pH

1. TNG QUAN :
pH l mt thut ng c s dng kh rng ri din t axit hoc kim ca mt dung dch. N l mt cch din t nng ion hydro, hay chnh xc hn, l hot ion hydro. pH l mt thng s quan trng trong hu ht mi lnh vc mi trng. Trong lnh vc cp nc, n lin quan n vn keo t, kh trng, lm mm nc, v kim sot tnh n mn. Trong lnh vc x l nc thi bng cc qu trnh sinh hc, pH phi c kim sot trong mt phm vi thch hp cho hot ng ca vi sinh vt. Trong cc qu trnh ha hc c s dng keo t nc thi, tch nc khi bn thi, hoc oxy ha cc hp cht no (v d nh ion xyanua), pH phi c kim sot trong mt gii hn kh hp. V nhng l do ny v v mi lin h gia pH v tnh axit-baz, chng ta cn phi thng hiu kha cnh l thuyt cng nh thc t ca vic o pH.

2. L THUYT :
Khi nim pH ra i t mt chui cc pht hin dn n s hiu bit y hn v cc axit v baz. Lc u, cc axit v baz c phn bit bi v ca chng, sau bi nh hng ca chng ln mt s cht no c gi l cht ch th. Cng vi s pht hin ra hydro vo nm 1766, ngi ta bit rng mi axit u cha nguyn t hydro. Chng bao lu sau, cc nh ha hc tm thy rng cc phn ng trung ha gia axit v baz lun lun sinh ra nc. T pht hin ny cng vi mt s thng tin khc, ngi ta kt lun baz cha nhm hydroxyl. Nm 1887, thuyt ion ha ca Arrhenius ra i. K t , axit c xem l cc cht m khi phn ly chng sinh ra ion hydro, v baz l cc cht m khi phn ly chng sinh ra ion hydroxyl. Theo thuyt ion ha, axit mnh v baz mnh s b ion ha mnh, cn axit yu v baz yu s b ion ha km hn trong dung dch nc. Lun im ny ch c kim chng khi ngi ta ch to c cc thit b o nng ion hydro.

o nng ion hydro :

S dng in cc hydro o nng ion hydro, ngi ta thy rng nc tinh khit c phn ly cho nng ion hydro bng 10-7 mol/L 25oC H2O H+ + OH(1)

Hng s cn bng ca phn ng phn ly :

[H ] [OH ]
+

[ H 2 O]

= K

(2) 1

Do nng ca nc l rt ln v b gim khng ng k do s phn ly, nn c th xem n l hng s. Khi , phng trnh (2) c th vit li thnh : [H+][OH-] = KW (3)

KW c gi l tch s ion hoc hng s ion ha ca nc, n l hng s mt nhit xc nh. V mt phn t nc phn ly to ra mt ion hydro v mt ion hydroxyl, nn hin nhin nng ca ion hydroxyl cng bng 10-7 mol/L 25oC. Th vo phng trnh (3), ta c tch s ion ca nc 25oC KW = [H+][OH-] = 10-7 x 10-7 = 10-14 (4)

Khi mt axit c thm vo nc, n ion ha lm cho nng H+ tng ln. Do tch s ion ca nc l hng s nn nng OH- phi gim xung m bo tun theo phng trnh (4). V d, nu axit c thm vo sao cho nng H + tng ln 10-1 th khi nng OH- gim xung cn 10-13. Ngc li, nu mt baz c thm vo nc sao cho nng OH - tng ln 10-3 th nng H+ s gim xung cn 10-11. Cn ch rng nng OH- hoc H+ khng bao gi gim xung bng khng, bt k lng axit hoc baz thm vo dung dch

Khi nim pH :
Vic din t nng ion hydro theo n v mol/L l kh bt tin. khc phc kh khn ny, nm 1909, Sorenson ngh din t di dng logarit m v k hiu l pH. Theo nh ngha ca Sorenson : pH = - log [H+] (5)

v thang pH thng chy t 0 n 14, vi pH 7 l im trung ha

Vng axit 0 7

Vng baz 14

Thang pH Tnh axit tng khi pH gim, v tnh kim tng khi pH tng. Do tng tc ion trong dung dch, ta cn phi dng hot ion thay cho nng mol. Khi phng trnh (5) vit li thnh : pH = -log aH+.

3. O pH :
C hai cch o pH Dng ch th mu (phng php gn ng) : Mt s ha cht, ch yu l cc hp cht hu c, c kh nng i mu ty theo pH ca dung dch. Ngi ta nghin cu khong pH i mu ca cc ha cht ny nh trong bng 1 Bng 1 : Tnh cht ca mt s cht ch th mu Cht ch th Methyl violet Malachite green (axit) Thymol blue (axit) Methyl orange Bromcresol green Methyl red Litmus Bromthymol blue Phenol red Thymol blue (kim) Phenolphthalein Thymolphthalein Alizarin yellow Malachite green (kim) Mu axit Vng Vng Vng Vng Vng Vng Khng mu Khng mu Vng Xanh l cy Mu baz Tm Xanh l cy-Xanh dng Vng Cam-Vng Xanh dng Vng Xanh dng Xanh dng Xanh dng Xanh dng Hoa c Khng mu Khong pH i mu 02 0 1.8 1.2 2.8 3.1 4.6 3.8 5.4 4.4 6. 2 4.5 8.3 6.0 7.6 6.8 8.4 8.0 9. 6 8.2 9.8 9.3 10.5 10.1 11.1 11.4 13.0

Bng cch s dng kt hp t 6 8 cht ch th, ta c th xc nh kh chnh xc gi tr pH. Dng in cc o pH : in cc hydro : l in cc chun tuyt i o pH. in cc hydro l mt bn platin c ph platin xp (bng phng php in phn) nhng trong dung dch c hydro i qua vi p sut 1 atm. Th ca in cc ny bng :
E= 2,303 RT lg H + F

trong , R = 8,314 J/(mol.K) l hng s kh T l nhit tuyt i F = 9,649.104 l hng s Faraday [H+] l nng ion hydro trong dung dch Theo phng trnh ny ta thy th in cc t l thun vi pH Trn thc t ngi ta rt t khi dng in cc hydro o pH v s phc tp cng nh kh nng thch ng ca n. Thay vo ngi ta dng in cc thy tinh in cc thy tinh : 3

Khong nm 1925, ngi ta khm ph ra mt in cc ch to bng thy tinh c th sinh ra th in cc t l vi nng ion hydro m khng b nh hng bi hu ht cc loi ion khc. Vic s dng n nhanh chng tr thnh phng php tiu chun o pH. Phn nhy ca in cc l mt bu bng thy tinh c tnh cht c bit v thnh phn cng nh dy. Cht in ly bn trong in cc thng l dung dch HCl c nng c nh. Khi nhng in cc vo dung dch, mt ngoi ca bu thy tinh b hydrat ha, v s trao i gia ion Na + v ion H+ to nn mt lp ion hydro trn b mt. Lp ion ny tng tc vi cc silicat tch in m to nn mt th in cc t l vi nng H+ trong dung dch. in cc thy tinh thng c s dng km vi mt ic cc qui chiu (in cc calomen), hoc loi in cc kt hp. mt nhit khng i no , th in cc sinh ra thay i tuyn tnh theo pH. Ngi ta dng ng chun biu din s ph thuc ca n vo gi tr pH ca cc dung dch m chun. pH ca mu c xc nh da theo ng chun ny. S thay i ca th in cc trn mt n v pH c gi l dc (slope) ca in cc. dc ca in cc tng theo nhit . 25oC dc ca in cc khong 60 mV. nh hng ca nhit ln php o pH ph thuc vo in cc qui chiu, pH ca dung dch bn trong in cc v pH ca dung dch mu. Tuy nhin, c tn ti mt gi tr pH m th in cc khng b nh hng bi nhit . Gi tr pH ny c gi l im ng th (isopotential point) v th in cc tng ng c gi l im khng ca in cc. Thng thng cc nh sn xut thit k in cc sao cho im ng th l pH 7,0 v im khng l 0 mV. dc v im ng th (hay im khng) l hai thng s quyt nh cht lng ca in cc c cn tt s dng hay khng. Chun my o pH : Vic chun my o pH thng c thc hin vi mt dung dch c pH 7 v mt dung dch c pH 4 hoc 9 (tu theo pH ca dung dch mu)
Th in cc, mV

Khi chun vi pH 7, my o s xc nh im khng ca in cc.

+500

Khi chun vi dung dch pH 4 hoc 9, my o s xc nh dc ca in cc. -500 0 7

Kim sot im khng, pH

14

Th in cc, mV
+500

100oC (74 mV/1 pH) 50oC (64 mV/1 pH) 0oC (54 mV/1 pH)

0 Ghi li cc gi tr im khng v slope vo phiu theo di my o pH o pH ca mu : Chn chc nng o pH trn my. -500 Chun b hai cc mu. Nhng in cc sch v kh vo cc 1. n START. 0 7 14 i vi mu c tnh m cao hoc hm lng mui ha tan cao, ngm in cc trong cc 1 mt pht, sau nhng Kimcc vo cc 2pH c gi tr pH trn mn hnh. in sot dc, v i vi mu c tnh m thp hoc hm lng mui ha tan thp, nhng in cc vi ln vo cc 1, sau nhng in cc vo cc 2 v c gi tr pH trn mn hnh. Trong qu trnh o pH, nn khuy tht nh mu bng c t m bo ng nht mu. Tuy nhin, i vi cc mu nc tinh khit ( dn in thp) th khng nn khuy v CO2 t khng kh c th b hp thu vo mu lm gim pH ca mu. Ly in cc ra, ra sch bng nc ct v ngm n trong dung dch bo qun. Ch : Do nh hng ca lc ion, php o pH ch chnh xc i vi cc dung dch long (<0.2 M) i vi cc mi trng khng nc, cc dung dch nh, keo hoc c lc ion ln th phi dng cc loi in cc c bit ph hp.

i vi cc dung dch c pH > 10, dng in cc loi low sodium error i vi cc dung dch c pH < 1, dng in cc mng lng (liquid membrane electrode).

4. BO QUN IN CC :
5

Cc in cc khi khng s dng thng c ngm trong dung dch bo qun theo hng dn ca nh sn xut. Thng thng, dung dch m pH 4 thch hp cho in cc thy tinh n, dung dch KCl bo ha thch hp cho in cc so snh (calomel hay Ag/AgCl) v in cc thy tinh kt hp. in cc dng cho cc dung dch cha anbumin : ngm in cc vi gi mi tun trong dung dch 5 % pepsin trong HCl 0.1 N. Sau , ra li bng nc ct. in cc dng cho nc sch (nc ung, nc ma) : im tip xc c th b nh hng bi s kt ta ca AgCl (im tip xc c mu nu). Ngm in cc vi gi trong NH4OH m c. Sau ra li bng nc ct . in cc dng cho cc dung dch cha sunfua : Ag2S mu en c th kt ta trong im tip xc. Khi , ngm in cc trong dung dch thiourea 7% mi pha (c axit ha nh bng axit xitric). Sau ra li bng nc ct. Nu dung dch cht in ly trong in cc b d hoc b kh : sc ra in cc vi ln bng dung dch in ly, sau np y li.

QUI TRNH HIU CHUN MY O pH

Thc hin hiu chun theo vn bn k thut o lng Vit Nam k hiu LVN 31 : 2001 Cc bc thc hin : 1. Kim tra n nh ca my Kim tra ti mt im o pH bt k v d : dung dch m chun pH 7 nhit chn, ghi nhn kt qu o vo mu bin bn hiu chun (xem ph lc). Sau 2 gi thc hin php o ln 2, ghi nhn kt qu. Chnh lch gia 2 ln o khng c ln hn sai s cho php 0,02 pH i vi my o c gi tr chia 0,01 pH hoc khng c ln hn sai s cho php 0,1 pH i vi my o c gi tr chia 0,1 pH. 2. Kim tra b nhit Chn mt dung dch m chun v d pH 7. o gi tr pH ca dung dch m chun c n nhit 25 oC, ghi nhn kt qu. Da dung dch m n nhit n 40 oC, ghi nhn kt qu. Chnh lch gia kt qu o vi gi tr pH ca dung dch m ti cc nhit tng ng khng ln hn sai s cho php 0,02 pH i vi my o c gi tr chia 0,01 pH hoc khng c ln hn sai s cho php 0,1 pH i vi my o c gi tr chia 0,1 pH. 3. Kim tra sai s o gi tr dung dch m chun th nht 7,00 pH nhit 25oC, ghi nhn kt qu. o gi tr dung dch m chun th hai mang tnh axt, ghi nhn kt qu. o gi tr dung dch m chun th ba mang tnh kim, ghi nhn kt qu. Chnh lch gia gi tr o c v gi tr chun pH khng ln hn sai s cho php 0,02 pH i vi my o c gi tr chia 0,01 pH hoc khng c ln hn sai s cho php 0,1 pH i vi my o c gi tr chia 0,1 pH.

BIN BN HIU CHUN MY O pH

6

Ni sn xut : Kiu : c tnh k thut : - Thang o pH : - Thang o nhit : - Thang o mV : Ni s dng : Phng php hiu chun : LVN 31 : 2001 Chun c s dng : dung dch m pH =

S hiu :

KT QU 1. Kim tra n nh Dung dch m pH = Nhit = t 2. Kim tra b nhit Nhit T = 25 oC T = 40 oC t 3. Kim tra sai s DD m pH Gi tr o pH Sai s Sai s cho php 0,02 Gi tr o pH DD m pH Sai s Sai s cho php 0,02 Khng t Gi tr o pH ln 1 gi : Gi tr o pH ln 2 Chnh lch pH (ln 1 - ln 2) Sai s cho php 0,02

Khng t

Khng t

Kt lun : Hiu lc n :

t chnh xc Ngy

Khng t thng nm 200

Ngi thc hin

Ngi sot li

BI TP
7

1. Cho bit mi quan h gia : - pH v nng ion hydro - pH v nng ion hydroxyl 2. Xc nh pH ca cc dung dch cha : 1,008 g ion hydro trong 1 L 0,1008 g ion hydro trong 1 L 1,7 x 10-2 g ion hydroxyl trong 1 L

3. Xc nh pH ca dung dch H2SO4 1,0 M. 4. Xc nh pH ca dung dch NaOH 0,02 M. 5. Mt dung dch c pH = 4. Xc nh nng ion hydro trong dung dch (g/L) 6. Mt dung dch c pH = 6. Xc nh nng ion hydroxyl trong dung dch (g/L) 7. Khi pH ca dung dch gim mt n v th nng ion hydro tng bao nhiu 8. Khi nng ion hydro gim 50% th pH ca dung dch tng bao nhiu 9. Xc nh nng ion hydroxyl nu nng ion hydro l 3,0 x 10-2 mol/L.