Dung dch ca cc cht in li

I- S in li ca cc axit, baz v mui trong dung dch 1. in li s mol cht tan phn li = tng s mol cht tan AnBm n Am+ + nBn ph thuc vo nng dung dch. Nng dung dch cng ln th in li cng nh. Ngay c vi cc ht in li mnh khi l dung dch long l cht in li hon ton nhng vi dung dch c th li ch in li 1 phn. Do khng nh gi ng mnh yu ca cht in li. 2. Hng s in li K=

[ A ] [B ]
m+ n

n m

[ An Bm ]

- vi nhng axit mnh, baz mnh l nhng cht in li hon ton nn ta khng dng khi nim cn bng in li - vi nhng a axit, a baz xy ra theo nhiu nc. Mi nc c c trng bi mt hng s in li ring VD: H3PO4 H+ + H2PO4; K1 = 7,5. 10-3 H2PO4- H+ + HPO42; K2 = 6,3. 10-8 HPO42- H+ + PO43; K3 = 1,3. 10-12 H3PO4 3H+ + PO43; K = K 1 . K2 . K3 K ph thuc vo nhit v bn cht ca cht in li * Mi lin h gia K v AmBn mAn+ + nBmt=0 C 0 0 tcb C(1- ) mC nC K =

[ mC ] m [ mC ] n
C (1 )

m n .n m .C m +n 1 . m +n 1

Vi cht in li yu : << 1 K = m n .n m .C m +n 1 . m +n 3. S in li ca nc H2O H+ + OHK

[H ][ . OH ]
+

[ H 2O]

K . [H2O] = K H

2O

= [H+].[OH-] = 10-14

298K [H ] = [OH-] = 10-7 (M) K H O ch ph thuc vo nhit 298K - vi dung dch axit: H+ c to thnh t 2 ngun: s phn li ca H2O v axit nn [H+] > 10-7
+
2

- vi dung dch baz: OH-c to thnh t 2 ngun: s phn li ca H2O v baz nn [OH-] > 10-7 [H+] < 10-7 * Qui c: pH = - lg[H+] - Nc ct: pH = 7 - dung dch axit : pH < 7 - dung dch baz : pH > 7 pH l i lng n gin c trng cho tnh cht axit baz ca cc dung dch II- Mt s quan im hin i v axit v baz

A- Thuyt proton ca Bronstet

a) nh ngha - Axit l phn t c kh nng cho proton HA H+ + A- Baz l phn t c kh nng nhn proton B + H+ BH+ VD: NH3 (k) + HCl(k) = NH4Cl (r) - Phn ng axit-baz l nhng phn ng ho hc trong c s cho v nhn proton b) H qu - Khi nh ngha axit HA vi: HA H+ + Ath ngc li: A- + H+ HA Vy A l mt baz lin hp ca axit HA ( k hiu HA/A- ) VD: CH3COOH CH3COO- + H+ CH3COO- l baz lin hp ca CH3COOH - Tng t, khi baz B nhn proton n to thnh BH+ B + H+ BH+ BH+ B + H+ BH+ gi l axit lin hp ca baz B Cc cp HA/A- v BH+/B gi l cp axit-baz lin hp, trong HA v BH + l dng axit cn A- v B l dng baz ca cp axit tng ng - Phn ng gia dung dch axit v dung dch baz HA + B BH+ + AAxit 1 baz 2 axit 2 baz 1 Phn ng xy ra theo chiu t tri sang phi khi axit 1 mnh hn axit 2 v baz 2 mnh hn baz 1 VD: NH3 + CH3COOH CH3COO+ NH4+ - Vai tr ca nc trong cc dung dch axit v baz + Vi axit HA + H2O H 3O + + AAxit 1 baz 2 axit 2 baz 1 + Cc cp axit v baz lin hp l HA/A ; H3O /H2O KHA =

[ H O ][ .A ]
3 +

[ HA]

( hng s axit )

+ Vi baz: B

+ H 2O BH+ + OHBaz 1 axit 2 axit 1 baz 2 + Cc cp axit v baz lin hp l BH /B v H2O/OH* Kt lun: trong quan h vi cc axit H2O ng vai tr l mt baz, trong quan h vi cc baz nc ng vai tr l mt axit nc l mt cht lng tnh Trong nc nguyn cht c qu trnh phn li 2H2O H3O+ + OHK H O = [H3O+]. [OH-] = 10-14 - i vi mt cp axit v baz lin hp: HA + H2O H3O+ + A2

KHA = A-

[ H O ][ A ]
3 +

[ HA]

+ H2O HA + OH[OH-].[HA] KB(A-) = [A-] KHA. K(A-) = [H3O+].[OH-] = Kw Vy vi mi cp axit baz lin hp u c : pKa + pKb = pKw = 14 * Nhn xt: Nu axit cng mnh th baz lin hp cng yu v ngc li

B- Thuyt electron ca Lewis

a) nh ngha + Axit l nhng phn t c kh nng nhn cp electron + Baz l nhng phn t c kh nng cho cp electron b) H qu - Cc axit, baz Areniuyt v Bronstet u nm trong phm vi cc axit, baz Lewis VD: Theo Areniuyt: H+ + OH- H2O Lewis: H+ + :OH- H:O:H Theo Bronstet: H+ + NH3 NH4+ Lewis: H+ + :NH3 NH4+ C phn ng khng c s trao i proton cng thuc loi phn ng axit-baz F3B + :NH3 = F3B:NH3 * u im : c tnh khi qut cao, n bao trm mt phm vi rng ln * Nhc im: Khng cho php nh gi nh lng c mnh yu ca cc axit-baz III- Tnh pH ca mt s dung dch

1. Vi dung dch axit

a) Vi dung dch axit mnh -Cc axit mnh in li hon ton trong dung dch HnX + nH2O = nH3O+ + X-

Ban u C 0 0 [ ] 0 nC C + [H3O ] = nC pH = -lgnC b) Vi dung dch axit yu in li b, nng [H3O+] do axit phn li b khng b qua c nng [H3O+] do axit phn li ra. Phi xt tt c cc cn bng tn ti trong dung dch HA + H 2O H3O+ + AKa = [H3O+].[A-]/[HA] (1) H2O + H2O H3O+ + OHKH 2 O = [H3O+].[OH-] (2) - Theo nh lut bo ton khi lng: C = [HA] + [A-] - Phng trnh bo ton in tch: [H3O+] = [A-] + [OH-] Gii h 4 phng trnh tm [H3O+] pH dung dch * Cch tnh gn ng: 1) Vi axit khng qu yu, nng axit khng qu nh: b qua s in li ca nc [H3O+] = [A-] 2) Axit yu nn in li b: << 1 C = [HA] Ka = [H3O+]2/C K a .C hay [H3O+]2 = Ka. C [H3O+] = pH = (1/2)pKa (1/2)lgC VD1: Tnh pH ca dung dch CH3COOH 0,1M bit pKa = 4,75 S: pH = 2,9 VD2: Tnh pKa ca dung dch NH4Cl 0,1M bit pH ca dung dch ny pH = 5,1 *Ch : - Gi tr pH thng ch ly 1 s l sau du phy - Vi a axit yu, nc phn li sau yu hn mc phn li trc rt nhiu, nn thng coi chng l nhng n axit ch tnh n nc phn li th nht VD: Tnh pH ca dung dch H2S 0,1 M H2S H+ + HSK1 = 10-6,96 HS- H+ + S2K2 = 10-15 S: pH = 4

2. Dung dch baz:

a) Vi baz mnh: M(OH)n = Mn+ + nOHpH = 14 + lgnC b) i vi baz yu B ( nhng khng qu yu c th b qua s phn li ca nc)

B + H 2O BH+ + OHC [OH-] K b .C [OH-] = [BH+] = pOH = (1/2)pKb - (1/2)lgC pH = 14 (1/2)pKb + (1/2) lgC VD: Tnh pH ca dung dch NH3 0,01M cho pKNH 4 = 9,24 V NH3 l baz lin hp ca NH4+ nn: pKb = 14 pKNH 4 = 14 9,23 = 4,77 pH = 10,6 VD2: Tnh pH ca dung dch CH3COONa. Cho pKa = 4,75 S: pH = 8,9
+ +

3. Dung dch hn hp: Axit v baz lin hp ca axit hay baz v axit lin hp ca baz . Dung dch m

a) VD1: dung dch cha ng thi 1 axit yu HA nng Ca v baz lin hp A- ca n di dng mui nng Cm = Cb HA + H2O H3O+ + AKHA Ban u CHA CA [ ] CHA-x x CA- + x KHA =
x(C A + x) (C HA x)

Gii ra x pH * Nu << 1 ( axit in li yu) x << CHA, CA KHA = x.CA/ CHA x = KHA. CHA/CA pH = - pKa lg (CHA/CA-) b) VD2: Vi dung dch hn hp baz yu v mui ca n vi axit mnh B v BH+ tng t : pOH = pKBH+ - lg (CBH+ / CB) pH = 14- pKBH+ + lg (CBH+ / CB) * Nhn xt: Vy pH ca cc dung dch hn hp ph thuc vo t l nng ca dng axit v baz ca cp axit-baz tng ng.Nu thay i t l ny ta thu c cc dung dch c pH khc nhau. c) Dung dch m - Gim s bin ng pH ca dung dch khi thm axit v baz vo dung dch VD: dung dch hn hp gm CH3COOH 0,1 M v NaCH3COO 0,1 M. pH ca dung dch ny l 4,75 Nu thm HCl (k) vo dung dch ny sao cho nng ca HCl t n 0,01 M th pH ca dung dch l bao nhiu ? Gii Khi cho HCl vo dung dch nng H3O+ tng. Cn bng CH3OOH + H2O H3O+ + CH3COOs chuyn dch v bn tri Gi s ton b lng H3O+ thm vo kt hp vi CH3COO- to thnh CH3COOH, ta c:

[CH3COOH] = 0,11 (M) [CH3COO-] = 0,09 (M) pH = 4,67 bin ng v pH l: pH = 0,08 n v * Nu thm lng axit tng t vo nc nguyn cht (pH=7) th pH ca dung dch thu c l pH = 2 pH = 5 v * Nu thm 0,01 mol NaOH vo 1 lit dung dch trn th CH 3COOH b trung ho bi NaOH khi : [CH3COOH] = 0,09 (M) [CH3COO-] = 0,11 (M) pH = 4,83 d) Kt lun: Cc h dung dch m HA/A- gi l cc h m axit dng iu chnh pH trong vng <7 Cc dung dch m BH+/B gi l cc h m baz dng iu chnh pH trong vng > 7 * Vai tr ca dung dch m: - Duy tr pH i vi nhng phn ng ho hc nht nh - Cc phn ng sinh ha trong c th ch c thc hin khi c duy tr trong mt gii hn nht nh ( rt hp ) VD: pH mu ( 7-7,9 ) pH nc bt ( 6,8 ) pH d dy ( 2,6 1,8 )

Tch s tan
I- Tch s tan
- Ho tan dn dn mt cht rn vo nc n mt lc no cht rn khng th tan thm c na, tc t ti gi tr tan v dung dch thu c lc gi l dung dch bo ho. - Khi dung dch bo ho, nu thm tip cht tan vo th gia cht tan v cc phn t cht trong dung dch thit lp mt cn bng ho hc : c bao nhiu phn t cht tan vo dung dch trong mt n v thi gian th c by nhiu phn t cht tan kt ta trn b mt cht rn * Vi cht in li kiu AnBm ta c cn bng: AmBn mAn+ + nBmHng s cn bng c biu din bng biu thc: [An+]m . [Bm-]n K=

[AmBn] V AnBm l cht rn nn ta coi [AnBm] l n v nhp vo vi hng s K thu c mt hng s mi gi l tch s tan T K.[AnBm] = [Am+]n. [Bn+]m = T trong biu thc tnh tch s tan, tt c nng cc ion u biu din theo mol/l

II- Tnh tch s tan theo tan ca mt cht: S ( mol/l)

AmBn mAn+ + nBmS mS nS m+ n n+ m n T = [A ] . [B ] = [nS] .[mS]m = nn. mm.Sn+m VD1: Tnh T ca CaSO4 bit tan ca ca CaSO4 200C bng 1,5. 10-2 mol/l. S: T = 2,25. 10-4 VD2: Bit T ca BaSO4 bng 10-10. Hi trong 100 ml dung dch bo ho BaSO4 c bao nhiu gam BaSO4. S: S = 10-5 mol/l = 0,233 g/ml * Ch : Khi tch nng cc ion thnh phn kt ta bng tch s tan ta c dung dch bo ho, nu ln hn tch s tan s to thnh kt ta, cn nu tch s nh hn tch s tan s khng c kt ta VD3: Trn 100 ml dung dch Pb(NO3)2 0,02 M vi 100 ml dung dch Na2SO4 0,02 M. Bit T ca PbSO4 = 2.10-8. Hi c bao nhiu gam PbSO4 kt ta v nng ca cc ion cn li trong dung dch sau phn ng. Nu nng ban u ca dung dch Na2SO4 l 0,1 M th nng Pb2+ trong dung dch sau phn ng l bao nhiu? S: mPbSO 4 = 0,617 (g) 2+ [SO 2 ] = 1,4.10-4 (M) 4 ] = [Pb [Pb2+] = 5.10-7 (mol/l)

III- Nhng yu t nh hng ti tan ca kt ta

1. nh hng ca ion chung - Ion chung l ion c trong thnh phn ca kt ta. Nu thm ion chung vo dung dch bo ho ca kt ta , tch s ion s ln hn tch s tan cn bng s chuyn dch v pha to thm kt ta, do lm gim tan ca n VD: Tnh tan ca PbSO4 trong nc nguyn cht: PbSO4 Pb2+ + SO42Ta c tan ca PbSO4 l : S = TPbSO = 1,6.10 = 1,26. 10-4 (M) - tan ca PbSO4 trong dung dch Na2SO4 10-2M Gi tan ca PbSO4 trong dung dch l S th Na2SO4 = 2Na+ + SO4210-2 10-2 PbSO4 Pb2+ + SO42Ban u S 0 10 -2 Cn bng 0 S 10 -2 + S
8
4

 T PbSO = [Pb2+].[SO42-] = S ( S + 10-2) Gi s S << 10-2 T PbSO = S. 10-2 = 1,6. 10-8 S = 1,6.10-6 (M) Vy tan ca PbSO4 trong dung dch Na2SO4 nh hn nhiu so vi tan trong nc nguyn cht 2. nh hng ca pH n tan ca kt ta tan ca kt ta s tng ln nu cc ion sinh ra c tham gia cc phn ng ph vi cc cht l c mt trong dung dch. phn nh c cc nh hng ca cc phn ng ph ngi ta dng tch s tan iu kin (T') Phng php tnh tch s tan iu kin v tan S ca kt ta trong iu kin c xy ra phn ng ph ca ion vi H +: AnBm nAm+ + mBnTAB m+ Gi s A khng tham gia phn ng ph, ch c Bn- tham gia phn ng vi ion H+ Bn- + H+ HB 1-n K1-1
4
4 n m

HB1-n + H+ H2B2-n K2-1 .. Gi [B'] l tng nng ca cc dng tn ti ca B [Bn-] l nng ca Bn- t do lc cn bng Gi S l tan ca AnBm AnBm nAm+ + mB' S nS mS m+ n m n m T' = [A ] .[B'] = (nS) .(mS) = nn.mm.Sn+m Khi : [B'] = [B ] +
n-

[B ][ .H ]
n +

= [Bn-] ( 1+ T' = [A
m+ n n- m

[H ]
+

K1

+
+ 2

[B ][ .H ]
n

+ 2

K1

+
+

[H ]
+

K 1 .K 2

+ +
+ n

[B ][ .H ]
n

+ n

] . [B ] . ( 1+

[H ]
K1
+ 2

K 1 .K 2

+ +

[H ]

K 1 ....K n

[H ]

K 1 ....K n

) )m

+ 2

= T. ( 1+ S=
n +m

[H ]
+

K1

[H ]

K 1 .K 2

+ +
+ n

[H ]

+ n

K 1 .K 2

+ +

[H ]

K 1 ....K n

K 1 ....K n

)m = nn.mm.Sn+m

T' n .m m
n
2

VD: Tnh tan ca CaF2 trong dung dch HCl 10-2M Cho KHF = 6.10-4 v T CaF = 4.10-11 Gii: CaF2 Ca2+ + 2FCa2+ khng tham gia phn ng ph, nn nu gi tan ca CaF 2 trong HCl l 10-2 M l S th : [Ca2+] = S Cn F- tham gia phn ng ph:

H+ + F- HF ; KHF = [H+].[F-]/[HF] Do : [F'] = [F-] + [HF] = [F-]. ( 1 + [H+]/KHF) T' = 4S3 = [Ca2+]. [F-]2. ( 1 + [H+]/KHF)2 = T. ( 1 + [H+]/KHF)2 S = 5,5.10-3 ( mol/l) 3. nh hng ca nhit - Tu qu trnh ho tan l to nhit hay thu nhit m s thay i nhit s lm tng hay gim tan ca mt cht kt ta - Ni chung tan ca cc cht ph thuc vo nhit khng c qui lut nn khng c nhng biu thc nh lng chung. 4. nh hng ca kch thc cc ht kt ta - Cc ht kt ta cng nh th kh nng ho tan cng d. Ngoi ra tan ca mt cht cn ph thuc vo mng li tinh th ca cht c sp xp nh th no. 5. nh hng ca cc cht trong dung dch c th to phc vi cation kim loi ca cht kt ta VD: Kt ta AnBm trong dung dch c ion A c kh nng to phc vi cht to phc L c trong dung dch: Trong dung dch c cc cn bng: AnBm nAm+ + mBnTAB A to phc vi L: A + L AL 1 = k 1 AL + L AL2 k2 AL2 + L AL3 k3 ALn-1 + L ALn kn B khng c qu trnh ph Gi S l tan ca kt ta [A] l nng ca A lc cn bng [B] l nng ca B lc cn bng [A'] l nng tt c cc dng tn ti ca A tr trong kt ta th: [A'] = nS = [A] + [AL] + [AL2] + .+ [ALn] Tnh nng ca cc dng phc ca A theo [A] [AL] = 1. [L].[A] [AL2] = 2. [A].[L]2 ( 2 = k1.k2 ) .. [ALn] = n. [A].[L]n (n = k1.k2.kn) 2 [A'] = [A]. (1 + 1.[L] + 2.[L] + . + n.[L]n) = [A]. -1A(L) T' = [A']n.[B]m = (nS)n.(mS)m = nn.mm.Sn+m ( T' gi l tch s tan iu kin) = [A]n. -nA(L) . [B]m = T. -nA(L)
n m

S=

n +m

T' = n n mm

n +m

T n n m .A ( L)
n m

VD: Tnh tan ca AgCl trong dung dch NH3 lun c duy tr l 10-3 mol/l . Bit TAgCl = 10-10 1 = 103,2, 2 = 107, TAg2O = 10-15,4 Gii: AgCl Ag+ + ClTAgCl + + + 2Ag + H2O Ag2O + 2H Ag = 10-13,6 Ag+ + NH3 AgNH3+ 1 + + Ag + 2NH3 Ag(NH3)2 2 + Gi [Ag '] l tng nng ca cc dng tn ti ca Ag+ [Ag+'] = [Ag+]. ( 1 + 1. [NH3] + 2.[NH3]2 + 1/2Ag+) = [Ag+]. ( 1 + 103,2-3 + 107-6 + 10-6,8) = 12,6 . [Ag+] T' = S2 = 12,6.[Ag+].[Cl-] = 12,6. TAgCl = 12,6.10-10 S = 12,6.10 = 3,55.10-5 mol/l
10

IV. Kt ta phn on

Nu trong dung dch c cha hai hay nhiu ion c kh nng to c kt ta vi cng mt ion khc, nhng cc kt ta hnh thnh c tan khc nhau nhiu th khi thm ion c kh nng to kt ta vi cc ion trong dung dch vo th cc kt ta ln lt c hnh thnh. Hin tng to thnh ln lt cc kt ta trong dung dch c gi l kt ta phn on. Nu cho thuc th A vo dung dch c cha hai ion kim loi M v N ( n gin ta khng ghi in tch cc ion) cng to c MA v NA M + A MA (1) N + A NA (2) Th th t xut hin cc kt ta ph thuc quan h gia nng ca cc thuc th v tch s tan ca cc kt ta Gi thit CM = C1, CN = C2; T (MA) = T1; TNA = T2 th + iu kin c kt ta MA xut hin l: CA(1). C1 T1 CA(1) T1/C1 (*) + iu kin c kt ta NA xut hin l: CA(2). C2 T2 CA(2) T2/C2 (**) Nu CA(1) < CA(2) kt ta MA s xut hin trc. Sau , khi nng M gim xung n mt mc no th c hai kt ta cng xut hin khi thm thuc th A Lc kt ta NA bt u tch ra th: [A] =
T2 C2

T1 [M ]

[M] cn li l: [M] = C2. T 2 Nu [M] 1/1000 CM th c th coi M c kt ta hon ton VD1: Trong mt dung dch c cha cc ion I- 0,01 M, ion Cl- 1M. Bit TAgI = 10-16, TAgCl = 10-10. C th kt ta ln lt cc ion I- v Cl- bng Ag+ c khng?

T1

Gii: Trong dung dch xy ra cc qu trnh: AgNO3 = Ag+ + NO3KCl = K+ + ClKI = K+ + IAg+ + I- AgI TAgI = 10-16 Ag+ + Cl- AgCl TAgCl = 10-10 Phn ng xy ra trong cng mt dung dch nn: [Ag +] l chung cho c 2 qu trnh. Vy: TAgI = [Ag+].[I-] = 10-16 TAgCl = [Ag+].[Cl-] = 10-10 [I-]/[Cl-] = 10-16/10-10 = 10-6 [I-] = 10-6.[Cl-] khi nng ca [I-] > 10-6.[Cl-] th AgI tip tc kt ta cn kt ta AgCl cha xut hin. Ch n khi [I-] = 10-6.[Cl-] th mi bt u xut hin kt ta AgCl Khi bt u xut hin kt ta AgCl th nng ca I- l : [I-] = 10-6 . 1 = 10-6 (M) [I-] / CI_ = 10-6/10-2 = 10-4 < 10-3 c th coi I- b kt ta ht th mi c AgCl xut hin C th kt ta ln lt cc ton I- v Cl- bng Ag+ VD2: Tnh nng ion Cl- cn li trong dung dch khi thm AgNO3 vo dung dch hn hp gm 10-2 mol/l Cl- v 10-2 mol/l CrO42- cho TAgCl = 10-10, TAg 2 CrO 4 = 10-12 Gii : TAgCl = [Ag+].[Cl-] = 10-10 TAg 2 CrO 4 = [Ag+]2.[CrO42-] = 10-12 Khi thm AgNO3 vo th Ag2CrO4 bt u kt ta khi: [Cl-]2 = [CrO42-].T2AgCl/ TAg 2 CrO 4 = 10-2 . 10-20/10-12 = 10-10 [Cl-] = 10-5 M [Cl-]/CCl_ = 10-3 c th coi khi Ag2CrO4 bt u kt ta th ion Cl- kt ta ht ri * Nhn xt: Khi trong dung dch c 2 hay nhiu ion A, B, C, cng to kt ta vi ion tri du M th ion no i hi nng ion M nh nht t ti gi tr tch s tan ca n th ion kt ta u tin