 1, nng lng c bo ton, do : Q = U2 - U1 - A .
2
Q = U - A = U + pdV
1
Nu bin i l ng tch th dV = 0, lc y : QV = U
3 HA I CNG 2
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Vy bin thin ni nng chnh l nhit ca phn ng trong iu kin ng tch. y
chnh l ngha thc t ca ni nng.
Lu :
- Nguyn l 1 gip chng ta tnh U, ch khng phi tnh U, v hu nh ta khng cn
thit bit n U, V vy ngi ta quen dng thut ng ni nng ch bin thin ni nng.
- Nu h thc hin mt bin i kn, tc trng thi u v cui ging nhau th U1 = U2
U = 0. Vy Q = -A. Khi h nhn nhit s phng thch cng v h pht nhit s thu cng.
cng l mt cch pht biu ca nguyn l 1- chnh l cch pht biu ngay t u.
Ta cn nh li quy c du :
- Khi h thu nhit th Q > 0 s phng thch cng A < 0
- Khi h to nhit th Q < 0 s nhn cng A > 0
1.3.2.Entalpi :
2
T nguyn l 1 : Q = U - A = U + pdV
1
2
Nu bin i l ng p (dp = 0) Qp = U + p dV
1
Qp = U2 - U1 + pV2 - pV1 = (U2 + pV2) - (U1 + pV1) Qp = (U + pV)2 - (U + pV)1

Ta thy rng nhit trao i trong iu kin p sut khng i bng hiu s ca (U +
pV) trng thi cui (2) v (U +pV) trng thi u (1). Vy (U + pV) ph thuc vo trng
thi u v trng thi cui, vy n cng l hm trng thi nh U .
Ngi ta gi n l entalpi, c k hiu : H H = U + pV (6)
Qp = H2 - H1 = H (7)
Vy bin thin entalpi chnh l nhit ca qu trnh trong iu kin ng p. Thng
thng phn ng c thc hin trong iu kin thng vi kh quyn bn ngoi - tc iu
kin ng p. Nh th i lng Qp = H c dng hn c U
Ly vi phn ca (6) khi p = const dH = dU + pdV
2 2 2
Ly tch nhn 2 v t trng thi u (1) n cui (2) ta c : dH dU pdV
1 1 1
Khi p = const th H = U + pV hay vit cch khc : Qp = Qv + pV (8)

Biu thc (8) ch c dng khi p = const
1.3.3.Nhit dung :
T cng thc : Q = m.c(t2 t1) = n.M.c. T . Vi Q l nhit lng trao i khi cht c
khi lng m, c nhit dung ring c, nhit t1 bin thin ln nhit t2. Nhit dung ring c
l nhit lng cn thit a 1 gam cht ln 10C.
t M.c = C. Vi C gi l nhit dung mol ca cht. Vy :
Q
C=
n.T
Vy nhit dung chnh l nhit lng cn thit a h ln 10.
4 HA I CNG 2
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V i lng Q ph thuc vo qu trnh, nn nhit dung C ca h cng ph thuc vo
iu kin tin hnh qu trnh.
Q dU
- Trong iu kin ng tch : CV = ( )V
n.dT n.dT
2
Hay : dU = n.CVdT. Hay U = n CV dT
1
Q dH
- Trong iu kin ng p : Cp = ( )p
n.T n.dT
2
Hay : dH = nCpdT Hay H = n C p dT
1
Gia Cp v Cv c mi lin h : T : Cp = dH v CV = dU
n.dT n.dT
dH dU d ( H U ) d ( pV )
Nn Cp - CV =
n.dT n.dT n.dT
* i vi cht rn v a s cht lng iu kin bnh thng, cng gin n c th
xem l khng ng k (s gin n th tch 0) dV 0
dV
iu kin ng p : Cp - Cv = p
n.dT
Tc i vi cht rn hoc cht lng : Cp - Cv = 0 hay Cp = CV
T (8) ta cng thy i vi cht rn hoc cht lng : H U
* i vi cht kh c xem l l tng th :
d ( pV ) d (nRT ) dT
pV = RT (cho 1 mol), nn Cp - CV = R
n.dT n.dT dT
Vy i vi cht kh : Cp - CV = R
1.3.4.Mt vi bin i :
1.3.4.1.Cng gin n trong chn khng :
Ta c : A = - p n dV Trong chn khng p n = 0 A = 0
Vy s gin n ca kh trong chn khng, khng cung cp cng.

1.3.4.2.Kh l tng bin i theo chu trnh :
Cng nh kh l tng bin i ng nhit. U = H = 0 Q = -A
1.3.4.3.Kh l tng bin i ng nhit v thun nghch
V2
ng nhit : dT = 0 U = H = 0 nn Q = -A = p dV
n
V1
nRT V2
Thun nghch nn pn = p kh = V vy : Q = -A = nRT ln
V V1
V2 p
V v T khng i nn = 1 (t phng trnh trng thi kh)
V1 p2
5 HA I CNG 2
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p1
Nn Q = -A = nRT ln
p2
1.3.4.4.Kh l tng bin i ng tch :
2
ng tch : dV = 0 A = - pn dV = 0 Qv = U = nCV dT
1
1.3.4.5.Kh l tng bin i ng p :

Lc y A = - pdV = -pV = -p(V2 - V1)
hay A = -(n2RT2 - n1RT1), nu ngoi ng p cn ng nhit th A = -RT n

Qp = H = U + RT n
1.3.4.6.Kh l tng bin i on nhit v thun nghch.
on nhit Q = 0. T nguyn l 1 : Q = dU - A dU = A
dV
m dU = nCVdT v A = -pdV = -nRT
V
dV dT R dV
Vy : nCVdT = - nRT
V T CV V
2 2
dT R dV
Ly tch phn 2 v :
T Cv V
1 1
T2 R V V T2 V
ln ln 2 ln ( 1 ) R / CV Vy : ( 1) R / CV
T1 C v V1 V2 T1 V2
1.3.5.Mt vi th d :
Th d 1 : Tnh cng sinh ra 25oC khi ha tan 56g Fe vo dung dch axit HCl d:
a) Trong mt bnh kn
b) Trong mt cc thy tinh h
Gii :
a) Trong bnh kn tc th tch khng i dV = 0 A = -pdV = 0.
b) Trong cc h :
T phng trnh phn ng : Fe + 2HCl FeCl2 + H2 nH2 = nFe = 56/56 = 1 (mol).
Cng sinh ra l do H2 : A = p.dV = -pV = -pn(V2 - V1). Trong bnh h nn p n = 1
atm. V1 : th tch kh (H2) khi cha phn ng = 0
V2 : th tch kh sau phn ng. Nn A = -p nV2 v nu xem H2 nh kh l tng th :
22,4
A = -p nV2 = -nRT = -1. ( 273 25) = -24,45 l.atm.= -2477,57 J
273
Th d 2 : Tnh U, H, A, Q khi 1 mol kh l tng gin n t p1 = 1atm n p 2 =
0,1atm ti 27,3oC.
Gii : Kh l tng gin n trong iu kin nhit khng i (ti 27,3oC) tc
dT = 0 U = H = 0.
2 2 2
nRT dV
T nguyn l 1 : Q = U - A = -A = p.dV = dV = nRT V
V
1 1 1
6 HA I CNG 2
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V2 p 22,4 1
Q =-A = nRTln =nRTln 1 = 1. (273 + 27,3) ln = 56,7357 l.atm = 5739,15 J
V1 p2 273 0,1
Th d 3 : Cho 10 lt kh He 0 oC v 10atm. Hy xc nh th tch cui v cng do h

thc hin khi gin n ti 1atm trong 3 trng hp sau :
a) ng nhit thun nghch
b) on nhit thun nghch
c) on nhit bt thun nghch.
Cho Cp = 20,9 J.mol-1.K-1 v CP khng ph thuc vo T ; R = 8,314J.mol-1.K-1
Gii : pV = nRT n = 4,46 mol. T Cp - CV = R CV = 20,9 - 8,314 = 12,586
p1V1T2
a) ng nhit, thun nghch : T phng trnh kh l tng : V2 = .
T1 p2
10.10
V ng nhit nn T 2 = T1 V2 = = 100 lt.
1
2 2 2
nRT dV V2 100
Cng: A = p.dV = dV = -nRT V = -nRTln = -4,46.8,314.273ln
V V1 10
1 1 1
A = -23309J
b) on nhit thun nghch : on nhit nn Q = 0 Q = 0.
T nguyn l 1 A = U thun nghch : pk = pn.
dV dV C dT
T A = U hay A = dU -p.dV = n.CV.dT -nRT = nCVdT V . . Ly
V V R T
tch phn 2 v t trng thi (1) n trng thi (2) ta c :
p1V1 C
T2 CV R T1 CV R T1 CV R V R
V
V2 V2 V2 pV
ln ln( ) ln( ) ( ) ( nR ) R ( 2 ) CV 1 1 m Cp- CV
V1 T1 T2 V1 T2 V1 p 2V 2 V1 p 2V 2
nR
Cp
p 10
= R nn : V2 V1 ( 1 ) CV . Th s vo : V2 = 10( )3/5 = 39,75 lt.
p2 1
p 2V2 p1V1
Tnh cng A : Li c . Th s vo T2 = 108,5K.
T2 T1
M A = U = nCV(T2 - T1) = 4,46.12,586(108,5 - 273) = -9234J

c) on nhit bt thun nghch : Q = 0 Q = 0. T nguyn l 1 A = U
Khng thun nghch : pn pk v pn = 1atm. Vy p 1 = 10, p2 = p n =1atm khng i trong c
2
qu trnh. A = - p n .dV = -p2(V2 - V1) v v A = U -p2(V2 - V1) = nCV(T2 - T1).
1
p 2V2 p1V1
V2 - V1 = - 4,46.12,586( ). Th s vo V2 = 64 lt.
nR nR
Cng A = -p2(V2-V1). Th s vo A = -54 l.atm. = -54.101,33 = -5471,65J
1.4.HIU NG NHIT CA QU TRNH HA HC, NHIT HA HC :
Nhit ha hc l khoa hc nghin cu hiu ng nhit ca cc qu trnh ha hc. C s
cho vic nghin cu hiu ng nhit l s vn dng nguyn l 1 ca nhit ng hc.
7 HA I CNG 2
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1.4.1.Hiu ng nhit : Nh phn trc, ta bit nhit phn ng Q ph thuc vo
ng bin i. V vy vi mi phn ng no nu ch ni hiu ng nhit ca phn ng no
l bao nhiu th l iu v ngha.
cho hiu ng nhit c th c cc gi tr xc nh, ngi ta phi quy nh nhng
iu kin tin hnh phn ng. Nhng iu kin thng chn :
- Phn ng tin hnh trong iu kin th tch hoc p sut khng i (V = const hoc
p = const)
- H khng thc hin cng no khc ngoi cng gin n ng p.
- Nhit ca trng thi u v trng thi cui nh nhau.
Thng thng ngi ta chn iu kin tiu chun l 1atm v 25oC, lc y hiu ng
nhit c k hiu l : Ho298K. (Hiu ng nhit ng tch tng ng l U 298K
0
). V ngi ta
cn ghi c trng thi ca cht lc phn ng. Phng trnh ghi y nhng d kin gi l
phng trnh nhit ha hc.
Th d : H2(k) + 1/2O2(k) H2O(l) Ho298K = -285565 kJ
C ngha : 1mol H2 th kh phn ng va vi mol O2 th tch kh cho ra 1mol
H2O th lng 1atm v 25 oC to ra mt lng nhit l 285565 kJ
1.4.2.Cc loi hiu ng nhit :
1.4.2.1.Sinh nhit : (cn gi l nhit sinh hay nhit to thnh) sinh nhit ca mt
cht l lng nhit thot ra hay thu vo khi to thnh 1mol cht i t cc n cht bn
vng iu kin .
Nu iu kin o l 1 atm v 298K th gi sinh nhit lc y l sinh nhit chun
0
H 298K . T khi nim nhit sinh ta suy ra nhit sinh ca n cht bn iu kin tiu chun
0
c H 298K (n cht) = 0
1.4.2.2.Hu nhit : (cn gi l nhit hu) hu nhit ca mt cht l lng nhit
cn thit phn hu 1 mol cht cho ra cc n cht bn vng iu kin .
Tng t, nu iu kin o qui v iu kin tiu chun th gi l nhit hu chun.
1.4.2.3.Thiu nhit : (cn gi l nhit chy hay nhit t chy) Thiu nhit ca
mt cht l lng nhit thot ra khi t 1 mol cht cho ra cc oxit trng thi bn.
Tng t, nu iu kin o qui v iu kin tiu chun th gi l thiu nhit chun.
1.4.3.nh lut Hess :
nhit khng i hiu ng nhit ca mt phn ng trong iu kin ng p hay
ng tch 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.
nh lut ny do Hess tm ra nm 1836, nhng theo logich c th coi n l h qu ca
nguyn l 1.
o
Th d : A + B
H 298 K
sn phm
Ho1 Ho3
H o
E + F 2 G+H
Theo Hess : Ho298K = Ho1 + Ho2 + Ho3
H qu :
8 HA I CNG 2
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a) Hiu ng nhit ng p hay ng tch ca phn ng thun bng hiu ng nhit
ng p hay ng tch ca phn ng nghch nhng ngc du :
Tht vy ta c th v s :
o
A + B
H 298 K
A + B
Ho1 Ho2
F+F
Theo Hess : Ho298K = Ho1 + Ho2 : Ho298K = 0 v h khng i.
Nn Ho1 + Ho2 = 0 Ho1 = - Ho2. l iu phi chng minh.
Ho
b) Mt h qu khc : xt phn ng : AB + EF
AE + BF
Ho
Ta c th v s : AB + EF AE + BF
Ho1 Ho2 Ho3 Ho4
A + B + E + F hay A + E + B + F
Theo Hess : Ho = Ho1 + Ho2 + Ho3 + Ho4
: Ho1, Ho2 chnh l nhit hu ca AB v EF, cn Ho3 v Ho4 l nhit sinh
ca AE v BF
do : Ho1 = - Ho(AB) v Ho2 = - Ho(EF)
Vy : Ho = Ho(AE) + Ho(BF) - ( Ho(AB) + Ho(EF))
Biu thc ny chnh l h qu khc ca Hess :
Hiu ng nhit ca mt phn ng bng tng nhit sinh ca cc sn phm tr i tng
nhit sinh ca cc cht ban u.
1.4.4.Xc nh hiu ng nhit ca phn ng ha hc :
Trn c s ca nh lut Hess v h qu, chng ta c th xc nh hiu ng nhit ca
phn ng nu bit hiu ng nhit ca mt s cht lin quan.
Th d 1 : Tnh hiu ng nhit ca phn ng : 2C (graphit) + O2(k) 2CO(k)
Bit : C(gr) + O2(k) CO2(k) c Ho1 = -393,129kJ
V 2CO(k) + O2(k) 2CO2(k) c Ho2 = -565,47kJ
H o ?
Gii : Ta c s : 2C(gr) + 2O2 2CO(K) + O2(K)
2Ho1 Ho2
2CO2
Theo Hess : 2 Ho1 o
= H + Ho2 H = 2Ho1 - Ho2
o
Ho = 2 (-393,129) - (-565,47) = - 220,788kJ

Th d 2 : Tnh Ho298K ca phn ng : C2 H4 (k) + H2 (k) C2H6 (k)
Cho bit : Ho298K (C2H4) = 52,368KJ/mol ; H298K (C2H6) = -84,68KJ/mol.
Gii : Theo h qu ca Hess : Ho298K = Ho298K (C2H6) - (Ho298K (C2H4) + Ho298K (H2))
Ho298K = -84,68 - (52,3 + 0) = 136,98 kJ
1.4.5.Nng lng ca mt s qu trnh :
1.4.5.1. Nng lng lin kt :
9 HA I CNG 2
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Khi to thnh lin kt, h bn hn v vy nhit lng c gii phng (H < 0), cn
khi ph v lin kt ta phi cung cp nng lng (H > 0). Nu cng mt cht v cng iu
kin th nghim, theo h qu ca nh lt Hess th nng lng to thnh lin kt s bng nng
lng ph v lin kt nhng ngc du. Ngi ta nh ngha : Nng lng ca mt lin kt
l nng lng cn thit ph v lin kt to thnh cc nguyn t th kh.
D dng thy rng : Nhit phn ly ca mt cht bng tng nng lng lin kt ha hc
ca tt c cc lin kt trong phn t ca n:
- V phn t H2 ch c 1 lin kt nn nng lng lin kt chnh bng nng lng phn
ly ca n : EH-H = Hpli = 435,556kJ.mol-1
- Vi phn t nhiu nguyn t ta c nng lng lin kt trung bnh.
Th d : CH4(k) H
C(k) + 4H(k). Th nng lng lin kt trung bnh ca C-H l :
1
EC-H = H Cch tnh ton cng da vo nh lut Hess
4
- Vi phn t phc tp hn, th d nh C2H6
C2H6 (k) H
2C(k) + 6H(k)
H1 H2 H3
2C(k) + 3H2(k)
Theo Hess : H = H1 + 2 H2 + 3 H3
Vi : H l nng lng phn ly ca C2H6 ; H1l nhit hu ca C2H6 = -H (C2H6) ;
H2 l nhit thng hoa ca C (r k) ; H3: Nhit phn ly ca H2
Trong : H = EC-C + 6EC-H (vi EC-C v 6EC-H l nng lng ca lin kt C-C v C-H)
1.4.5.2.Nhit chuyn pha : Chuyn pha l qu trnh mt cht bin i t trng thi
ny sang trng thi khc m khng lm thay i cht.
l cc qu trnh bin i t trng thi rn sang lng, t trng thi lng sang rn, t
trng thi lng sang hi, t trng thi hi sang lng, t trng thi rn sang hi, chuyn dng
th hnh. Lng nhit thot ra hay thu vo ca qu trnh gi l nhit chuyn pha. Qu
trnh chuyn pha thng l ng nhit.
Th d : Tnh nhit ha hi ca H2O. Bit :
HoH2O(l) = -285,58kJ.mol-1 v HoH2O(h) = -241,6kJ.mol-1
o
Ta c qu trnh: H2O(l)
H
H2O(h)
Theo h qu ca Hess: Ho = HoH2O(h) - HoH2O(l) = -285,58- (-241,6) = -43,97kJ.mol-1
1.4.5.3.Nhit hydrat ha v nhit ha tan :
Khi ha tan mt cht tan c vo mt dung mi xc nh, thng qu trnh ny cng
thu hoc pht nhit - Lng nhit ny gi l nhit ha tan.
Tht ra s ho tan gm 2 qu trnh:
- Qu trnh vt l : qu trnh ph v mng tinh th li ko cht tan ta khi mng (do
dung mi chuyn ng khng ngng, lc y dung mi li ko ion ra khi mng bng lc tnh
in. Qu trnh ny thng thu nhit : H1 > 0
- Qu trnh ha hc : Cc ion c n nh nh tng tc vi dung mi (H2O). Quanh
mt ion c nhiu phn t dung mi v u m ca phn t dung mi hng vo ion (+) v
10 HA I CNG 2
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ngc li u dng ca phn t dung mi hng vo ion (-) : qu trnh ny gi l solvat ha
(nu dung mi l H2O gi l hydrat ha). Thng qu trnh ny pht nhit :
H2 < 0. Vy, nhit ha tan : H = H1 + H2
V H1 thng ln hn 0 v H2 thng nh hn 0 nn c qu trnh ha tan thu nhit,
li c qu trnh ho tan pht nhit do H1 so vi H2
S tnh ton v nhit ho tan hay nhit hydrat ha cng da vo nh lut Hess hoc
h qu ca Hess.
Th d : Xc nh nhit ha tan ca qu trnh ha tan NaCl trong H2O
H o ?
Qu trnh ha tan : NaCl(r) + (m+n) H2O Na+.mH2 O + Cl-.nH2O
Theo Hess : Ho = HoNa+m.H2O + HoCl-.nH2O - HoNaCl(r)
Tra bng nhit to thnh tiu chun ca ion hydrat ha ta c:
HoCl-.mH2O = -240,22kJ.mol-1 ; HoCl-.nH2O = -167,2kJ.mol-
Tra bng nhit to thnh tiu chun ca cht : HoNaCl = -412,15kJ.mol-1
Nhit to thnh ca cc ion khng th xc nh bng thc nghim v khng th tch
c cc ion (+) v (-) ring l c. V vy nhit to thnh tiu chun ca ion ch c th xc
nh bng tnh ton nhit ha. V chn sinh nhit chun ca H+.nH2O bng khng. Tc l :
1/2H2(k) + nH20 H+.nH2O c H 0H .nH O = 0
2
V sinh nhit tiu chun ca ion hydrat ha tng t nh nh ngha sinh nhit ca cht.
Sinh nhit tiu chun ca ion hydrat ha l lng nhit pht ra (hay thu vo) to
thnh mt mol ion hydrat ha i t cc n cht trng thi bn vng.
1.4.6. S ph thuc ca hiu ng nhit vo nhit v p sut :
Hiu ng nhit ca mt phn ng ph thuc vo nhit , p sut. Khi p sut cao
th mi gy ra hiu ng nhit ng k, cn p sut thng th c th b qua.
S ph thuc ca hiu ng nhit vo nhit do Kirchoff tm ra.
Gi s c phn ng : aA + bB eE + fF
Vn t ra l tnh c hiu ng nhit HT2 nhit T2 khi bit hiu ng nhit
HT1 nhit T1 ca phn ng .
Theo nh lut Hess :
HT
T2 : aA + bB 2
eE + fF
H3 H4
T1 : aA + bB
HT1
eE + fF
Vy : HT2 = H3 + HT1 + H4
m H3 v H4 l hiu ng nhit ca s bin i cht nguyn cht theo nhit nn :
T1 T2 T2
H3 = (aC p A bC pB )dT (aC pA bC pB )dT v H4 =

T2 T1
(eC
T1
pE fC pF )dT
T2
Vy : HT2 = HT1 + (eC pE fC pF - aC pA bC pB )dT

T1
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t : eCpE + fCpF - aCpA - bCpB = Cp ( : CP = Cp sn phm - Cp cht phn ng)
T2
Vy : HT2 = HT1 + C dT
T1
p
Th d : Tnh Ho1100K ca phn ng : CaCO3(r) CaO(r) + CO2(k). Bit :

Cht Ho298K (KJ mol-1) Cop(J.K-1.mol-1)
CaO(r) -635,09 48,83+4,52.10-3T +6,53.10-5T-2
CaCO3(r) -1206,87 104,52+21,92.10-3T-25,94.105T-2
CO2(k) -393,51 28,66+35,7.10 -3T
Gii : Ho298K = Ho298K (CaO) + Ho298K (CO2) - Ho298K (CaCO3)

= -635,09 -393,51 - (-1206,87) = 178,27 (KJ)
Cp = 48,83+4,52.10 -3T +6,53.10 -5T-2 + 28,66+35,7.10-3T-(104,52+21,92.10-3T-25,94.105T-2)
CP = -27,03 + 0,0183T - 19,42.10-3T-2
T2 T2
-3 -2
C
T1
P dT = ( -27,03 + 0,0183T - 19,42.10
T1
T )dT
0,0183 2 1 1
= -27,03(T2-T1) + (T2 T12 ) + 0,1942 . Th T1 = 298 v
2 T2 T1
T2
T2 = 1100, t tnh c Ho1100K theo Kirchoff : Ho1100K = Ho298K + C P dT

T1
1.5.NGUYN L 2, 3 CA NHIT NG HC :
T u chng ta t vn : Mc tiu ca nhit ng hc l tr li cho c 3 vn
:
Vn th nht : khi trn 2 hay nhiu cht th phn ng c xy ra hay khng ? Nu c
th xy ra theo hng no ?
Nguyn l 1 khng gip chng ta tr li c vn ny mc d mt phn gip d
on - l nh hiu ng nhit ca phn ng - Phn ng pht nhit th nng lng ca h
gim xung v thng phn ng xy ra sao cho nng lng cc tiu. Nhng khng phi lun
lun l nh vy. C nhng qu trnh thu nhit, qu trnh y vn xy ra nhit cao.
V vy t mc tiu, chng ta cn phi tm hiu mt s vn khc.
1.5.1.Nguyn l th 2 :
Nguyn l ny c tnh cht tru tng- kh tip thu hn nguyn l 1. Nguyn l 2 c
th pht biu di rt nhiu dng ph thuc vo li ch ca vic s dng. Nhng khm ph
u tin l do vic kho st s chuyn ha gia nhit v cng trong ng c nhit.
1.5.1.1.Cch pht biu ca Clausius :
Nhit khng th t truyn t vt lnh sang vt nng hn.
y l mt nh - c rt ra t thc tin, l s thc hin nhin, s d tay ta (vt
nng) s vo vt lnh gy nn cm gic lnh v tay ta b mt nhit cho vt lnh, ch khng
phi nhit lnh truyn sang tay ta.
1.5.1.2.Cch pht biu ca Thomson :
12 HA I CNG 2
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Khng th ch to c mt ng c m kt qu duy nht l s chuyn nhit thnh
cng.
n t duy nht- iu c ngha ch to c mt ng c nhit th ng
c ly nhit ngun nhit Q1 (c T1), n s sinh ra mt cng A, ng thi phi mt mt lng
nhit Q2 (Q2 < Q1) mt lng no .
Hai cch pht biu c v khc nhau tht ra c th suy ra t nhau. Ta c th chng
minh bng phn chng :
Gi s c th ch to ra mt my ch cn ly nhit t mt ngun v bin hon ton
thnh cng A (ngc vi Thomson). My gi s ly nhit t ngun lnh Q 2 v bin hon
ton thnh cng A, sau bin cng A hon ton thnh nhit (iu ny th hin nhin) ri
nhng nhit ny cho vt nng. Nh vy l c th chuyn nhit t ngun lnh sang ngun
nng hn - tri vi Clausius.
Tr li vi cch pht biu ca Thomson : Thomson cng c ngha : Nhit khng th
bin han ton thnh cng m khng c s n b (cn gi l s b chnh)
y cng l cch pht biu ca nguyn l 2. Nh vy my ly nhit ngun nng Q1
bin thnh cng A ng thi phi n b (s mt i) mt lng nhit Q2 (Q2 < Q1).
Lng nhit Q2 ny lm g?
- lm thay i trng thi ca h (V, p) nu h thc hin qu trnh bin i h.
- Hoc Q2 truyn cho vt truyn nhit ri mt nhit ra mi trng ngoi (c T2 < T1) nu
l bin i kn. Q1 = A + Q2
Q2 mt trong vic lm bin i trng thi hoc cho bt i. l iu bt buc trong vic
bin nhit thnh cng A.
Nh vy :
Nguyn l 1 khng nh s tng ng gia cng v nhit v mt s lng.
Trong khi :
Nguyn l 2 khng nh s khng tng ng gia nhit v cng v mt cht lng.
Tm li : Cng c th bin hon ton thnh nhit, nhng nhit khng th bin hon
ton thnh cng m phi mt bt i mt phn nhit.
Nh vy ta c th thy : trong mt chu trnh ng nhit thun nghch th cng bng
khng (0), cn trong mt chu trnh ng nhit bt thun nghch th cng nh hn khng. Bi
v, chu trnh l bin i kn - th theo nguyn l 2 h mun thc hin cng phi mt nhit cho
mi trng ngoi - th nhit phi thay i.
Kh l tng nhn nhit mt ngun no lm gin n th nh vy nhit c th bin
hon ton thnh cng khng ? c, nhng phi n b bng vic thay i th tch ca h.
1.5.2.Entropy :
1.5.2.1.Khi nim : T nguyn l 1 khi ni th mi quan h gia nhit v cng th
xut hin hm trng thi : ni nng, entalpi. Cng vy, t nguyn l 2 khi kho st mi quan
h gia nhit v cng, lc y li xut hin mt hm trng thi khc c gi l entropy.
- Khi h chu mt bin i thun nghch v cng b trong h trao i vi mi
trng ngoi mt nhit lng Qtn nhit T. S bin i entropy trong qu trnh ny l
Qtn
dS =
T
Qbtn
- i vi qu trnh bt thun nghch (tc l qu trnh t xy ra) th dS >
T
13 HA I CNG 2
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Q
Tm li dS
T
Khi t trng thi (1) sang trng thi (2), i vi qu trnh thun nghch :
2 2 2
Qtn Qtn
dS T
S 2 S1 S T
1 1 1
2
Qbtn
- Tng t i vi qu trnh bt thun nghch : S > T
1
Qtn
Nu qu trnh l thun nghch, ng nhit : S =
T
Nu qu trnh l thun nghch, on nhit : dS = S = 0

Vy qu trnh thun nghch, on nhit chnh l ng entropy
Nh vy i vi qu trnh bt thun nghch, ta xc nh chnh xc S ca qu trnh
Qbtn
bng cch no ? (v i vi qu trnh bt thun nghch ta mi ch c : S > )
T
Mun tnh S ca qu trnh bt thun nghch, ta hnh dung mt qu trnh thun nghch
c cng trng thi u v trng thi cui vi qu trnh bt thun nghch . Lc y, ta c:
2 b
Qtn
S =
T
1 ng b : bt thun nghch
ng a : thun nghch (1) (2)
a
(V S l hm trng thi nn ch ph thuc vo trng thi u v trng thi cui m khng ph
thuc vo ng i)
1.5.2.2.Tnh bin thin entropy cho mt s qu trnh :
a) Qu trnh thun nghch ng nhit : Loi qu trnh ny p dng cho nhng loi
chuyn pha (khi T = const) : bc hi, ho lng, nng chy, ng c, thng hoa,
T dS = Q . Ly tch phn 2 v trong iu kin ng nhit ta c : S Q . Tu trng

T T
hp, nu cn th Q = U p.dV S
U p.dV .
T
Th d : Tnh bin thin entropy ca qu trnh nng chy ca nc 00C v 1atm.
Bit c 1 mol nc khi nng chy cn mt lng nhit l 6002,5J.
Gii : iu kin ng nhit nn S Q 6002,5 21,987J.mol-1.K-1.

T 273
b) S bin thin entropy ca cht nguyn cht theo nhit :
Qu trnh thun nghch ng tch :
ng tch : dV = 0 A = 0 QV = U .
T2
QV dU dT dT
Nn dSV = nCV S V nCV .
T T T T
T1
14 HA I CNG 2
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T2
Nu CV khng ph thuc vo T th : ST nCV ln
T1
Qu trnh thun nghch ng p :

2
dH dT dT
ng p : dp = 0 Qp = H . Nn dS nC p
S nC p .
T T T
1
T
Khi Cp khng ph thuc vo T th : S T nC p ln 2
T1
c) Qu trnh thun nghch ca kh l tng :

Q dU A dU p.dV nCV dT nRTdV dT dV
dS nCV nR .
T tn T T T T T V
V2 T
Khi CV khng ph thuc vo T S nR ln nCV ln 2 .
V1 T1
Cng t biu thc dS dU pdV , ri da vo cc biu thc trc ta cng chng minh c :
T
p2 dT
S nR ln
p1
nC p
T
Qbtn
d) Qu trnh bt thun nghch : i vi qu trnh bt thun nghch ta c : dS ,
T
nhng biu thc ny khng th tnh c entropy c th. V vy i vi qu trnh bt thun
nghch ta phi tm con ng bin i khc sao cho ng bin i mi l thun nghch v
tnh bin thin entropy theo ng thun nghch (d nhin c 2 ng bin i : thun nghch
v bt thun nghch u c cng trng thi u v trng thi cui), v theo nh lut Hess, S l
hm trng thi nh U, H, nn S ch ph thuc vo trng thi u v cui m khng ph thuc
vo ng bin i. Trong ha hc ta thng gp bin i bt thun nghch l qu trnh chm
ng (ng c nhit thp hn)
Th d : Tnh S ca qu trnh kt tinh benzen trong 2 trng hp :
nhit ng c t = 5 0C (thun nghch)
nhit chm ng t = - 5 0C (bt thun nghch).
Nu nhit nng chy ca benzen 5 0C, 1atm l 9906,6J/mol ; Cp(l) = 126,65J.mol-1.K-1
Cp(r) = 122,47J.mol-1.K-1.
Gii :
Q
Thun nghch 50C, 1atm. T dS = . Trong iu kin ng nhit, nn
T
Q 9906,6 -1
S 35,61J .mol 1. K .
T 278
Bt thun nghch : Ta hnh dung n i qua con ng thun nghch gm 3 giai on
:
- Giai on 1 : ( S1 ) nng nhit t -50C ln 5 0C v cng chm (bin i thun nghch)
- Giai on 2 : ( S 2 ) kt tinh 50C nh qu trnh thun nghch.
- Giai on 3 : ( S 3 ) h nhit t 5 0C xung -50C v cng chm (bin i thun
nghch) C6H6 (l, 278K)
S2 ( tn )
C6H6 (r, 278K)
S1 S 3
15 HA I CNG 2
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S
C6H6 (l, 268K) C6H6 (r, 268K)
Theo nh lut Hess : S S1 S 2 S3 .
T2
M i vi cc qu trnh thun nghch ng p th : S p nC p ln
T1
278 268
Nn : S1 1.126,65 ln 4,64 v S 3 1.122,47 ln 4,47
268 278
cn S 2 = - 35,61 . V vy : S S1 S 2 S3 = - 35,45J.mol-1.K-1
1.5.2.3. ngha ca entropy :
a) Entropi trong h c lp : Trong t nhin, khi khi qut c th xem c hai loi qu
trnh : qu trnh t din bin v qu trnh khng t din bin.
- Qu trnh t din bin l qu trnh t n xy ra khng cn c mt cng bn ngoi
tr lc l qu trnh bt thun nghch, th d nh electron chuyn ng quanh ht nhn
nguyn t, hnh tinh quay quanh mt tri (khng sn ra cng c ch), nh nc chy t cao
xung thp, s to nhit ca mt tri (sn ra cng c ch) u l qu trnh t din bin (cn
gi qu trnh t xy ra).
- Qu trnh khng t din bin : t n khng xy ra c nu khng c cng bn
ngoi tr lc, nh nng vt t thp ln cao, nhit truyn t lnh sang nng.
Trong h c lp ch c qu trnh t din bin (hay t xy ra)
T khi nim v h c lp ta thy vi h c lp chnh l on nhit : Q = Q 0 .
Qtn
Nu trong h c lp din ra qu trnh thun nghch th dS = =0
T
S 0 : Entropi ca h c lp khng i.
Nu trong h c lp din ra qu trnh bt thun nghch (l qu trnh t xy
Qbtn
ra) th dS > dS > 0 S 0 . Vy trong h c lp, vi qu trnh bt thun nghch
T
th entropi ca h tng ln. Entropi s tng mi trong h c lp t n cn bng, lc y S =
S max. Vy chnh entropi l thc o tnh khng thun nghch ca qu trnh, hay ni cch khc
entropi trong h c lp c trng cho chiu din bin ca qu trnh.
Nh vy : Qu trnh no trong h c lp c S 0 th n s t din bin cho n khi
S = S max tc l n cn bng th dng li.
(Lu rng : h c lp = h kho st + mi trng ngoi.)
r hn ta xt th d sau :
Th d 1 : Xt qu trnh bay hi ca n-hexan nhit si 68,7 0C v c nhit ho hi
l H = 28825,28J.mol-1.
Gii : y l qu trnh ng nhit thun nghch, nn :
Qp H 28825,28
S 84,36 J .mol 1 .K 1 . Ta thy qu trnh bay hi ca n-hexan c
T T 273 68,7
S 0 . Nh vy t trng thi lng sang trng thi hi th entropi ca h tng.
Ta rng S y l ca h ang kho st ch khng phi ca h c lp. M h
c lp = h kho st + mi trng ngoi. V h kho st nhn nhit 28825,28 J, do mi
trng ngoi phi mt mt lng nhit : - 28825,28 J. Vy mi trng ngoi (mtn) c :
H mtn
S mtn 84,35 J .mol. 1 K 1 . Nn, bin thin entropi chung ca h c lp :
T
16 HA I CNG 2
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0
S hcl S he S mtn 0 . Nh vy qu trnh bc hi ca n-hexan 1atm v 68,7 C l qu trnh
cn bng, khng t din ra c.
Th d 2 : Xt qu trnh trn ln mt h gm hai bnh thng nhau c kho cng p
sut v nhit vi nhau v bng mi trng ngoi, mt bnh cha 2 mol N2, bnh kia cha 1
mol H2.
Gii : nhit thng N2 khng phn ng vi H2, ta xem hai kh nh kh l tng.
N2 chim th tch Va, H2 chim th tch Vb. Do khi trn ln, th hai kh s chim ht th
tch Va + Vb. Bin thin entropi ca N2 kh trn ln :
2
Q
U p.dV V2 V Vb
S a 1
nR ln 2 R ln a
T T V1 Va
(Ch : kh l tng bin i ng nhit nn U = 0)
3
V ng p, ng nhit nn : Va = 2.Vb S a 2 R ln 6,74 J .mol 1.K 1 .
2
3
Tng t, bin thin entropi ca H2 : S b 1R ln 9,134 J .mol 1 .K 1 .
1
Bin thin entropi chung ca c h : S S a Sb = 15,87 J.mol-1.K-1.
Vy qu trnh trn ln cc kh (lm cho s hn lon tng ln) lm entropi tng. Hai kh
trn ln trong bnh kn, khng trao i nhit vi mi trng ngoi (v qu trnh trn ln cc
kh khng xy ra phn ng, khng pht hay thu nht), nh vy ta xem h l h c lp v c
S 0 . Nn qu trnh trn ln cc kh l qu trnh t xy ra.
b) Entropi l thc o hn lon : Nh vy trong th d 2 va xt, s khuych tn
ca kh vo nhau l qu trnh t din bin. Khi ban u, mi kh trong mi bnh, lc y s
chuyn ng ca cc phn t kh c trt t hn trng thi cui. Tc l s tng entropi tng
ng vi s tng hn lon. Nh vy c th ni rng :
Entropi l thc o hn lon ( v trt t) ca h.
Cng c th ni : Khi kho st v bin thin entropi, th vt cht lun c khuynh
hng i t trng thi trt t sang trng thi hn lon.
c) ngha thng k ca entropi : Nu h khng chu mt s bin i no, th trng
thi cui ging trng thi u, c ngha cc gi tr nng lng ca c h khng i, nhng
nng lng ring ca cc tiu phn trong h th thay i khng ngng, v cc tiu phn trong
h nhit ng vn khng ngng chuyn ng, nhng v ton th tiu phn (ca c h) c nng
lng khng i (do bo ton nng lng) nn c mt s (ln) tiu phn c nng lng tng
ln, th cng c mt s (ln) tiu phn trong h li c nng lng gim xung. Nh vy ng
vi mi trng thi nhit ng ca h (v m) c th tn ti nhiu s phn b nng lng khc
nhau gia cc tiu phn (vi m). S trng thi vi m ng vi mi trng thi v m ca h gi
l xc sut nhit ng ca h. Boltzmann l ngi u tin quan tm n s kin ny v
chng minh c rng : S = klnW.
Vi k l hng s Boltzmann, W l xc sut nhit ng ca h v S l entropi ca h.
Ta cng thy rng khi h c hn lon cng cao th cc tiu phn cng c nhiu trng
thi nng lng khc nhau, tc l xc sut nhit ng ca h t l vi hn lon ca h
1.5.3.nh lt Nernst, nguyn l 3 :
Khi kho st v tnh cht ca vt cht nhit rt thp (gn 0K) Nernst a ra
mt kt lun tr thnh nh lut :
17 HA I CNG 2
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Bin thin entropy (S) ca cc cht nguyn cht di dng tinh th hon ho gn
khng tuyt i l bng khng.
Sau ny Planck m rng kt lun ny khi ng a ra gi thit cho rng khi T 0,
khng nhng S = 0 m bn thn gi tr entropy ca cc cht nguyn cht trng thi tinh th
hon ho cng bng khng.
nh lut Nernst v c tin Planck thng c coi l nguyn l 3 ca nhit ng
hc.
Nguyn l 3 ca nhit ng hc cng cn c th l : Nguyn l khng th t ti 0K.
V khi gn ti 0K th nhit dung Cp, CV ca vt tin ti 0, do khng th no ly bt
c nhit ca vt vt t ti chnh xc 0K
1.5.4.S bin i entropy trong phn ng ha hc v trong mt s qu trnh thng
dng :
1.5.4.1.Qu trnh thun nghch ng nhit : Qu trnh ny p dng cho nhng
loi chuyn pha (T = const) : bc hi, ha lng, ng c, thng hoa, l nhng qu trnh
2
Qtn Qtn Q H
thun nghch nn : dS = S = . V ng nhit nn : S = tn
T T T T
1
Th d : Tnh S ca qu trnh nng chy ca nc 0 oC v 1atm. Bit c 1mol
nc khi nng chy cn 1 lng nhit l 6002,48J
6002,48
Gii : S J.K -1.mol-1
273
1.5.4.2.Qu trnh thun nghch (S bin i theo T)

Qv dU dT
* ng tch : dV = 0 QV = U dSV = nCv
T T T
T2
dT T2
SV = nCv (nu CV T SV = nCV ln )
T T1
T1
2
Q dH dT dT
* ng p : dp = 0 Qp = H => dS = nC p S nC p
T T T T
1
Th d : So 298 K ( H 2 0 ) = 69,89J.mol-1.K-1. Nhit dung mol ng p Cp(H2O) = 75,24J. mol-1.K-1

Xc nh entropi : S o 273 K ( H 2 0 ) ca H2O 273K
Gii : S = S o 298 K S o 273 K

y l qu trnh thun nghch ng p nn :
2
dT T 298
S = nC p m Cp T nn : S = nCp ln 2 S = 75,24 ln = 6,59J.mol-1.K-1
T T1 273
1
S o 273 K S o 298 K - S = 69,89 - 6,59 = 63,3J.mol-1.K-1

1.5.4.3.Trong phn ng ha hc :
V entropi l hm trng thi nn n tun theo nh lut Hess v cc h qu ca Hess.
aA + bB
S?
eE + fF. Th bin thin entropi ca phn ng l :
S = (e.SE + f.SF) - (a.SA + b.SB)
18 HA I CNG 2
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D on du ca S : Khi cht trng thi rn hay lng th entropy S b cn trng
thi kh th entropy S ln, nn khi mt phn ng m sau phn ng tng s mol kh sn
phm nhiu hn tng s mol kh ca cht phn ng th S > 0 v ngc li .
Th d : Xt phn ng : N2 (k) + 3 H2 (k) 2 NH3 (k)
Ta thy tng s mol kh trc phn ng l : 1 + 3 = 4 . Tng s mol kh sau phn ng = 2
Vy n = 2 - 4 = - 2 nn bin thin entropi ca phn ng l S < 0
S ph thuc ca entropy phn ng vo nhit :
Xt phn ng nhit T : aA + bB eE + fF. p = const
S
Ta c th vit : aA + bB ( T)
T
eE + fF ( T)
S1 S2
aA + bB ( To)
ST 0
eE + fF ( To)
Theo Hess : ST = S1 + STo + S2
To T
dT dT
m S1 = (aC p ( A) bC P( B ) ) =- (aC p ( A) bC p(B) ) T
T
T To
T
dT
V S2 = (eC p (E ) fC p ( F ) ) T
To
T
dT
Vy ST = STo + (eC p (E ) fC p( F ) aC p ( A) bC p( B) ) T
To
T
C P
M : C p = eCp(E) + fCp(F) - (aCp(A) + bCp(B)). Nn ST = STo + dT
T
To
1.6.TH NG NHIT, NG P. CHIU HNG DIN BIN CA QU TRNH.

1.6.1.Th ng p, ng nhit :
T nguyn l 1: Q = dU - A
Qtn
Theo nguyn l 2 vi bin i thun nghch : dS =
T
Nh vy : TdS = dU - A
Trong trng hp tng qut cng A gm cng gin n v cng c ch A,
t : TdS = dU + PdV + A A = TdS - dU - PdV (*)
(Vi bin i bt thun nghch, chng minh tng t ta c A <TdS - dU - PdV)
Biu thc (*) l biu thc nh lng hai nguyn l.
Khi iu kin ng p v ng nhit (tc l dp = 0 v dT = 0)
Lc y : TdS = d(TS) v pdV = d(pV), th vo (*)
A = d(TS -U - pV) = - d(H- TS) (v H = U + pV)
19 HA I CNG 2
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2 2
Khi h bin i t trng thi (1) sang trng thi (2) th :
A' d (TS H )
1 1
(trong iu kin ng nhit, ng p)
A = -[(H - TS)2 - (H - TS)1] hay A = - [(H - TS)2 - (H - TS)1]
Biu thc ny ni ln rng cng c ch (ta) nhn c v gi tr bng hiu s hm (H -
TS) trng thi cui v trng thi u.
Vy H - TS l hm trng thi gi l th ng nhit, ng p do Gibbs tm ra - nn cn
gi l hm Gibbs : G. Vy A = - G vi G = H - TS (**)
Cng c ch thu c s bng bin thin th ng p ca h pht ra trong qu trnh .
Ly vi phn ton phn (**) : dG = dH - SdT - TdS
2 2
Khi chuyn t trng thi (1) sang trng thi (2) tc l : dG dH SdT TdS
1 1
Vy : G = H - TS (trong iu kin ng nhit). G gi l bin thin th ng

nhit ng p, cng c gi l nng lng t do
Ngi ra cng quy c : Th ng nhit iu kin chun ca n cht bng khng
(Go298K(n cht) = 0)
V v G cng l hm trng thi nn n cng tun theo Hess.
Biu thc G = H - TS l biu thc c bn d on chiu hng ca qu trnh.
1.6.2.Chiu din bin ca qu trnh :
Chiu hng ca qu trnh c quyt nh do s cnh tranh ca hai yu t H v S,
m biu thc G trn (G = H - TS) li cha c hai yu t ny. Vy ta xem xt cc
trng hp c th xy ra trn biu thc :
- Khi S = 0 l nhng qu trnh trong khng c s bin i hn lon, nh nhng
phn ng thc hin pha rn hoc lng, cn khi pha kh th n = 0 (n : hiu s mol kh
sau v trc phn ng). Lc y qu trnh s t din bin khi H < 0 (pht nhit) nh vy l :
G < 0 : qu trnh t din ra trong trng hp ny.
- Khi H = O tc l nhng qu trnh khng xy ra s trao i nhit. V d kh l tng
gin n, lc y qu trnh t din bin khi S > 0 (theo hn lon tng), tc l G < 0 l qu
trnh t din bin trong trng hp ny.
- Khi H < 0 v S > 0 c 2 qu trnh u thun li cho s t din bin ca qu trnh,
lc y G < 0
- Khi H > 0 v S < 0 c 2 qu trnh u khng thun li t xy ra - Lc y qu trnh
khng t din ra G > 0
Nh vy tiu chun v t din bin ca qu trnh - i vi ha hc gi l kh nng t
phn ng - t xy ra c khi G < 0
Lu : Ta ni phn ng c kh nng t din ra, ch ta khng ni chc chn phn ng
s din ra v lc y ta khng th khng nh trong bao lu th phn ng mi xy ra c, v li
cho phn ng xy ra th cn cn phi tho cc iu kin ng hc (s xt chng 3)
Th d : Xt phn ng CaCO3(r) CaO(r) + CO2(k)
20 HA I CNG 2
Simpo PDF Merge
Bit :
Cht CaCO3(r) CaO(r) CO2(k)
Ho298K (kJ. mol-1) -1205,93 -634,94 -392,92
So298K (J. mol-1.K-1) 92,63 39,71 213,43
1) Xc nh chiu ca phn ng 298K.

2) Xc nh nhit ti CaCO3(r) bt u b phn hu.
Gii :
1) Gi s phn ng xy ra theo chiu : CaCO3(r) CaO(r) + CO2(k).
Theo Hess ta c : Ho298K (p) = Ho298K(CaO) + Ho298K(CO2) - Ho298K(CaCO3)
Ho298K(p) = - 634,94 - 392,92 - (- 1205,93) = 178,07J.mol-1.
Tng t : S 0298K ( pu ) = So298K(CaO) + So298K(CO2) - So298K(CaCO3)
S0298K ( pu ) = 39,71 + 213,43 - 92,63 = 160,51J.mol-1.K-1 = 160,51.10-3 kJ.mol-1.K-1
T cng thc : G = H - TS Go298K(p) = 178,07- 298.160,51.10-3 = 130,24kJ.mol-1
Ta thy G = 130,24 > 0. Nn 298K phn ng trn (phn hu CaCO3) khng c kh nng
xy ra
2) Nhit ti thiu cho CaCO3 phn hu khi G t > 0 chuyn sang G < 0, hay
H 178,07
ti thiu G = 0, tc l H - TS 0 T = 1109,4 K . Vy nhit ti
S 160,51.10-3
thiu CaCO3 bt u b phn hu l 1109,4K hay 836,40C
1.7.TH HO HC :
Trong nhng phn trc, ta mi ch bn n cc h kn - h ch trao i nng lng
vi mi trng ngoi m khng trao i cht. Nhng trong ha hc, phn ng thng xy ra
trong h h - c trao i cht vi mi trng ngoi. V vy thnh phn ca h thay i (nh
trong phn ng : lng cht tham gia phn ng gim, lng sn phm tng, hoc khi cht
chuyn t pha ny sang pha khc). Khi thnh phn ca h thay i th lm cc hm trng thi
nh U, H, S, G thay i theo. V vy chng ta cn kho st hm trng thi (nht l hm G)
trong iu kin lng cht thay i.
Trong h kn, t trc ta c : G = H - TS m H = U + pV G = U + pV - TS
Ly vi phn ton phn : dG = dU + pdV + Vdp - TdS - SdT (1)
M theo nguyn l 1: Q = dU - A = dU + pdV dU = Q - pdV (2)
Q
Theo nguyn l 2 : i vi qu trnh thun nghch : dS = Q = TdS, th vo
T
(2) ta c : dU = TdS - pdV, li th vo (1) dG = TdS - pdV + pdV + Vdp - TdS - SdT
Vy vi h kn ta c : dG = Vdp - SdT (3)
T (3) c th vit : Vi bin i ng p : ( G ) p S (4)
T
G
Vi bin i ng nhit : ( )T V (5)
p
By gi ta gi s trong h gm nhiu cht : cht 1, cht 2, cht 3, ....cht i vi s mol
tng ng l n1, n2, n3,...ni. Lc y th nhit ng G : G = G(p, T, n1, n2, ... ni)
21 HA I CNG 2
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G G G
Ly vi phn ton phn ta c : dG = ( ) T ,n dp ( ) p ,n dT ( ) T , p nj ni d ni
p T ni
G
Th (4) v (5) vo v t ( )T , p ,nj ni i (6)
ni
Ta c dG = Vdp - SdT + idni (7)
y l phng trnh c bn v tng qut ca nhit ng ha hc. i c gi l th

ha ca cht i
T (6) ta thy th ha ca mt cht l th ng p mol ring phn ca cht trong
hn hp.
* Nu cc qu trnh l ng p, ng nhit th (7) tr thnh : dG = idni (8)
Ly tch phn (8) ta c G = ini (9)
Ly vi phn ton phn (9) dG = idni + nidi (10)
So snh (8) v (10) nidi = 0 (11)
T phn trc (1.5.5.2.Chiu din bin ca qu trnh) ta bit cho qu trnh t
din ra th dG < 0 nn t (8), i vi cc qu trnh ng p, ng nhit, qu trnh t din ra
th : idni < 0
i vi phn ng ha hc : aA + bB eE + fF
Theo h qu Hess : G = eE + fF - (aA + bB). Hay G = i(sn phm) - i(phn ng)
cho qu trnh t din ra th : G < 0 hay i(sn phm) < i(phn ng)
Hay ni cch khc, s chuyn vt cht theo hng lm gim ha th.
Khi G = 0 phn ng t ti cn bng : i(sn phm) = i(phn ng)
Vy th ha cng chnh l i lng cho bit s t din bin v cn bng ca qu trnh
1.8.CC YU T NH HNG N TH NG P V TH HO
1.8.1.nh hng ca nhit n th ng p :
T trc (1.7.Th ho hc) c : t phng trnh (3) : dG = Vdp - SdT
G ( G )
Khi p = const dG = -SdT hay ( )p= - S. ( ) p S (*)
T T
( G )
Ta cng c : G = H - TS Th (*) vo G = H + T ( )p
T
( G )
T( ) p G
( G ) 2 T H
T ( ) p G H . Chia 2 v cho T ta c : 2

T T T2
G G
Ta thy v tri ca phng trnh chnh l o hm ca theo T : ( ) p.
T T T
G H
Nn : ( )p . Phn ly bin s ri ly tch phn t T 1 n T2 :
T T T2
T2 T2 T2
G H GT2 GT1 H T
d( ) T2 .dT - =- .dT
T1
T
T1
T2 T1
T1
T2
Phng trnh ny dng tnh th ng nhit ng p GT2 nhit T2 theo th ng nhit

ng p GT1 nhit T1.
GT2 GT1 1 1
Ch khi HT khng ph thuc vo T H T ( )
T2 T1 T2 T1
22 HA I CNG 2
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1.8.2.nh hng ca p sut p n th ng p v th ha :
G
T dG = Vdp - SdT. Khi T = const th dG = Vdp ( hay ( ) T V )
p
2 P2 P2
Ly tch phn 2 v t p1 n p2 : dG Vdp GT p2 GTp1 Vdp
1 P1 P1
* i vi cht rn hay lng, c th xem V = const khi p thay i (trong khong p sut
khng qu ln) : GTp2 -GTp1 = V(p2 - p1)
RT
* i vi cht kh c xem l l tng vi 1mol khi th V = nn :
p
P2
dp p
GTp2 - GTp1 = RT . V T = const nn : GTp2 - GTp1 = RT ln 2
p p1
P1
Nu p1 = 1atm GTp - GoT = RT ln p (*)

(Ch trong biu thc (*) p phi tnh bng atm, v p 1 = 1 atm)
T (9) mc 1.5.6.Th ho hc c : G = ini.
Nu xt 1 cu t th G = .n. V vy nu trong trng hp n = 1 = G
T : khi h ch c 1 cu t T khng i vi n = 1 th t (*) T = oT + RT lnp
(Cng nh trong biu thc (*), cn lu l trong biu thc ny p phi tnh bng atm)
BI TP
1) a) Mt bin i theo chu trnh kn ca kh l tng vi A = 418 J. Tnh Q ?

b) Cng cu trn nhng vi kh khng l tng
2) Tnh cng ca 10 mol kh l tng dn n trong chn khng
3) a) Tnh Q, A, U v H ca 1 mol kh l tng dn ng nhit v b c
2p1
thun nghch 27 0C t V1 n V2 = 10 V1
b) Cng cu trn nhng c em dn n trong chn khng
4) Tnh cng, nhit, ni nng v entalpi trong qu trnh abc (theo hnh
bn) c thc hin bi 1 mol kh l tng theo CV, p1, V1, R p1 a
5) Tnh Q, A, U ca qu trnh chuyn 1 mol H2 O(l) H2O(h)
100 oC,1 atm. Bit nhit ho hi ca nc bng 40.630 J.mol-1
6) Tnh U khi ho hi 1kg nc 150 oC, 1atm bit nhit ho hi lc O
V1 2V1
-1
y l 37,95 kJ.mol . Xem hi nc nh kh l tng.
7) Hai mol kh n nguyn t (nh l tng) dn on nhit v thun nghch t V1 n V2 =
10 V1. Nhit ban u l 27 oC. Tnh Q, A, U v H. Bit CV = 3/2 R
0
8) Tnh Q, A, U v H khi mt mol kh l tng dn n t 10 atm n 0,4 atm 0 C
0
9) Tnh cng ca s bin i thun nghch v bt thun nghch 42 g kh N2 300 C khi :
a) Dn n t 5 atm n 1atm.
b) Nn t 1atm n 5 atm.
23 HA I CNG 2
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0
10) Cho 100g CO2 0 C v 1atm. Xc nh nhit, cng, bin thin ni nng, bin thin
entalpi trong nhng qu trnh sau c tin hnh thun nghch nhit ng :
a) Dn ng nhit n th tch 0,2 m3
b) Dn ng p n th tch 0,2 m3
c) Nn on nhit n p sut gp i lc u
d) Nu nng ng tch ti p sut gp i lc u.
Xem CO2 l kh l tng v nhit dung ng p ca n khng i trong iu kin kho st
v bng 37,1 J.mol-1K-1
11) Tm hiu ng nhit ng tch v ng p ca phn ng gia Zn v H2SO4(long,d)
250C. Bit khi cho 32,5g Zn khi tc dng vi H2SO4 iu kin ng tch th thot ra mt
lng nhit l 71,478 kJ 250C
0
12) 25 C phn ng : 2H2(k) + O2(k) 2 H2O(h) to ra mt lng nhit l 483,626 kJ
iu kin ng p l 1atm. Nhit bay hi ca H2O(l) 250C v 1atm l : 44 kJ.mol-1.
a) Tnh nhit sinh chun ca H2O(h) v H2O(l) 250C.
b) Tnh nhit lng to ra khi cho 6g H2 bin hon ton thnh H2O(l)
13) Tnh H298K ca Ca3(PO4)2 (tinh th). Bit : Khi t 12g Ca to ra 1 lng nhit l 190,48
kJ ; 6,2g P chy to 154,66 kJ ; 168g CaO tc dng vi 142g P25 to 670,9 kJ
o 0
14) Tnh nhit lng cn thit khi chuyn 0,5 mol H2O - 50 C,1atm thnh 500 C cng 1atm.
Bit nhit nng chy ca nc 273K l 5,852kJ.mol . Nhit bay hi l 40,5kJ.mol-1 ;
-1
C P0 ( H 2O r ) =35,53J.mol-1.K-1; C P0 ( H 2O l ) =75,24J.mol-1.K-1; C P0 ( H 2O h) = 30 + 4,18.10-3T.J.mol-1.K-1

0
15) Xt phn ng : 2SO2 (k) + O2 (k) 2SO3 (k) c entalpi to thnh chun 25 C ca SO2
-1
(k) v SO3(k) ln lt l - 296,8 v - 395,7 kJ.mol .
Nhit dung mol ca cc cht C 0 p = a + bT + cT - 2 (J/ mol.K) nh sau :
a 10 3.b 10 - 5 .c
SO2 (k) 43,45 10,63 - 5,94
SO3(k) 57,34 26,87 -13,06
O2 (k) 29,97 4,18 - 1,67
Tnh H0 ca phn ng trn 673K

16) D on du S trong nhng trng hp sau :
a) NO(k) + 1/2 O2(k) NO2(k)
b) C2H4(k) + HCl(k) C2H5Cl (k)
c) N2(k) + 3 H2 (k) 2 NH3(k)
d) CaCO3 (r) CO2 (k) + CaO (r)
e) Ca (r) + 1/2 O2 (k) CaO (r)
17) i vi qu trnh on nhit th Q = 0, Q = 0 do dS = Q/T = 0. Ti sao vi qu trnh
dn n on nhit kh trong chn khng th S > 0 ?
18) Tnh S ca qu trnh bin i nc thnh nc lng, bit nhit nng chy ca nc
1atm l 6019J.mol-1
19) Tnh Q, A, U, H, S ng vi s bc hi ca 1 mol toluen 110oC,1atm. Bit nhit bc
hi ca toluen tng ng vi iu kin trn l 361,57J.g-1. Cho R = 8,314J.mol-1.K-1
20) Tnh S khi 1 mol kh l tng dn ng nhit v thun nghch khi :
a) T th tch V0 n V1 = 10 V0
b) T 2atm n 1atm.
21) 1mol kh l tng c mang t trng thi 22,4 lt, 273K n trng thi 2atm, 303K. Tnh
U, H, S trong bin i trn. Cho CV = 3/2 R v R = 8,314J. mol-1.K-1
0 0
22) Tnh s bin thin entropi ca qu trnh un nng 0,5 mol H2O t -50 C n 500 C
1atm. Bit nhit nng chy ca nc 0 0C l 6002,5J.mol-1. Nhit bay hi ca nc
24 HA I CNG 2
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100 0C l 40.658,86J.mol-1. Nhit dung mol ng p ca nc v nc lng ln lt l
35,53 v 75,24J.mol-1.K-1. Nhit dung mol ca hi nc l 30,18 + 8,36.10-3T J.mol-1.K-1
0 0
23) Tnh S ca kh Ar 25 C, 1atm, 500 ml c dn n n 1000 ml 100 C.
Cho CV = 3/2 R
0 0
24) Nhng mt ming st 10 g 200 C vo mt bnh cha 1 lt nc 25 C. Tnh S ca h
-1 -1 -1
bit : CP(Fe) = 25,58J.mol .nguyn t ; CP(H2O)(l) = 78,04J.mol
0 0
25) Tnh S trong s trn 10g nc 0 C vi 50g nc lng 40 C trong mt h c lp.
Nhit nng chy ca nc l 334,4 J.g . Nhit dung ring ca nc l 4,18 J.g-1.K-1
-1
0
26) Tnh G ca phn ng to thnh H2O (l) t cc n cht 25 C, 1 atm . Bit :
0
Sinh nhit ca H2O (l) l - 285,57 kJ/mol ; S 298 K(H2) = 130,42 J/mol.K
S0298K (O2) = 204,86 J/mol.K ; S0298K(H2O) = 70,14 J/mol.K
27) Phn ng : C2 H4 (k) + H2O (h) C2H5OH (h) c cc s liu sau:
C2H5OH (h) C2H4 (k) H2O (h)
0
G 298K ( kJ/mol ) - 168,58 68,13 - 229,48
S0298K (J/mol.K) 281,98 219,45 188,73
a) iu kin tiu chun phn ng theo chiu no ?
b) Tnh H298K ca phn ng. Phn ng to nhit hay thu nhit ?
28) Lu hunh c 2 dng th hnh l n t v dng thoi. Bit :
Dng thoi n t
H0298K (kJ/mol ) 0 0,3
S0298K (J/mol.K ) 31,85 32,52
0
a) 25 C dng no bn hn ?
b) Ti nhit no 2 dng cn bng ?
29) Tnh bin thin th ng p ca qu trnh dn n ng nhit 250C ca 2 mol kh l tng
t p sut 1atm n 0,1 atm ?
30) Tnh S, G ca s hnh thnh 1 mol kh (xem l kh l tng ) gm 20% N2 ; 50% H2
v 30% NH3 theo th tch. Cc kh ban u 3 bnh thng nhau c kho. Nhit , p sut
cc kh u 0 0C v 1 atm.
0 -1
31) 0 C, nhit nng chy ca nc l : 6002,48J.mol , nhit dung mol ca nc v
nc lng ln lt l: CP(r) = 37,2 v CP(l) = 75,24J.mol-1.K-1. Tnh H, S, G ca qu trnh
chuyn 1 mol nc t trng thi rn sang trng thi lng -10 0C
32) Xt phn ng : CH4 (k) + 2H2O (k) CO2 (k) + 4H2 (k)
a) Tnh G0298K ca phn ng trn.
b) Tnh G01000K ca phn ng . Qua so snh kh nng v chiu hng ca phn
ng trn 298K v 1000K. Cho :
CH4 (k) H2O (k) CO2 (k) H2 (k)
0 -1
H 298K (kJ.mol ) - 74,78 - 241,6 - 393,39 /
S0298K (J.mol-1.K-1) 186 188,64 213,6 130,46
CP(J.mol-1.K-1) 36,7 33,57 37,08 28,8
33) Ti nhit no s chuyn 1 mol nc lng thnh hi p sut kh quyn l mt qu
trnh t din bin, bit nhit ho hi 1 mol nc lng bng 40587,80 J v bin thin entropi
ca s chuyn trng thi ny bng 108,68J.K-1
34) Qu trnh chuyn O2 thnh O3 l khng th thc hin c v phng din nhit ng hc
(qu trnh c H > 0 v S < 0). Hy gii thch ti sao c th thu c O3 t O2 khi phng
in hay trong cc qu trnh quang ho ?
25 HA I CNG 2
Chng 2 : CN BNG HA HC, CN BNG PHA
CHNG 2
CN BNG HA HC, CN BNG PHA
2.1.KHI NIM V CN BNG HO HC :

Trong thc t c nhng phn ng xy ra n cng, mt (hoc nhiu) cht phn ng n
ht, v d nh phn ng nhit phn KClO3 c MnO2 xc tc, phn ng s xy ra n khi ht
KClO3,... l phn ng mt chiu.
Nhng c mt s phn ng khc nh phn ng ester ha, phn ng thy phn, phn
ng phn hy HI,... cc phn ng y khng bao gi tc dng nhau n cng d ta c bao
lu i na, nhng phn ng nh th gi l phn ng thun nghch.
Ti sao gi l phn ng thun nghch ? V loi phn ng ny cc cht phn ng phn
ng vi nhau cho ra sn phm th cng lc y khi cc sn phm n mt lng no n
s phn ng li vi nhau cho li cc cht ban u - nh vy ng thi cc cht phn ng
phn ng vi nhau theo chiu thun th cng thi gian cc cht to thnh li phn ng vi
nhau theo chiu nghch.
Lc u khi cc cht ban u c nhiu (nng ln) th xc sut ca s va chm gia
cc cht phn ng ln nn phn ng thun xy ra nhanh, lc y sn phm mi to nn rt t
nn xc sut ca s va chm gia cc sn phm nh, phn ng nghch xy ra chm v cng
lc th phn ng thun cng chm li do nng cht phn ng gim v phn ng nghch
nhanh dn ln (do nng ca sn phm tng), n mt lc no khi tc phn ng ca
hai chiu bng nhau, th lc y s lng cc cht trong mt n v th tch trong mt n v
thi gian s khng i ta gi phn ng t n cn bng - cn bng ng, cn bng s gi mi
nu iu kin bn ngoi khng i. Ti sao li l cn bng ng ? Do ti thi im cn bng
cc cht phn ng, cht sn phm, vn phn ng vi nhau theo hai chiu ngc nhau vi
tc nh nhau lm cho nng cc cht khng i.
i vi phn ng mt chiu, trn c s s thng nht 2 nguyn l (G) ta bit c
kh nng phn ng. Cn i vi phn ng thun nghch khi t ti cn bng, d nhin G =
0, nhng mc phn ng ra sao ? n u ? Tr li cu hi ny cng da trn s thng nht
2 nguyn l v gip chng ta tnh ton c cc nng lc y.
2.2.HNG S CN BNG :
Xt phn ng th kh : aA (k) + bB (k) eE (k) + fF (k) (k) : th kh
nhit v p sut khng i th : G = e E f F (a A b B )
T chng 1 ta c : T = oT + RT lnp. (Ch : p tnh bng atm)
Nn : G e E0 eRTlnp E f F0 fRTlnp F (a A0 aRTlnp A b B0 bRTlnp B ) .
Hon v cc s hng :
G (e E0 f F0 ) (a A
0
b B0 ) (eRTlnp E fRTlnp F ) (aRTlnp A bRTlnp B )
p Ee . p Ff
M : (e E0 f F0 ) (a A0 b B0 ) G 0 . Nn : G G 0 RT ln( ) (2.1).
p aA . p bB
p Ee . p Ff
Khi cn bng T = const, th G 0 . Nn : Go = - RTln( )cb (2.2)
p aA . p bB
G o pe .p f
Hay : - = ln( Ea Fb )cb
RT p A. pB
Go chnh l nng lng t do iu kin chun nhit T ca phn ng xc nh :
aA + bB eE + fF l mt i lng xc nh, hay ni cch khc T khng i ca mt
G o
phn ng xc nh th Go l hng s. V vy : - l hng s v ngi ta t :
RT
26 HA I CNG 2
G o
- = lnKP (2.2) hay : Go = - RTlnKP (2.4)
RT
KP gi l hng s cn bng. T (2.2) ta thy hng s cn bng Kp ch ph thuc vo Go
v T, m Go li ch ph thuc vo bn cht cht phn ng v vo nhit m thi. Vy Kp
ch ph thuc vo bn cht cht phn ng v nhit .
[V n v ca Kp : n v ca Go l J.mol-1, R c n v l J.mol-1.K-1, T c n v l K. V
G o J .mol 1
vy n v ca Kp = - = 1 . Vy Kp khng c n v]
RT ( J .mol 1 .K 1 ) K
f
p eE . p F
So snh (5) v (6) KP = ( )cb (2.5)
p aA . p bB
f
p eE . p F
rng : ( )cb s khc vi lc trc khi cn bng
p aA . p bB
Khi ta hiu l : KP bng tch ca p sut ca sn phm chia cho tch ca p sut cht
phn ng, (c s m l h s hp thc ca phn ng) lc cn bng v ngi ta thng vit
f
p eE . p F
gn : KP = (2.6) (Ch : v trong biu thc T = oT + RT lnp. p tnh bng atm
p aA . p bB
nn trong biu thc ny cc p sut p cng phi tnh theo atm)
ni
- Nu xem kh l l tng th : pi = RT = CiRT
V
f
[ E ]e .[ F ]
lc y : KP = .( RT ) (e f a b ) .
[ A] a .[ B ]b
[ E ]e .[ F ] f
t : KC = . (2.7) KC gi l hng s cn bng biu din theo nng .
[ A]a .[ B]b
V (e + f) - (a + b) = n KP = KC.(RT)n (2.8)
Vi n = tng s mol kh sn phm tr tng s mol kh cht ban u
T (2.8) ta thy KC cng ch ph thuc vo bn cht phn ng v nhit m thi.
- Nng phn mol : biu din nng ca mt cht ngoi cc nng %, CM,
ni
ngi ta cn dng mt khi nim khc l nng phn mol Ni : Ni =
ni
Theo Dalton : p i = Ni.p vi pi, p ln lt l p sut ring phn v p sut ton phn ca h.
f f
N Ee . N F N Ee . N F
Th pi vo biu thc KP ta c : KP = .p (e +f-a-b). t KN = .
N Aa .N Bb N Aa .N Bb
Vi KN l hng s cn bng tnh theo phn phn mol
Vy Kp = KN.p n (2.9)
T (2.9) ta thy KN ngoi vic ph thuc vo bn cht cht phn ng, nhit , n cn
ph thuc vo p sut ca h.
Ch khi tnh K :
* Kp, KC, KN : ph thuc vo bn cht cht phn ng v nhit , ring KN cn ph
thuc vo p sut chung ca h.
* Hng s KC, KN c suy t KP, m KP li ph thuc vo Go, m Go ca phn ng
li ph thuc vo h s hp thc (h s cn bng phn ng) ca phn ng. V vy khi ni
n KP, KC, KN ca mt phn ng no ta phi ni c th cc h s hp thc ca phn ng
27 HA I CNG 2
2
p NH
3
. Th d vi phn ng : N2 + 3H2 2NH3 th Kp = . Trong khi cng vi phn ng
p N 2 . p 3H
2
1 3 p NH
nhng khi ghi h s cn bng : N 2 H 2 NH3 th K p 1 33
2 2
p N2 . p H2
2 2
* Nu ta vit ngc li : eE + fF aA + bB. C hng s cn bng K'. Th t :

G' = - G (Vi G' v G ln lt l th ng nhit ng p ca phn ng nghch v phn
1
ng thun) ta d dng c : K' =
K
* Nu trong phng trnh phn ng c s hin din ca cc pha rn, lng, kh, th trong
biu thc ca Kp ch c s hin din ca pha kh v trong biu thc ca Kp, cc p sut p phi
tnh bng atm. V d nh vi phn ng :
CaCO3 (r) CaO (r) + CO2 (k). Th Kp = pCO2
* Trong biu thc ca KC s khng c mt :
- Nng cc cht pha rn (xem nng ca pha rn = const)
- Nng ca cht rt d so vi cc cht khc.
V d : RCOOR' (t tan) + H2O (nhiu) RCOOH + R'OH
Lc y : KC = [RCOOH] [R'OH]
2.3.PHNG PHP XC NH HNG S CN BNG :

2.3.1.T nng cc cht lc cn bng :
Theo phng php ny cn phi bit :
- Nng ban u ca cht tham gia phn ng
- Nng ca mt cht lc cn bng.
Th d : Xc nh hng s cn bng KC ca phn ng 850 0C :
CO (k) + H2O (h) H2 (k) + CO2 (k)
Bit nng ban u : [CO] = 1mol/l ; [H2O] = 3mol/l v lc cn bng : [CO2] = 0,75 mol/l.
Gii : CO (k) + H2O (h) H2 (k) + CO2 (k)
Nng ban u : 1 3 0 0
Nng lc cn bng : 1 - 0,75 3 - 0,75 0,75 0,75
[ H 2 ][CO2 ] 0,75.0,75
Vy KC = 1
[CO ][ H 2 O ] (1 0,75)(3 0,75)
2.3.2.T phng php nhit ng :
G o
o o
T phng trnh G = - RT lnKp. Khi ta xc nh c G ca phn ng KP = e RT
Go ca phn ng c xc nh nh h qu ca nh lut Hess.

Th d : Xc nh hng s cn bng ca phn ng :
H2(k) + CO2(k) H2O(h) +CO(k) 298K. Bit :
Cht H2(k) CO2(k) CO(k) H2O(h)
Ho298K (kJ.mol-1) - -393,51 -110,52 -241,83
So298K (J.mol-1.K-1) 130,59 213,64 197,91 188,72
Gii : T phn ng : H2(k) + CO2(k) H2O(h) +CO(k)
Theo h qu ca nh lut Hess, ta c :
Ho298K = Ho298K(CO) + Ho298K(H2O) - Ho298K(H2) - Ho298K(CO2)
Ho298K = -110,52 + (-241,83) - 0 - (-393,51) = 41,16 kJ
Tng t : So298K = 197,91 + 188,72 - 130,59 - 213,64 = 42,4 J = 42,4.10-3 kJ.K-1
T Go298K = Ho298K - T.So298K Go298K = 41,46 - 298.42,4.10-3 = 28,82484 kJ
G 0 28824,8
T phng trnh Go = - RT lnKp lnKp = 11,6
RT 8,314 . 298
28 HA I CNG 2
Kp = 9,16.10 -6
2.4.QUAN H GIA BIN THIN TH NG P, NG NHIT V HNG S

CN BNG :
f
p eE . p F
T phn (2.2.Hng s cn bng) ta c : G = Go + RTln
p aA . p bB
f
p eE . p F
Th Go = - RTlnKp vo ta c : G = -RTlnKp + RTln
p aA . p bB
f
p eE . p F
Hay: G = RT[ln - ln Kp]. Biu thc ny gi l phng trnh ng nhit Van't Hoff.
p aA . p bB
f
p eE . p F
T phng trnh ta thy khi > KP G > 0 phn ng xy ra theo chiu nghch,
p aA . p bB
f
p eE . p F
ngc li khi > Kp G > 0 phn ng xy ra theo chiu thun
p aA . p bB
T chng 1, khi ni v nh hng ca nhit n th ng p ta c biu thc :
G H
( )p =- . Nu iu kin chun (p = 1atm) biu thc tr thnh :
T T T2
G 0 H 0 lnKp H o
( )p = - . Th Go = - RT lnKP vo ta c : ( )p .
T T T2 T RT 2
T2
T2 H 0
Phn ly bin s ri ly tch phn 2 v t T1 T2 ta c : lnK p T1 = RT 2 dT
T1
Phng trnh ny chnh l phng trnh ng p Van't Hoff
2.5.CC YU T NH HNG N CN BNG HA HC, NGUYN L LE

CHTELIER :
Xt phn ng : aA (k) + bB (k) eE (k) + fF (k)
f
p Ee . p F
T phng trnh ng nhit Van't Hoff : G = RT (ln - lnKp)
p aA . p Bb
Khi phn ng t n cn bng th G = 0. Khi G 0 th phn ng khng cn trng
thi cn bng na, ta ni cn bng b chuyn dch v cn bng s chuyn dch cho n khi t
n cn bng mi. Nhn vo biu thc, v phi ta thy nu thay i mt trong nhng s liu
th G lc y s khc khng
- Ta bit Kp ph thuc vo nhit , v vy nu thay i nhit s lm Kp thay i,
dn n G thay i. Vy nhit c nh hng n cn bng.
- Khi thay i nng mt cht, cht E chng hn s a n p E thay i, dn n G
thay i. Vy nng cc cht c nh hng n cn bng.
- Nu thay i p sut chung ca h th p sut ring phn s thay i v vy p sut ca
h cng c nh hng n cn bng.
2.5.1.nh hng ca nng :
Cng xt phn ng : aA + bB eE + fF
Khi phn ng ti cn bng ta c KC =
E e F f (*)
Aa Bb
By gi gi s ta thm vo h cht A chng hn (nng A tng), th mu s trong (*)
tng, m KC khng i (khi nhit khng i) nn t s phi tng, tc phn ng s theo
chiu to ra cht E, F - l chiu lm gim nng cht A. Tng t, nu ta thay i nng
29 HA I CNG 2
ca cc cht khc (B, E, F) ta c kt lun : Phn ng s chuyn dch theo chiu chng li s
thay i nng
2.5.2.nh hng ca p sut :
Cng ly v d t phn ng trn : aA + bB eE + fF (Vi cc cht th kh)
n
T biu thc : Kp = KN . p
* Khi n > 0 (s mol kh sn phm > s mol kh cht phn ng) :
N Ee .N Ff
Khi ta tng p sut ca h (tc p tng), m Kp khng i v th KN gim, m KN =
N Aa .N Bb
nn khi KN gim tc t s gim, tc gim cht E, F phn ng chuyn dch theo chiu to ra
cht A, B l chiu t s mol kh hn - gy ra hu qu p sut chung gim. Cng vy, nu
lm gim p sut, lp lun tng t ta thy phn ng di theo chiu c s mol kh nhiu hn.
Vy khi phn ng t ti cn bng, nu ta thay i p sut th cn bng chuyn dch
theo chiu chng li s thay i p sut .
* Khi n < 0 : cng l lun tng t, ta c kt qu nh trn.
2.5.3.nh hng ca nhit :
H o
T phng trnh ng p Van't Hoff : lnKp = 2
T RT
n gin ta xem Ho khng ph thuc vo nhit
K p (T 2 ) H o 1 1
ln = ( )
K p (T 1) R T1 T2
H o
* Vi phn ng thu nhit th Ho > 0 >0
R
1 1 1 1
Nu khi h ang cn bng ta tng nhit tc T2 > T1 < - > 0.
T2 T1 T1 T2
Vy v phi > 0 K PT 2 > K PT 1
Ngha l phn ng xy ra theo chiu to ra cht E, F l chiu thu nhit. Vy khi tng
nhit cn bng chuyn dch theo chiu thu nhit ( nhit gim).
Hoc khi h nhit ta cng c kt lun tng t l phn ng s dch chuyn theo
chiu pht nhit
* Khi Ho < 0 : cng chng minh tng t, ta cng c kt qu nh trn.
2.5.4.Nguyn l Le Chtelier :
Tng kt t ba yu t : nng , nhit v p sut trn ta c nguyn l Le Chtelier
Khi h ang trng thi cn bng, nu ta thay i mt trong cc yu t bn ngoi (nng
, nhit , p sut) th cn bng s chuyn dch theo chiu chng li s thay i
2.6.CN BNG PHA :

Phn trc l cn bng ha hc, trong phn ny s cp n cn bng trong h d th,
m trong phn ng ha hc khng xy ra nhng xy ra qu trnh chuyn pha.
2.6.1.Mt s khi nim c bn :
2.6.1.1.Pha : Pha l tp hp cc phn ng th ca h c thnh phn, tnh cht
ging nhau v c phn cch vi cc phn khc ca h bng mt b mt.
Th d : Nc lng v nc ng trong mt cc l hai pha.
2.6.1.2.H ng th v d th :
- H ng th : l h ch c mt pha duy nht.
- H d th : l h c t 2 pha tr ln.
2.6.1.3.Cu t : Phn t cu thnh nn h v c th tn ti bn ngoi h.
V d : dung dch nc mui NaCl c 2 cu t l H2O v NaCl mc d trong h tn ti :
H2O, Na+, Cl-, nhng Na+ v Cl- khng th tn ti c lp.
Cu t c lp : S cu t ti thiu m t thnh phn ca h.
S cu t v s cu t c lp c mi lin h :
30 HA I CNG 2
S cu t c lp = s cu t - s h thc lin h gia cc cu t.
V d : dd NaCl : S cu t c lp = s cu t.
- Hn hp CaCO3 (r), CO2 (k), CaO (r) nm cn bng vi nhau th s cu t l 3, nhng
s cu t c lp c th l 2 hoc 1.
+ Nu ban u khng bit s mol ca tng cht th s cu t c lp l 2
+ Nu ban u gi s ch c CaCO3 th s cu t c lp l 1, nu ban u c CaO v
CO2 nhng gi s c t l v s mol l 1 : 1 th s cu t c lp cng l 1
2.6.1.4.Bc t do :
L s thng s trng thi ca h c th thay i ty (trong mt gii hn nht nh) m
khng lm thay i s pha v s cu t ca h.
T v d trn, hn hp CaCO3 (r), CO2 (k), CaO (r) nm cn bng vi nhau th bc t
do l 2 v ta c th thay i n ba thng s trng thi (trong mt khong no ) vn gi
c hai pha (rn v kh), vn gi c ba cu t l CaCO3, CO2, CaO. (S thng s trng
thi l : nhit , p sut, nng ca cht).
2.6.1.5 Cn bng pha :
L cn bng trong h d th, trong cc cu t khng phn ng vi nhau, nhng xy
ra qu trnh bin i pha gia cc cu t.
iu kin cn bng gia cc pha trong h : Phi thit lp ba cn bng : v nhit, c
v ha. Tc l :
- Nhit gia cc pha phi bng nhau.
- p sut cc pha phi bng nhau.
- Ha th cc pha phi bng nhau.
2.6.2.Quy tc pha v gin trng thi ca h mt cu t.
2.6.2.1.Quy tc pha :
- Khi h cn bng th nhit v p sut cc pha bng nhau do c 2 thng s trng
thi chung cho c h.
- Mi pha c C cu t, mi cu t c mt thng s v nng , nhng v ta ch cn bit
(C - 1) nng c th suy ra nng th n. Vy c F pha th c F(C-1) thng s Tng
s thng s trng thi c h = F (C - 1) + 2
- Khi cc pha nm cn bng vi nhau do nu mi cu t c 2 pha th c mt phng
trnh lin h, c ba pha th c hai phng trnh lin h, ... gia F pha c (F - 1) phng trnh
lin h C cu t c C(F - 1) phng trnh lin h.
- Mi mt h thc lin h lm gim i mt bc t do ca h. Vy s bc t do ca h s
l : B = F (C - 1) + 2 - C(F - 1) = C - F + 2. Vy B=C-F+2
Vi B : s bc t do; C : s cu t v F : s pha.
2.6.2.2.Phng trnh Clapeyron - Clausius :
Gi s ta c mt mol cu t i tn ti hai pha L (lng) v K (kh) nm cn bng vi
nhau p sut p v nhit T. V y ch c mt cu t i nn ha th cng chnh l th
ng p i Gi . Nn : GiL( p ,T ) GiK( p,T ) (*).
Khi thay i ng thi c p sut p v nhit T mt khong v cng nh l dp v dT,
th th ng p cng thay i mt i lng v cng nh dG, lc y trong h cc pha vn cn
bng, nn : GiL( p ,T ) dGiL( p,T ) GiK( p ,T ) dGiK( p,T ) (**).
So snh (*) v (**) dGiL( p,T ) dGiK( p ,T ) (***)
T chng 1, (phn 1.5.6. Th ha hc) ta c : dG = Vdp - SdT. Th vo (***) :
K L
K K L L dp S i ( p ,T ) S i ( p ,T ) S
V .dp S
i ( p ,T ) .dT V
i ( p ,T ) .dp S
i ( p ,T ) .dT .
i ( p ,T ) .
dT V K L V
i ( p ,T ) Vi ( p,T )
H
M qu trnh chuyn pha l qu trnh thun nghch, nn : S .
T
dp H
Th vo biu thc trn
dT T .V
31 HA I CNG 2
Phng trnh ny gi l phng trnh Clayperon - Clausius. Phng trnh ny l biu
thc nh lng ca nguyn l Le Chtelier, phng trnh ch ra : khi tng p sut th cn
bng s chuyn dch theo chiu lm gim th tch. Phng trnh ny c th p dng cho cc
qu trnh chuyn pha ca mt cht nguyn cht nh: Rn Lng ; Lng Hi ;
Rn Hi ; gia cc dng th hnh vi nhau.
Nu qu trnh l t Rn Hi hay Lng Hi th Vhi >> Vrn , Vhi >> Vlng. Nn
dp H
V V hi. V vy, t biu thc : , v nu xem kh l l tng, vi 1mol kh th :
dT T .V
H H H . p dp H . p dp H dT H dT
. Nn : . . Hay : d ln p . .
T .V T .Vhoi RT 2 dT RT 2 p R T2 R T2
Trong khong bin i nh ca nhit c th xem H const . Lc y, ly tch phn
p2 H 1 1
biu thc trn ta c : ln ( ).
p1 R T2 T1
V d 1 : Nhit nng chy ca nc 0 0C l 6002,48 J.mol-1, th tch mol ca nc
nhit ny l 19,652 ml v ca nc lng bng 18,018 ml. Xc nh s ph thuc ca
nhit nng chy vo p sut.
dp H
Gii : T phng trnh Clayperon-Clausius : . y ta ch sao cho n v
dT T .V
phi ph hp. Nu p sut p tnh bng atm th H cng tnh theo n v atm.mol-1. Ta bit :
22,4/273 atm.mol-1 tng ng vi 8,314 J. Vy 1 atm.mol-1 tng ng vi 101,327 J.
6002,48
H 59,24atm.mol 1 . Vy :
101,327
dp H 59,24 dT 1
132,8 atm.K 1 . Hay 7,53.10 3 K .atm 1 . Nh vy khi
dT T .V 273(18,018.10 3 19,652.10 3 ) dp 132,8
p sut tng thm 1 atm th nhit nng chy ca nc gim 0,00753K .
V d 2 : p sut hi bo ha ca ru etylic 19,50C bng 42,64mmHg, 20,50C
bng 44,96mmHg. 200C, khi lng ring ca ru lng bng 0,7894g/ml, ca hi ru
bo ha bng 1,11.10 -4g/ml. Tnh nhit ha hi ca 1 gam ru etylic 20 0C.
Gii : Ru lng 1 ml c khi lng 0,784g 1g ru lng c th tch Vl =
1
1,276ml. g 1 (i lng ny c gi l th tch ring ca ru lng). Tng t ta c th
0,784
1 Vh 9009
tch ring ca hi ru Vh = 9009ml.g 1 . Ta thy : 7060 ln. Nn : V =
4 Vl 1,276
1,11.10
Vh. Trong khong bin i nh v nhit : 10, ta xem H const .
p2 H 1 1
V vy c th p dng cng thc : ( ) . Th cc gi tr c vo ta c :
p1 R T2 T1
H =37778,84 J.mol . Vy nhit ha hi ca 1 gam ru etylic l: 37778,84 821,28 J.g-1

-1
46
2.6.2.3.p dng quy tc pha xt gin trng thi ca h mt cu t
Vi h mt cu t tc C = 1, vy s bc t do l : B = 1 - F + 2 B = 3 - F
- Khi trong h c 2 pha nm cn bng nhau : R L;L H;R H th
B=3-2=1
C ngha nu mt trong 2 thng s (T hoc p) bin i th thng s kia phi bin i
theo, tc l mi gi tr xc nh ca nhit v p sut tn ti nhng pha hon ton xc
nh. V ngi ta biu din s ph thuc ny trn th - gi l gin (hoc th) trng
thi ca cc cht.
ng cong AO l ng thng hoa, ng OC l ng nng chy, cn ng OB l
ng ha hi. Ba ng (biu din 3 cn bng p - T) chia mt phng ra lm ba vng khc
nhau, mi vng ng vi mt trng thi ca H2O.
32 HA I CNG 2
- Ba ng gp nhau ti O gi l C
im 3. Ti im 3 ny l s cn bng
ca ba pha : p (atm)
R L 218 B
H
(R : rn ; L : lng ; H : hi)
c bc t do B = 1 - 3 + 2 = 0 R L
V bc t do = 0 nn khng th
bin i c thng s no. V tr ny
ch ph thuc bn cht ca cht nghin 1
cu. 0,00602 H
Nh H2O, im 3 c ta p = O
0,006 atm v T = 273,1599 oK A
ng ha hi OB dng li ti T (0K)
272,16 272 647,2
im gii hn B c ta ng vi p
sut p = 218 atm v nhit T =
647,2K. Vt qua im ny th khng cn kh nng phn bit trng thi lng v hi na.
33 HA I CNG 2
BI TP
1) Phn ng : CO (k) + Cl2 (k) COCl2 (k) xy ra trong bnh kn nhit khng i, lc
u [CO] = [Cl2]. Ti lc cn bng cn 50% lng CO ban u. Xc nh p sut ca hn
hp lc cn bng bit p sut u ca hn hp bng 75 mmHg
2) Trong bnh kn : CO2 (k) + H2 (k) CO(k) + H2O (k) c KC = 1. Xc nh : C bao
nhiu % CO2 chuyn thnh CO ( nhit khng i ) khi trn 1 mol CO2 v 5 mol H2.
Nu lc cn bng c 90% lng H2 ban u tham gia phn ng th t l th tch ca CO2 v
H2 c trn l bao nhiu ?
3) Phn ng : FeO (r) + CO (k) Fe (r) + CO2 (k) ti nhit cao c KC = 0,5. Xc nh
[CO] v [CO2] lc cn bng nu ban u c [CO]b = 0,05 mol/l ; [CO2]b = 0,01 mol/l
4) mt nhit cho cn bng ca h : 2NO2 2NO + O2 c thit lp cc nng
: [NO2]cb = 0,006 mol/l ; [NO]cb = 0,024 mol/l. Tm hng s cn bng KC ca phn ng
v nng ban u ca NO2
5) BaCO3 b phn hu nhit cao theo p : BaCO3 (r) BaO (r) + CO2 (k)
BaCO3 BaO CO2 (k)
0
H 298K (kJ/mol ) -1216,7 -553,7 -393,5
S0298 K (J/mol.K) 112,2 70,4 213,7
a) Tnh p sut ca CO2 nm cn bng vi BaCO3 298K.
b) Hn hp BaCO3 (r) v BaO (r) trong khng kh. p sut ca CO2 trong khng kh
l 3,33.10-4 atm. Tnh G298K ca p trong iu kin ny. T rt ra chiu p.
6) Nu H0 v S0 ca phn ng 2NO2 (k) N2O4 (k) khng thay i theo nhit . Bit :
a) Tnh nhit hng s cn bng KP
ca phn ng bng 10. NO2 N2 O4
0 -1
b) Cn bng s chuyn dch theo chiu no H 298K (kJ.mol ) 33,82 9,65
nhit thp hn nhit tm c ? S0298 K (J.mol-1.K-1) 240,18 304
7) NOCl b phn hu theo phn ng : 2NOCl(k) 2NO (k) + Cl2 (k). Lc u ch c

NOCl. Khi cn bng 500K c 27% NOCl b phn hu v p sut tng cng ca h l 1
atm. Tnh 500K :
a) KP v G0 ca phn ng.
b) p sut ring phn ca tng cht khi cn bng?
c) Nu h p sut ca h xung di 1 atm th s phn hu ca NOCl tng hay gim ?
V sao?
8) Cho phn ng : CH4 (k) C(gr) + 2H2 (k) c H0298K = 74,82kJ v cc s liu sau :
CH4 (k) C(gr) H2 (k)
S0298K (J.mol-1.K-1) 186,18 5,68 130,58
CP (J.mol-1.K-1) 36,7 8,65 28,84
a) Tnh KP ca phn ng 250C.
b) Xem CP khng ph thuc vo T. Tnh KP 1000K.
c) So snh KP hai nhit . C ph hp vi nguyn l Le Chtelier khng ?
9) Xt phn ng : 2SO2 (k) + O2 (k) 2 SO3 (k). Phn ng c thc hin trong bnh cu
c th tch V lt lc cn bng TK c s mol cc cht l :
nSO2 = 0,04 mol ; nO2 = 0,04 mol ; nSO3 = 0,08 mol.
a) Tnh hng s cn bng KC.
b) Theo l thuyt KC ph thuc yu t no ? C ph hp vi cu a) khng ? Gii thch.
34 HA I CNG 2
Chng 3 : NG HA HC
CHNG 3
NG HA HC
Nhit ng hc gip chng ta d on chiu hng, mc phn ng. Nhng cha cho
chng ta bit khi no th phn ng xy ra, ng thi nhit ng hc cng khng cho bit
ng i - tc c ch ca phn ng.
Trong ni dung ny s gip chng ta nm bt c s nhanh chm ca phn ng - tc
l tc phn ng - ch khng phi ch l kh nng - Cng gip ta bit c nhng yu t
nh hng n vn tc phn ng - qua cho php ta chn iu kin ti u tin hnh phn
ng.
V mt l thuyt, ng ha hc gip ta hiu c ti sao c nhng phn ng, bng kin
thc nhit ng tnh c G < 0 m sn phm chng ta ch i li khng ng theo
mong mun, nh phn ng gia H2 v O2 iu kin thng, d ta ch i bao lu cng
khng th thy mt t sn phm no.
3.1.MT S KHI NIM :

Thng thng tc gn lin vi s dch chuyn c hc nh tc ca mt ngi i
b, tc ca mt my bay... c lc tc biu th tru tng hn nh chng ta ni : nc
chy chm qu, ta nh thi cng nhanh, cc sinh vin tip thu bi nhanh... cng u biu hin
trn mt n v thi gian ca : th tch, khi lng, kin thc...
Vi ha hc biu th s nhanh chm ca mt phn ng - ngi ta gi l tc
(hay vn tc) phn ng.
Tc phn ng l g ? V cc yu t no nh hng n tc ?
Xt phn ng : A + B E + F
Khi phn ng bt u xy ra th cht A, B mi lc mt gim, cht E, F mi lc mt
tng, nu cht phn ng (A, B) gim nhanh hoc sn phm tng nhanh ta ni phn ng xy ra
nhanh. Vy ta thy tc phn ng v t l vi lng cht trong mt n v thi gian.
chnh l vn tc phn ng.
Vy vn tc phn ng chnh l biu din bin thin ca nng cht trong mt n
v thi gian.
Vi phn ng trn : A + B E + F
thi im t1 cc cht c cc nng : [A]1 , [B]1 , [E]1 v [F]1 v thi im t2 cc
cht c nng l [A]2 , [B]2 , [E]2 v [F]2
Vn tc trung bnh vm trong khong thi gian t t1 n t2 l :
[ A]1 [ A] 2 [ F ] 2 [ F ]1
vm = =...=
t 2 t1 t 2 t1
[ A]2 [ A]1 [ F ] 2 [ F ]1 [ A] [ F ]
Hay vm = - =...= =- =
t2 t1 t 2 t1 t t
Vi [A] : Nng cht phn ng v [F] l nng cht sau phn ng
iu c ngha vn tc phn ng c th biu din theo cht phn ng hoc sn phm
mt cch ty .
Trong trng hp tng qut : aA + bB eE + fF
1 [ F ]
th vm = - 1 [ A] = - 1 [ B] = 1 [ E ] =
a t b t e t f t
Khi t 0 th vm v : vn tc tc thi, lc y [A] d[A], . . . [F] d[F]
1 d[ F ]
Vy v = - 1 d [ A] = - 1 d [ B] = 1 d[ E ]
=
a dt b dt e dt f dt
y l biu thc tng qut c dng tnh vn tc v ca phn ng trong mt thi
im ty . Cng rng trong cng mt phn ng cng mt iu kin, vn tc v trong
tng thi im s khc nhau.
35 HA I CNG 2
Chng 3 : NG HA HC
Bng thc nghim, ngi ta tm c cc yu t nh hng n tc phn ng l :
nng (hoc p sut ring phn ca cht kh), nhit , bn cht cht phn ng, s c mt
ca cht khc trong h (ngi ta gi l cht xc tc). Nu phn ng xy ra trong dung dch,
vn tc phn ng cn ph thuc vo bn cht ca dung mi na.
3.2.NH HNG CA NNG CC CHT PHN NG N TC PHN

NG :
Thot u, ngi ta l lun rng : Mun c sn phm th u tin cc cht phn ng
phi va chm nhau, s va chm nhau cng nhiu th kh nng xy ra phn ng cng ln, ngha
l vn tc phn ng cng ln, m mun va chm cng nhiu th nng cc cht phn ng
phi cng ln. Nh vy vn tc phn ng t l vi tch s nng ca cc cht phn ng vi
s m l h s t l trong phng trnh phn ng.
Th d vi phn ng : aA + bB eE + fF th v = k[A]a [B]b. Vi k l h s t l.
Biu thc ny c gi l nh lut tc dng khi lng. Sau ny khi kho st hng lot
cc phn ng ngi ta thy rng, biu thc trn ch ng cho nhng phn ng n gin - l
nhng phn ng ch do mt va chm duy nht gia cc cht phn ng l c th dn n sn
phm. Ngi ta gi c mt va chm ng thi gia cc cht phn ng lm phn ng c tin
trin gi l giai on c bn (hoc giai on c s, hoc tc ng c bn).
Trong trng hp tng qut, khi kho st phn ng trn, biu thc nh lut tc dng
1 d [ A] 1 d[F ]
khi lng c vit : v = - . =...= . = k[A]m [B]n
a dt f dt
Hng s t l k gi l hng s vn tc ca phn ng, hng s ny ch ph thuc vo bn
cht cht phn ng, nhit , cht xc tc m khng ph thuc vo nng cht phn ng. Ta
thy khi nng cc cht bng 1 th k = v.
Vy hng s tc chnh l tc ca phn ng khi nng cc cht bng n v -
gi l tc ring. y chnh l ngha thc t ca hng s vn tc k
Cn m v n gi l bc phn ng - n ch c xc nh bng thc nghim.
Nh vy trong trng hp tng qut ta thy vn tc phn ng cng t l vi tch nng
cc cht phn ng, nhng rng s m s khng cn bng vi cc h s t l trong
phng trnh ha hc.
Cn bc phn ng l g?
Nh t phn ng trn, ta ni phn ng c bc m vi cht A (bc ring ca A) v bc n
vi cht B (bc ring ca B) v phn ng c bc tng qut l m + n
Th d nh phn ng n gin : H2 + I2 2HI
V phn ng thuc loi n gin nn : v = k[H2 ].[I2]. Ta ni phn ng c bc mt theo
H2 v bc mt theo I2 v c bc tng qut l hai.
Bc phn ng c xc nh bng thc nghim, c ngha i vi tng phn ng mt,
phi qua nghin cu thc nghim mi xc nh c bc phn ng. Ch vi nhng phn ng
n gin, khi ta bit chc n l phn ng n gin, lc y bc phn ng tng qut mi bng
tng cc h s t lng.
Vy vi phn ng phc tp th khng phi ch c mt va chm duy nht ng thi gia
cc cht phn ng l c kh nng xy ra phn ng.
V d nh phn ng :
10FeSO4 + 2KMnO4 + 8H2SO4 5Fe(SO4)3 + 2MnSO4 + K2SO4 + 8H2O th ta thy khng
th no c s va chm ng thi ca 20 phn t cng mt lc xy ra phn ng c.
R rng l xc sut cho s va chm ng thi gia cc phn t cng b khi s phn
t cng ln. Bng thc nghim ngi ta xc nh khng c phn ng c bc t 4 tr ln. Bc
phn ng c th c : 0, 1, 2, 3 hoc phn s. Tnh phc tp ca bc phn ng l do mt phn
ng phi qua nhiu giai on (i vi cc phn ng phc tp - m a phn l phc tp) v bc
phn ng c xc nh giai on chm nht, bi v chnh giai on quyt nh tnh
nhanh chm ca phn ng, nh tc ca bc in tn quyt nh khng phi l vn tc ca
lc truyn in m chnh l vn tc ca ngi a th.
36 HA I CNG 2
Chng 3 : NG HA HC
Th d nh phn ng thy phn clorua ter Butyl :

(CH3)3CCl + H2O OH (CH3)3C-OH + HCl.
Phn ng ny khng phi l bc hai nh thot nhn, v phn ng tri qua 2 giai on,
giai on u chm, giai on sau nhanh :
Giai on 1 : (CH3)3C-Cl chm
(CH3)3C + + Cl-

Giai on 2 : (CH3)3C + + H2O OH (nhanh)
(CH3)3C-OH + H+
Vy, phn ng thu phn clorua ter Butyl phi c bc 1 : v = k [(CH3)3CCl]
Mi giai on m phn ng chuyn mnh l mt giai on c bn. S cc phn t c
mt trong mt tc ng c bn gi l phn t s. Vy phn t s l s phn t cht phn ng
c mt ng thi trong mt tc ng c bn. Khi nim phn t s c suy ra t l thuyt v
chnh n ch ra mt phn ng phi tri qua nh th no n c sn phm.
V vy i vi nhng phn ng n gin, ch c mt tc ng c bn - th phn t s
mi trng vi bc phn ng. ( rng phn t s khng th no l s thp phn c)
Cn trong trng hp tng qut th phn t s vi bc phn ng phi khc nhau.
Ngi ta cng cho rng s phn t va chm ng thi gy ra mt tc ng c bn l
khng bao gi qu 3. Khi :
- Phn t s bng 1 : ta ni phn ng ny l phn ng n phn t.
- Phn t s bng 2 : phn ng c gi l phn ng lng phn t.
- Phn t s bng 3 : phn ng c gi l phn ng tam phn t.
Nh vy bc phn ng l i lng hnh thc v c xc nh bng thc nghim m
khng cho bit phn ng din ra nh th no. Cn chnh phn t s ch c din tin
ca phn ng - l mt khi nim v l thuyt v tht ra ch phn ng ny, phn ng kia
i con ng ny,.. con ng kia ch l gi thit.
3.3.XC NH HNG S TC V BC PHN NG :

3.3.1.Phng trnh ng hc ca mt s phn ng mt chiu n gin :
3.3.1.1.Bc 1 : Thuc loi phn ng ny l cc phn ng phn hy, phn ng
phng x, phn ng c 2 cht tham gia v trong c mt cht c nng rt ln so vi cht
kia.
Xt phn ng : A Sn phm
Cc nng thi im ban u : a 0
Cc nng thi im t : a-x x
d A d ( a x) dx
Vn tc phn ng ti thi im t : = - k A k ( a x) k ( a x )
dt dt dt
dx
Phn ly bin s ri ly tch phn 2 v : kdt - ln (a - x) = kt + C

a x
a 1 a
Khi t = 0 th x = 0 C = - ln a. Vy ln = kt (1) hay k = ln
ax t ax
-1
n v ca k i vi bc mt l : (thi gian)
Chu k bn r (bn hu) l thi gian cn thit phn hu lng cht ban u :
a ln 2
vy x = lc y t = = = hng s.
2 k
Ta thy chu k bn hu ca phn ng bc mt khng ph thuc vo nng u ca
cht phn ng
T biu thc (1) ta thy tnh hng s vn tc k hay thi gian t khng nht thit phi
bit r nng u v nng ti thi im kho st m ch cn bit t s ca n, hoc t s
ca t l ca n (nh t l p sut, t s nguyn t (phn t, ...)
3.3.1.2. Bc 2 :
l cc phn ng kiu : 2A sn phm, hoc A + B sn phm
Kt qu ca biu thc ph thuc vo 2 trng hp :
37 HA I CNG 2
Chng 3 : NG HA HC
* Khi nng u cc cht bng nhau : A + B sn phm

Nng cc cht ti thi im ban u : a a 0
Nng cc cht ti thi im t : a-x a-x x
d A d (a x) dx
Vn tc ti thi im t : v = - k ( a x) 2
dt dt dt
Phn ly bin s, ly tch phn, xc nh hng s tch phn C, cui cng ta c :
1 1 1 1 1
kt (2) hay k= ( )
ax a t ax a
T (2) ta thy n v ca k l s-1.l. mol-1
1
Chng minh tng t ta c chu k bn r : =
ka
Chu k bn hy ca phn ng bc hai t l nghch vi nng ban u ca cht phn
ng
* Khi nng u 2 cht khc nhau : A + B sn phm
Nng cc cht ti thi im ban u : a b 0
Nng cc cht ti thi im t : a-x b-x x
1 b( a x )
Chng minh tng t ta c : ln kt
a b a(b x)
3.3.1.3.Bc 3 : Khi cc cht c nng bng nhau = a
A + B + E sn phm
Nng cc cht ti thi im ban u : a a a 0
Nng cc cht ti thi im t : a-x a-x a-x x
1 1
Chng minh tng t ta c : 2
= kt
2( a x ) 2a 2
Vi phn ng mt chiu bc 3, hng s vn tc k c n v l l2.mol-2.s-1
3
Chu k bn hu : = .
2ka 2
Ta thy chu k bn hy ca phn ng bc ba t l nghch vi bnh phng nng u
ca cht phn ng.
3.3.1..4. Bc 0 :
L phn ng m tc ca n khng ph thuc vo nng cc cht phn ng
d A dx
v=- k k x = kt
dt dt
Khi t tng th x tng, tc (a - x) gim. Vy nng ca cht phn ng gim t l theo
thi gian.
a
Chng minh tng t, ta cng c chu k bn hu : = . Ta thy chu k bn hu
2k
trong trng hp ny t l thun vi nng ban u ca cht phn ng
3.3.2. S lc v phng php xc nh bc phn ng :
3.3.2.1.Phng php th :
Nh tn gi ca phng php, nhng th ci g v vo u ?
D nhin ta cha bit bc ca phn ng ang xt, nhng rng mi phn ng c mt
bc ring ch ph thuc vo bn cht phn ng, nhit , xc tc. V vy vi mt phn ng
xc nh mt nhit xc nh th yu t bc phn ng cng xc nh v khi cng iu kin
nhit , xc tc th phn ng cng c hng s vn tc k xc nh. Nh th nu phn ng
a
ang tm hiu l bc mt th phng trnh ng hc s l : ln = kt. V vy khi nu ta thay
a x
cc gi tr (a - x) (l nng ca cht phn ng ti thi im t) theo t (cc gi tr ny c xc
nh bng thc nghim) th nu phn ng ng l mt chiu bc mt th hng s vn tc k
phi khng i khi t v (a - x) thay i - (ng hn k dao ng rt t quanh mt gi tr no
38 HA I CNG 2
Chng 3 : NG HA HC
) - Cn nu k thay i ng bin (hoc nghch bin) th phn ng ang xt khng phi l
bc mt.
Tng t vi bc 2, bc 3, bc 0. Nu phng trnh no tha mn gi tr k khng i
khi a - x v t thay i th ta nhn bc ca phn ng ng theo phng trnh .
Nu khng c phng trnh ng hc no tha mn th phn ng thuc loi phc
tp.
3.3.2.2.Phng php th :
Tng t nh phng php th, nhng y ta v th, nu th no (bc 0, hoc
bc 1, hoc bc 2, hoc bc ba) ph hp th bc phn ng tng ng vi th . Th d nh
1 1 1
gi s phn ng l bc 2 th c phng trnh ng hc : kt . Ta v theo t, nu
a x a a x
th l ng thng th phn ng ng tht bc 2 v c h s gc chnh l k. Cn nu
th khng phi l ng thng th phn ng khng phi bc 2.
3.3.2.3.Phng php tc u :
Xt phn ng : aA + bB eE + fF.
Theo nh lut tc dng khi lng ta c biu thc v = k[A] m [B]n. Ta rng khi
nng ban u ca cc cht phn ng [A], [B] thay i th dn n vn tc phn ng v thay
i, nhng i vi mt phn ng xc nh nhit xc nh th hng s vn tc k v bc
phn ng m, n phi khng i.
V vy nu ta bit c nng ban u [A], [B] v vn tc v cho tng th nghim, ta
s tm c bc phn ng m, n.
V d : v1 = k[A]1 m [B]1n;.vi = k[A]i m [B]in. Th tm m, n ta chia cc vi cho nhau, ta s
c m, n
V d : Xt phn ng : A + B E c cc kt qu sau :
Ln th Nng u (mol/l) ca Thi gian th Nng
nghim [A] [B] nghim (gi) cui ca A
1 0,1 1 0,5 0,0975
2 0,1 2 0,5 0,09
3 0,05 1 2 0,045
Xc nh bc phn ng v gi tr trung bnh ca k.
0,1 0,0975
Gii : - Vi ln 1 : v1 = vm1 = 0,005
0,5
0,1 0,09
- Vi ln 2 : v2 = vm2 = 0,02
0,5
0,05 0,045
- Vi ln 3 : v3 = vm3 = 0,0025
2
Theo nh lut tc dng khi lng ta li c : v = k[A] m [B]n. Nn :
v1 = k(0,1)m.1n = 0,005 (1) ; v2 = k(0,1)m.2n = 0,02 (2) ; v3 = k(0,05)m.1 n = 0,0025 (3)
(2) 2n 0,02 (1) 0,1m 0,005
2n 4 n 2 ; 2m 3 m 1 .
(1) n 0, 005 (3) m 0, 0025
1 0,05
Vy phn ng trn c bc mt i vi A, bc 2 i vi B v c bc tng qut l 1 + 2 = 3.
0,005 2 -2 -1
T (1) k = 1 2
0,05 l .mol .gi
0,1 .1
3.3.2.4.Phng php d (hay phng php c lp)
Theo phng php ny xc nh bc phn ng ca mt cht (cht A chng hn) th ta
ly cc cht khc vi nng rt ln (d) so vi cht A. Vy nng cc cht phn ng khc
(khc cht A) xem nh khng i ti thi im t, nn trong biu thc ca nh lut tc dng
khi lng s khng c mt cc cht phn ng khc, m ch c mt cht A. T xc nh
bc phn ng ca A bng mt trong nhng phng php khc (nh trn chng hn). Tng
t cng lm nh vy ln lt vi cc cht phn ng khc.
3.3.2.5.Phng php chu k bn hu
39 HA I CNG 2
Chng 3 : NG HA HC
Theo phng php ny ta phi ly cc cht phn ng vi nng u bng nhau. T
cc cng thc ca chu k bn hu :
a
- Bc khng : = . Chu k bn hu t l thun vi nng u ca cht phn ng.
2k
ln 2
- Bc 1 : = . Chu k bn hu l hng s i vi nng u ca cht phn ng.
k
1
- Bc 2 : = . Chu k bn hu t l nghch i vi nng u ca cht phn ng.
ka
3
- Bc 3 : = . Chu k bn hu t l nghch i vi bnh phng nng u.
2ka 2
V vy nu ta theo di cc chu k bn hu (thi gian phn hu lng cht phn ng)
theo s thay i nng u ca cht phn ng, nu thy chu k bn hu t l thn vi nng
u ca cht phn ng, ta kt lun phn ng c bc khng i vi cht phn ng ,
cn nu chu k bn hu l mt hng s khi ta thay i nng u ca cht phn ng, th
phn ng y c bc mt,
3.4.NH HNG CA NHIT N TC PHN NG :

3.4.1. Quy tc Vant Hoff
khong nhit khng cao, Vant Hoff khi kho st thc nghim khi qut : thng
thng c tng ln 10oC th tc phn ng tng t 2 n 4 ln. S ln tng tc c tng
vT 10
mi 10 oC gi l h s nhit tc l : =
vT
Khi T phn ng c vn tc v
Khi tng ln 10oC (T1 = T +10) th v1 = v .
Khi tng ln 20oC (T2 = T +20) th v2 = v1 . = v. 2
Tc Td
( )
Khi tng ln Tc [(Tc = T +(Tc- T)] th vc = v . 10
V d : Nu phn ng 0 oC c vn tc v th 100 oC tc phn ng tng ln bao

nhiu ln, nu h s nhit = 3 ?
T T 1000
( c d)
Gii : T cng thc : vc = v . 10
. Th s vo v100C = v. 3 310 = 59049 v.
10
Vy khi = 3, t 00C tng ln 100 0C vn tc tng ln 59049 ln.

3.4.2.Phng trnh Arrhenius :
Phng trnh Vant Hoff ch l phng trnh gn ng. Khi phn ng thc hin nhit
cao th biu thc ca Vant Hoff khng cn dng c.
Nhng nghin cu ca Arrhnius v cc phn ng a ra phng trnh thc nghim
B
biu din mi quan h gia hng s vn tc k v nhit T : lnk = - +C (1)
T
Vi B v C l cc hng s ch ph thuc vo bn cht cht phn ng (B > 0)
B
A
(1) c th vit thnh : k = A e T . Vi A = eC . Hoc vit li k = B/T
e
Ta thy T nm phn s m nn mt s bin i nh ca T cng dn n bin i ln
v k - tc tc .
Lin h vi phn nng lng hot ho Ea (chng ta sp nghin cu), ngi ta nhn thy
Ea
E
B = a . V vy phng trnh Arrhenius thng c vit : k Ae RT .
R
Vi R l hng s - n bng vi hng s kh l tng
40 HA I CNG 2
Chng 3 : NG HA HC
y l biu thc thc nghim (nh thc nghim tm c), nn ngi ta gi Ea l nng
lng hot ho thc nghim
3.4.3.Nng lng hot ha :
Chng ta bit cc cht phn E
ng mun to thnh sn phm th phi
va chm nhau v ta cng bit khng
phi bt c va chm no cng c hiu
qu dn n to thnh sn phm.
Vy th va chm no c hiu qu, va
chm no khng ? Ta bit bt c
Ea
nguyn t, phn t hay ion no cng
c cc electron xung quanh. V vy cc
cht phn ng mun chuyn ha thnh E a'
sn phm - th phi c s phn b li
cc electron ngoi cng - mun vy A
cc phn t phi xm nhp vo B
nhau n mt mc no - mun H
th iu u tin l cc phn t phi
thng c lc y ca cc electron sn phm
ngoi cng ca cc phn t - lc y
Tin trnh phn ng
ny nh mt hng ro ngn chn s
xm nhp - gi l hng ro th nng, Ea : nng lng hot ho phn ng thun.
nhng phn t bnh thng th khng Ea' : nng lng hot ho phn ng nghch
nng lng vt qua c hng H : hiu ng nhit ca phn ng
ro th nng, ch nhng phn t no c
nng lng cao hn (cc phn t bnh
thng), thng lc y - nhng phn t gi l nhng phn t hot ng v mc
chnh lch nng lng m cc phn t hot ng c c so vi cc phn t khc - gi l
nng lng hot ha Ea. Chnh nhng va chm do cc phn t hot ng gy ra l va chm
c hiu qu. Th th nng lng hot ha Ea ny c sn trong cc phn t khng ? Nng
lng hot ha c t u, lm g ? Ea khng th c sn (trong cc phn t c), n c
c t vic cung cp nng lng nh mi trng ngoi (nh chiu sng, un nng, ), cc
phn t bnh thng khi nhn nng lng ny s ph v mt phn lin kt c. Nh vy khi
tng nhit vn tc phn ng tng khng phi do s tng s va chm gia cc phn t m
chnh l do s tng s va chm c hiu qu.
Chnh nng lng hot ho E a gip chng ta hiu ti sao c nhng phn ng rt thun
li v mt nhit ng (G < 0) li khng xy ra iu kin bnh thng (khi tip xc nhau).
Ta c th hiu c ti sao giy, g, xng, du vi O2 th G < 0, nhng v trong chng cha
c phn t no c nng lng ti thiu so vi Ea, nn phi cn mt nhit ti thiu no
gip n vt qua hng ro th.
3.5.THUYT VA CHM HOT NG V THUYT PHC CHT HOT NG

3.5.1. Thuyt va chm hot ng :
Thuyt ny xem nhng phn t cht phn ng nh nhng ht c bn knh xc nh. Khi
mi v 2 i
cc ht chuyn ng n c mt ng nng Ei = . Khi 2 ht A v B va chm vo nhau
2
m A v 2A m B v B2
th nng lng chung : E = EA + E B
= +
2 2
Ti lc va chm, ng nng E chuyn thnh th nng. C th c 2 cch chuyn ha tip
theo ca th nng. (1) Nu th nng chuyn ngc li thnh nng lng ca chuyn ng tnh
tin th cc ht bay theo chiu ngc li - va chm nh th gi l va chm n hi. (2) Nu
41 HA I CNG 2
Chng 3 : NG HA HC
nng lng E ln hn (hay ti thiu bng) nng lng hot ha Ea ca phn ng th s va
chm s dn n s tin trin ca phn ng.
cho s va chm l c hiu qu E Ea th cc phn t phi c nng lng chnh lch
so vi cc phn t bnh thng, nh ni trn - l cc phn t hot ng - S phn t bnh
thng Z, s phn t hot ng Z* c tnh ton :
Z* Ea / RT Ea / RT
e hay Z * Ze
Z
B
Nh li phng trnh thc nghim ca Arrhnius : lnk = - C hay k Ae B / T
T
Lin h phng trnh ny vi thuyt va chm hot ng - l nhng va chm ca cc
phn t hot ng - Cc phn t khi va chm c tng nng lng E Ea.
Kt hp 2 phng trnh ny ta c : k = Ae-Ea/RT
S trng hp ca dng phng trnh rt ra t l thuyt - thuyt va chm hot ng vi
dng phng trnh Arrhnius - rt ra t thc nghim l mt thnh tu ca thuyt va chm hot
ng.
Nhng thuyt ny c mt s hn ch :
- Cha quan tm n v tr va chm ca phn t.
- Cha ch n vic t v rp cc lin kt, n cn ph thuc vo dng phn b.
Chnh nhng thiu st ny ca thuyt va chm hot ng to tin cho s ra i
cho thuyt trng thi chuyn tip, l thuyt ch n chi tit hn trong lc va chm gia
cc phn t.
3.5.2.Thuyt trng thi chuyn tip (phc cht hot ng)
Khi nhn nng lng t mi trng ngoi, cc phn t tr nn hot ng hn - v vy
km bn hn. Khi nu cc phn t ny va chm vo nhau v nu ngay lin khi y, cc
electron ngoi cng c phn b li, lin kt mi c hnh thnh, sn phm mi c to
ra v nng lng c gii phng (do to lin kt mi). Nhng khng phi ngay khi va chm
th lin kt c b t ra v lin kt mi c hnh thnh mt cch t ngt m khong cch
gia cc nguyn t (trong phn t c v trong phn t mi sp hnh thnh) bin i mt cch
lin tc - ngi ta gi trng thi ny l trng thi chuyn tip (hoc phc cht hot ng) - n
khng phi l mt cht ha hc thc s, ch l mt trng thi trung gian ca trng thi u v
trng thi cui
Th d : H I HI
+ +
H I HI
Lc u 2 phn t H2 v I2 xa nhau (i vi kch thc nguyn t) khong cch gia
H v I rt ln so vi khong cch gia H v H hoc I v I. Khi cc phn t ny nhn nng
lng, th lin kt H - H v I - I b t mt phn lm cho khong cch H - H v I - I c xa
hn ra v khi 2 phn t tin li gn theo ng ni tm nguyn t H vi nguyn t I theo
khong cch gia H v I t tin dn n khong cch d bng khong cch trong phn t H -
I. Lc y phn t H2 v I2 mt dn c tnh v dn dn hnh thnh nn H-I
H---------------I H---------I H-----I H-I

H---------------I H---------I H-----I H-I
(1) (2) (3)
(1), (2), (3) : trng thi dn chuyn tip.
3.6.NH HNG CA CHT XC TC N TC PHN NG :

Xc tc c mnh danh l cy a thn trong ho hc - chnh xc hn trong cng ngh
ha hc. Nh n, ngi ta s t c sn phm mong i mt cch kinh t.
Nhng khoa hc v xc tc ra i mun mng nn n hin nay xc tc ang cn l vn
nghin cu.
3.6.1.Khi nim v c im ca xc tc :
42 HA I CNG 2
Chng 3 : NG HA HC
Khi un KMnO4, thuc tm s phn hu chm, nhng khi cho thm vo mt t MnO2 th
phn ng s xy ra nhanh chng. Lng MnO2 cho vo khng khc vi MnO2 sinh ra t
phn ng k c v lng v cht - MnO2 gi l cht xc tc.
Cht xc tc l cht khi thm vo h n lm thay i tc phn ng m cui qu trnh
n vn c gi nguyn v lng v cht.
ng v gc nh hng n vn tc phn ng c th chia cht xc tc ra lm 2 loi :
cht xc tc thun (dng) : lm tng tc phn ng v cht xc tc nghch (m, cht c
ch) : lm vn tc phn ng gim.
ng v gc pha, ngi ta chia cht xc tc ra lm 2 loi : xc tc ng th v xc
tc d th.
Xc tc c gi l ng th khi cht xc tc cng pha vi cht phn ng.
Xc tc c goi l d th khi cht xc tc khc pha vi cht phn ng.
Do vic tc ng ca cht xc tc vo h ng th v d th khc nhau nn c ch ca
vic xc tc ng th v d th cng khc nhau.
c im : D l ng th hay d th, cht xc tc c nhng c im :
a) Khng lm thay i nhng c trng nhit ng.
Ni n nhit ng th ch n trng thi u v trng thi cui m khng xt n
qu trnh. M ta thy ngay t nh ngha ca cht xc tc : t trng thi u sang trng thi
cui cht xc tc khng i. Vy th cht xc tc khng lm thay i n tnh cch nhit ng
- tc khng gy nh hng n G. Vy th : E
- Khi mt phn ng khng th xy ra v mt
nhit ng (G > 0) th d c hay khng c cht xc
tc cng khng th lm cho phn ng xy ra c.
Ni nm na, khi ta tnh c mt phn ng (d kin)
c G < 0 th lc y mi tm kim cht xc tc
thc y cho phn ng din ra nhanh hay chm hn
theo ngi s dng.
-V cng vy khi mt phn ng cn bng (G
= 0) th cht xc tc khng lm dch chuyn cn bng
- ngha l khng th to ra sn phm nhiu hay t hn
A [AK]
m cn bng ch, cht xc tc ch thc y phn
B
ng nhanh (hay chm) t n cn bng, ngha l khi
phn ng l cn bng th cht xc tc l tng (hay
gim) vn tc phn ng thun th cng lm tng (hay
gim) vn tc phn ng nghch. sn phm
b. Cht xc tc c tnh chn lc : ngha l nu Tin trnh phn ng
mt cht c th cho nhiu sn phm th vi xc tc
thch hp, ngi ta c th hng phn ng n sn : c xc tc
phm mong i : : khng c xc tc
0
Th d : Al
2O
3 , 400 C
C2H4 + H2O.
0
C2H5OH CuO , 200 C
CH3CHO + H2O.
3.6.2.C ch xc tc :
Vi xc tc ng th do cht xc tc cng pha vi cht phn ng, phn ng xy ra
trong khng gian 3 chiu, cn trong xc tc d th do cht xc tc khc pha vi cht phn ng
nn phn ng ch xy ra trong 2 chiu nn c ch ca n khc nhau.
3.6.2.1.Xc tc ng th :
S d cht xc tc lm thay i tc phn ng v khi c cht xc tc tham gia n lm
cho nng lng hot ha ca phn ng gim. Ta bit tnh cht quan trng ca nng lng
hot ho Ea n vn tc phn ng qua phng trnh: k = Ae-Ea/RT. Ea nm phn ly tha v
vy vic thay i Ea d nh cng lm thay i nhiu n k - dn n vn tc v ca phn ng
thay i nhiu
43 HA I CNG 2
Chng 3 : NG HA HC
Cht xc tc d phn nh th no trong vic gim Ea ? Ngi ta cho rng chnh cht
xc tc tham gia vo phn ng v bin phn ng thnh nhiu giai on hn v trong mi
giai on n s c Ea nh hn, nh mun qua mt ngn ni qu dc, ngi ta phi qua nhng
ng o zic zc.
K
A + B sn phm. K : l cht xc tc
Ngi ta cho rng : A + K [AK]. Sau : [AK] + B sn phm + K
V vy vn tc ca phn ng ph thuc vo nng cht xc tc.
3.6.2.2.Xc tc d th :
Do tnh cht c th ca xc tc d th : phn ng ch xy ra trn khng gian 2 chiu -
trn b mt cht xc tc. Nh vy vn tc phn ng phi t l vi din tch b mt ca cht
xc tc. V mun phn ng din ra nhiu (trn b mt cht xc tc) th nng trn b mt
cht xc tc phi cao. Mun vy cht xc tc phi c kh nng hp ph tt v ngi ta cho
rng c ch ca cht xc tc xy ra theo 5 giai on :
- Giai on 1: Khuych tn cht phn ng n min xc tc
- Giai on 2: Hp ph, cht xc tc hp ph cc cht phn ng.
- Giai on 3: Cc cht phn ng phn ng trn b mt cht xc tc.
- Giai on 4: Gii hp : sn phm thot khi s hp ph ca cht xc tc.
- Giai on 5: a sn phm ra khi min xc tc.
Chng ta thy trong 5 giai on th c n 4 giai on ph thuc s hp ph, ch c giai
on 3 l khng phi hp ph nhng chnh l giai on chm nht - v vy ngi ta cho
rng c im ca xc tc d th chnh l s hp ph.
S hp ph c hp ph l hc v hp ph ha hc.
Hp ph l hc l do cc nguyn t xc tc nm trn b mt ch c lc lin kt gia cc
nguyn t vi cc nguyn t trong lng tinh th ca cht xc tc, v vy cc nguyn t trn
b mt ny thiu lc lm cho cc nguyn t b mt s c lc ht vi cc cht phn ng - s
hp ph ny gii thch c ch xc tc nhit thp.
Quan trng hn l s hp ph ha hc, ngi ta cho rng cc nguyn t trn b mt do
ch to lin kt vi cc nguyn t bn trong nn pha ngoi cn c nhng orbital nguyn t
(AO) trng v vy khi cht phn ng tin n, nh H2 chng hn, lm cc C C C C
AO trng ca cht xc tc Ni ph vi cc AO 1s ca H to mt phn lin
kt vi H v lm yu i lin kt H -H. Khi cc phn t anken C=C tin H H H H
n th d to lin kt vi anken v H2. Nh vy d nhin lin kt Ni-H
cng khng mnh lm d t. S hp ph ha hc ny khng b nh
Ni Ni Ni Ni
hng khi nhit cao, n khc vi s hp ph vt l khi nhit cao s
hp ph s gim.
Ni Ni Ni Ni
3.7.PHN NG DY CHUYN :
Phn ng dy chuyn l phn ng trong c s tham gia ca cc gc t do. c
trng i vi phn ng dy chuyn l s lp li tun hon mt trnh t nht nh ca mt giai
on c bn.
Di tc ng ca mi trng ngoi, cht phn ng no b bin thnh cht c hot
tnh cao (c nng lng cao) gi l trung tm hot ng (hoc tiu phn hot ng) - l cc
nguyn t, ion hoc gc c cc electron c thn.
Cc trung tm hot ng sau khi c hnh thnh do c nng lng cao nn khi va
chm vi phn t khc s to thnh cht khc (c th l sn phm) ng thi sn sinh ra trung
tm hot ng mi. Cc trung tm hot ng mi li tng tc vi phn t khc... v c th
dy chuyn tip din. Chnh trung tm hot ng l ni to ra cc chui chuyn ha cc cht
lin tip.
44 HA I CNG 2
Chng 3 : NG HA HC
Th d nh khi chiu sng bnh cha H2 v Cl2. H2 v Cl2 khi hp th lng t nng
lng = h , cc phn t b kch thch, khi nng lng ln, phn t Cl2 s b ct to thnh
h
2 nguyn t Cl : Cl2 2Cl Giai on ny gi l khi mo phn ng .
Cc nguyn t Cl va to thnh c nng lng cao rt khng bn khi va chm vi H2
th : Cl + H2 HCl + H
Li n lt H khi gp phn t Cl2 khc : H + Cl2 HCl + H
V nh vy phn ng c tip din. Mi giai on gi l mi mt xch - s mt xch c
th t n 100.000
Dy chuyn c th b t khi trung tm hot ng va chm vo thnh bnh, tp cht
hoc hai trung tm hot ng va chm vo nhau.
Cc phn ng xy ra theo c ch nh trn, gi l phn ng dy chuyn khng phn
nhnh - ch c mt mch, tc l mt tiu phn hot ng ny mt i ch to c mt trung
tm hot ng mi. Loi phn ng ny c th phn thnh 3 giai on : giai on khi mo,
khi mi sinh ra c tc cao, n giai on 2 gi l giai on pht trin th tc phn ng
khng i v khi n giai on cui cng - giai on tt mch th c tc chm li.
Ngoi ra cn c phn ng dy chuyn phn nhnh, l loi phn ng dy chuyn m t
mt trung tm hot ng, phn ng s cho 2, 3 trung tm hot ng khc, mi trung tm to
dy chuyn mi cng vi cc trung tm hot ng mi, nh vy cc trung tm s tng ln rt
nhanh, n pht trin theo cp s nhn,
nn loi phn ng dy chuyn phn H2O H2O
. .
....
+H2 +H2
nhnh ny nu khng kim sot c OH OH
.+ O2
OH.
thng gy ra hin tng n. Phn H + O H H
ng phn r ht nhn, phn ng
2 2
. H2
H2O
O+. H 2
...
crackinh du m, phn ng trng hp OH + ... .
l loi phn ng dy chuyn phn .
H + O2
H
nhnh, phn ng gia hidro v oxi ...
(theo t l 2 : 1) khi un nng cng vy
(nh hnh bn)
c im ca phn ng dy chuyn :
a) Tc ca phn ng ph thuc nhiu vo di mch - di mch bin ng rt
nhiu ph thuc vo tng phn ng - n ph thuc vo s mch sinh ra v mt i trong cng
khong thi gian.
b) Tc ca phn ng dy chuyn cn ph thuc vo hnh dng, cht liu, ng
knh bnh phn ng - do yu t di mch gy ra - bnh cng nh xc sut lm mt trung
tm hot ng cng ln, mch cng ngn li, vn tc gim.
c) Cn ph thuc vo cht l (tp cht), d vi du vt, n c kh nng "ht" cc trung
tm hot ng, lc y mch ngn li tc vn tc gim, thm ch ngng phn ng.
d) Nhng phn ng dy chuyn c vn tc cao cn ph thuc vo p sut na. Vi
mi loi phn ng c mt p sut nht nh gy n.
3.8.PHN NG QUANG HA :
Phn ng quang ha l phn ng ha hc xy ra di tc dng ca nh sng.
V d kinh in ca loi phn ng ny l phn ng quang hp, phn ng v chp nh:
trong c s phn hu AgBr. Khi c chm tia sng chiu n, Br - hp th nng lng tia
sng ny : = h. Nh nng lng ca nh sng ny, electron t Br- s c chuyn n Ag+.
h 1
AgBr Ag + Br2.
2
Cc phn ng ny tun theo cc nh lut quang ho sau :
a) nh lut Grothus - Draper : Ch nhng bc x no b hp th bi h mi c th xy
ra phn ng quang ho.
45 HA I CNG 2
Chng 3 : NG HA HC
nh lut ny ch r nguyn nhn gy ra phn ng quang ho chnh l cc bc x,
nhng s hp thu c tnh chn lc ch khng phi l bt k bc x no (thng cc bc x
0
vng kh kin n vng t ngoi tc cc bc x c bc sng trong khong t 4000 A n
0
7000 A ). Ta cng thy khi hp th bc x th c th xy ra phn ng ch cha chc phi xy
ra v c th phn t "dng" nng lng vo vic pht nhit hay dao ng chng hn.
b) nh lut Lambert - Beer : Xc sut hp thu ca h t l thun vi nng cc phn
t hp thu.
nh lut ny thng c biu din bng phng trnh sau : dI k .C.dl .
I
Vi : I l cng nh sng c bc sng xc nh ; dI l bin thin cng nh sng
khi n i qua lp mng cht c dy dl v nng C c s phn t n ; k l h s t l ph
thuc vo bc sng, bn cht cht hp thu v nhit .
I l
dI I
Ly tch phn 2 v phng trnh trn : k .C.dl . Ta c : ln
k .C.l . Hay : I =
I Io
I0 0
-kCl
I0e . Vi I0 v I ln lt l cng nh sng trc khi i qua lp hp thu
(l = 0) v sau khi i qua lp hp thu c b dy l.
Hay nng lng b hp thu E : E = I0 - I = I0(1- e-k.C.l).
c) nh lut ng lng quang ho ca Einstein : Di tc dng ca nh sng, mi
phn t phn ng hp thu mt lng t bc x gy ra phn ng.
c
Nh vy mi phn t hp thu mt nng lng : = h = h .

Vi h l hng s Planck ; l tn s ca bc x c bc sng ; c l vn tc nh sng.
Khi bc sng cng ngn th lng t nng lng cng ln, th phm vi phn ng gy nn bi
nh sng cng rng.
Theo nh lut Einstein th mt lng t c hp th gy nn s chuyn ha ca mt
phn t. Nhng thng thng ngi ta nhn thy s phn t phn ng trong phn ng quang
ho khng bng s lng t b hp thu. V vy ngi ta a ra khi nim Hiu sut lng t
n
. Vi p . Trong : np l s phn t ca cht phn ng v na l s lng t nh
na
sng hp thu. C nhng phn ng c = 1, cng c nhng phn ng c < 1 v c nhng
phn ng c > 1, cn c >> 1.
Ti sao < 1 ? Do cc phn t khi hp thu lng t bin mt phn thnh nng lng
khc m khng to phn ng nh chuyn nng lng sang phn t khc hay chuyn ho thnh
nhit nng. Nhng ti sao > 1, li cn >> 1 ? Do khi ban u cc phn ng khi mo xy
ra ng vi hiu sut lng t = 1, nhng sau cc trung tm hot ng sinh ra t cc phn
ng khi mo ny li l nhn t cho cc phn ng giai on pht trin tc l phn ng th
cp din tin m khng cn nhn nng lng na nh phn ng dy chuyn ni trn.
Vy nh sng khng phi l cht xc tc m chnh nh sng l tc nhn gy ra
trung tm hot ng.
Phn ng quang hp : Chc nng quan trng, c l l quan trng nht ca nh sng l vai tr
ca n trong phn ng quang hp, n cng vi clorophil, mt cht phc tp ca magie c
trong cht mu xanh ca thc vt l tc nhn gy ra phn ng ny - l phn ng gia cacbonic
1
v nc, c th vit thnh s : CO2 + H2O + h. clorophil
(CH 2 O) n + O2.
n
T nng lng ca phn ng ny cho tng loi sn phm (glucoze, xenluloze,), tnh ton
0
c rng cho phn ng xy ra cn phi c bc x trong vng t ngoi ngn (< 2300 A ).
Bc x loi ny khng c trong vng kh kin, v vy ngi ta cho rng clorophil c tc dng
nh cht cm quang - chnh n hp thu nh sng v to iu kin cho qu trnh quang hp.
46 HA I CNG 2
Chng 3 : NG HA HC
BI TP
1) Xt phn ng trong dung dch : S2O82- + 2 I- 2 SO42- + I2. Nu tng nng ca S2O82-
ln gp 3 ln th vn tc ca phn ng tng gp 3 (nng I- khng i). Nu tng [I- ] ln
gp i v gi nguyn [S2O82-] th vn tc phn ng tng gp i. Vit biu thc vn tc
theo nh lut tc dng khi lng v cho bit bc phn ng.
2) Xt phn ng n gin : A + B C. Tm gi tr ca hng s vn tc, bit [A] v [B] ln
lt l 0,05 mol/l v 0,01 mol/l. Vn tc ca phn ng bng 5.10 - 5 mol.l-1.ph- 1
3) Tc ca phn ng n gin : 2A + B C thay i bao nhiu ln khi tng nng cht
A ln 2 ln v nng cht B gim xung 2 ln ?
4) Cho phn ng n gin : A + 2B C. Nng ban u ca cc cht : [A]0 = 0,03 mol/l ;
[B]0 = 0,06 mol/l. Hng s vn tc phn ng k = 0,4. Tm vn tc ban u v vn tc ca
phn ng sau mt thi gian khi nng cht A gim i 0,01 mol/l.
5) N2O5 d phn hu theo phn ng sau : 2N2O5 (k) 4 NO2 (k) + O2 (k). Phn ng l bc
mt vi hng s vn tc k = 4,8.10 - 4 s -1.
a) Tnh chu k bn hu ca phn ng.
b) p sut ban u ca N2O5 (k) l 500 mmHg. Tnh p sut ca h sau 10 pht.
6) Xt phn ng n gin : 2NO (k) + O2(k) 2NO2 (k). Vn tc thay i nh th no nu
a) Tng p sut ca h ln 3 ln.
b) Gim th tch h xung 3 ln.
c) Tng nng NO ln 3 ln.
7) Xt phn ng xy ra trong dung dch : C2 H5Br + KOH C2H5OH + KBr. Nng ban
u ca KOH l 0,07N. Sau 30 pht ly ra 10 ml dung dch hn hp phn ng th thy n p
va vi 12,84 ml dd HCl 0,05N. Tnh vn tc trung bnh ca phn ng trong khong thi
gian trn.
8) Trong dung mi CCl4, 250C, nghin cu phn ng : C2 H4 + Br2 C2 H4Br2 bng cch
cho tin hnh phn ng cc nng bng nhau ca C2H4 v Br2 v theo di thi gian
phn hu mt na lng Br2 ( ), c cc kt qu sau :
[Br2]ban u 0,05 0,01 0,03 0,0075 0,02

(s) 117000 590000 196000 785000 295000
Xc nh bc phn ng v hng s tc phn ng.
9) Xt phn ng : A + B C c cc kt qu vi nhng nng u sau :
Ln th nghim [A]0 [B]0 10 - 3 v0
1 0,1 0,1 2
2 0,2 0,2 8
3 0,1 0,2 8
Xc nh bc phn ng ring v tnh k.
10) Xt phn ng bc nht : A B + C 5000C, chu k bn hu ca phn ng l 1000 giy
a) Tnh hng s vn tc k 5000C.
b) Tnh k 520 0C nu nng lng hot ho ca phn ng l Ea = 83,6kJ.
11) Xt phn ng x phng ho axetat mtyl bit nng u cc cht bng nhau v c bng
kt qu sau :
t (pht) 3 4 5 8 10 15 25
% x phng ho 26 31,7 36,6 48,1 53,6 63,7 74,6
a) Xc nh bc phn ng.
b) Tnh k v chu k bn hu.
12) Mt cht phng x c chu k bn hu l 30 nm. Hi cn mt thi gian bao lu 99 %
s nguyn t ca n b phn hu.
47 HA I CNG 2
Chng 3 : NG HA HC
13) Phn ng bc mt : (CH3)2O (k) CH4 (k) + CO (k) + H2 (k). mt nhit xc nh,
lng eter c p sut ban u l 300 mmHg. Sau 10 s, p sut ca hn hp l 308,1 mmHg.
Hi sau bao lu th p sut ca hn hp l 608,1 mmHg ?
14) Khi un nng dung dch acid dibromsuccinic b phn hu thnh acid brommaleic v HBr
theo phng trnh :
HOOCCH(Br)CH(Br)COOH HOOCCHC(Br)COOH + HBr
Sau t pht, chun mt lng xc nh dung dch mt n.10- 6 ml kim.
(pht) 0 214 380
n. 10- 6 ml 12,11 12,45 12,68
a) Tnh k
b) Sau bao lu th 1/3 acid dibromsuccinic b phn hu ?
15) 150 0C mt phn ng kt thc trong 16 pht. Tnh xem 200 0C v 800C phn ng
ny kt thc trong bao lu ? Cho bit h s nhit ca phn ng bng 2,5
16) Xt phn ng : C2H5 I + OH- C2 H5OH + I-. Bit k = 5,03.10 - 2 l.mol -1.s -1 298K v
333K c k = 0,71l.mol -1.s -1
a) Tnh Ea
b) Tnh k 306K
17) Xt phn ng : H2 (k) + Cl2 (k) 2HCl (k) phn ng thun c Ea = 154,66kJ.mol -1 ;
phn ng nghch c Ea' = 247,29kJ.mol-1. Tnh hiu ng nhit ca phn ng trn.
18) Phn ng thu phn CH3(CH2)6CH(Cl)CH3 trong tanol 80% xy ra theo bc nht,
theo bng sau :
t0 (C) 0 25 35 45
-1 -5 -4 -4
k(s ) 1,06.10 3,19.10 9,86.10 2,92.10 - 3
a) Tnh Ea bng phng php th.
b) Tnh tha s A.
19) 100C mt phn ng kt thc sau 95 s v 20 0C sau 60 s. Tnh Ea.
20) Khi tng nhit ca mt phn ng t 520C n 82 0C th tc phn ng tng bao
nhiu ln bit phn ng ny c E a = 83,6kJ.mol -1
48 HA I CNG 2
Chng 4 : DUNG DCH
CHNG 4
DUNG DCH
Thng thng cc cht di dng hn hp. Nhiu khi di dng hn hp li c nhiu ng

dng rng ri hn, nh HCl chng hn. Vic bit tnh cht ca dung dch qu tht l cn thit. V
th chng ta s nghin cu dung dch - mt trng thi thng thng ca ha cht.
4.1.KHI NIM :
4.1.1.Cc h phn tn :
H phn tn l h c t nht 2 cu t v phn b u trong nhau .
Trong cht quyt nh dng tn ti (rn : r ; lng : l ; kh : k) gi l mi trng phn tn
v cc cht cn li gi l cht phn tn.
Th d : Nc ng th nc l mi trng phn tn cn ng l cht phn tn.
Khi bi th cht phn tn l cc cht rn (cc ht than, ht bi) cn mi trng phn tn l
khng kh
Ty theo kch c ca cht tan ngi ta c cc h phn tn :
0
- H phn tn th : khi cht phn tn c kch thc ln hn 1000 A
+ Nu cht phn tn l cht rn : ngi ta gi h l huyn ph, nh nc ph sa
+ Nu cht phn tn l cht lng : gi h l nh tng, v d nh sa
0 0
- H phn tn keo : cht phn tn c kch thc trong khong t 10 A n 1000 A .
- H phn tn tht (cn gi l dung dch tht, gi tt l dung dch) : khi kch thc cht phn
0
tn l kch thc ca phn t : nh hn 10 A .
V vy, dung dch c nh ngha : l h ng th, bn nhit ng, gm t nht hai cu t
v thnh phn c th bin thin lin tc trong nhng gii hn xc nh.
Cu t no c mt nhiu nht trong dung dch gi l dung mi , cn cc cu t khc gi l
cht tan. Vi dung dch l cht kh, hoc rn trong cht lng ngi ta thng xem cht lng l dung
mi.
4.1.2.Nng dung dch : Nng dung dch l lng cht tan trong mt n v khi lng
hoc th tch ca dung mi hoc dung dch.
Ty thuc vo n v biu din ta c cc nng thng gp :
a/ Nng phn trm : c k hiu l % hoc C%, c nh ngha l s gam cht tan tan
mct
trong 100 gam dung dch. T C% = . 100 ; mdd = mdm + mct
m dd
Quy tc ng cho : thng dng cho vic pha ch dung dch theo nng phn trm v
c tnh theo khi lng : iu ch m gam dung dch C% t ma gam dung dch a% v mb gam
dung dch b%.
ma b c
ma a bc Ta c :
mb ac
C
ma bc
mb b ac Hay :
m ba
Th d: T dung dch HCl 10% v HCl 30%. Hy pha ch 600g dung dch HCl 15%.
Gii : Theo quy tc ng cho :
m30% 5 600.5
m30% 30 15 - 10 = 5 Ta c : m30% 150 g
m 5 15 20
15
m10% 10 30 - 15 = 15 m10% = 600 - 150 = 450g
b/ Nng mol : (k hiu : M, CM) l s mol cht tan tan trong 1 lt dung dch
n
Vy : CM = .
V (l )
49 HA I CNG 2
Chng 4 : DUNG DCH
c/ Nng ng lng : (k hiu : N, CN) l s mol ng lng cht tan tan trong 1 lt
n'
dung dch. Vy CN = ( n' : s ng lng cht tan ).
V (l )
Loi nng ny thng c dng trong ha phn tch, tin cho vic chun
T nh lut ng lng, nghin cu trong hc phn trc : Mt ng lng cht ny
tc dng va vi mt ng lng cht khc.
S ng lng cht A c trong th tch VA l NAVA. S ng lng cht B c trong th
tch VB l NBVB. Khi hai cht A v B phn ng va th theo nh lut ng lng, ta c c :
NAVA = NBVB
Khi s dng nng ny ta cn n mol ng lng ca cht c th thay i ph
thuc vo tng phn ng c th.
Th d nh trong phn ng : H2SO4 + 2NaOH Na2SO4 + 2H2O th H2SO4 c mol ng
lng l 98/2 = 49g.mol -1. Cn trong phn ng H2SO4 + NaOH NaHSO4 + H2O, th H2SO4 lc
ny li c mol ng lng l 98/1 = 98g.mol -1.
d/ Nng molan : (k hiu : m, Cm) l s mol cht tan c trong 1000g dung mi. Nng
1000n ct
ny thng s dng trong ha l. Vy Cm =
mdm
e/ Nng phn mol : (Ni) l s mol cht tan (hay dung mi) c trong 1 mol dung dch.
ni
Ni = . Vi ni l s mol tng cht trong dung dch (Ni < 1 ; N i 1 )
ni
f/ Mi quan h gia cc nng :
- C% v CM : Mun chuyn ha qua li gia hai loi nng ny, cn phi bit khi
lng ring d ca dung dch v khi lng mol M ca cht tan, c chng minh
1000.d .C
Ta c 100g dung dch c C g cht tan. Vy 1 lt dung dch l 1000d gam c gam
100
10.C.d
cht tan. Tc l 1 lt dung dch c 10Cd gam cht tan Trong 1 lt dung dch c mol cht
M
tan. y chnh l CM. Vy : C M 10.C %.d
M
- CM v CN : Gi n'' l ha tr ca cht tan v l mol ng lng. T khi nim
n
mol ng lng ta c : = M . Li c CM = (n : s mol cht tan).
n' ' V (l )
Vy : C M m / M m . Th M = .n'' C M m
. M m/ chnh l s ng lng.
V M .V .n' '.V
CN
Vy CM = s ng lng/V.n'' = . Hay CN = n''.CM
n' '
4.2.S HNH THNH CC LOI DUNG DCH :

- Dung dch kh : p sut khng cao lm cc kh c th ha tan khng hn ch vo nhau,
v vy cc hn hp kh u l dung dch kh.
- Dung dch rn : Khi cc cu t ha tan vo nhau to thnh mt pha rn. Loi dung dch ny
thng ch tn ti nhng nng xc nh (nhng c nhng dung dch rn theo bt k t l no
nh vng ty ...)
- Dung dch lng : dung mi l cht lng cn cht tan c th l cht rn, cht kh hoc cht
lng. Loi dung dch ny ta s nghin cu k trong chng ny.
- Dung dch keo : Ta s cp n cui chng ny.
4.3.S HA TAN :
4.5.1.C ch ca qu trnh ha tan :
Cht tan tan c trong dung mi, tng qut l do hai qu trnh l qu trnh l hc v qu
trnh ha hc.
Qu trnh l hc l qu trnh do dung mi chuyn ng khng ngng, nhng do lc tnh
in gia dung mi v cht tan, nn khi dung mi chuyn ng n li ko cht tan ra khi tinh th
50 HA I CNG 2
Chng 4 : DUNG DCH
(nu l cht rn). Qu trnh vt l thng phi tiu tn nng lng (do cn nng lng tch cc
phn t ra khi trng thi n nh c) gi l Hl. (Hl > 0)
Qu trnh ha hc : qu trnh ny k lin theo qu trnh l hc, l cc phn t, ion cht
tan c an nh bi dung mi gi l solvat ha (nu dung mi l nc th gi l hydrat ha). Qu
trnh ha hc thng ta nhit : Hh < 0
4.5.2.Hiu ng nhit ca qu trnh ha tan :
Vy hiu ng nhit cho qu trnh ha tan gi l nhit ha tan : H = Hl + Hh.
Vy nhit ha tan l lng nhit pht ra hay thu vo khi ha tan mt mol cht
V vy H c th l m hoc dng ph thuc vo tr tuyt i ca Hl v Hh .
i vi cht rn v cn phi tiu tn nng lng vo vic ph v mng tinh th l ln nn
thng H > 0 (thu nhit). Vy ti sao qu trnh ha tan li xy ra ? Ta bit rng cho qu trnh t
din bin th G < 0. M G khng ch ph thuc vo H m cn ph thuc vo S na. Ta d
dng thy rng khi t trng thi tinh th sang trng thi dung dch th h tng entropi.
Cn i vi cht kh khi ha tan vo cht lng thng km theo s gii phng nng lng
do Hl 0 .
4.5.3. ha tan v cc yu t nh hng : Khi ta ha tan cht tan vo mt dung mi no
th thng n mt lc no cht tan khng th tan c na, lc y xy ra qu trnh cn bng (d
nhin l cn bng ng) :
Cht tan trong dung dch cht tan kt ta
Khi cn bng, nu thay i mt trong cc yu t bn ngoi th nh mi qu trnh cn bng, n
tun theo nguyn l Le Chtelier, ngi ta gi dung dch khi t n cn bng l dung dch bo
ha mt nhit xc nh (v cn bng ph thuc vo nhit ), nng ca dung dch bo ha
mt nhit no gi l ha tan. Nh vy ha tan ph thuc vo bn cht cht tan, dung
mi, nhit v nu cht tan l cht kh th ha tan cn ph thuc vo p sut na.
- V nh hng ca bn cht ca cht tan v dung mi ln ha tan, n hin nay cha c
mt nh lut no, m ch c qui tc thc nghim : Ngi ta nhn thy rng cc cht c cu to phn
t tng t nhau th c th ha tan trong nhau, c ngha dung mi khng phn cc th d ha tan
nhng cht khng phn cc, cn dung mi phn cc th d ha tan cc hp cht ion hay hp cht c
cc. Th d nh nc l dung mi phn cc tt nn d ha tan cc mui, cc hp cht phn cc
mnh nh HCl, NH3,v kh ha tan cc cht khng phn cc nh benzen, CO2, .
- Vi cht tan l cht rn, lng khi c cn bng : Cht tan trong dd cht tan c H > 0
(nh ni trong phn 4.5.2.Hiu ng nhit ca qu trnh ha tan) theo chiu nghch nn khi tng
nhit th cn bng s chuyn dch theo chiu thu nhit c ngha ha tan s tng.
- Vi cht tan l cht kh khi c cn bng : Kh trn b mt cht lng kh ha tan. (cn
bng ny c H < 0 theo chiu thun) nn cng theo Le Chtelier khi h nhit cn bng s
chuyn dch theo chiu pht nhit l chiu cht kh ha tan v khi tng p sut cn bng cng s
chuyn dch theo chiu to t phn t kh hn cng l chiu cht kh ha tan, cng c ngha i vi
cht kh ha tan s tng khi h nhit hoc (v) tng p sut.
Khi xt nh hng ca p sut ln ha tan ca cht kh, Henry pht biu thnh nh
lut mang tn ng : nhit khng i, khi lng cht kh ha tan trong mt th tch cht lng
xc nh t l thun vi p sut ca n trn b mt cht lng : m = kp.
Vi m l khi lng cht kh ha tan, p l p sut ca kh trn b mt cht lng v k l h s
t l, h s k ny ph thuc vo bn cht ca cht kh em ha tan v bn cht ca dung mi.
(nh lut ch ng khi cht kh tan khng c phn ng vi dung mi).
4.4.TNH CHT CA DUNG DCH LONG CHA CHT TAN KHNG IN LY,
KHNG BAY HI :
V h c hai cu t - c tng tc gia cht tan v dung mi nn tnh cht ca dung dch
khc vi tnh cht ca dung mi nguyn cht.
4.4.1.p sut hi bo ha :
4.4.1.1.p sut hi bo ha ca dung mi :
51 HA I CNG 2
Chng 4 : DUNG DCH
Mt dung mi nguyn cht nh H2O chng hn iu kin thng cng t nhiu b bay hi
v nu lu cht lng s bay hi n ht. Nhng nu cc nc c y kn li th nc cng bay
hi, nhng n mt lc no trong th tch gii hn , khi vn tc H2O bay hi bng vn tc
H2O ngng t, tc l t n cn bng :
H2O (l) H2O(h) . Lc y hi H2O trong chu gi l hi nc Hi bo ha
bo ha. N gy ra p sut hi bo ha (ca dung mi) p0.
Nhng nu by gi ta thay dung mi nguyn cht bng
dung dch nc ng chng hn th vn c hi bo ha do H2O
gy ra, lc y ta gi hi bo ha l hi bo ha ca dung dch
v p sut do hi H2O bo ha gy ra lc y l p sut hi bo H2O
ha ca dung dch p.
4.4.1.2.p sut hi bo ha ca dung dch, nh lut Raoult 1 :
p sut hi bo ha ca dung dch v dung mi khc nhau hay khng ?
n gin ta ly dung mi l H2O. Khi nc nguyn cht t n hi bo ha gy ra p0 tc
l xy ra qu trnh cn bng gia nc lng v hi nc trn b mt nc lng :
H2O (l) H2O (h). Nu ngay ti thi im ny ta ha tan mt lng cht tan khng bay hi (nh
ng) vo H2O (l), lc y nng ca H2O (l) s gim v theo nguyn l Le Chtelier th cn
bng s chuyn dch theo chiu to ra H2O(l), nh vy lng hi H2O s gim, tc hi bo ha
gim. Vy p sut hi bo ha ca dung dch s gim
Nh vy p sut hi bo ho ca dung dch p nh hn p sut hi bo ho ca dung mi
nguyn cht p 0.
Ta cng thy khi nng cht tan cng ln th p sut hi bo ha p ca dung dch cng h
(cng nh), hay ni cch khc, nng dung mi cng ln th p sut hi bo ha ca dung dch p
cng tng. Vy p t l vi nng dung mi.
Nu gi p0, p ln lt l p sut hi bo ha ca dung mi nguyn cht v ca dung dch.
Gi No, N l nng phn mol ca dung mi v cht tan. T lp lun trn ta c :
p = k.N0. Vi k l mt hng s t l. ( N0 + N = 1) v khi N = 0 tc l dung mi nguyn
cht th p = p 0 k = p0 . Vy : p = p0N0.
Cng thc ny chnh l ni dung ca nh lut Raoult 1 v p sut hi bo ha :
p sut hi bo ha ca dung dch bng p sut hi bo ha ca dung mi nguyn cht nhn
cho nng phn mol ca dung mi.
nh lut ny cng c th pht biu di dng khc. Thay N0 = 1 - N vo biu thc trn ta
c : p = p0(1-N). Nn p = p 0- p = p 0 - p 0 (1-N) ; p l h p sut hi bo ha tut i.
p p p0 p p
h p sut hi bo ha tng i l = =N
p0 p0 p0 p0
Vy : h p sut hi bo ha tng i ca dung dch bng nng phn mol ca cht tan.
y cng l mt dng pht biu khc ca nh lut Raoult.
Th d : Ngi ta xc nh c p sut hi bo ha ca dung dch cha 23g cht tan trong
250g ru etylic 500C l 27623,8Nm -2 ; p sut hi bo ha ca C2H5OH 500C l 29303,73Nm
-2
. Xc nh khi lng phn t ca cht tan.
p n
Gii : T nh lut Raoult : = N. M N (Vi n, n0 ln lt l s mol ca cht
p0 n0 n
23
M 23.46
tan v dung mi). Li c : n = m/M. Vy : N
23 250 23.46 250.M

M 46
29303,73 27623,8 23.46
M = 69,58 g.mol -1
29303,73 23.46 250.M
4.4.2.S tng nhit si v s gim nhit ha rn ca dung dch, nh lut Raoult 2
xt v gii thch cc qu trnh ny ta c th dng quy tc pha, hoc dng nguyn l Le
Chtelier
4.4.2.1.Nhit si, nhit ng c ca cht nguyn cht.
52 HA I CNG 2
Chng 4 : DUNG DCH
S si ca mt cht nguyn cht l qu trnh chuyn ha cht t trng thi lng sang
trng thi hi. Th d nh iu kin thng (1 atm) th nc si 1000C l v ti nhit p
sut hi bo ha ca nc nguyn cht bng vi p sut kh quyn (=1 atm). Cng nh vy, nhit
ng c ca mt cht l nhit ti p sut hi bo ha ca pha rn bng vi p sut hi bo
ha ca pha lng. Do khi p sut hi bo ha ca nc nh hn 1 atm th nc cha si, cn nu
p sut hi bo ha ln hn 1 atm th nc thnh hi. Nh vy mun nc si ta phi cung cp
nhit lng nng nhit ca khi nc ln 1000C lm cho p sut hi bo ha ca n bng
kh quyn v lc d ta c cung cp thm nhit lng th nc vn 1000C, nhng nu ta thi
cung cp th s si s dng li. V ch cn gi nguyn 1000C th nc c tip tc si, nn khi nc
ang si ta ch gi nguyn nhit lng gi n lun 1000C m khng cn phi cung cp thm
nhit lng. Cng gii thch tng t, vi cht nguyn cht th trong sut qu trnh ng c nhit
ng cng khng thay i
4.4.2.2.S tng nhit si ca dung dch so vi dung mi :
By gi ta s kho st s si ca dung dch, n c khc vi dung mi nguyn cht khng ?
Dung mi nguyn cht - ta chn H2O chng hn, di 1atm v 1000C lc y xy ra cn bng :
H2O (l ) H2O (h). [Ghi ch : (l) : lng ; (h) : hi]
Ngay ti im si ny, ta ha tan mt lng cht tan khng bay hi nh ng chng hn
vo trong H2O(l), do nng H2O(l) b gim (khi ha tan ng) nn theo nguyn l Le Chtelier,
cn bng b ph v v chuyn dch v pha to H2O (l) , tc lng hi H2O b gim, tc lc y H2O
khng si c na, mun nc tip tc si phi tng lng hi nc tr li, mun vy phi tng
nhit - tc l nhit si ca dung dch cao hn nhit si ca H2O (dung mi nguyn cht) .
Nhng khi dung dch si th dung mi (nh H2O) bay hi, lm nng cht tan tng ln, khi
nng cht tan tng th p sut hi bo ha gim, dung dch lc y khng si c na - mun
dung dch tip tc si ta phi tng nhit ln - li lp li qu trnh H2O bay hi - p sut hi bo
ha gim - mun gi dung dch tip tc si li phi tng nhit . Vy khi dung dch si mun duy
tr s si phi tng dn nhit - nhit si dung dch ngy cng tng. Nhit lng cung cp phi
ngy cng tng.
Nhng nhit si ca dung dch khng phi tng v hn, v n mt lc no , dung dch
tr thnh dung dch bo ha - lc y nng dung dch khng i - khi y nhit si ca dung
dch khng thay i na.
Gi Tsdd - Tsdm = Ts ; Ts : tng ca nhit si.
T trn ta thy rng Ts t l vi nng cht tan .
Bng nhiu thc nghim, Raoult a ra cng thc : Ts = Ks.Cm
Vi Ks : l hng s nghim si, n ch ph thuc vo bn cht ca dung mi ;
Cm : nng molan.
Nhn vo cng thc ta thy rng : tng nhit si ca dung dch ch ph thuc vo bn
cht ca dung mi v nng ca cht, m khng h ph thuc vo bn cht ca cht tan.
4.4.2.3. S gim nhit ha rn :
Cng chng minh tng t nh tng nhit si, ta cng c nhit ng c ca dung
dch thp hn nhit ng c ca dung mi v trong qu trnh ng c mun cho dung mi tip
tc ng c th nhit cng phi tip tc h : Cng t nguyn l Le Chtelier, khi H2O nguyn
cht 1 atm v 00C s c cn bng : H2O (l) H2O (r). By gi nu ta ha tan mt lng cht tan
khng bay hi no vo nc (cht tan tan trong nc lng) th nng ca nc lng gim, theo
nguyn l Le Chtelier nc s tan ra to nc lng. Do mun cho dung dch tip tc ng
c th phi h nhit . Cng vy, nh lut Raoult v nhit ng c ca dung dch :
T = K.Cm (K : hng s nghim ng, cng ch ph thuc vo bn cht ca dung mi ; Cm :
nng molan ca cht tan)
Ngi ta thng dng nh lut Raoult xc nh khi lng mol phn t M ca cht tan
khng bay hi.
V d : Nhit ha rn ca dung dch cha 0,244g axit benzoic trong 20 g benzen l
5,232 0C. im ha rn ca benzen tinh khit l 5,4780C. Xc nh dng tn ti ca axit benzoic
trong dung dch. Bit benzen c hng s nghim ng K = 4,9 .
53 HA I CNG 2
Chng 4 : DUNG DCH
Gii : Ta bit axit benzoic c cng thc phn t l C6 H5COOH, nhng trong benzen -
dung mi khng phn cc, n tn ti th no ? Ta th xc nh khi lng phn t ca axit benzoic.
Trn cng thc Raoult v h bng im : T = K.Cm .
T 0,246
Vi T = 5,478 - 5,232 = 0,3460C Cm =
-1
0,05 mol.g .
K 4,9
Tc l trong 1000g benzen c 0,05 mol axit benzoic. Vy trong 20g benzen c
0,05 x 20 0, 244
0,001mol axit benzoic khi lng mol ca axit benzoic trong benzen = 244 vC .
1000 0,001
M khi lng mol ca C6H5COOH l 122 vC. Vy th O ...... H O
trong benzen, axit bezoic tn ti di dng nh phn t : C
C
(C6H5COOH)2 : O H .......O
4.4.3.p sut thm thu :

4.4.3.1.Hin tng thm thu :
Dng pipet nh nhng cho dung dch c mu vo trong dung mi (cht mu phi tan trong
dung mi) th d ta khng cn khuy trn m do s chuyn
ng hn lan khng ngng ca cht lng, cng lm cho ton
b h c cng nng . l qu trnh t din bin v
entropy S tng. (qu trnh ha tan cc cht lng vo nhau
thng H khng i)
By gi ta gi s c mt mng ngn no , ngn h
gia dung dch mu vi dung mi nguyn cht, nhng mng
A
ngn ny c nhim v ch cho cc phn t dung mi qua li, Nc ng
m khng cho cc phn t cht tan vt qua th lc c
hin tng g xy ra ? Mng ngn nh th gi l mng bn
thm, l mng t bo, bong bng heo, hay bng colodion.
..Ngi ta lm th nghim v s thm thu nh sau, dng H2O
c gm : B
- Bnh A c ct thy tinh, y bnh l mng bn
thm, trong bnh cha nc ng.
- Bnh A c nhng vo chu B, chu B ng nc mng bn thm
nguyn cht. Lc y ct nc trong ng thy tinh ca bnh A
tng ln dn n mt chiu cao h (so vi mt thong trong bnh B) th dng li.
4.4.3.2. p sut thm thu :
Do tnh cht ca mng bn thm (khng cho ng ra) ch cho nc ra v vo bnh A, v
nng ca H2O trong B ln hn A, qu trnh t din bin (entropy tng) th H2O t ni c nng
cao chuyn sang ni c nng thp cho n khi t n cn bng (cng nng ). V th lng
H2O t B vo A s nhiu hn lng H2O t A ra B trong cng mt n v thi gian, ni cch khc
vn tc nc i vo ln hn vn tc H2O i ra, lm cho ct H2O trong A ngy cng cao so vi mt
thong ca B.
L ra lng H2O trong B s vo A cho n ht, nhng khi H2O trong A dng ln n mt
chiu cao h no (so vi mt thong B) th dng li. L do khi nc dng ln th n gy ra mt
lc thy tnh tc dng xung y bnh, khi h cng ln th p sut do ct H2O gy ra cng cao, n
khi p lc do ct H2O gy ra lm cho vn tc H2O vo bng vn tc H2O ra - lc y nc s khng
dng ln na.
Sau nhiu ln th nghim, Van't Hoff nhn thy chiu cao ct nc t l vi nng cht tan
v nhit th nghim m khng ph thuc vo bn cht ca cht tan.
n
ng thit lp cng thc = CRT = RT hay V = nRT, vi l p sut thm thu.
V
y chnh l nh lut Van't Hoff : p sut thm thu ca cht tan trong dung dch long
bng vi p sut kh nu nh cht tan trng thi kh v chim cng mt th tch cng mt
nhit nh dung dch.
54 HA I CNG 2
Chng 4 : DUNG DCH
m
T V = nRT V = RT M
M
p sut thm thu cng dng xc nh khi lng mol phn t cht tan .
4.5.DUNG DCH CHT IN LY :

4.5.1.Tnh cht ca cc dung dch axit, baz, mui :
Ngi ta nhn thy dung dch long ca cc cht : axit, baz, mui c mt s tnh cht bt
thng so vi dung dch khng in ly ta nghin cu, l :
- Khi cng iu kin (nng , nhit ) th nhng dung dch loi ny c p sut hi bo ha
nh hn, im si cao hn, im ng thp hn, p sut thm thu ln hn dung dch khng in ly
mt s i ln. Bng thc nghim ngi ta nhn thy :
p ' T ' '
i = Vi i : h s Van't Hoff (i > 1)
p T
H s i rt phc tp, n ph thuc vo bn cht ca cht tan, ca dung mi v nng , khi
dung dch cng long th i tin dn n cc gi tr nguyn 2, 3, 4.. ; p', T', ' : tng p sut
hi bo ha, tng (gim) nhit si (ng c) ca dung dch in ly ; p, T, : tng p
sut hi bo ha, tng (h) nhit si (ng c), p sut thm thu ca dung dch khng in
ly
- Dung dch loi ny (dung dch in ly) khc vi dung dch khng in ly mt im na
l dung dch ny dn c in, d khi di dng tinh th cht tan n khng dn in.
V ngi ta gi nhng cht m khi ha tan vo trong dung mi no m dung dch ca n
dn in c l cht in ly.
4.5.2.Thuyt in ly :
gii thch cc tnh cht khc thng ca loi dung dch in ly ny (h s Van't Hoff i v
dn in). Arrhenius cho rng, nhng cht ny khi ha tan vo trong nc n tch thnh nhiu
phn t nh hn, cc phn t ny tn ti c lp, khng tng tc vi nhau - nn nng ca cht
tan lc y dng nh tng ln - a n h s Van't Hoff i cao hn so vi cc tnh cht ca dung
dch phn t v dung dch loi ny dn in c, chng t rng trong dung dch c cha cc phn
t mang in - l nhng phn t c tch ra t cht tan khi n tan trong nc, nhng v ton b
dung dch u trung ha v in nn tng s in tch dng phi bng tng s in tch m - cc
phn t tch in ny Arrhenius gi l ion.
Hin tng phn ly ca mt cht trong nc gi l s in ly, cht tan gy nn c s in
ly l cht in ly v dung dch ny gi l dung dch in ly. Cc cht in ly khng phn ly hon
ton m ch mt phn no b phn ly. V vy h s Van't Hoff i chnh l t s phn t c trong
dung dch vi s phn t ha tan
L thuyt ca Arrhenius v c bn gii quyt c hai tnh cht ca loi dung dch ny.
Nhng ng cha ch n dung mi.
Thuyt in ly hin i b sung thm thiu st ny v cho rng nh tnh cht ca dung
mi v bng lng cc ca cc phn t dung mi (u m ca dung mi hng vo u dng ca
phn t cht tan, hoc ion dng v ngc li), ri do chuyn ng nhit - cc phn t dung mi
khng ngng dao ng phn ly cht tan thnh cc ion v sau c mt s lin kt no nh
kiu Van der Walls chng hn gia dung mi v cc ion. Nh vy c th s phn ly nhiu hay t cn
ph thuc vo dung mi na, tht vy s in ly ph thuc vo c hai cht : cht in ly v dung
mi, ngi ta gi tc dng ny l s solvat ha cc ion. Bng thc nghim ngi ta chng minh
c c tn ti t hp Cu2+.5H2O, c ngha l ion Cu2+ c an nh (solvat ha) nh 5 phn t
H2O. Khi cht tan c nng cao dn ln th phi k n mt tng tc khc na l tng tc gia
ion - ion ca cht tan. V khi nng cng cao khong cch gia cc ion cng gn, cc lp v
solvat lng vo nhau th lc y do tng tc tnh in c s phn phi li cc ion - quanh mt ion
dng c nhiu ion m hn v ngc li - gi l kh quyn ion - n nh mt trung gian gia tinh th
v cht kh - c s chuyn ng nhit (to ln xn) nhng cng c s sp xp trt t.
Tng qut : AnBm + pH2O nAm+.q H2O + mBn-.(p - q) H2O.
55 HA I CNG 2
Chng 4 : DUNG DCH
Nhng tin dng ngi ta vn vit : AnBm nAm+ + mBn- nhng vn lu s phn ly ch
xy ra c khi c dung mi phn cc.
Tm li dung dch in ly c to bi cht in ly v dung mi, di tc dng ca dung mi
s tch cc cht in ly thnh cc phn t nh - cc ion gi l s solvat ha, nu dung mi l nc
gi l hydrat ha, vy trong dung dch cht in ly c cc dng tng tc c bn (khng phi l
khng tng tc nh thuyt in ly ca Arrhenius) : ion - lng cc v ion - ion.
4.5.3.Cht in ly mnh, yu :
- Cht in ly mnh l cht khi ha tan vo nc th tt c cc phn t ca chng phn ly
hon ton thnh cc ion. l cc axit mnh, cc baz mnh v a phn cc mui tan . Th d :
HCl, Ba(OH)2, NaCl,
- Cht in ly yu l cht khi ha tan vo nc ch mt phn cc phn t phn ly thnh cc
ion. l cc axit yu nh H2S, CH3COOH,; cc baz yu nh NH3, amin, mt s t mui nh
CuCl2, CdCl2, HgCl2 ...
V vy, trong dung dch cht in ly yu, phn t khng phn ly nm cn bng vi cc ion
ca chng. Khi c cn bng, ta c th p dng nhng kin thc v cn bng ha hc cho loi cht
in ly yu ny nh p dng cch tnh hng s cn bng K, nguyn l Le Chtelier ...,
4.5.4. in ly, hng s in ly :
4.5.4.1. in ly : biu din kh nng phn ly ca mt cht trong mt dung dch,
ngi ta a ra i lng in ly
S phn t b phn ly
in ly = Nh vy : 0 < 1
S phn t ha tan
Ngi ta cn biu din in ly di dng %, th d mt dung dch HX 0,2M c 0,1
hay c in ly bng 10%, tc c ngha 1 lt dung dch ny ha tan 0,2 mol HX v trong c
0,02 mol HX b phn ly cho H+ v X-.
in ly ph thuc vo bn cht cht in ly, bn cht dung mi, nhit v nng .
Ngi ta quy c khi > 30% th l cht in ly mnh.
4.5.4.2.Hng s in ly, nh lut Ostwald :
Hng s in ly chnh l hng s cn bng ca phn ng in ly.
V vy, hng s in ly K ch s dng i vi cht in ly yu v K cng ch ph thuc vo
bn cht cht in ly, bn cht ca dung mi v nhit m thi.
Vi cht in ly yu, khi ha tan vo trong nc c cn bng : AmBn mAn+ + nBm-
[ A n ] m [ B m ] n
Hng s in ly K ca phn ng : K
[ Am B n ]
S lin quan gia in ly v hng s in ly K. nh lut Ostwald.
Gi s AB l cht in ly yu : AB A+ + B-
Nng lc ban u : C O O
Nng lc cn bng : C - C C C
[ A ][ B ] C 2 2 C 2
Vy : K=
[ AB ] C C 1
Biu thc c nh trn gi l biu thc Ostwald. T biu thc Ostwald ta thy khi tng th
2
(1- ) gim. Vy tng m K l hng s nhit khng i, nn C phi gim. Nh vy khi
1
dung dch cng long, th in ly cng ln.
4.5.5. Cht in ly mnh, hot :
Theo nh ngha v cht in ly mnh : phn ly hon ton tc l ra = 1, nhng trong thc
t vi cht in ly mnh v khi dung dch khng long th < 1, ch khi dung dch rt long
1. Nh vy nhng cht in ly mnh nng khng long n m c trong dung dch vn cn
phn t ? Khng phi vy, khi kho st bng quang ph vi nhng dung dch m c ca cht
in ly mnh vn khng thy du vt phn t. iu ny c gii thch th no ?
Vi nhng cht in ly mnh s phn ly l hon ton v vi nng m c th nng
cc ion rt ln, khong cch gia cc ion rt nh v nh vy c tng tc tnh in gia cc ion -
56 HA I CNG 2
Chng 4 : DUNG DCH
cc ion cng du th y nhau, cn ion ngc du th ht nhau, iu ny a n hu qu l c s
sp xp li cc ion : quanh mt ion c cc ion ngc du, khuynh hng sp xp ny ging nh
trong mng tinh th, ch khc l gia cc ion c cc phn t dung mi v dung mi chuyn ng
hn lon, li ko theo cc ion, s sp xp ny l trung gian gia mng tinh th v cht lng.
Hu qu ca n l c s li ko - dng nh c s kt hp gia cc ion to thnh phn
t, mt ion ny di chuyn b nhng ion khc gi li lm linh ng ca ion b gim i v vy
in ly gim, nng ion cng dng nh gim, s tng tc tnh in dng nh lm gim
nng mt phn (tht ra nng ion tnh c vn khng i), nng thc t tham gia ny l
nng hiu dng - chnh l nng hot ng trong cc phn ng ha hc. Nng hot ng
gi tt l hot .
Nh vy hot l nng tc dng (hu hiu) ca n trong cc phn ng ha hc
a = f.C. Vi : a l hot ; f : h s hot ; C l nng
Nng v in tch ca ion cng ln th f cng nh th a cng khc C. Khi C long v in
tch ion nh th f cng tin dn n 1 lc y a tin dn n C.
4.5.6. dn in : Trong ha hc, ngi ta dng i lng dn in K l nghch o ca
1
in tr R : K ; c n v l 1 . Ngi ta cn chia thnh :
R
1
- dn in ring : k hiu l , vi = . ( : in tr sut, cn gi l in tr ring).

Vy dn in ring chnh l dn in ca dung dch c b dy 1 cm nm gia 2 bn cc c
tit din 1 cm2. Hay ni cch khc dn in ring bng nghch o ca in tr ca khi dung
dch lp phng c cnh 1cm. dn in ring ph thuc vo bn cht ca dung dch, nhit v
hot .
dn in t l vi s ion. Khi pha long dung dch, nng C gim nn in ly
tng, tng s ion c trong dung dch cng tng, nhng ng thi th tch dung dch cng tng - tng
nhanh, v vy nng ion gim xung nn dn in ring gim. Vy t l vi C
- dn in ng lng : c k hiu l
L dn in ca mt lng cht in ly bng mt mol ng lng. Nh vy c phi
dn in ng lng chnh l dn in khi nng ng lng ca cht bng 1 khng ?
iu ny khng ng. ch l dn in c cha 1 mol ng lng cht tan bt k th tch v
b dy ca dung dch. Vy 1 . Vi R : in tr ca 1 mol ng lng.
R
Nu V l s mililt (cm3) dung dch cha 1 mol ng lng. T cc nh ngha ca dn
in ring v dn in ng lng, ta c : V .
Li c : Vml dung dch cha 1 mol ng lng. Vy 1lt = 1000ml dung dch cha CN.
1000 1000
Nn V . Vy : (*)
CN CN
(n v ca : t (*) = 1 .cm 1 .mol ng lng -1.cm3 = cm2. 1. mol lng -1)
T (*) ta thy ngc li vi dn in ring , dn in ng lng tng t khi
pha long dung dch ( t l nghch vi C). Khi CN 0 th . gi l dn in
ng lng gii hn l dn in khi dung dch rt long. Trong thc t khi t n th nu
tip tc pha long dn in ng lng s khng i na.

Ngi ta chng minh c khi dung dch rt long th :

4.5.7.Cc phng php xc nh in ly :
- Theo gim nhit ng c :
Gi n : s phn t ha tan, n' : s phn t c trong dung dch
q : s ion m mt phn t in ly phn ly ra.
Vy th : s phn t phn ly = n. Nn s ion trong dung dch = qn
S phn t khng phn ly : n - n
Vy n' = qn + n - n = n (q +1 - )
57 HA I CNG 2
Chng 4 : DUNG DCH
n' i 1
Ta c : i = = q + 1 - hay =
n q 1
Bng thc nghim ta o c T'. Vy tnh c i, ri suy ra
Th d : Dung dch cha 8 g NaOH trong 1000g H2O ng c -0,677 0C. Xc nh bit
hng s nghim ng ca H2O l K = 1,86 .
Gii : Theo nh lut Raoult v h bng im, i vi dung dch phn t :
8 T ' 0,677
T K .C m = 1,86. = 0,372. Vy : i = 1,82
40 T 0,372
i 1 1,82 1
T = 0,82 . Hay 82%
q 1 2 1
- Xc nh in ly bng cch o dn in.
Bng cch o dn in ca mt dung dch mt nng xc nh ta c v ta
tnh c in ly .
Th d : 250C dn in ng lng ca axit propionic pha long v cng l
385,6cm2.mol lng-1. 1 . Xc nh in ly v hng s in ly ca dung dch axit propionic
0,05M cng nhit , bit dn in ring ca n nhit ny l : = 3,16.10-4
1000
Gii : Vi axit propionic th CN = CM = 0,05. T cng thc : . Suy ra :
CN
1000.3,16.10 4 2 -1 1 6,32
6,32 cm .mol lng . . Li c : 1,64.10 2 .
0,05 385,6
l axit yu nn : C2H5COOH + H2O C2H5COO- + H3O+
C 2 0,05.(1,64.10 2 ) 2
K 1,37.10 5
1 2
1 1,64.10
4.6.AXIT, BAZ :
4.6.1.S in ly ca H2O, pH :
Nc l cht in ly yu - rt yu (c 550 triu phn t H2O mi c 1 phn t H2O b phn
[ H 3 O ][OH ]
ly), phn ly theo phng trnh : 2H2O H3O+ + OH- . Vy K =
[ H 2 O] 2
Nhng v H2O l cht in ly rt yu nn s phn t H2O b phn ly so vi s phn t H2O
ban u l khng ng k v vy xem [H2O]2 l hng s . Lc y, ngi ta t :
K [H2O]2 = Kn = K H 2O K W
Kn = [H3+O ] [ OH- ] gi l tch s ion ca H2O.
Phng trnh phn ly ca H2O l thun nghch - v vy hng s Kn ch ph thuc vo nhit
. 220C th Kn = 10-14 .
Trong khong dao ng nhit iu kin thng th tch ny thay i rt t, v vy ngi
ta xem i vi H2O v i vi c dung dch long th : [H3O+] [OH-] = 10-14 .
i vi H2O nguyn cht - mi trng trung tnh th : [H3O+] = [OH-] = 10 -7
Vy mi trng axit [H+] > 10 -7 [OH-] < 10 -7
Mi trng baz [H+ ] < 10-7 [OH-] > 10-7
Theo thi quen, ngi ta t dng s m, nn ngi ta t : pH = -lg[H3O+] v pOH = -lg[OH-]
V vy mi trng trung tnh : pH = pOH = 7
Mi trng axit : pH < 7 pOH > 7. Mi trng baz pH > 7 pOH < 7
V ngi ta cng t pKa = -lgKa v pKb = -lgKb .
4.6.2.Cht ch th mu :
xc nh pH ca mi trng, ngi ta dng cht ch th mu, l cht c mu thay i
theo pH ca mi trng , cht ch th mu thng l cc axit hoc baz hu c (yu) m mu ca
ion ca n phi khc vi mu ca phn t khng phn ly .
r hn ta th kho st phenolphtalein, trong dung dch c cn bng :
58 HA I CNG 2
Chng 4 : DUNG DCH
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HO
+
C C O C C O + H
O
O-
HO HO
Khng mu Mu
- Khi thm axit (H+) vo dung dch th theo nguyn l Le Chtelier cn bng s chuyn dch
v pha tri, l chiu to nn phn t phenolphtalein, nn dung dch khng mu.
- Cn khi cho vo dung dch mt lng baze (OH-) th OH- s phn ng vi H+ to H2O lm
nng H+ gim th theo Le Chtelier, cn bng s chuyn dch theo chiu to ra H+, tc l chiu
to ra ion, nn lm dung dch c mu .
Tng qut : Gi cht ch th mu l HInd. Trong dung dch c cn bng :
HInd + H2O H3O+ + Ind -
[ H 3O ][ Ind ] [ HInd ] [ Ind ]
K= [ H 3O ] K a . Vy : pH = -lg[H3O+] = pKa + lg
[ HInd ] [ Ind ] [ HInd ]
Mt ngi, thng phn bit gia mu ny v mu khc khi t s nng 2 dng 10.
Nn khi :
+ [Ind -] [HInd] pH = pKa : dung dch mang mu hn hp ca 2 ion.
[ Ind ]
+ > 10 mu dung dch l mu ca ion Ind - pH = pK + 1
[ HInd ]
[ Ind ]
+ < 10 mu dung dch l mu ca HInd. pH = pK -1
[ HInd ]
Khong pH trong mu ca cht ch th bin i c gi l khang i mu.
Th d : pH pH
Phenolphtalein : khng mu < 8 hng < 10
heliantine (metyl da cam) : hng < 3,1 da cam < 4,4 vng .
Qu : <6 tm <8 xanh .
4.6.3.Thuyt axit - baz :
Nm 1923 b sung nhng thiu st ca thuyt Arrhenius, xut hin 2 thuyt mi hn
v axit, baz l thuyt Bronsted - Lowrry v thuyt Lewis.
4.6.3.1.Thuyt Bronsted - Lowrry :
a) Ni dung :
Axit l nhng cht c kh nng cho proton v baz l nhng cht c kh nng nhn proton.
- Thuyt ny bao hm c thuyt Arrhenius, v vy nhng axit ca Arrhenius cng u l ca
Bronsted - Lowrry, ngoi ra c thm mt s cht i vi Bronsted l axit th khng th xp loi n
vo loi axit theo Arrhenius nh Al3+, Fe3+, Zn2+ ... V theo Bronsted khi ha tan cc ion ny vo
trong nc : Mn+ + 2H2O M(OH)(n - 1) + + H3O+
- Thuyt ny quan nim axit, baz c tnh tng i - ph thuc vo tng phn ng nh
HCl + H2O H3O+ + Cl- (1)
Vy theo nh ngha Bronsted th HCl l axit do n cho H+v cht nhn H+ l baz H2O
Cn trong phn ng : NH3 + H2O NH4+ + OH- (2)
Ta li thy NH3 l mt baz v n nhn proton ca H2O. Vy H2O li ng vai tr l axit
H qu : Ta thy vi phn ng (2) NH3 l baz sau khi nhn H+ ca H2O bin thnh NH4+,
li n lt NH4 + do c ion H+ nn nu gp cht c tnh baz mnh th NH4+ s chuyn H+ cho cht
. Vy NH4 + l axit . V vy ngi ta ni NH4 + l axit lin hp ca baz NH3, tng t OH- l
baz lin hp ca axit H2O. Ta ni NH4 +/NH3 l cp axit - baz lin hp. Ta cng d dng thy
59 HA I CNG 2
Chng 4 : DUNG DCH
rng axit cng mnh thi baz lin hp cng yu v ngc li, v d nh phn ng (1) do HCl l axit
mnh nn Cl- l baz lin hp yu - yu n ni tr thnh trung tnh.
b) Cng ca axit, baz :
mnh ca cp axit - baz lin hp c mi quan h :
HA l mt axit khi tan trong H2O : HA + H2O Ka H3O+ + A-
[ H 3 O ][ A ]
Ta c hng s in ly ca axit : KHA = (3)
[ HA]
K
A- l baz lin hp, trong H2O c th xy ra phn ng : A- + H2O A HA + OH-
[ HA][OH ]
V vy ta li c hng s in ly ca baz lin hp A- : KA- = (4)
[ A ]
(3) x (4) KHA.KA- = [ H+] [ OH- ] = 10 -14 .
Da vo biu thc ny ta c th tnh hng s in ly cho bt k mt axit hay baz lin hp
no, t ta tnh c pH ca mui.
4.6.3.2. Thuyt Lewis :
Lewis coi proton ch l mt trng hp c bit ca axit v a ra mt thuyt c tnh tng
qut hn :
- Axit l nhng cht c kh nng nhn cp electron
- Baz l nhng cht c kh nng cho cp electron
V vy cc axit v baz ca Bronsted u l axit v baz Lewis, nhng ngc li c nhng
cht l axit baz theo Lewis li khng phi ca Bronsted - Lowrry .
Th d : + -
- Nh H+ v OH- : H + O H H2O
F F
- Nh BF3 v NH3 : H H
F B + : N H F B N H
H H
F F
V tnh cht qu tng qut ca thuyt ny, bin cc cht tr thnh khng axit th l baz,
khng ph hp lm cho vic phn loi phn ng. V li, thuyt Lewis khng gii quyt c vn
v mnh ca axit v baz nh Bronsted
4.6.4.Tnh pH cho mt s dung dch :
a/ pH ca dung dch axit mnh : axit mnh phn ly hon ton, nn i vi loi ny rt l n
gin. Nu HA l axit mnh
HA + H2O H3O+ + A-
v H2O H3O+ + OH-
Cc phn t trong dung dch : H2O+, A- , H2O, OH- .
Khi nng axit khng qu b, ta xem s in ly ca H2O l khng ng k, lc y [H3O+]
= [A-] = [HA] = Ca pH = -lg[H3O+] = - lgCa .
Th d : Tnh pH ca dung dch H2SO4 0,1M.
Gii : H2SO4 l axit mnh li c nng khng qu b, do b qua s in ly ca H2O. V
vy xem nh H+ l ch ca H2SO4 : H2SO4 2H+ + SO42 - . Nn [H+] = 2[H2SO4]
[H+] = 2.0,1 = 0,2 pH = - lg[H+] = - lg0,2 = 0,7
Nhng nu nng ca axit qa b, chng hn Ca = 10-8 th nu ta khng n s in
ly ca nc ta tnh pH = - lg[H3O+] = 8. V l - axit long l dung dch baz ! .
V th lc y [H3O+] l ca c axit v nc .
- HA l axit mnh (phn ly hon ton) : [A- ] = [ HA] = Ca
10 14
- Kn = [H3O+] [OH-] = 10 -14 [OH-] =
[ H 3O ]
- Bo tan in tch : [ H3O ] = [A ] + [OH-]
+ -
60 HA I CNG 2
Chng 4 : DUNG DCH
10 14
[H3O+] = Ca +
[H3O+]2 - Ca [H3O+] -10 -14 = 0
[ H 3O ]
C a C a 2 4.10 14
Vy [H3O+] =
2
[H3O+] lun lun dng, v th ch chn nghim ( +)
C a C a 2 4.10 14
T : pH = - lg [H3O+] = -lg (*)
2
-8
Vi th d nh trn, tnh pH ca dung dch HCl 10 M. Lp lun nh trn ta c cng thc
(*), th Ca = 10 -8 ta c pH = 6,98
b/ pH ca dung dch baz mnh : chng minh tng t nh trn. Th d tnh pH ca dung
dch Ba(OH)2 1M.
Ba(OH)2 l baz mnh, li c nng tng i ln, b qua s in ly ca H2O.
10 14
Ba(OH)2 Ba2+ + 2OH- [OH-] = 2[Ba(OH)2] = 2x1 = 2 [H+] = 5.10 15
2
pH = - lg[H+] = - lg(5.10 -15) = 14,3
c/ pH ca dung dch n axit yu . Gi axit yu HX
Kx
Cc phng trnh in ly : HX + H2O H3O+ + X-
Kn
2H2O H3O+ + OH-
Trong dung dch lc y c cc phn t : HX, H2O, H3O+, X- v OH-. Ta c cc h thc lin
h :
[ H 3O ][ X ]
KX = (1) ; [H3O+] [OH-] = 10 -14 (2)
[ HX ]
Bo ton khi lng : CX = [ HX ] + [ X- ] (3)
Bo ton in tch : [H3O+] = [ X-] + [ OH- ] (4)
T 4 phng trnh ny ta c : [H3O+]3 - Kx[H3 O+]2 - (Kn + KX.CX ) [H3O+] - KnKX = 0
Gii phng trnh ny l mt vic phin phc, nn ngi ta xt di dng gn ng.
- Nu Cx ln, xem s in ly ca H2O l khng ng k, c ngha [OH-] << [H3O+]. T (4)
[H3O+] [X-], th vo (1), cui cng c :
K X K 2X 4 K X C X
[H3O+] + KX [H3O+] - KXCX = 0 [H3O+] =
2
- Cn nu khi axit rt yu ( v nng khng qu b) th CX - [H3O+] CX
1
Khi : [H3O+] = ( KXCX )1/2 pH = (pKX -lgCX )
2
d/ pH ca dung dch n baz yu : chng minh tng t.
Th d tnh pH ca dung dch NH3 0,01M, bit NH3 c Kb = 1,8.10 -5.
Gii : NH3 l baz yu c nng 0,01M khng qu b, nn b qua s in ly ca H2O.
[ NH 4 ][OH ]
NH3 + H2O NH4+ + OH-. K b . M ta lun c [NH4+] = [OH-]. Nn
[ NH 3 ]
[OH ] 2 [OH ]2
Kb
[ NH 3 ] 0,01 [OH ]
NH3 c nng ln so vi Kb nn b qua [OH-] so vi 0,01.
[OH-] = 0,01.K b 0,01.1,8.10 5 4,24.10 4 pH = 10,63
e/ Hn hp axit mnh v axit yu n chc : Gi axit mnh l HX c nng CHX, HA l
axit yu c nng l Ca v hng s in ly l Ka
Trong trng hp tng qut, ta vn lp lun nh phn c/ pH ca dung dch n axit yu: lp
cc phng trnh theo hng s in ly, theo nh lut bo ton khi lng, theo nh lut bo ton
in tch,. Nhng n gin, trong thc t ta thng gp cc nng ca cc axit khng qu
b, lc y b qua s in ly ca nc v c th gii cch khc cho nhanh hn :
Axit mnh HX in ly han ton : HX + H2O H3O+ + X-.
61 HA I CNG 2
Chng 4 : DUNG DCH
Nn [H3O+] = [HX] = CHX. Vy trong dung dch c H3O+ vi [H3O+] = CHX
Trong khi HA l axit yu nn : HA + H2O H3O+ + A-.
Nng cc cht ti thi im ban u : Ca CHX 0
Nng cc cht lc cn bng : Ca - x CHX + x x
(Vi x = [A-] v vi n axit th lun lun c [H3O+] do HA phn ly bng vi [A-] = x)
Tng nng [H3O+] ca c dung dch : [H3O+] = CHX + x.
(C HX x ) x
Nn K A . T suy ra x, ri [H3O+] = CHX + x. pH. Xem th d phn f/
Ca x
f/ Hn hp baz mnh v baz yu n chc : tng t nh phn e/
Th d : Tnh pH ca dung dch c cha NH3 0,1M v Ba(OH)2 0,05M. Bit NH3 c
Kb = 1,8.10-5.
Gii : Cc nng ln, nn ta b qua s in ly ca H2O. Ba(OH)2 l baz mnh, nn
[OH-] (ca Ba(OH)2) = 2[Ba(OH)2] = 2.0,05 = 0,1. Cn baz NH3 l baz yu nn :
(Gi x l [NH4 +] lc cn bng) NH3 + H2O NH4 + + OH-
Nng cc cht ti thi im ban u : 0,1 0 0,1
Nng cc cht lc cn bng : 0,1 - x x 0,1 + x
[ NH 4 ][OH ] x (0,1 x) x (0,1 x)
Kb 1,8.10 5 . Gii ra c : x 1,8.10 5
[ NH 3] 0,1 x 0,1 x
10 14 10 14
[OH-] = 0,1 + x = 0,1 + 1,8.10 5 0,1 [H+] =
1013 pH = 13.
[OH ] 0,1
g/Hn hp 2 n axit yu : Gi 2 axit yu l HA v HX c nng ln lt l Ca v Cx v
c hng s cn bng l Ka v Kx. Thng thng nng cc axit thc t ln b qua [H+] do
nc in ly. C cc phng trnh in ly :
K K
HX + H2O x H3O+ + X- v HA + H2O a H3O+ + A-
Trong dung dch c cc phn t : HA, HX, H2O, H3O+, A- v X-
[ H 3 O ][ X ] [ H 3O ][ A ]
- Theo cc hng s cn bng : Kx = (1) v Ka = (2)
[ HX ] [ HA]
- Theo nh lut bo ton khi lng: Ca = [A-] + [HA] (3) v Cx = [X-] + [HX] (4)
- Theo nh lut bo ton in tch : [H3O+] = [A-] + [X-] (5).
H 5 phng trnh s gii c khi nng ca cc axit khng qu b, lc y gn ng xem nh :
(3) Ca [HA] v t (4) Cx [HX]. Th vo (1) v (2), ta c :
K a .C a K x .C x
[ A ] (1'). V [ X ] (2'). Cng (1') v (2'), kt hp vi (5)

[ H 3O ] [ H 3O ]
K a .C a K x .C x
[ H 3O ]

[ H 3O ] [ H 3O ]
[H3O+]2 = KaCa + KxCx [H3O+] = K a C a K x C x pH = - lg [H3O+]
h/ Hn hp 2 n baz yu : tng t nh trn.
4.7.DUNG DCH M :
4.7.1.nh ngha : L dung dch c pH thay i rt t khi ta pha long dung dch hay thm
mt lng nh axit hay baz.
Dung dch m thng to bi : hn hp axit yu v mui ca n vi baz mnh hoc baz
yu v mui ca n vi axit mnh .
V d : dung dch hn hp : CH3COOH v CH3COONa hay NH3 v NH4Cl .
Gii thch :
Do CH3COONa l cht in ly mnh, n phn ly hon ton
CH3COONa CH3COO- + Na+ c [CH3COO-] = [Na+] = CM (CM : nng mui)
Trong khi CH3 COOH l axit yu : CH3COOH + H2O CH3COO- + H3O+
Vy khi ta thm [H3O+] vo th n s kt hp vi CH3COO- do mui to nn CH3COOH
(phn ng nghch) nn [H3O+] thm vo khng cn bao nhiu nn [H3O+] thay i rt t.
62 HA I CNG 2
Chng 4 : DUNG DCH
Cn khi thm OH- vo th n s kt hp vi H3O+ cho H2O lng H3O+ va b mt s
c CH3COOH phn ly tip tc n b to cn bng mi.
4.7.2.Tnh pH ca dung dch m :
Ly th d l dung dch hn hp CH3COOH v CH3COONa.
V CH3COONa l cht in ly mnh :
CH3COONa CH3COO- + Na+ nn [CH3COO-] ca mui = [Na+] = CM .
Nu nng ca axit CH3COOH ln, b qua s in ly ca H2O :
CH3COOH + H2O Ka CH3COO- + H3O+
Thi im ban u : Ca CM O
Thi im cn bng : Ca - x CM + x x = [H3O+]
Ka =
C M x x x [H O+] pH
3
C a x
(Vi Ca, CM l nng ca axit v ca mui)
4.8.S THY PHN :
4.8.1.C ch v iu kin ca phn ng thy phn :
Khi ha tan vo H2O, cc mui s phn ly thnh cc ion b hydrat ha.
- Nu ion ca mui u l sn phm ca axit mnh v baz mnh nh : NaCl Na+ + Cl-,
cc ion ny l nhng ion trung tnh (theo Bronsted) nn chng khng kt hp c vi H2O v vy
loi mui ny - mui to bi axit mnh v baz mnh th khng b thy phn v dung dch lun c
pH = 7.
- Cn khi cc ion c to t axit yu hoc (v) baz yu th cc ion ny s tng tc c
vi H2O, ta ni c s thy phn .
Th d nh mui NH4Cl c xem nh to thnh t baz yu NH3 v axit mnh HCl nn
axit lin hp ca baz yu NH3 l axit NH4+ tng i mnh nn n tng tc c vi H2O, cn
baz lin hp Cl- ca axit mnh HCl s l baz rt yu - c tnh trung tnh khng kt hp c vi
H2O. Vy th : NH4+ + H2O NH3 + H3O+
4.8.2.Tnh pH ca dung dch mui to bi axit mnh v baz yu :
Ta c th dng li th d trn vi mui NH4Cl. Khi tan trong nc NH4Cl phn ly hon ton :
NH4Cl NH4+ + Cl-. Cl- c tnh trung tnh, n khng b thy phn, cn NH4 + b thy phn theo
phng trnh : NH4+ + H2O Ka NH3 + H3O+.
[ H 3 O ][ NH 3 ]
Hng s cn bng Ka = ny c gi l hng s thy phn. Ta cng
[ NH 4 ]
thy rng vic tnh pH ca dung dch ny chnh l tnh pH ca axit NH4+ l axit lin hp ca baz
yu NH3. Trn quan im ca Bronsted - Lowrry th pH ca s thy phn chnh l pH ca axit
(hoc baz) v Ka. K NH 3 = 10 -14. V Ka.CNH4+ >> KH2O, nn b qua s in ly ca H2O.
Bo ton in tch : CM = [Cl-] = [NH4+ ] + [H3O+]
Bo ton khi lng : CM = [ NH4+] + [ NH3].
T phng trnh thy phn NH4 + ta lun lun c : [H3O+] = [NH3]
[ H 3O ] 2 10 14
Ka =
. T suy ra [H3O+] pH
C M [ H 3O ] K NH 3
thy phn (h) : l t s ca s mol mui b thy phn vi s mol mui tan. Qua nh
ngha ta thy thy phn ging vi in ly - v vy mi quan h gia thy phn h vi hng
s thy phn cng ging nh mi quan h gia in ly vi hng s in ly. Nn thy phn
ngoi vic ph thuc vo bn cht ca mui, cn ph thuc vo nhit - nhit cng cao th
thy phn cng ln (v phn ng thy phn l phn ng nghch vi phn ng trung ha), thy
phn cng ph thuc vo nng - khi dung dch cng long thy phn cng ln (chng minh
nh in ly).
4.8.3.Tnh pH ca dung dch mui to t axit yu v baz mnh :
Nh mui CH3COONa chng hn, cng chng minh tng t nh trn. CH3COONa khi tan
trong nc : CH3COONa CH3COO- + Na+. Na+ trung tnh khng b thy phn, cn CH3COO- b
thy phn theo phng trnh : CH3COO- + H2O Kb CH3COOH + OH-. Vi hng s thy phn Kb =
63 HA I CNG 2
Chng 4 : DUNG DCH
10 14
. Thng thng Kb.CCH3COO- >> KH2O, nn b qua s in ly ca H2O. Ri p dng bo
K CH 3COOH
ton khi lng v bo ton in tch nh trn s tnh c pH. Cng c th chng minh mt cch
Kb
n gin hn : CH3COO- + H2O CH3COOH + OH-
[ban u] CM - 0 0
[cn bng] CM x - x x = [OH-]
10 14 x2
Vi CM l nng mui ban u. T : Kb = = .
K CH 3COOH CM x
T tnh c x chnh l [OH-], ri suy ra pH
4.8.4.Tnh pH ca dung dch mui to t axit yu v baz yu :
Ta c th ly mui CH3COONH4 lm th d minh ha. CH3COONH4 l cht in ly mnh :
CH3COONH4 CH3COO- + NH4+. B qua s in ly ca H2O. V CH3COO- l baz yu v NH4 +
l axit yu nn b thy phn :
10 14
CH3COO- + H2O CH3COOH + OH- c K CH COO =
3 K CH 3COOH
+ +
+ NH4 + H2O NH3 + H3O c K NH
4
+ - 1 14
H3O + OH 2H2O c KH 10 Cng 3 phng trnh phn ng ta c :
2O
K NH
CH3COO- + NH4+ CH3COOH + NH3 C K = K CH COO . K NH . K H1 O = 4
3 4 2 K CH 3COOH
[ban u] CM CM 0 0
[cn bng] CM x CM x x x
K NH K NH 1
x2 x
Vy : K = 4
= ( 4
)2 .
K CH 3COOH (C M x ) 2 CM x K CH 3COOH
K NH 1
[CH 3 COOH ] [ NH 3 ]
Hay : ( 4
) 2 (*).
[CH 3 COO ] NH 4 K CH 3COOH
[H+] c tnh do phn ng : CH3COOH + H2O CH3COO- + H3O+.
[ H 3 O ][CH 3 COO ] [CH 3COOH ]
K CH 3COOH [ H 3O ] .K CH 3COOH (**)
[CH 3 COOH ] [CH 3COO ]
1
K NH 1
Th (*) vo (**) ta c : [ H 3 O ] ( 4
) 2 .K CH 3COOH ( K NH .K CH 3COOH ) 2 .
K CH 3COOH 4
1
Hay : [ H 3 O ] ( K a 1 .K a2 ) 2 . Vit cch khc : [H3O+] = K a1 .K a 2 .
1
Vy : pH = - lg [H+] = - lg(Ka1.Ka2)
2
Ta thy i vi mui to bi axit yu v bazo yu pH ca mui khng ph thuc vo
nng mui m ch ph thuc vo bn cht ca mui.
4.9.PHN NG TRUNG HA :
Phn ng trung ha l phn ng gia axit v baz. Ngi ta thng dng phn ng ny
xc nh nng ca dung dch axit hay baz.
Nu gi Na, Va ln lt l nng ng lng v th tch ca cht a.
Nu gi Nb, Vb ln lt l nng ng lng v th tch ca cht b.
Nu 2 cht a v b ny phn ng va . Theo nh lut ng lng : s mol ng lng
ca cht a l na = Na.Va. Cht b : Nb.Vb = nb. V a v b tc dng va nn :
NaVa = NbVb . V vy nu bit c NaVa v Vb ta c th tm c Nb. Ngi ta gi cch
xc nh nng ng lng Na hay Nb nh th gi l cch chun . im m ti 2 cht a v
64 HA I CNG 2
Chng 4 : DUNG DCH
b va ht (va ) gi l im tng ng. Cn tp hp cc im pH trong vic chun gi l
ng cong chun .
Ta xt s chun qua 3 trng hp :
4.9.1.Chun mt axit mnh (a ) bng mt baz mnh (b)
n gin ta xt s chun dung dch HCl bng dung dch NaOH.
- Thi im ban u cha chun , lc y [H+] ln nht, v vy pH b nht.
- Khi cho dung dch NaOH vo th nng H+ gim dn, v vy pH tng dn.
V HCl + NaOH NaCl + H2O hay H+ + OH- H2O.
N a V a N b Vb
Lc y NaVa > NbVb [HCl]d = [H+] d =
Va Vb
N a V a N b Vb
pH = - lg[H+]d = -lg
Va Vb
- Khi ti im tng ng : NaVa = Nb.Vb
V HCl v NaOH l axit mnh v baz mnh nn dung dch NaCl c tnh trung tnh nn pH
= -lg[H+] = 7 .
N b Vb N a V a
- Thm tip NaOH vo, lc y NbVb > NaVb [OH-]d =
Va Vb
N b Vb N a V a
pOH = - lg[OH- ]d = -lg
Va Vb
pH
N V N aV a
pH = 14- pOH = 14 + lg b b
Va Vb 12
Th d : Chun 100ml dung dch HCl 1 N t dung dch NaOH 10
.
- Cha chun : pH = 0
8 100
100 99
- Khi cho 99 ml NaOH [H+] = pH 2,3 7
VNaOH (ml)
199 6
+ 0,1 4
- Khi cho 99,9 ml NaOH [H ] = pH 3,3
199,9
2
- Khi cho 99,99 ml NaOH pH 4,3
- Khi cho 99,999 ml NaOH pH 5,3 0
- Khi cho 100 ml NaOH pH 7
Trong qu trnh trung ha n 99,9% axit lc y pH t 0 - 3,3. n y khi thm 1 lng rt
b NaOH th pH t 3,3 -10,7 - khong ny gi l bc nhy chun .
Da trn ng cong chun (gia axit mnh v baz mnh) c th dng cht ch th
m khong i mu nm trong bc nhy nh : metyl da cam : 3,1 - 4,4 ; Qu : 6 - 8 ;
phenolphtalein t : 8 - 10.
4.9.2.Chun mt axit yu bng baz mnh
( Nh CH3COOH bng NaOH )
1
- Khi Vb = 0 pH = (pKa - lgNa)
2
- Khi VbNb < VaNa dung dch lc by gi cha axit yu CH3COOH d v mui
CH3COONa. Vy dung dch l dung dch m .
Va N a Vb N b
pH = pKa -lg
Vb N b
- Khi VbNb = VaNa : im tng ng, dung dch lc y l dung dch mui CH3COONa c
1 1 V N
tnh baz pH = 7 + pKa + lg a a .
2 2 V a Vb
65 HA I CNG 2
Chng 4 : DUNG DCH
- Khi VbNb > VaNa, dung dch c NaOH d v CH3COONa :
Vb N b V a N a
pH = 14 + lg
Va Vb
lm th d ta kho st khi chun 100ml dung pH
dch CH3COOH 1N t dung dch NaOH 1N.
Bc nhy chun t pH = 8 n pH = 11. Trong 13
trng hp ny dng cht ch th phenolphtalein. 11
4.9.3.Chun mt baz yu bng axit mnh :
9
Cch lm tng t nh chun mt axit yu 7
bng baz mnh nhng cc xut pht im s khc v 6 VNaOH (ml)
bc nhy chun nm trong mi trng axit. V vy 4
trong trng hp ny dng metyl da cam.
2
4.10.DUNG DCH CHT IN LY T TAN : 0
Tch s tan v s quan h gia tch s tan v tan :
Cc cht in ly t tan nn n tan rt t, nh vy n to thnh dung dch rt long. V vy cc
cht ny in ly han ton, lc y c cn bng d th : AmBn (r) mAn+ + nBm-
Khi c cn bng, ta p dng cc thnh qu ca cn bng, lc y hng s cn bng trong h
d th ny gi l tch s tan T : TAmBn = [An+]m [Bm-]n. Vy tch s tan ca mt hp cht t tan l tch
s nng cc ion ca n trong dung dch bo ha.
Xut x ca tch s tan l hng s cn bng, vy tch s tan ca mt cht ph thuc vo bn
cht ca cht tan, bn cht ca dung mi v nhit . (nu cht in ly t tan l cht kh th tch s
tan cn ph thuc vo p sut na).
Tch s tan T c th xc nh bng thc nghim hay c xc nh bng cc d liu nhit
ng hc ( G 0T RTlnT )
Trong nhng iu kin nh nhau, cht no c tch s tan cng b th cht cng t tan,
ngha l tan cng b. Nh vy ta thy gia tch s tan v tan c mi quan h rt mt thit, khi
bit ha tan ca mt cht, ngi ta d dng tnh c tch s tan ca cht v ngc li. Th d
nh trong nc AgI t tan hn AgBr, cn AgBr th li t tan hn AgCl v thc nghim cho bit
TAgI = 1,5.10 -16 < TAgBr = 7,7.10 -13 < TAgCl = 1,56.10 -10 (Theo Ho cht tinh khit)
Nu gi S l ha tan (mol/l). Th d : CaF2(r) Ca2+ + 2F-. T phng trnh cn
bng d th ny ta thy, nu CaF2 tan c S(mol/l) th s b phn ly han ton cho S mol Ca2+ v
2S mol F-. Vy TCaF2 = [S] [ 2S] 2 = 4S3. Tra bng tch s tan ta c
4.10 11
TCaF2 = 4.10 -11. Vy tan S ca CaF2 l S = 3 2,15.10 4 mol/l.
4
iu kin to thnh kt ta hay ha tan kt ta :
Bit tch s tan ca mt cht ngi ta c th d on d dng mt cht c kt ta hay khng
khi trong dung dch c mt cc ion to thnh hp cht :
- Nu khi tch s cc ion to thnh kt ta trong dung dch ln hn tch s tan T ca cht
th lc y s c hin tng kt ta.
- Ngc li khi tch s cc ion c th to thnh kt ta trong dung dch nh hn tch s tan
T ca cht t tan th cha c kt ta.
Th d : Khi trn ln hai th tch bng nhau ca dung dch SrCl2 0,02M v dung dch K2SO4
0,04M. Lc y c kt ta khng ? Bit TSrSO = 3,6.10-7.
4
Gii : Khi trn 2 th tch bng nhau ca 2 cht th nng mi cht gim i mt na, v vy
sau khi trn th : [Sr2+] = [SrSO4] = 0,02/2 = 0,01 v [SO42-] = [K2SO4] = 0,04/2 = 0,02
Tch s cc ion lc y : [Sr2+] [SO42-] = 0,01.0,02 = 2.10 -4 > TSrSO = 3,6.10-7. Vy khi trn hai dung
4
dch trn theo nng cho th lc y kt ta SrSO4 c to nn.
By gi cng th d trn, nu ta cho thm vo dung dch bo ha SrSO4 trn 0,01mol/l
dung dch H2SO4, th lc y do khi cho thm [SO42-] = [H2SO4] = 0,01 mol/l th theo nguyn l Le
66 HA I CNG 2
Chng 4 : DUNG DCH
Chtelier cn bng s chuyn dch theo chiu lm gim nng SO42- thm vo tc lm tng lng
kt ta, khng nhng vy da vo tch s tan ta cn c th tnh c tan ca SrSO4 trong dung
dch H2SO4 lc : Gi x = [Sr2+] trong dung dch sau khi to kt ta na vi H2SO4 trong dung
dch lc y ngoi nng ca SO42- c x (mol/l) cn c mt lng SO42- mi thm vo do H2SO4 =
0,01 (mol/l) na [SO42-] = x + 0,01. Dung dch ny l dung dch bo ha, nn : [Sr2+] [SO42-] =
TSrSO = 3,6.10 -7 x (x + 0,01) = 3,6.10 -7 x = 3,6.10-5 mol/l. Vy tan ca SrSO4 trong dung
4
dch H2SO4 b hn tan ca n trong nc nguyn cht (S = T SrSO4 3,6.10 7 6.10 4 ) v b
6.10 4
hn : 16,67 ln
3,6.10 5
4.11.S TO PHC TRONG DUNG DCH :

Phc cht c cp trong hc phn cu to cht, by gi ch tm hiu v cn bng khi
to phc. Nu trong dung dch c ion trung tm (k hiu chung l Mn+) c cc phi t (k hiu L),
vi iu kin thch hp c th to thnh phc.
Tng qut : Mn+ + mL MLmn+ (Vi m l s phi t trung ha quanh ion trung tm)
[ MLnm ]
Khi t cn bng ta c : K =
[ M n ][ L]m
Nu phc cht cng bn th [MLnn+] cng nhiu, K cng ln, v vy hng s cn bng K ny
cn gi l hng s bn ca phc (gi l Kb).
Ngc li nu ta vit : MLmn+ Mn+ + mL
[ M n ][ L]m 1
Lc y K' = ta d dng thy rng K' =
[MLnm ] Kb
Nn ngi ta gi hng s K' l hng s khng bn ca phc (gi Kkb). Vy vi mt phc xc
nh cng iu kin nhit th : Kb.Kkb = 1.
Cc hng s bn (hay khng bn) gip ta tnh c nng cc ion c trong dung dch, qua gip
chng ta xc nh c c kt ta hay to phc khi c s c mt ng thi ca cc ion trong dung
dch.
Th d : Tnh nng ti thiu ca amoniac ha tan 0,1 mol AgCl trong 1 lt dung dch
amoniac. Bit tch s tan ca AgCl l T = 10 -10 v hng s bn ca [Ag(NH3)2]+ l Kb = 10 7,2.
Gii : Trong dung dch c cc phn ng :
AgCl (r) Ag+ + Cl- c TAgCl
+ +
Ag + 2NH3 [Ag(NH3)2] c Kb
AgCl (r) + 2NH3 [Ag(NH3)2]+ + Cl- c K = TAgCl.Kb = 10 -10.107,2 = 1,585.10-3
Cb : 0,1 C 0 0
Ccb : - C-0,2 0,1 0,1
(V AgCl tan ht 0,1mol.l-1 s cho c 0,1mol.l-1 cc sn phm)
(0,1) 2
Vy : K = 1,585.10 3 C = 2,71mol.l-1
(C 0, 2) 2
Vy nng ti thiu ca NH3 cn 2,71 mol/l
4.12.DUNG DCH KEO :

4.12.1.Dung dch keo, cu to ca dung dch keo :
Dung dch keo (cn gi l sol) c c khi kch thc cht tan ln hn kch thc phn t
0 0
nhiu, vo khong t 10 A n 1000 A , nn chng to ra b mt phn chia gia ht keo v mi
trng, v vy ngi ta cho rng dung dch keo l dung dch gi, n thuc h vi d th, n c iu
ch t mt cht tan no vi dung mi rt t ha tan, nn ngi ta cho rng khng c cht keo m
ch c dung dch keo.
67 HA I CNG 2
Chng 4 : DUNG DCH
Ht keo c cu trc bn trong khc nhau, n bao gm nhn keo v lp hp ph. Ht keo v
lp khuych tn hnh thnh nn micelle (mixen) keo. Nhn keo thng sinh ra trong mi trng c
cht in ly, n l tp hp nhiu phn t c cu trc tinh th hp ph mt s ion m hoc dng
trn b mt ca chng to thnh ht tch in, (mi loi keo nht nh hp th nhng ion cng du)
th d keo AgI trong dung dch KI : nhn keo AgI ht v trn b mt ca chng cc ion I-, chng c
th to thnh mng tinh th vi cc phn t AgI, nhn keo ny mang in tch m. Nhn keo m ny
li ht mt s cc ion ngc du K+ (gi l i ion) to thnh lp hp ph, in tch ca lp hp
ph ny cha trung ha in tch ca nhn keo. Mt phn cc i ion K+ khc xa ht keo
hn ( trung ha in tch cn li ca ht keo) gi l lp khuych tn. Khi ht keo chuyn ng
trong mi trng phn tn, ch c nhn keo v lp hp ph trt theo nhau, cn lp khuych tn
tng i ng yn.
C th biu din micelle keo AgI nh sau :
{[mAgI] nI- (n - x)K+} xK+
Nhn lp ion quyt lp i ion lp i ion
nh hiu th hp ph khuych tn
Nhn keo
Ht keo
Micelle keo
Vi m : s phn t hp cht t tan ; K+

K+
n : s ion quyt nh hiu th
n - x : s i ion trong lp hp ph ; K+
x : s i ion trong lp khuych tn I- -
K+
Ph thuc vo quan h gia ht keo K+ I- I
vi mi trng do lc gia cc phn t trn - K+
ranh gii phn chia pha, ngi ta chia ht keo I- mAgI I
lm 2 nhm : nhm a dung mi v nhm k
dung mi. K+ I- I- K+
-
-Keo a dung mi khi tng tc gia I
dung mi v ht keo kh ln t hnh thnh K+ K+
nn lp solvat bn vng. Th d nh keo K+
anbumin, nh x phng,
- Keo k dung mi khi tng tc gia dung mi v ht keo yu v vy ht keo hu nh
khng hp ph cc phn t ca mi trng. Th d nh dung dch keo ca cc kim loi,
4.12.2.Tnh cht ca dung dch keo :
- Tnh cht quang hc : Khi chiu chm tia sng vo dung dch keo th cc ht keo s
khuych tn nh sng hay (v) hp th nh sng. Trong s khuych tn nh sng m hin tng
Tyndahl l mt in hnh, l hin tng xut hin khi chiu chm nh sng mnh qua dung dch
keo, th c mt chp nh sng rt r trn ng i ca chm sng.
Hin tng do Tyndahl pht hin ny c gii thch l do tia sng trn ng i ca n gp
nhng ht keo c kch thc ln gy ra hin tng nhiu x, tia sng s khuych tn theo khp mi
hng v bin thnh cc im sng lm ta trng thy r ng i ca tia sng. Hin tng ny ta c
th thy c khi chiu n pha trong m ti v cng r hn khi c bi hoc hi nc trong lung
nh sng. Ngi ta li dng hin tng Tyndahl ch to knh siu hin vi.
Ngoi hin tng khuych tn dung dch keo cng ging dung dch phn t, n cng hp th
nh sng v tun theo cc nh lut quang hc
- Tnh cht ng hc : V ht keo c kch thc ln hn phn t, nn khi trong dung
dch, n b cc phn t ca mi trng trong khi chuyn ng nhit va p hn lon ln, nn ht
keo s chuyn ng theo chiu ca hp lc trong thi im , nn cc ht keo chuyn ng rt
phc tp. Ngoi ra khi lc va p ca cc phn t mi trng ln ht keo b lch tm th ht keo cn
c chuyn ng quay.
68 HA I CNG 2
Chng 4 : DUNG DCH
Trong qu trnh chuyn ng hn lon, nng ti mt im no trong dung dch keo
khc vi cc im khc, v vy c s khuych tn xy ra : cc ht (ht keo v phn t mi trng)
s di chuyn t ni c nng cao sang ni c nng thp cho n lc t c s cn bng v
nng , nhng v ht keo c kch thc ln nn s khuych tn ca dung dch keo b.
S chuyn ng hn lon ca cc ht cn gy ra hin tng thm thu nh dung dch phn
t, nhng cng v kch thc ln ca ht keo so vi phn t nn dung dch keo gy ra p sut thm
thu cng b.
- Tnh cht in : Ht keo thng tch in, nn dung dch keo hay c hin tng in di l
hin tng m cc ht keo di chuyn v mt cc no di tc dng ca in trng. Ngi ta
ng dng hin tng in di tch cc oxit ra khi cao lanh, to lp ph latex ln b mt kim loi,
tch cc protit,
4.12.3.iu ch dung dch keo :
Do ht keo c kch thc trung gian gia phn t v cc ht th, nn c 2 phng php tng
qut iu ch dung dch keo l phng php ngng t v phng php phn tn. Nguyn tc ca
cc phng php ny l : trong phng php ngng t th t cc ion, nguyn t, phn t tp hp li
thnh ht keo, ngc li trong phng php phn tn, ngi ta chia nh cc ht th n kch thc
ht keo.
Nhng d l phng php no th cng tun theo 2 iu kin :
- Ht keo phi t tan hay hon ton khng tan trong mi trng phn tn.
- Phi c cht n nh (cn gi l cht lm bn), cht ny c hp ph ln b mt ca ht
keo lm pht sinh in tch hay "c lp" ht keo, n c nhim v lm cho cc ht keo khng lin kt
li vi nhau c thnh cc ht ln hn. Cht n nh c th l cht c cho t ngoi vo hoc l
c sn trong h do s hnh thnh trong qu trnh iu ch.
* Trong phng php ngng t do xut pht im ca phng php, li c phng php vt
l hay phng php ha hc. Trong phng php vt l, thng l thay i mt s thng s ca h
(nhit , dung mi,) lc y trong h s xut hin nhng cht khng tan ri vi mt s iu kin
thch hp, ht keo s hnh thnh, th d nh trn lu hunh bo ha trong nc vi ru etylic th
keo lu hunh s c to nn. Cn vi phng php ha hc th trn cc cht thch hp li vi
nhau sao cho sn phm to nn l cht t tan (hoc khng tan) ri kt hp vi cht n nh ht keo
c hnh thnh. Trong phng php ha hc khi trn cc cht phi c mt quy trnh nghim ngt,
th d nh khi trn dung dch long AgNO3 vi dung dch long KI, lc y s xy ra phn ng :
AgNO3 + KI AgI + KNO3
Mt trong cc cht phn ng d (nhiu) l cht n nh, nu d AgNO3 th AgI s hp ph
Ag+, lc y nhn keo s tch in dng, cc ion NO3- s to thnh lp hp ph v lp khuych tn
to thnh micelle keo, nu d KI th I- s b AgI hp ph to thnh nhn keo tch in m v cc i
ion K+ s to thnh lp hp ph v lp khuych tn.
* Vi phng php phn tn nh vo c hc (nghin) hoc bng siu m hay bng h
quang, ngoi ra cn c phng php pepti ha
4.12.4.S ng t keo :
Khi cc ht keo bng cch no va chm vi nhau v kt hp c vi nhau, lc y s to
thnh kt ta, hin tng ny c gi l s ng t keo.
- Vi keo k dung mi do trn cc ht keo tch in cng du, nn cc ht keo s y nhau
v cc ht khng dnh li vi nhau c. S ng t keo xy ra khi ta lm mt in tch ca ht keo
bng cch cho cht in ly vo dung dch keo, lc y cc ht keo tch in s ht cc ion ngc du
(do c nhiu trong dung dch) v lm trung ha ht keo khi cc ht keo trong khi chuyn ng
nhit s kt hp li vi nhau v kt ta s lng xung, s sa lng ph sa ca sng (vi bin) l
mt th d.
- Cn vi keo a dung mi th s ng t s kh hn do ht keo khng tch in, m cc
ht keo c "bo v" bng cc lp solvat (hoc hydrat, nu dung mi l nc). Do vy loi keo
ny ch ng t khi bng cch no ph v cc lp solvat ny - ngi ta thng cho vo dung
dch keo cc mui a dung mi, cc ion ca mui ny dnh ly lp solvat, cc ht keo s mt lp
69 HA I CNG 2
Chng 4 : DUNG DCH
bo v v s b ng t. Th d nh tch x phng ra khi dung dch keo, ngi ta cho mui n
vo, x phng b tch khi nc mui v ni ln trn
BI TP
1) Ho tan 50 g tinh th FeSO4.7H2O vo 250g nc. Tnh nng % ca dung dch ny.
2) Tm khi lng nc v sulfat ng tinh th CuSO4.5H2O cn thit iu ch 1 lt dung dch
cha 8% CuSO4 Cho khi lng ring ca dung dch CuSO4 8% l 1,084g.ml -1.
3) Cn phi ly bao nhiu ml H2SO4 96% (d = 1,84 g.ml -1) iu ch 100 ml dung dch H2SO4
15% (d = 1,1g.ml -1).
4) Tm nng molan, CN , CM ca dung dch H2SO4 15% (d = 1,1 g.ml -1).
5) Tm nng molan v nng phn mol ca cht tan trong dung dch ng saccaroze
C12H22O11 67%.
6) trung ho 42ml dung dch H2SO4 cn 14 ml dung dch kim 0,3 N. Xc nh nng mol
ca H2SO4.
7) Lm lnh 364,4 g dung dch c cha 0,2 mol Na2SO4 xung 70C th khi lng tinh th ngm
10 phn t nc kt ta l bao nhiu ? Bit dung dch bo ho ny 70C c nng 7,1%.
8) Nhit si ca dung dch nc saccaroze l 101,040C. Tnh nng % ca saccaroze trong
dung dch. Dung dch ny ng c nhit no ? Cho khi lng ring ca dung dch ny
bng 1. Hng s nghim ng v nghim si ca nc ln lt l : 1,86 v 0,52.
9) Nhit si ca CS2 nguyn cht l 319,2K . Dung dch cha 0,217g S trong 19,31g CS2 si
319,304K. Hng s nghim si ca CS2 l 2,37. Xc nh s nguyn t S trong 1 phn t lu
hunh khi tan trong CS2. Cho S = 32
10) Mt hp cht hu c X c cha 50,69% C ; 4,23% H v 45,08% O. Khi ho tan 2,08 g X trong
60g benzen th dung dch lc y s ng c 4,250C. Xc nh cng thc phn t ca X. Bit
nhit ng c ca benzen tinh khit l 5,50C v hng s nghim ng ca benzen l K =
5,12.
11) 20 0C, p sut hi (bo ho) ca nc nguyn cht l 17,54 mmHg, p sut hi ca dung dch
cht tan khng bay hi, khng in ly l 17,22 mmHg. Xc nh p sut thm thu ca dung dch
400C, bit nhit ny khi lng ring ca dung dch l 1,01 g.ml -1, khi lng mol ca
cht tan l 60.
12) Nng H+ trong dd acid formic 0,2M c Ka = 0,8.10 - 4 s gim xung bao nhiu ln khi thm
0,1 mol mui HCOONa vo 1 lt dung dch ny ?
13) C dung dch CH3COOH 0,1M. (bit Ka = 1,8.10- 5)
a) Cn phi thm bao nhiu mol CH3COOH vo 1 lt dung dch in ly ca acid gim i
mt na (xem th tch dung dch khng i khi thm). Tnh pH ca dung dch mi.
b) Nu thm vo 1 lt dung dch CH3COOH 0,1M mt lng HCl l 0,05 mol (xem Vdd khng
i khi thm) th pH ca dung dch l bao nhiu ?
14) Xt dung dch NH3 0,01M (Kb = 1,8.10 - 5)
a) Tnh pH ca dung dch.
b) Nu trong 100 ml dung dch trn c 0,535 g NH4Cl ho tan th pH s l bao nhiu ?
15) Tnh lng NaF c trong 100 ml dung dch HF 0,1M. Bit dung dch c pH = 3, Ka ca HF l
3,17.10- 4.
16) Ngi ta trung ho 100ml dung dch CH3COOH 0,1N (Ka = 1,8.10- 5) bng dung dch NaOH
0,1N. Tnh pH ca dung dch:
a) Trc khi thm NaOH
b) Khi thm 50ml NaOH.
c) Khi thm 100ml NaOH.
17) a) Cho 0,001 mol NaOH vo 100ml nc. Tnh pH ca dung dch.
b) Mt dung dch m to bi 0,5mol/l CH3COOH v 0,5mol/l CH3COONa. Tnh pH ca dung
dch khi ta thm 0,001mol NaOH vo 100ml dung dch trn. Bit CH3COOH c Ka = 1,8.10 - 5
70 HA I CNG 2
Chng 4 : DUNG DCH
18) Cho TAgCN = 1,6.10- 14 .
a) Tnh theo mol/l ho tan ca mui ny trong nc.
b) Mt lt dung dch cha 10- 8 mol Ag+. Phi thm ti thiu bao nhiu mol CN- AgCN bt
u kt ta.
19) Mg(OH)2 c T = 8,9.10- 12. Tnh :
a) ho tan ca cht ny trong nc.
b) ho tan ca cht ny trong KOH 0,01M.
c) dung dch c pH = 5, mt dung dch cha 0,01M Mg2+ kt ta di dng Mg(OH)2
cha ?
20) CaC2O4 c T = 3,6.10- 9. C 0,768g CaC2O4
a) Tnh th tch ti thiu ca nc nguyn cht cn ho tan hon ton lng CaC2O4 trn.
b) Nu dng dung dch CaCl2 0,06M ho tan hon ton lng CaC2O4 trn th cn th tch
ti thiu bao nhiu ?
21) Tnh khi lng cht kt ta c c (nu c) trong mi trng hp sau :
a) 100 ml dung dch BaCl2 10 -4 M + 10 -5 mol Na2SO4.
b) 50 ml dung dch AgNO3 2.10 - 4M + 50 ml dung dch HCl 2.10 --4M
Bit BaSO4 c T = 10-10 v AgCl c T = 1,6.10 - 10
22) Nng H+ sinh ra trong dd Al3+ ch yu do p : Al3+ + H2O Al(OH)2+ + H+ c Ka = 10-5.
3+
Tnh nng ban u ca Al khi Al(OH)3 bt u kt ta v pH ca dd ny, bit rng tch s tan
ca Al(OH)3 l 10-32.
23) Tnh lng ti a CuS tan trong 1 lt dd HCl 1M, bit : CuS c T = 10 -40.
H2S c K1 = 10 -7 v K2 = 1,3.10 -13
24) Ngi ta d nh lm kt ta CdS t 1 dung dch c cha Cd2+ v Zn2+ (c nng [Cd 2+] =
[Zn2+] = 0,02M) bng cch lm bo ho mt cch lin tc dung dch vi H2S .
a) Ngi ta phi iu chnh pH ca dung dch trong gii hn no c th lm kt ta mt s
lng ti a CdS m khng lm kt ta ZnS ?
b) Tnh s mol Cd 2+ cn li trong dung dch khi ZnS bt u kt ta, bit rng :
Dung dch bo ho H2S c [H2S] = 0,1M.
H2S c K1= 10- 7 v K2= 1,3.10 - 13
CdS c T = 10 - 28
ZnS c T = 10 - 22
25) Xt phn ng : Fe3+ + 2H2O Fe(OH)2+ + H3O+ c Ka = 10- 2,2. Hi nng no ca FeCl3
th bt u c kt ta Fe(OH)3. Tnh pH ca dung dch . Bit Fe(OH)3 c T = 10- 38
26) C 1 mu dung dch acid propionic b ln tp cht acid acetic. Pha long 10g dung dch ny
thnh 100ml (dung dch A). Gi tr pH ca dung dch A bng 2,91. trung ho 20ml dung dch
A cn dng 17,6ml dung dch NaOH 0,125M. Tnh nng % ca cc acid trong dung dch ban
u. Bit CH3COOH c Ka = 1,75.10-5 ; C2H5COOH c Ka = 1,34.10-5.
27) Sc kh H2S (pK1 = 7 v pK2 = 14) vo nc. Dung dch bo ho H2S bt k u bng 0,1M.
a) Thit lp phng trnh pS = -lg [S2-] = f(pH).
b) Mt dd cha cc ion Pb2+, Zn2+, Fe2+ v Mn2+ u c nng 10-2M. Cc gi tr tng ng pTt =
-lgTt l 28 ; 22 ; 17 v 10. Hi pH1 no th bt u kt ta tng sunfua mt v pH2 no th tng
sunfua y kt thc s kt ta. S kt thc kt ta c coi gn ng khi [M2+] = 10 -4M.
28) Nu pha long dd Al3+ th thy Al(OH)3 bt u kt ta pH = 5. Tnh nng mol ban u ca Al3+
khi bt u xut hin kt ta, bit tch s tan ca Al(OH)3 l T = 10-32.
29) Dd Mn2+ 10-2M c bo ho bng H2S nng 0,1M. C kt ta MnS khng ? Bit MnS c T = 10-
15
v H2S c K1 = 10-7 v K2 = 10-14.
30) Trong 1 lt dd cha 1 mol AgNO3 v 2 mol NH3.
a) Tnh nng cc ion Ag+, [Ag(NH3)2]+ v NH3 khi cn bng.
b) Thm HNO3 vo dd trn (xem th tch dd khng bin i). Tnh pH ca dd khi 99% [Ag(NH3)2]+
b phn hu.
Cho : Hng s khng bn ca [Ag(NH3)2]+ l Kkb = 10-7,2 v NH3 c Kb = 1,58.10 -5.
71 HA I CNG 2
Chng 5 : PHN NG OXI HO KH - HO HC V DNG IN
CHNG 5
PHN NG OXI HA KH
HA HC V DNG IN
5.1.PHN NG OXI HA KH :
C th ni trong phn ng ha hc c hai loi : phn ng khng lm thay i mc oxi
ha nh phn ng trung ha, phn ng trao i,v phn ng c thay i mc oxi ha - l
phn ng oxi ha kh, n l loi phn ng xy ra nhiu nht trong ha hc.
thay i mc oxi ha th trong phn ng c s chuyn di electron - khi c s
chuyn di electron th c dng in pht sinh v vy gia phn ng oxi ha kh v dng in
c mi tng quan cht ch.
5.1.1. Mc oxi ha
L in tch quy c - l ion gi tng do con ngi t ra tin phn loi phn ng.
Th d nh ngi ta xem nh phn t HNO3 c to thnh t 1 ion H+, 1 ion N+5 v 3 ion O-
2
, trong thc t khng c ion N+5 (m c ion NO3-). V vy vi mc oxi ha phi vit du (+
hay -) trc ri n s sau. (Cn ion c tht tn ti trong dung dch th phi vit s trc du
sau, nh Na2SO4 phn ly hon ton trong nc cho Na+ v SO42 )
Ngi ta quy c :
- Mc oxi ha ca O trong cc hp cht l -2 (tr trong cc peroxit th oxi c mc oxi
ha l -1, cn trong OF2 th oxi c mc oxi ha l +2)
- Mc oxi ha ca cht (n cht, hp cht, ion) th bng in tch ca cht . Th d
mc oxi ha ca phn t H2SO4 th bng 0, ca SO42 bng -2)
- Mc oxi ha ca cht bng tng cc mc oxi ha ca cc nguyn t cu to nn cht.
T ta tnh c tt c cc mc oxi ha ca cc nguyn t trong tng cht.
Th d : nh vi CH3 CHO th mc oxi ha trung bnh ca C trong phn t (C2H4O) l
: 2x + 4(+1) + (-2) = 0 x = -1 (vi x l mc oxi ha trung bnh ca C), cn mc oxi ha ca
C(1) (l C ca CHO) c tnh : 0 + y + (+1) + (-2) = 0 y = +1, mc oxi ha ca C (l C
ca nhm CH3) l : z + 3 (+1) + 0 = 0 z = -3
Mt nguyn t thng thng c nhiu mc oxi ha, trong mc oxi ha thp nht
i vi phi kim th = s phn nhm - 8, cn cc kim loi c mc oxi ha thp nht = 0
Mc oxi ha cao nht thng thng bng vi s nhm, c mt s ngoi l nh : O, F,
Fe, Cu, Au... V F l nguyn t c m in mnh nht nn n khng th b mt in t
trong phn ng ha hc, nn F khng th c mc oxi ha dng m mc oxi ha cao nht ca
F l = 0 (trong n cht F2), cng l do tng t O cng c mc oxi ha cao nht l +2 trong
mt hp cht duy nht OF2
5.1.2.nh ngha
- Cht oxi ha : l cht nhn electron trong phn ng ha hc. Do sau phn ng th
mc oxi ha ca cht gim
- Cht kh : l cht nhng electron trong phn ng ha hc. V vy sau phn ng th
mc oxi ha ca n tng.
Th d : Cu 2+ + Zn Cu + Zn2+
72 HA I CNG 2
Ta thy trong phn ng Cu 2+ nhn 2 electron thnh Cu, nn Cu 2+ l cht oxi ha
(sau phn ng mc oxi ha ca n t +2 gim xung cn 0), cn Zn l cht kh v trong phn
ng n b mt 2 electron t 0 tng ln +2 (sau phn ng mc oxi ha ca n tng). Hay ni
mt cch khc, trong phn ng trn, Cu2+ b Zn kh, cn Zn b Cu2+ oxi ha. Ta thy cht oxi
ha cn gi l cht b kh v cht kh cn gi l cht b oxi ha.
Ngi ta cn ni trong phn ng trn l thc hin qu trnh (s) oxi ha km bi
Cu 2+, hoc l thc hin s kh Cu2+ bi km
Nh vy :
- Cht b oxi ha : l cht kh
- Cht b kh : cht oxi ha
- Qu trnh (s) oxi ha mt cht l qu trnh thu nhn electron t cht .
- Qu trnh (s) kh mt cht l qu trnh nhng electron cho cht .
Ta bit mt cht c nhiu mc oxi ha (t nht l 2). Khi :
* Cht c mc oxi ha cao nht, n ch ng vai tr cht oxi ha trong phn ng oxi
ha kh. V khi cht c mc oxi ha cao nht th n khng th mt electron c na (d
nhin n c th oxi ha c mt cht c th no hay khng li l vn khc - s bn
sau)
* Cht c mc thp nht l nhng cht ch ng vai tr cht kh trong phn ng oxi
ha kh, v n khng th nhn electron c na.
* Cht c mc oxi ha trung gian th n va c th l cht kh (nu n gp cht oxi ha
mnh hn), va c th ng vai tr l cht oxi ha trong mt phn ng khc (nu n gp cht
kh mnh hn n)
Cng nn rng : trong mt phn ng oxi ha kh, khng th c phn ng m trong
ch cha ton l cht kh (hoc ton l cht oxi ha), iu ny rt d hiu v cht oxi ha
mun ly electron th phi c t nht mt cht no cho electron - l cht kh. T ta
d dng hiu nh lut bo ton electron :
Trong mt phn ng oxi ha kh, tng s electron m cht kh cho phi bng tng s
electron m cht oxi ha nhn.
nh lut ny c p dng khng nhng cn bng cc phng trnh phn ng oxi
ha kh m cn dng gii nhng bi ton oxi ha kh phc tp na
5.1.3. Cp oxi ha kh
Cu 2+ + Zn Cu + Zn2+
Cht oxi ha : Cu 2+ sau phn ng bin thnh cht kh Cu. Cht kh Zn sau phn ng
bin thnh cht oxi ha Zn2+. Nn ngi ta gi Cu2+/Cu ; Zn2+/Zn l cc cp oxi ha kh.
D dng nhn thy rng trong mt cp oxi ha kh, dng oxi ha (nh Cu2+) cng c tnh oxi
ha mnh th dng kh (nh Cu) c tnh kh cng yu v ngc li.
5.1.4.Cn bng phn ng oxi ha kh
Thng c 2 phng php : l cn bng theo phng php electron v cn bng
theo phng php ion - electron.
5.1.4.1.Phng php electron :
Th d nh vi phng trnh phn ng : As2S3 + HNO3 H3AsO4 + H2SO4 + NO
Ta lm theo cc bc sau :
73 HA I CNG 2
a) Xc nh cht oxi ha v cht kh v vit cc bn phn ng oxi ha v bn phn ng
kh, nu mt phn ng c nhiu cht oxi ha, nhiu cht kh ta vit thnh cm cht kh v
cm cht oxi ha :
Cht kh : As+3 As+5 + 2e- v S-2 S+6 + 8e- y ta thy gia As v S trong
hp cht As2S3 theo t l 2 : 3 nn ta nhn cc phng trnh theo t l :
2As+3 2As+5 + 4e-
V 3S-2 3S+6 + 24e-
Bn phn ng kh : As2S3 2As+5 + 3S+6 + 28e- (1)
+5 - +2
Bn phn ng oxi ha : N + 3e N (2)
b) bo ton electron, ta nhn cc bn phng trnh cho cc s thch hp sao cho tng
s electron trao i nh nht. Vi th d ny ta nhn phng trnh (1) cho 3 v (2) cho 28, ri
cng li ta c : 3As2S3 + 28N+5 6As+5 + 9S+6 + 28N+2
c) Thm cc nguyn t thch hp cho to thnh cc phn t theo phng trnh phn t
t u : 3As2S3 + 28HNO3 6H3AsO4 + 9H2SO4 + 28NO
d) Kim tra s nguyn t H 2 v, v no thiu thm H2O vo ( lm mi trng), ri
kim tra li s nguyn t O hai v xem ng cha. (Vi phn ng ny ta thy v trc
thiu 8H v trc do v trc cn 4 phn t H2O tham gia)
3As2S3 + 28HNO3 + 4H2O 6H3AsO4 + 9H2SO4 + 28NO
5.1.4.2.Phng php ion - electron :
Phng php ny ch dng cho cc phn ng oxi ha kh trong dung dch, khi vit cc
bn phn ng oxi ha v kh phi vit cc cht tham gia phn ng di dng thc t tham
gia, ngha l vi cht in ly mnh vit di dng ion, cn cht in ly yu, bay hi, kt ta
vit di dng phn t. Th d cn bng theo phng php ion - electron phn ng
KMnO4 + Na2SO3 + H2SO4 MnSO4 + Na2SO4 + K2SO4 + H2O.
a) Vit cc bn phn ng oxi ha v kh di dng ion vi cht in ly mnh :
oxi ha : MnO4- + 5e- Mn2+ (1) v bn phn ng kh : SO32- SO42- + 2e- (2)
b) Thm cc ion H+ (nu mi trng l axit), OH- (nu mi trng baz) hoc H2O (nu
mi trng trung tnh) vo 2 v sao cho in tch c bo ton, cn v kia ta thm H2O
cho cc nguyn t c bo ton cho tng bn phn ng. Ngha l theo phng php ny
trong tng bn phn ng phi cn bng in tch v nguyn t. Nh phn ng lm th d
trn, ta thy phng trnh (1) v trc c 6 in tch (-), cn v sau c sau c 2 in tch
(+), v vy bo ton in tch ta phi thm vo v trc 8 in tch (+) tc 8H+, hoc phi
thm vo v sau 8 in tch (-) tc 8OH-, nhng y phn ng xy ra trong mi trng axit
(H2SO4) nn ta phi thm vo v trc ca bn phn ng (1) : 8H+ v nh vy ta thy v trc
hn v sau 8 nguyn t H v 4 nguyn t O, v vy phi thm vo v sau 4H2O. Bn phn ng
(1) tr thnh :
MnO4- + 5e- + 8H+ Mn2+ + 4H2O (1')
Tng t vi bn phn ng (2), v sau hn v trc 2 in tch (-), nn ta thm vo v
sau 2H+ (mi trng H2SO4), v vy phi thm vo v trc 1 phn t H2O
Vy : MnO4- + 5e- + 8H+ Mn2+ + 4H2O (1')
SO32- + H2O SO42- + 2e- + 2H+ (2')
c) bo ton electron, ta nhn (1') cho 2 v (2') cho 5, ri cng li :
2MnO4- + 5SO32- + 16H+ + 5H2O 2Mn2+ + 5SO42- + 8H2O + 10H+
74 HA I CNG 2
d) n gin 2 v : 2MnO4- + 5SO32- + 6H+ 2Mn2+ + 5SO42- + 3H2O
e) Thm cc ion tng ng vo 2 v :
2KMnO4 + 5Na2SO3 + 3H2SO4 2MnSO4 + 5Na2SO4 + K2SO4 + 3H2O
5.2.TH IN CC :
M
5.2.1.in cc : Khi nhng mt thanh kim loi M (khng
phi l kim loi tan c trong nc) vo trong H2O, do s
li ko ca cc phn t H2O b phn cc lm cc ion trn b
mt thanh kim loi thot ra v i vo trong H2O di dng H2O
cc ion hydrat ha, cc electron khng tan vo trong H2O,
nm li trn b mt thanh kim loi lm cho b mt thanh
kim loi tch in m, gy ra lc ht tnh in ln cc ion (+) trong dung dch lm cc
ion (+) khng i su vo dung dch c m chung quanh thanh kim loi. Thanh kim
loi ta ang xt khng phi l kim loi tan trong nc nn khi cc ion (+) thot ra n
mt lc no li c th kt hp vi electron trn thanh kim loi lm kt ta li kim
loi trn thanh. Lc y xy ra qu trnh cn bng : M Mn+ + ne- l lc vn tc cc ion
kim loi tan bng vi vn tc cc ion (+) kt hp vi electron. Tht ra s thit lp cn
bng ny xy ra rt nhanh chng. Lc y trn ranh gii gia thanh kim loi M v dung
dch hnh thnh lp ip kp - v v c s chnh lch v in nn c mt th hiu sinh ra
gia kim loi v dung dch. Th hiu ny gi l th in cc. (in cc : thanh kim loi
M trong H2O hoc trong dung dch no ). Th in cc khng th o trc tip c.
Cc yu t nh hng n th in cc : Qu trnh to thnh in cc l cn bng,
nn ta c th p dng tt c nhng thnh qu ca cn bng (nh hng s cn bng, cc yu t
nh hng n cn bng, nguyn l Le Chtelier). Vy th in cc ph thuc bn cht ca
kim loi, ca dung mi, nhit v nng ca Mn+. Ti sao li ca Mn+ ? Gii thch nh vo
nguyn l Le Chtelier
5.2.2.in cc chun
Th in cc khng th o trc tip c, cho n hin nay cha c phng php thc
nghim hay l thuyt no c th xc nh c cc hiu th tuyt i ca tng in cc ring
l, v vy ngi ta phi xc nh th in cc tng i bng cch chn mt in cc lm
chun ri cc in cc khc c so snh vi
in cc chun , t suy ra th in cc cho
tng cht.
in cc chun c chn l in cc
tiu chun Hydro, n c cu to :
- Thanh Pt ph bt Pt ( d hp th H2)
c nhng vo dung dch H+ c [H+] = 1
mol/l
- Thi kh H2 cho bo ha trn thanh Pt v
lun gi cho p sut ca H2 bng 1atm
298K.
- Trong iu kin nh vy ngi ta cho
th in cc chun Hidro = 0,00 volt
Trn c s ca in cc tiu chun
Hidro, ngi ta c th xc nh c cc th
in cc bt k bng cch ghp in cc cn o
vi in cc hidro tiu chun ri o hiu th
75 HA I CNG 2
gia 2 in cc, v quy c th in cc chun ca in cc tiu chun Hidro = 0,00 volt,
nn hiu th o c chnh l th in cc ca cht cn o. Ngi ta quy c du ca th in
cc l du trng vi du ca in cc so vi H, ngha l nu in cc ng vai tr cc
m (cho electron) so vi hidro th th in cc c du m (-), ngc li nu in cc cn
o ng vai tr cc dng (nhn electron) so vi hidro th th in cc c du dng (+)
- Th in cc ph thuc vo nng v nhit . Nh vy ng vi mt cht c v s
th in cc ty thuc vo nhit v nng . Ngi ta quy c th in cc chun ca mt
cht tng ng vi iu kin :
* 298K
* Kim loi M nhng vo dung dch mui ca n vi [Mn+] = 1mol/l. Nu l cht
kh, th chn Pt lm "dy dn" nh in cc H tiu chun, v p sut ca pha kh bng 1atm.
Th in cc c 2 dng : dng kh v dng oxi ha
- Ngi ta thng s dng th kh : ng vi qu trnh Mn+ + 2e- M
Mn / M
V khi ghi ngc li chnh l dng oxi ha, lc y phi i du, nhng thng t
c dng. .
Th kh ca cp Mn+/M c k hiu : M n / M . Th kh chun c k hiu : M0 n / M
Th d : 0 2 0,337Volt ; 0 = - 0,763 Volt

Cu / Cu Zn 2 / Zn
V iu kin chun (25 0C v [Cu2+] = 1M) Cu l cc dng so vi in cc tiu

chun H v c hiu th l 0,337 Volt, ng vi qu trnh : Cu2++ 2e- Cu. Tng t Zn l cc
m so vi in cc chun H v c hiu th l 0,763 Volt, th kh chun ca Zn l
- 0,763 volt. Vy qu trnh ngc : Cu Cu2++ 2e- s l 0 2 = - 0,337 volt,.
Cu / Cu
Nh vy ly in cc tiu chun hidro lm chun, ngi ta o c rt nhiu th kh

chun ca cc cht v lp thnh bng - gi l bng th kh chun ca cc cht. Bng th kh
chun thng ghi t trn xung di theo th kh tng dn (theo i s)
K hiu Phn ng in cc 0 ( Volt ) K hiu in Phn ng in cc 0 (Volt )
in cc cc
Li+/Li Li++ e- Li - 3,045 Sn2+/Sn Sn2++2e- Sn - 0,14
K+/K K++ e- K - 2,925 Pb2+/Pb Pb2++2e- Pb - 0,13
+ + - + + -
Cs /Cs Cs + e Cs - 2,92 H3O /H2,Pt 2H3O + 2e H2 +H2O 0,00
2+ 2+ - 2+ 2+ -
Ba /Ba Ba +2e Ba - 2,90 Cu /Cu Cu + 2e Cu + 0,337
Ca2+/Ca Ca2++2e- Ca -2,87 Cu +/Cu Cu + + e- Cu + 0,52
Na+/Na Na++ e- Na - 2,71 I2/I- I2 + 2e- 2I- + 0,54
2+ + - 3+ 2+ 3+ - 2+
Mg /Mg Mg +2e Mg - 2,37 Fe /Fe |Pt Fe + e Fe + 0,77
2+ 2+ - + 2+ - 2+
Be /Be Be +2e Be - 1,85 Ag /Ag 2Hg + 2e Hg2 + 0,789
3+ 3+ - 2+ + -
Al /Al Al + 3e Al - 1,66 Hg /Hg Ag + e Ag + 0,8
Mn2+/Mn Mn2++2e- Mn - 1,18 Hg2+,Hg22+|Pt Hg2++ 2e- Hg2+ + 0,85
Zn2+/Zn Zn2++2e- Zn - 0,76 Br2/Br-,Pt Br2 + 2e- 2Br- + 1,07
3+ 3+ - - - -
Cr /Cr Cr + 3e Cr - 074 Cl2/Cl Cl2 + 2e 2Cl + 1,36
2+ 2+ - 3+ 3+ -
Fe /Fe Fe +2e Fe - 0,44 Au /Au Au + 3e Au + 1,5
76 HA I CNG 2
Co2+/Co Co2++2e- Co -0,277 Au +/Au Au + + e- Au + 1,7
2+ 2+ - - - -
Ni /Ni Ni +2e Ni - 0,25 F2/F F2 + 2e 2F + 2,87
BNG TH KH CHUN
Cn khi nng khng iu kin chun th th no ? Ta c th tnh ton c khng ?
5.2.3.Phng trnh Nersnt :
Dng tnh th kh ca cc cp oxi ha kh cc nng khc nhau khi bit th kh
chun 0oxh / k
S hnh thnh cp oxi ha kh theo bn phn ng : Oxh + ne- Kh (1)
(Ghi ch : Oxh : dng oxi ha ; Kh : dng kh)
Nu gy ra cng c ch A' l cng chuyn n mol electron trong in trng c hiu
in th E l : A' = -nFE
T nhit ng hc : A' = G nn : G = - nFE
F 96500 coulomb : hng s Faraday
E chnh l hiu in th gia dng kh v dng oxi ha, chnh l th kh ca cp
oxi ha kh nn : G = - nF oxh / k .
Nu cp oxi ha kh iu kin chun (nng cc cht u bng 1, nu l cht kh
th c p sut p = 1atm) th nng lng t do Go = -nF 0oxh / k
T phng trnh ng nhit Van't Hoff (mc 2.3.Quan h gia bin thin th ng p,
ng nhit v hng s cn bng - chng "cn bng ha hc"). (1) vit c :
[ Kh] [ Kh]
G = Go + RTln Nn : - nF oxh / k = - nF 0oxh / k + RTln
[Oxh] [Oxh]
RT [Oxh]
Hay : oxh / k = 0oxh / k + ln . y l phng trnh Nernst v th in cc.
nF [ Kh]
Vi oxh / k , 0oxh / k ln lt l th kh iu kin bt k v iu kin chun ; n : s

electron trao i trong bn phn ng ; T : nhit trong iu kin phn ng ; [oxh] v [Kh]
ln lt l nng dng oxi ha v nng dng kh
Trong iu kin T = 298K, R = 8,314J.mol-1.K- v v lna = 2,303lga. Lc y
0,059 [Oxh]
oxh / k = 0oxh / k + lg
n [ Kh]
Mt s ch khi vit phng trnh Nernst :

- Nu trong bn phn ng c cht rn tham gia, trong biu thc ca phng trnh Nernst
s khng c mt cht rn (nh trong biu thc hng s cn bng K)
V d : i vi cp Zn2+/Zn : Zn2+ + 2e- Zn
RT
Phng trnh Nernst c vit : Zn2 0
= Zn 2 / Zn + ln[Zn2+]
/ Zn 2F
- Nu trong bn phn ng c s tham gia ca H+ hoc OH-, th nng ca cc ion
ny cng c mt trong phng trnh Nernst.
Nh : MnO4- + 5e- + 8H+ Mn2+ + 4H2O
77 HA I CNG 2
RT [ MnO4 ][ H ]8
Th : 2 = o MnO4 / Mn 2 + ln
MnO4 / Mn 5F [ Mn 2 ]
5.2.4.Cc loi in cc : T cc nguyn t c th to thnh nhiu in cc. Nhng da

trn mt s tnh cht, trng thi, ngi ta c th phn loi in cc thnh mt h thng no
. Vic phn loi c th da trn nhng im xut pht khc nhau a n kiu phn loi
khc nhau. Tht ra khng c s phn loi no l tuyt i. Vn l ch h thng cho d nh,
d hiu.
5.2.4.1.in cc loi 1 : Cn gi l in cc thun nghch cation. Thng loi
ny c hot dung dch bin i khi pin lm vic. Tng qut : M n+ + ne- M.
Trong dng Mn+ l dng oxi ha v dng M l dng kh ca cng mt cht, cn n l
s electron trao i. Th in cc loi ny c tnh t phng trnh Nernst.
Trong s in cc loi ny c :
a) in cc kim loi : l kim loi nhng vo dung dch mui ca kim loi nh
kim loi Cu nhng vo dung dch CuSO4, nh Ag+/Ag, Zn2+/Zn, Fe2+/Fe,
RT
Phng trnh : Cu2+ + 2e- Cu. C Cu2 0
= Cu 2 / Cu + ln[Cu 2+]
/ Cu 2F
b) in cc hn hng : Dng thy ngn ha tan kim loi, nh in cc :
Cd 2+|[Cd] (Hg) Trong : Cd2+ + 2e- Cd
RT [Cd 2 ]
C Cd 2 / Cd 0 2 ln
Cd / Cd 2 F [Cd ]trongHg
c) in cc kh : nh in cc hidro : Pt, H2|H+

RT [ H ] 2
2H+ + 2e- H2 c H / H 0 ln
2 H / H2 2F pH 2
5.2.4.2.in cc loi 2 : cn gi l in cc anion, ch yu c cu to t mt

kim loi ph bi mt mui t tan ca kim loi nm cn bng vi dung dch cha anion ca
mui t tan . Tng qut : MX (t tan) + ne- M + Xn-. Vi MX l mui t tan to bi kim
loi M v anion X . Nh vy in cc c ghi : M, MX|Xn- hoc Xn-|M, MX. Th kh loi
n-
RT
ny : M ,MX / X n 0 ln[ X n ] . Trong s ny c :
M , MX / X n nF
a) in cc kh : nh Pt, Cl2|Cl- c phn ng in cc : 1/2Cl2 + e- Cl-

1
p Cl2
RT 2
C Cl 0 ln
2 / Cl Cl 2 / Cl F
[Cl ]
b) in cc calomen : Hg, Hg2Cl2 |Cl- . C phn ng in cc :

RT
Hg2Cl2 (r) + 2e- 2Hg + 2Cl-. C Hg , Hg 0 ln[Cl ] 2
2Cl2 / Cl Hg , Hg 2Cl2 / Cl 2F
c) in cc bc clorua : Cl-|AgCl, Ag. Vi phn ng : AgCl (r) + e- Ag + Cl-

RT
Ag , AgCl / Cl 0 ln[Cl ] .
Ag , AgCl / Cl F
0
Lu , ng nhm ln Ag , AgCl / Cl vi Ag
/ Ag
v thc cht cng l Ag+ thu thm
electron, nhng vi Ag, AgCl/Cl- th dng kh dng rn, v vy n c th in cc khc.
78 HA I CNG 2
5.2.4.3.in cc oxi ha - kh : Cn gi l in cc redox (do reduction : kh ;
oxidation : oxi ha). Tc l bn thn in cc va ng vai tr cht oxi ha va ng vai tr
cht kh, nh vy in cc loi ny c nhim v tip nhn v chuyn giao electron. in cc
l cht trung gian. N thng c cu to t mt kim loi tr nhng vo mt dung dch cha
dng oxi ha v dng kh, kim loi tr thng l Au hay Pt. Trong loi ny c :
a) in cc n gin : Th d nh : Fe3+, Fe2+, Pt. Phng trnh in cc :
RT [ Fe 3 ]
Fe3+ + e- Fe2+ c phng trnh Nernst : Fe3 / Fe 2 0 3 2 ln
Fe / Fe F [ Fe 2 ]
Hay : MnO4- + e- MnO42- cng tng t.

b) in cc phc tp : MnO4- + 5e- + 8H+ Mn2+ + 4H2O.

RT [ MnO4 ][ H ]8
C phng trnh Nernst : MnO / Mn2 0 3 2 ln
4 MnO4 / Mn 5F [ Mn 2 ]
5.2.5.Chiu hng v mc din bin ca phn ng oxi ha kh.

5.2.5.1.Xc nh chiu ca phn ng oxi ha kh
T chng 1 (Nhit ng hc), cho mi qu trnh (trong c c phn ng oxi ha
kh) t xy ra khi G < 0
i vi mt cp oxh kh ta li c G = - nF . T ta thy th kh c th dng
d on chiu hng ca phn ng oxi ha kh.
Gi s ta c cp oxh1/Kh1 v oxh2/Kh2 v nu xy ra c phn ng :
Oxh1 + Kh2 Kh1 + oxh2 (1) Phn ng ny l t cc bn phn ng:
oxh1 + ne- Kh1 c 1 (2) v Kh2 - ne- oxh2 c 2 (3)
Phn ng (2) c G1 = - nF1 = - nFoxh1/Kh1
(3) c G2 = - nF2 = - nF(- oxh2/Kh2) = nFoxh2/Kh2
(1) c G = - nFE (*)
V (2) + (3) = (1) nn : G = G1 + G2 - nFE = nF.oxh2/Kh2 - nF.oxh1/Kh1
E = oxh1/Kh1 - oxh2/Kh2
(1) xy ra th G < 0 v t (*) E > 0. Hay oxh1/Kh1 > oxh2/Kh2
Vy phn ng oxi ha xy ra th th kh ca cht oxi ha phi ln hn th kh ca
cht kh.
Hay ni cch khc cp oxi ha kh no c th kh ln th dng oxi ha ca n s oxi
ha c dng kh ca cp c th kh nh hn.
Lu rng y ta ang cp n th kh tng qut cn bng th in cc chun
trong sch gio khoa hoc dy in ha l th kh chun (nng cc cht u bng 1, p
sut cc cht u bng 1atm).V vy khi d on chiu hng ca phn ng oxi ha kh th
nu th kh chun gia hai cp chnh lch nhau nhiu (hoc hai cp cch xa nhau trong dy
in ha) ta c th da vo th kh chun d on, cn nu khi 2 cp oxi ha kh c th
kh chun chnh lch nhau t (< 0,2 volt) (hoc gn nhau trong dy in ha) th khng th
ch cn c vo th kh chun d on, m cn phi cn c vo nng , hoc mi trng
na - tc l phi tnh bng phng trnh Nernst (ch khng phi ch l o)
V d 1 : Xt chiu phn ng : 5Fe+3 + Mn+2 + 4 H2O 5Fe+2 + MnO4- + 8H+
79 HA I CNG 2
Mun vy ta so snh th kh chun ca 2 cp o Fe3 / Fe2 l o MnO 4 / Mn 2 . Tra bng th
chun ta c : o Fe3 / Fe2 = 0,771 volt v o MnO 4 / Mn 2 = 1,51 volt
Ta thy o 2
ln hn o 3 2 nhiu, nn phn ng s xy ra theo chiu dng oxi
MnO 4 / Mn Fe / Fe
ha ca cht c o ln (MnO4-) s oxi ha dng kh ca cht c o nh (Fe2+). Vy phn ng

trn s xy ra theo chiu nghch.
V d 2 : Xt phn ng Hg2+2 + 2Fe+2 2Hg + 2Fe+3.
Xc nh chiu ca phn ng khi :
a) [Hg2 +2 ] = [Fe+2 ] = 0,1 ; [Fe+3 ] = 10-4
b) [Hg2+2 ] = [Fe+2 ] = 10-4 ; [Fe+3 ] = 0,1
Bit o Hg 2 2 / Hg = 0,789 volt v o Fe3 / Fe3 = 0,771 volt
Nhn xt : V th kh chun ca 2 cp gn nhau, nn chiu ca phn ng oxi ho kh ngoi
vic da vo th kh chun cn phi tnh n nng cc cht phn ng na. Tc l phi so
snh 2 v Fe 3 / Fe 2
Hg 2 / Hg
a. Xt cc bn phn ng
Hg2 +2 + 2e 2Hg. T phng trnh Nernst : Hg

2
2
/ Hg
= o Hg2 2 / Hg
RT
2F

ln Hg 2 2
Th cc gi tr vo ta c : Hg 2
/ Hg
= 0,76 volt (1)
2
3
RT [ Fe ]
Fe3+ + e Fe+2 Fe3 / Fe 2 = o Fe3 / Fe2 + ln
F [ Fe 2 ]
Th cc gi tr vo ta c : Fe3 / Fe2 = 0,59Volt (2)
So snh (1) v (2) Hg 2 / Hg > Fe3 / Fe 2

2
nn phn ng xy ra theo chiu : Hg 22 + 2Fe+2 2Hg + 2Fe+3

b. Tng t nh trn trong trng hp ny ta li c :
Hg 2 / Hg = 0,67 v Fe3 / Fe2 = 0,95 Volt
2
nn phn ng xy ra theo chiu : 2Fe+3 + 2Hg 2Fe+2 + Hg 22

5.2.5.2.Cn bng oxi ha kh. Hng s cn bng
Xt phn ng oxi ha kh : oxh1 + kh2 kh1 + oxh2
trn ta chng minh c E = oxh1 / kh1 oxh 2 / kh 2
Khi phn ng t ti cn bng tc G = -nFE = 0. Tc l E = 0 hay

oxh1 / kh1 oxh 2 / kh2
RT [oxh1 ] RT [oxh2 ]
T phng trnh Nernst o oxh1 / kh1 ln = o oxh2 / kh2 ln
nF [kh1 ] nF [ kh2 ]
RT [kh1 ][oxh2 ]
0 oxh1 / kh1 0 oxh2 / kh2 = ln
nF [oxh1 ][kh2 ]
80 HA I CNG 2
nF [kh ][oxh2 ]
hay ( 0 oxh1 / kh1 0 oxh2 / kh2 ) = ln 1
RT [oxh1 ][kh2 ]
nhit xc nh (T = 298K) th v tri l hng s v ngi ta t :

nF ( o oxh1 / kh1 o oxh2 / kh2 ) [kh1 ][oxh2 ]
= lnK K . Nu gi Eo = o oxh1 / kh1 o oxh2 / kh2
RT [oxh1 ][kh2 ]
nFE o
Th lnK = . Hay : E0 = RT ln K . 250C : E 0 0,059 lg K Vi K l hng s
RT nF n
cn bng ca phn ng oxi ha kh ; n : s electron trao i trong phn ng oxi ho kh
Th d : Dng v d 2 trn : Hg2+2 + 2Fe+2 2Hg + 2Fe+3.
Tnh hng s cn bng ca phn ng oxi ha kh . V tnh nng cc cht lc cn bng
khi ban u : [Hg2+2 ] = [Fe+2 ] = 0,1 ; [Fe+3 ] = 10-4
Vi E0 = o oxh1 / kh1 o oxh 2 / kh 2 = 0,789 - 0,771 = 0,018. V vi n = 2 ; F = 96500 ;
nFE o
R = 8,314J.mol-1.K-1 ; T = 298K. Th vo cng thc lnK = . Ta c K = 4,06.
RT
T : Hg2 +2 + 2Fe+2 2Hg + 2Fe+3.
Nng cc cht lc ban u : 0,1 0,1 10 -4
Nng cc cht lc cn bng : 0,1 - x 0,1 - 2x 10 -4 + 2x
(Vi 2x l nng ca Fe3+ to nn lc cn bng, iu kin : 0,1- 2x > 0 x < 0,05) T
[kh1 ][oxh2 ] 10 4 2 x
K 4,06 . Gii ra c x = 0,393 v x' = 3,29.10 -3. T iu kin
[oxh1 ][kh2 ] (0,1 x)(0,1 2 x)
trn ta nhn nghim : x = 3,29.10-3. Vy lc cn bng :
[Hg2+2 ] = 0,0967 ; [Fe2+] = 0,0934 v [Fe3+] = 6,68.10 -3
5.3.CC QU TRNH IN HA :
Ta bit dng in c c do s di chuyn cc electron
Trong phn ng oxi ha kh c s chuyn dch electron t cht kh sang cht oxi ha.
V cc cht oxi ha v kh tip xc nhau, nn nng lng ha hc cng lm l bin thnh
nhit nng, nhng by gi bng cch no ta cch ly c cht oxi ha v cht kh, lc y
dng electron nh vy "kim sot" c, n chuyn theo mt chiu xc nh. Vy ta
thy c s lin quan gia phn ng oxi ha kh v dng in :
T ha nng (phn ng oxi ha kh) chuyn thnh in nng - dng c nh th gi l
pin. Cn t in nng, di tc dng ca dng in mt chiu - gy ra phn ng ha hc -
chuyn thnh ha nng, l s in phn.
5.3.1.Pin :
5.3.1.1.Cu to v hot ng ca pin
Pin cn gi l nguyn t Ganvanic - nguyn
t in ha, n l ngun in ha hc bin ha Volt k
nng thnh in nng. Thut ng "nguyn t"
y mun ni n pin l phn t c bn ban u.
- Cu to : Gm 2 in cc, mi in cc Zn KCl Cu
gi l bn pin. Mi in cc gm mt kim loi
nhng vo dung dch mui ca kim loi v khi
81 HA I CNG 2
ZnSO4 CuSO4
ni 2 in cc bng mt dy dn th c dng in qua, cho dng in tn ti th cn phi c
mt cu ni gia 2 in cc (nh hnh v)
Th d : Pin Daniels - Jacobi (Pin Cu - Zn)
- S hot ng ca Pin
T phn th in cc ta bit
* in cc Zn : Xy ra qu trnh oxi ha Zn Zn2+ + 2e- (1)
* in cc Cu : Xy ra qu trnh kh : Cu2+ + 2e- Cu (2)
Nu khng c dy dn th cc bn phn ng (1) v (2) mau chng t n cn bng.
By gi nu ta ni hai in cc bng mt dy dn th do th kh ca 2 in cc khc nhau
(ph thuc vo bn cht ca in cc, dung mi, nng ) nn thanh Zn tch t lng in
tch m (electron) nhiu hn thanh Cu, v vy c s khuych tn electron t ni nhiu sang
ni t ( entropy tng), do lng electron ni thanh Zn s chuyn qua thnh Cu (t
electron hn) nh vy dng in pht sinh v lm ph v cn bng c - cn phi lp li cn
bng mi, tc thanh Zn tip tc tan ra cho electron b p li lng electron b chuyn
i, trong dung dch ZnSO4 lng in tch dng (Zn2+) tng ln trong khi lng in tch m
SO42- khng i.
Lng electron t thanh Zn theo dy dn qua thanh Cu li ph v cn bng ni thanh
Cu, nn xy ra qu trnh : Cu2+ + 2e- Cu. Cc ion Cu2+ trong dung dch nhn electron tr
thnh Cu kim loi bm vo in cc - trong dung dch CuSO4 b mt Cu2+ nn lng in tch
dng gim i, trong khi lng in tch m SO42- khng i.
-Tc dng ca cu ni : Ta thy dng electron t thanh Zn chuyn sang thanh Cu nn
dng in pht sinh v dng in s ngng ngay lp tc, v c s chnh lch in tch trong
dung dch c hai in cc lm ngn tr s chuyn di electron. lm bin mt s chnh
lch in tch, ngi ta lm mt cu ni gia 2 in cc - cu ni l dung dch in li - c
nhim v lm cn bng in tch 2 in cc - nh vy dng in c tip din n khi no
thanh Zn tan ht hoc ion Cu2+ trong dung dch ht.
Ngi ta k hiu pin : (-) ZnZn2+Cu 2+Cu (+)
Thng c quy c : cc m vit trc, trong mi in cc th gia cc pha cch
nhau bng mt vch thng ng, gia 2 in cc cch nhau bi 2 vch thng ng.
5.3.1.2.Sc in ng ca pin
Sc in ng ca pin l th hiu cc i gia hai in cc lc pin khng lm vic.
Sc in ng ca pin c k hiu l E.
T phn 5.2.3.phng trnh Nersnt, ta c G = - nFE
Vi G : nng lng t do ca phn ng to pin ; n : s electron trao i trong pin ;
F : hng s Faraday = 96500 coulomb ; E : sc in ng ca pin
Vi pin Daniels- Jacobi : (-) ZnZn2+Cu2+Cu (+). Trong pin xy ra phn ng :
Cu 2+ + Zn Cu + Zn2+. Cng chng minh tng t nh th in cc, ta c :
RT [Cu 2 ] 0,059 [Cu 2 ]
E = E0 + . ln . Nu 25 0
C th E E0 lg V :
nF [ Zn 2 ] n [Zn 2 ]
G0 = - RT.lnKC
Vi Eo, G0 ln lt l sc in ng v th ng p ca pin iu kin chun ;
KC : hng s cn bng ca phn ng to pin
82 HA I CNG 2
Mi quan h gia sc in ng ca mt pin bt k v th kh :
Cng ly th d vi pin Daniels-Jacobi : mi in cc xy ra phn ng :
Cc m : Zn Zn2+ + 2e- (1) Cc dng : Cu2+ + 2e- Cu (2).
2+
Nu gi 1 l th kh ca cp Zn /Zn, vy 1 = Zn 2 / Zn . T (1) G 1 2F(1 )
(Vi bn phn ng (1) ta vit di dng oxi ha nn th kh ca n l - 1 )
V 2 l th kh ca cp Cu 2+/Cu ( 2 Cu 2 / Cu ). T (2) G 2 2F. 2 .
Phng trnh phn ng xy ra trong pin l (1) + (2) : Cu2+ + Zn Cu + Zn2+. (3)
Phng trnh (3) c sc in ng l E v c G 2 FE
V (3) l tng ca (1) v (2) nn theo Hess : G G 1 G 2
-2FE = -2F(- 1 ) - 2F 2 E = 2 1 . Tng t : E0 = 20 10

Nh vy sc in ng ca mt pin bt k bng hiu s th kh ca cc dng v cc
m to ra pin .
5.3.1.3.Pin ha hc v pin nng : T cc in cc, c ghp hai in cc s to
thnh mt pin, ngi ta chia pin thnh hai loi : pin ha hc v pin nng .
a) pin ha hc : l loi pin sinh in nh s tin hnh cc phn ng oxi ha kh cc
in cc - do bn cht ca 2 in cc khc nhau, th d nh pin Daniels-Jacobi thuc loi pin
ny.
b) pin nng : c cu to t 2 in cc c bn cht khng khc nhau, nhng 2
bn pin ch khc nhau do nng ca cc cht tham gia phn ng in cc. Nh vy dng
in c c do s dn n san bng nng .
Th d pin : Pt, H2 (p1) | HCl | H2 (p 2), Pt
cc m : H2 (p1) 2H+ + 2e-. cc dng : 2H+ + 2e- H2 (p 2)
RT p
Tng qut : H2 (p1) H2 (p2). Sc in ng ca pin : E = - ln 2
nF p1
Tht ra s phn loi pin ch c tnh cht h thng, ch khng th c bin gii r rng.
Th d nh pin ha hc u phi bt buc nng ca cht tham gia phn ng in cc phi
bng nhau.
5.3.2.S in phn :
l s chuyn ha nng lng theo kiu in nng bin thnh ha nng. N ngc
li vi s chuyn ha trong pin ta kho st.
5.3.2.1.nh ngha : in phn l qu trnh oxi ha kh xy ra trn b mt cc
in cc di tc dng ca dng n mt chiu ln dung dch cht in ly hay ln cht in
ly nng chy.
Tng qut, trong dung dch cht in ly, cc cht tan di dng ion b solvat ha, khi
c mt th hiu ln hai u in cc, dung dch ny dn in do s chuyn vn cc ion, cc
ion s di chuyn v cc in cc ngc du. Ti cc m (catod) xy ra qu trnh kh, ti
cc ion dng nhn electron to thnh nguyn t hay phn t trung ha bm vo catod nu l
cht rn, cn nu l cht kh th khi nhn electron s to thnh nguyn t ri kt hp li to
thnh phn t v bay ln. Cn anion th i v anod, ti xy ra phn ng oxi ha, cc anion
(hoc in cc) s mt electron cho nguyn t (hoc tan) ri nguyn t kt hp vi nhau
83 HA I CNG 2
cho phn t. y l cc phn ng s cp l cc phn ng do tc ng trc tip ca s in
phn.
Th d nh in phn dung dch CuCl2 vi in cc tr c mng ngn, vi th hiu
ln : Ti cc m c : Cu2+ v H2O, lc y c qu trnh : Cu2+ + 2e- Cu (1).
Ti cc dng : Cl- v H2O, xy ra bn phn ng : 2Cl- Cl2 + 2e- (2)
Phng trnh tng qut khi in phn dung dch CuCl2 :
(1) + (2) : Cu 2+ + 2Cl- Cu + Cl2 hay CuCl2 Cu + Cl2
Nhng cn c th xy ra cc phn ng th cp - do cc nguyn t va sinh ra cc in cc
c phn ng rt cao, d dng tc dng vi dung mi, in cc hoc nhng cht khc c
mt trong dung dch. Th d nh Cl- v cc dng bng Ag th Ag s d dng tc dng vi Cl-
cho AgCl.
5.3.2.2.Th phn cc :
Nu khi p t hai u in cc mt th hiu b th s in phn khng xy ra c,
hin tng nh vy gi l s phn cc, c phn thnh 2 loi : phn cc ha hc v phn
cc nng .
a) Phn cc ha hc : Xt s in phn dung dch Chiu dng in ngoi
NiCl2 vi in cc tr Pt. Khi c dng in mt chiu i
qua, anod xut hin kh Cl2 v cc m c Ni bm vo
(in cc). rng lc y cc dng ca bnh in Chiu
phn c kh Cl2 bo ha trong dung dch Cl- vy to thnh dng
in cc PtCl2Cl- v cc m c Ni bm vo - thnh ra in
2+ do pin
cc m lc y tr thnh in cc NiNi . Nh vy to
2+ - to ra
thnh pin : (-) NiNi Cl Cl2Pt (+)
(V Cl Ni 2 / Ni ) - tc l lc y cc dng ca
2 / Cl
bnh in phn (c Cl2 bm vo) s bin thnh cc dng bt kh dd NiCl2 Ni bm
ca pin v cc m ca bnh in phn s bin thnh cc Cl2
m ca pin (do Ni bm vo). Mc d cc cc vn cng tn,
nhng ta phi thy rng chiu ca dng in do pin to ra ngc vi chiu dng in in
phn. Nh vy pin ny gy ra mt th hiu cn tr li s in phn, gi l th phn cc.
Vy mun in phn th phi cn mt hiu th ti thiu bng hiu th do pin to ra.
b) Phn cc nng : S phn cc ny l do nng gy ra mt sc in ng ngc
chiu vi dng in bn ngoi. V d nh in phn dung dch CuSO4 vi in cc Cu.
cc dng cc ion Cu 2+ c to thnh (do thanh Cu mt electron), do vy nng
Cu cc dng ln, cn cc m, Cu kim loi bm vo do Cu2+ nhn electron t cc m -
2+
nh vy nng Cu2+ b gim khu vc cc m. Nh vy trong bnh in phn quanh 2 in

cc c nng khc nhau gy ra sc in ng ngc chiu (pin nng ) vi dng ngoi.
s in phn xy ra c cn phi c mt th hiu ti thiu p t ln 2 in cc.
5.3.2.3.Th phn hu v qu th :
Nh vy ta bit khng phi bt k hiu th no cng c th gy ra s in phn
c, m phi c mt th hiu ti thiu no .
Hiu th ti thiu gy ra s in phn c gi l th phn hy
Trn nguyn tc th phn hu ch cn ln hn th phn cc mt lng rt nh l
gy ra s in phn. Nhng trong thc t th phn hy thng ln hn th phn cc kh
nhiu.
84 HA I CNG 2
Nu gi Uph: Th phn hy ; Upc : th phn cc U = Uph - Upc ; U gi l qu th
Ngi ta nhn thy rng qu th rt phc tp, n ph thuc vo :
- Bn cht ca cht thot ra in cc (thng thng qu th ca cht kh ln hn cht rn)
- Bn cht ca in cc : ngi ta cha pht hin c quy lut no v yu t ny, cng mt
cht thot ra in cc, nhng vt liu lm in cc khc nhau cng a n qu th khc
nhau.
- Qu th cn ph thuc vo trng thi b mt ca in cc (thng b mt xp c qu th
thp hn nhn bng)
- Nht , thnh phn dung dch, mt dng...
Hin nay c ch ca qu trnh ang cn tranh ci. Ta ch cn n thc cht ca
kt qu in cc l do th phn hy. Th phn hy cng nh th qu trnh ng vi n cng
d xy ra v n c gii phng in cc
5.3.2.4.in phn mui nng chy
V d nh in phn NaCl nng chy. Khi nng chy : NaCl nng chay
Na+ + Cl-
Ion Cl v anod v b oxi ha : 2Cl Cl2 + 2e ; cn Na v catod b kh : Na + + e- Na.
- - - +
Phn ng tng cng : NaCl pnc

Na + 1/2Cl2
5.3.2.5.in phn dung dch mui
a) catod : Cc ion (+) v catod v xy ra s kh, cng vy ngoi cc ion (+)
ca cht in ly, cn c H+ ca H2O. S kh cng tun theo th t : Cht no c th kh ln
nht s kh trc, nhng cc ion kim loi ng trc Al3+, k c Al3+ khng bao gi b in
phn trong dung dch nc m thay vo l H2O b kh v th kh ca H2O ln hn th kh
o
ca cc ion kim loi . Ta bit H / H2 = 0,00 volt, cn cc kim loi t Pb tr v trc
trong dy in ha u c M n / M < 0. Vy l ra H+ ca H2O phi in phn trc c Pb2+
o
ch ? Nhng ti sao H+ ca H2O li phi di n sau Al ? V vi dung dch trung tnh th

RT
[H+] = 10-7 nn t phng trnh Nernst : H / H = o H / H 2 + ln [H+]2 = -0,41 volt, v li
2 2F
qu th ca H2 li ln, nn th kh ca n li nh hn na.
b) anod tr (Pt, Cgr,..) : Cc ion (-) v anod v xy ra s oxi ha, nhng
rng ngoi cc ion ca cht in ly, cn c OH- ca H2O. S oxi ho s theo th t th kh
(ch th kh ch khng phi th kh chun) ca cp no thp nht s b oxi ha trc. Vi
cc anion thng gp th s kh theo th t : S2- > I- > Br- > Cl- > OH- > H2O. Vy th cc
anion phc tp c cha oxi (nh SO42 , NO3-, PO43 ,) s khng bao gi b in phn.
c) Anod tan (cc kim loi khc) : i vi trng hp ny cng rt n gin, ta
ch cn chnh cht lm in cc cng l cht c th tham gia vo phn ng oxi ha kh
do dng in mt chiu gy ra, do cc kim loi ny c th kh nh hn cc ion v in cc
nn thay v cc anion nh I-, Cl-, b oxi ha th chnh kim loi lm in cc (t Cu tr v
trc trong dy in ha) b oxi ha.
Th d : Th xt in phn dung dch NiCl2 vi in cc tr v vi in cc Ni.
Khi NiCl2 tan trong nc s phn ly : NiCl2 Ni2+ + 2Cl- . Khi c dng in mt
chiu qua dung dch th cc ion i v cc in cc ngc du :
- Vi in cc tr : cc m : Ni2+ + 2e- Ni (1)
- -
Ti cc dng : 2Cl Cl2 + 2e (2)
Phng trnh in phn tng qut : NiCl2 dpdd
Ni + Cl2.
85 HA I CNG 2
- Vi in cc Ni : cc m, cng nh trn.
Cn ti cc dng c : Cl-, H2O v chnh in cc lm bng kim loi Ni. So snh th
kh ca 3 cht ny th th kh ca Ni l b nht nn chnh Ni s l cht kh :
Ni Ni2+ + 2e- (3). Phng trnh ion tng cng : Ni2+ + Ni Ni + Ni2+
Phng trnh in phn : NiCl2 + Ni Ni + NiCl2
Ngoi ra nh ni trn (phn 5.3.2.1.nh ngha), ngoi nhng phn ng s cp
nh trn, cn c phn ng th cp nh cp trong phn nh ngha
5.3.2.6.Cc nh lut v s in phn
Do Faraday tm ra nm 1832-1833 di 2 dng gi l nh lut Faraday th nht v
th hai. Cn gi l nh lut nh lng v s in phn.
- nh lut Faraday 1 :
Lng cht to thnh hay ha tan in cc khi in phn t l vi lng in (Q =
I.t) i qua dung dch. (Q : in lng ; I : cng qua mch ; t : thi gian in phn)
- nh lut Faraday 2 :
Nhng lng in bng nhau s to thnh hay ha tan in cc khi in phn nhng
lng ng lng nh nhau ca cc cht.
V mun gii phng mt mol ng lng bt k cht no u cn phi c mt in
lng F (F : hng s Faraday, c lm trn l 96500 Coulomb)
T 2 nh lut Faraday, lp lun :
C 1 F (Coulomb) gii phng 1 mol ng lng cht.
m m I .t
Vy I.t (Coulomb) = Q gii phng s mol ng lng. Vy : (*)
F
[Vi m, ln lt l khi lng v ng lng cht thot ra in cc. Vy s mol ng

m A
lng cht = . Li c = . Vi A, n ln lt l khi lng mol nguyn t v ha tr (s
n
e- trao i) ca cht. (Xem li Cu to cht chng 1, phn ng lng)]
A A.I .t I .t
Th = vo (*) ta c : m = hay nng.t =
n n.F n.F
Vi m : khi lng cht thot ra (hay tan) t in cc ; A : khi lng mol cht thot
ra cc in cc ; I : cng dng in ; t : thi gian in phn (tnh bng giy)
n : s electron trao i (hay ha tr ca cht) ; F: s Faraday 96.500 coulomb
I .t
V c l tin dng nht ta nn dng cng thc : n e
F
Vi ne- : s mol electron qua mch
Cng thc trn chnh l nh lut hp nht ca Faraday v dng n tnh ton nh
lng cc cht xut hin cc in cc trong cc phn ng s cp ca s in phn, nu hiu
sut l 100%
5.4.N MN KIM LOI, CC PHNG PHP CHNG N MN KIM LOI :

Cc vt liu kim loi, hp kim khi tip xc vi mi trng xung quanh u b ph hu
vi mt tc no . Mc d s n mn lun lun xy ra trn b mt cht, nhng khi c
86 HA I CNG 2
iu kin qu trnh n mn bt u, n s pht trin su n bn trong. Hai s n mn
thng gp l n mn ha hc v n mn in ha.
n mn ha hc l s ph hu b mt kim loi xy ra di tc dng ca oxi, H2S,
SO2, HCl, HNO3, ... vi s c mt ca hi m. V vy n mn ha hc cn gi l n mn kh,
s n mn trong kh xy ra nhit cao hn nhit thng, khi m s ngng t hi m
trn b mt kim loi l khng th c, nh thit b trong cc l, cc chi tit trong ng c t
trong, cc turbin,...
n mn in ho l s n mn xy ra trong khng kh m nhit thng. S oxi
ha kim loi do vic n mn in ha c th to thnh sn phm khng tan (nh g) hoc
chuyn kim loi thnh ion v tan vo dung dch.
Cc kim loi, phn ln c ln tp cht. Mt lp mng H2O trn b mt kim loi ha
tan mt s kh (CO2, SO2,...) tr thnh dung dch din ly. Nh vy c iu kin tr
thnh pin : kim loi, tp cht (kim loi khc) tip xc vi nhau v cng tip xc vi dung dch
in li - chnh xc hn l to ra v s vi pin. Electron t kim loi hot ng mnh hn chuyn
n kim loi yu hn - Kim loi hot ng hn vy l b oxi ha thnh cc ion i vo dung
dch - cn kim loi yu hn b kh - gy ra s ph hy cc kim loi.
V d : S n mn st c ln tp cht Cu, Fe3C.
Trong khng kh m, do vy c mt lp nc mng bm ln b mt st, ha tan mt t
CO2 hay SO2 (c trong khng kh) tr thnh dung dch in ly
(CO2 + H2O HCO3- + H+), lc y Fe do c th kh nh hn Cu (hay C) tr thnh in cc
m, n b mt electron v ion Fe2+ tan vo dung dch in ly : Fe Fe2+ + 2e-. Electron c
dn n cc dng Cu (hay C) v c ion H+ trong dung dch in ly n ly bin thnh H
v li b O2 oxi ha thnh H2O, ion Fe2+ li b O2 ca khng kh cng vi hi nc oxi ha
tip thnh Fe2O3.nH2O l thnh phn ch yu ca g st, lp g xp d b bung ra v lp Fe
bn trong tip tc b g tip.
Cc phng php chng n mn in ha :
- i vi n mn ha hc, ngi ta chng n mn bng cch cch ly kim loi vi mi
trng ngoi, l ph ln kim loi mt lp du, m, sn,...
- Cn i vi n mn in ha, ngi ta cng dng phng php cch li kim loi vi
mi trng ngoi, bng cch to ra trn b mt kim loi mt lp che ph nh sn du, men,
hp cht cao phn t,Nhng lp bo v ny c tc dng sut trong thi gian m lp bo v
cn kn, khi lp cch ly ny v mt l do no b rn nt (try, xt) th s n mn s din
ra. Nhng hu hiu hn ht l phng php in ha bng cch ni kim loi cn bo v vi
mt kim loi khc c tnh hot ng hn. Lc y kim loi cn bo v ng vai tr catod, cn
kim loi hot ng hn s ng vai tr anod - chng s b oxi ha thay cho kim loi cn bo
v.
5.5.MT S NGUN IN HA THNG DNG : PIN, ACCU :

to c pin ch cn 2 in cc v dung dch in li, nhng trong thc t ngun
in ha c c ng dng cn phi c :
- Sc in ng cao, cng ln, cng sut ln
- Gn nh, khng nguy him.
- Kinh t
Cc pin thng gp :
5.5.1.Pin Leclanch :
87 HA I CNG 2
a) Pin km, MnO2 : Vi v bc cng l cc m c lm bng km, gia l li than -
loi in cc tr - lm cc dng, ngn cch gia 2 cc l MnO2 tm cht in ly NH4Cl,
ZnCl2 trn vi h tinh bt. NH4Cl ngoi nhim v l cht in ly cn ha tan Zn2+ to
phc, pin c k hiu : Zn | NH4Cl (20%), ZnCl2 | MnO2, C. Pin ny c sc in ng
khong 1,5V
Cc bn phn ng ca pin :
Cc m : Zn - 2e- Zn2+ ri Zn2+ + 2NH4Cl Zn(NH3)2Cl2 + 2H+
Cc dng : 2MnO2 + 2e- + 2H+ 2MnOOH.
Phng trnh tng cng : Zn + 2MnO2 + 2NH4Cl Zn(NH3)2Cl2 + 2 MnOOH
b) Pin km khng kh : Zn | NaOH | C (O2) . Phn ng trong pin :
Zn + NaOH + 1/2 O2 NaHZnO2 Pin c sc in ng khong 1,4V
5.5.2.Pin nhin liu : l dng c bin trc tip ha nng thnh in nng m khng lu
tr nng lng, nh t chy nhin liu bin thnh in nng.
Cht in ly c dng l dung dch NaOH hay Na3PO4 nng chy
Nhin liu nh H2, CH4, cc cacbua hidro, CH3OH, CO, c dn n cc m, ti
xy ra qu trnh oxi ha nh : 2H2 + 4OH- 4H2O + 4e-.
Cn khng kh (m cht phn ng l O2) c dn n cc dng bng than xp, ti
xy ra qu trnh kh : O2 + 2H2O + 4e- 4OH-.
Phng trnh tng cng : 2H2 + O2 2H2O Cc in cc ng vai tr cht xc tc
5.5.3.Accu ch :
Accu l loi nguyn t Ganvanic trn c s mch thun nghch
Accu ch c cu to : Hai in cc l hai tm ch ph PbO nhng vo trong H2SO4
38%. C hai u xy ra phn ng (khi cha ni dng in 1 chiu) :
PbO + H2SO4 PbSO4 + H2O
* Khi ni vi dng in mt chiu, Accu nh mt bnh in phn, ti cc (+) xy ra
qu trnh kh : PbSO4 + 2H2O PbO2 + H2SO4 + 2e- + 2H+
Ti cc m xy ra qu trnh oxi ha : PbSO4 + 2e- + 2H+ Pb + H2SO4
Vy trong qu trnh np in trong Accu xy ra phn ng :
2PbSO4 + 2H2O Pb + PbO2 + 2H2SO4
Nh vy khi np in xong ta c mt cc l Pb, cc kia l PbO2, cht in li l H2SO4 :
tr thnh pin.
* Lc y, nu ta s dng Accu - l qu trnh phng in s xy ra qu trnh ngc li :
Ti cc (+) ca pin nhn electron : PbO2 + 2e- + 2H+ + H2SO4 PbSO4 + 2H2O
Ti cc (-) : Pb + H2SO4 PbSO4 + 2H+ + 2e-
V c th, qu trnh lp i, lp li.
Nu ta ghp ni mt s accu ring l, ta s c b accu, lc y s c sc in ng,
cng sut ln. Nhc im ca accu ch l khi lng ln v thi gian s dng tng i
ngn.
5.5.4.Accu kim :
88 HA I CNG 2
Accu kim thng gp l accu st - niken, trong cc in cc l Ni v Fe, dung dch
in ly l KOH. C cc phn ng :
- Ti cc dng : Ni2+ Ni3+ + e- - Ti cc m Fe2+ +2e- Fe.
(Qu trnh np in theo chiu thun, cn qu trnh phng in theo chiu nghch)
np in
Phn ng tng qut trong pin : 2Ni(OH)2 + Fe(OH)2 2Ni(OH)3 + Fe
phng in
Ngoi ra, cn c accu kim Cd - Ni, accu kim Ag - Zn, v cn bn s hot ng cng
ging nh accu st - niken
BI TP
1) Xt cc nguyn t Ganvani sau :
a) Mg Mg2+ Pb 2+ Pb d) Pt Fe3+,Fe2+ Cl- Cl2 Pt
b) Pb Pb(NO3)2 Cu(NO3)2 Cu e) Pt H2 H+ Cl- Cl2Pt
2+ +
c) Cu Cu Ag Ag f) ZnZn2+ Cl- AgCl Ag
Electron mch ngoi ca pin s chuyn nh th no ( ktc) ?
Vit cc phn ng trong tng in cc, trong pin
Kim loi no tan
2) Vit s cc pin theo cc phn ng sau :
a) H2 + 2Ag+ 2H+ + 2Ag
b) Cu + Cl2 Cu2+ + 2Cl-
3+
c) Zn + 2Fe Zn2+ + 2Fe2+
Cho bit cc dng, cc m, chiu electron v chiu dng in.
3) Cho : 0Sn2+/Sn = - 0,14 Volt v 0Sn4+/Sn = + 0,005 Volt
a) Tnh th kh chun 25 0C ca cp Sn4+/Sn2+ .
b) Xt pin sau ktc 250C : Sn Sn2+ Sn4+,Sn2+ Pt Vit phng trnh phn ng xy
ra trong pin. Ch r in cc m, dng. Tnh sc in ng (s) chun E0 ca pin v G0
ca phn ng 25 0C.
4) Cn bng sau xy ra trong dd nc 250C : 2Cr2+ + Cd2+ 2Cr3+ + Cd
0 0
Bit Cr 3
/ Cr 2
0,41V ; Cd 2
/ Cd
0,4V
a) iu kin chun p xy ra theo chiu no ?
b) Trn 25ml dd Cr(NO3)3 0,4M vi 50ml dd Cr(NO3)2 0,02M 25ml dd Cd(NO3)2
0,04M v bt Cd. Hi chiu p trn trong iu kin ny ?
5) Tnh th ca in cc hydro 25 0C nhng vo nc nguyn cht ; vo dung dch c pH =
5 ; vo dung dch c pH = 10,7.
6) Tnh th ca in cc ch trong dung dch bo ho PbBr2 250C nu nh [Br- ] = 1mol/l
v T(ca PbBr2) = 9,1.10- 6
7) C th to 1 nguyn t Ganvani c electron mch ngoi chuyn t in cc c th kh
chun dng sang in cc c th kh chun m hn khng ? Gii thch.
8) Cn bng sau xy ra trong dung dch nc 25 0C : Fe + Cd 2+ Fe2+ + Cd.
a) Hi chiu ca phn ng xy ra iu kin chun.
89 HA I CNG 2
b) Tnh nng cc ion Fe2+ v Cd 2+ trng thi cn bng, bit rng phn ng bt u
iu kin chun.
Cho th kh chun ca : Fe2+/ Fe = - 0,44 volt v Cd 2+/Cd = - 0,4 volt.
0 - -
9) Th kh chun 25 C ca cc cp sau : H3AsO4/ H3AsO3 = 0,559V ; I3 / I = 0,536V.
a) Hy cho bit chiu ca phn ng sau iu kin chun :
H3AsO4 + 3I - + 2H+ H3AsO3 + I3- + H2O .
b) Nu ch bin i pH th gi tr no ca pH phn ng trn bt u i chiu ?
c) Tnh hng s cn bng ca phn ng trn.
0
10) Xt pin sau 25 C : Ag|dd AgCl bo ho, HCl 1M || AgNO3 1M| Ag. C 0 Ag / Ag =
0,799V ; 0 AgCl / Ag = 0,222V. Vit phng trnh phn ng xy ra khi pin hot ng v tnh
tch s tan ca AgCl.
-2 0
11) Dd MgCl2 10 M 25 C bt u kt ta Mg(OH)2 pH = 9,5.
a) Tnh tch s tan ca Mg(OH)2.
b) Tnh th kh ca cp Mg2+/Mg khi pH = 11, bit rng th kh chun ca n l
-2,36V.
c) Ti sao Mg ghp vo cc thit b bng thp c th bo v c thp khi b n mn
in ho ?
12) ho tan ca Ag2SO4 trong nc nguyn cht 250C l 1,4.10-2mol/l. Tnh s E ca
pin sau 25 0C : Ag dd bo ho Ag2SO4 AgNO3 2M Ag. Vit phng trnh phn ng
xy ra trong pin.
0 3+ 2+ 3+ 2+
13) Xt pin sau 25 C : Pt Fe 0,1M ; Fe 0,2M Fe 0,2M ; Fe 0,1M Pt.
a) Tnh G ca phn ng xy ra trong pin.
b) Tnh nng cc ion Fe3+ v Fe2+ cc in cc khi cn bng.
0 3+
14) Xt phn ng sau 25 C : Cu (r) + 2Fe Cu2+ + 2Fe2+. Nu cc cht c nng sau
[CuSO4] = 0,5M ; [FeSO4] = 0,025M ; [Fe2(SO4)3] = 0,125M
a) Cho bit chiu ca phn ng.
b) Tnh hng s cn bng ca phn ng.
c) Tnh t l Fe3+/Fe2+ c gi tr ti thiu phn ng i chiu
0 0
(Cho : Cu 2
/ Cu
= 0,34 V ; Fe 3
/ Fe 2
= 0,77V)
15) Sc kh Cl2 (p = 1atm) vo nc nguyn cht 250C xy ra p sau :
Cl2 (k) + H2O HClO + H+ + Cl-. Tnh hng s cn bng K ca p, nng cc ion,
0
phn t trong cn bng v pH ca dd. Bit : Cl0 / Cl = 1,36V v HClO / Cl
= 1,49V
2
0
16) Phn ng sau xy ra theo chiu no 25 C khi : [CuSO4] = 0,1M ; [NaCl] = 0,2M ; Cu
d ; CuCl d. Cu + Cu 2+ + 2Cl- 2CuCl. Bit CuCl c T = 10- 7 ; 0Cu2+ / Cu+ = 0,15V ;
Cu+/ Cu = 0,52V. Tnh hng s cn bng K ca phn ng trn v nng ca cc ion Cu2+
0
v Cl- lc cn bng .
2-
17) Ion MnO4 t phn hu trong dd theo phn ng :
3MnO42- + H2O 2MnO4- + MnO2 + 4OH-
2-
a) Ion MnO4 bn v t bn trong mi trng no (axit, baz) ?
b) Tnh hng s cn bng K 250C ca phn ng t phn hu MnO42- trong 2 mi trng pH
= 0 v pH = 14.
0 0
Cho cc th kh trong mi trng axit : MnO / MnO 2 = 0,56V v MnO 2 / MnO = 2,25V
4 4 4 2
0
18) Hai phn ng sau xy ra trong dd iu kin tiu chun v 25 C.
4Fe2+ + O2 + 4 H+ 4Fe3+ + 2H2O .4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3
Fe (II) b oxi oxi ho trong mt no d hn ? Bit :
-14
0
Fe 0 0
3 / Fe 2 = 0,77V ; O / H O = 1,23V ; O / OH = 0,4V ; TFe(OH)2 = 10 ; TFe(OH)3 = 10 -36.
2 2 2
0 + -16
19) Th kh chun 25 C ca cp Ag /Ag l 0,8V ; tch s tan ca AgI l 1,5.10 . Ag c y
-2
c H2 khi dd HI 1M v HI 10 M khng ?
20) Phn tch nhng kin thc sai ca mt u bi tp ra cho hc sinh :
90 HA I CNG 2
" Trong mt ng thch anh c t 3 thuyn s 1, 2, 3 ln lt ng CaO, Fe2O3, CuO
vi khi lng bng nhau l 0,5607 gam. Dng nn kh nung 3 thuyn n 2270C, sau cho
lung kh H2 c iu ch t Zn tinh khit vi H2SO4 80% v c lm kh bng dung
dch H2SO4 30% i qua ng.
Sau khi phn ng kh hon ton oxit kim loi c 3 thuyn kt thc :
Sn phm phn ng thuyn 1 cho tan vo nc, sau pha long n 250 ml thu
c dung dch B trong sut.
Sn phm phn ng thuyn 2 cho tan va ht trong 40 ml dung dch H2SO4 0,21 M
thu c dung dch C ; lc dung dch C vi bt Cu thy dung dch khng c kh nng i
mu.
Cn sn phm thuyn 3 th c 0,448 gam cht rn.
a) Hy gii thch qu trnh th nghim trn bng cc phng trnh phn ng.
b) Tnh khi lng kim loi to ra thuyn 1 v 2.
c) Tnh nng mol/l ca cc ion c trong dung dch B.Tnh s mol mui to ra trong
dung dch C. Tnh s mol H2 phn ng thuyn 3."
Vi cc s liu tham kho sau :

-Tch s tan ca Ca(OH)2 l T = 5,5.10 -6.
0 0
-Th in cc chun : Cu 2
/ Cu
= 0,34 V ; Fe 3
/ Fe 2
= 0,77V.
-Nhit to thnh chun v entropi chun ca mt s cht :
0 -1 -1 0 -1 -1
Cht H0298K(kJ.mol-1 ) S 298K(J.mol .K ) Cht S 298K(J.mol .K )
H2O (h) - 241,6 188,52 H2 (k) 130,42
CuO (r) - 156,75 43,47 Cu (r) 33,44
CaO (r) - 634,11 39,71 Ca (r) 41,8
Fe2O3 (r) -829,73 89,87 Fe (r) 27,17
91 HA I CNG 2
TI LIU THAM KHO
1. V ng . C s l thuyt cc qu trnh ha hc. NXB Gio dc - 1994

2. Nguyn Hnh. C s l thuyt ha hc, phn 2. NXB Gio dc HN 1995.
3. Trn Vn Nhn - Nguyn Thc Su - Nguyn Vn Tu. Ha l, tp I. NXB Gio dc
1996.
4. ng Trn Phch. Ha c s, tp 2. NXB Gio dc 1990
5. Nguyn nh Soa. Ha i cng, tp 2. Trng H Bch Khoa TP HCM, 1989.
6. Chu Phm Ngc Sn. C s l thuyt HC, phn 2. HKH T nhin TP HCM.
7. Farrington Daniels - Robert A. Alberty. Ha l, tp I. NXB i hc v trung hc
chuyn nghip HN 1979. (Ngi dch Phm Ngc Thanh - Nguyn Xun Thng)
8. Ren Didier. Ha i cng, tp mt. NXB Gio Dc 1997. (Ngi dch Nguyn
nh Bng - V ng - L Ch Kin - Trn Ngc Mai - Phan Vn Tng)
9. L. Nicolaiev. Chimie Moderne. Editions Mir Moscou 1981
10. Glinka. General Chemistry, vol 1. Mir Publishers Moscow 1981
92

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y l chng khi u ca hc phn l thuyt cc qu trnh ha hc.

1.1.MT S KHI NIM C BN :

- Nu s bin i l bt thun nghch : lc y p n p k v thng p n = p kq= const

Vi pkq l p sut kh quyn.

1.3.NGUYN L TH NHT CA NHIT NG HC V MT S I LNG

Qp = U2 - U1 + pV2 - pV1 = (U2 + pV2) - (U1 + pV1) Qp = (U + pV)2 - (U + pV)1

Khi p = const th H = U + pV hay vit cch khc : Qp = Qv + pV (8)

Vy s gin n ca kh trong chn khng, khng cung cp cng.

1.3.4.5.Kh l tng bin i ng p :

hay A = -(n2RT2 - n1RT1), nu ngoi ng p cn ng nhit th A = -RT n

Th d 3 : Cho 10 lt kh He 0 oC v 10atm. Hy xc nh th tch cui v cng do h

M A = U = nCV(T2 - T1) = 4,46.12,586(108,5 - 273) = -9234J

Ho = 2 (-393,129) - (-565,47) = - 220,788kJ

H3 = (aC p A bC pB )dT (aC pA bC pB )dT v H4 =

Vy : HT2 = HT1 + (eC pE fC pF - aC pA bC pB )dT

Th d : Tnh Ho1100K ca phn ng : CaCO3(r) CaO(r) + CO2(k). Bit :

Gii : Ho298K = Ho298K (CaO) + Ho298K (CO2) - Ho298K (CaCO3)

T2 = 1100, t tnh c Ho1100K theo Kirchoff : Ho1100K = Ho298K + C P dT

Nu qu trnh l thun nghch, on nhit : dS = S = 0

T dS = Q . Ly tch phn 2 v trong iu kin ng nhit ta c : S Q . Tu trng

Gii : iu kin ng nhit nn S Q 6002,5 21,987J.mol-1.K-1.

Qu trnh thun nghch ng p :

c) Qu trnh thun nghch ca kh l tng :

1.5.4.2.Qu trnh thun nghch (S bin i theo T)

Th d : So 298 K ( H 2 0 ) = 69,89J.mol-1.K-1. Nhit dung mol ng p Cp(H2O) = 75,24J. mol-1.K-1

Gii : S = S o 298 K S o 273 K

S o 273 K S o 298 K - S = 69,89 - 6,59 = 63,3J.mol-1.K-1

S = (e.SE + f.SF) - (a.SA + b.SB)

1.6.TH NG NHIT, NG P. CHIU HNG DIN BIN CA QU TRNH.

Vy : G = H - TS (trong iu kin ng nhit). G gi l bin thin th ng

1) Xc nh chiu ca phn ng 298K.

y l phng trnh c bn v tng qut ca nhit ng ha hc. i c gi l th

Phng trnh ny dng tnh th ng nhit ng p GT2 nhit T2 theo th ng nhit

Nu p1 = 1atm GTp - GoT = RT ln p (*)

1) a) Mt bin i theo chu trnh kn ca kh l tng vi A = 418 J. Tnh Q ?

C P0 ( H 2O r ) =35,53J.mol-1.K-1; C P0 ( H 2O l ) =75,24J.mol-1.K-1; C P0 ( H 2O h) = 30 + 4,18.10-3T.J.mol-1.K-1

Tnh H0 ca phn ng trn 673K

2.1.KHI NIM V CN BNG HO HC :

* Nu ta vit ngc li : eE + fF aA + bB. C hng s cn bng K'. Th t :

2.3.PHNG PHP XC NH HNG S CN BNG :

Go ca phn ng c xc nh nh h qu ca nh lut Hess.

2.4.QUAN H GIA BIN THIN TH NG P, NG NHIT V HNG S

2.5.CC YU T NH HNG N CN BNG HA HC, NGUYN L LE

2.6.CN BNG PHA :

H =37778,84 J.mol . Vy nhit ha hi ca 1 gam ru etylic l: 37778,84 821,28 J.g-1

7) NOCl b phn hu theo phn ng : 2NOCl(k) 2NO (k) + Cl2 (k). Lc u ch c

3.1.MT S KHI NIM :

3.2.NH HNG CA NNG CC CHT PHN NG N TC PHN

3.3.XC NH HNG S TC V BC PHN NG :

* Khi nng u cc cht bng nhau : A + B sn phm

3.4.NH HNG CA NHIT N TC PHN NG :

V d : Nu phn ng 0 oC c vn tc v th 100 oC tc phn ng tng ln bao

Vy khi = 3, t 00C tng ln 100 0C vn tc tng ln 59049 ln.

3.5.THUYT VA CHM HOT NG V THUYT PHC CHT HOT NG

3.6.NH HNG CA CHT XC TC N TC PHN NG :

[Br2]ban u 0,05 0,01 0,03 0,0075 0,02

Thng thng cc cht di dng hn hp. Nhiu khi di dng hn hp li c nhiu ng

4.2.S HNH THNH CC LOI DUNG DCH :

4.4.3.p sut thm thu :

4.5.DUNG DCH CHT IN LY :

dch H2SO4 b hn tan ca n trong nc nguyn cht (S = T SrSO4 3,6.10 7 6.10 4 ) v b

4.11.S TO PHC TRONG DUNG DCH :