Co So Hoa Hoc Phan Tich Hoang Minh Chau Tu Van Mac Tu Vong Nghi

HOANG MINH CHAU (cut Bien TU VAN MAC TU VONG NGHI CO SO Hoa hoc phan tich ms NHA XUAT BAN KHOA HOC VA KY THUATHOANG MINH CHAU, TU VAN MAC, TU VONG NGHI COSGO HOA HOC PHAN TiCH * Gido trink ding cho sinh vién cdc truéng dai hoc Béch khoa, Su pham, Khoa hoc Tu nhién, K5 thudt... Cn lan thit hai) NHA XUAT BAN KHOA HOC VA KY THUAT LANOLLoi MG DAU Héa hoc phan tich lic mén khoa hoc vé cde phuang phap xtc dink thanh phan dink fink vie dink luong ctia cde chat vie hdn hop cita ching. Nhu vdy, héa phan tich bao gon. cde phuong phap phat hien, nhén biét eang rhu ede phitong phép xac dink ham htong cia. ee chat trong cde mau cin phan tich. Dé tidn himh phén tich dinh tink cing nh dinh luong cae chat, dgc bigt khi phan tich cde chat trong cde mdu co thanh phan phite tgp, ngudi ta thuang phai sit dung cde phuang phép tach chdt mot edch thich hap. Céc Rhdi nigm vica new, nguoi doe cing nhit sink vion da duge lam quen Xhi hoe tap ve nghien eitu cde tai lieu v8 ede man hoe Héa sa cdip, Hoa hoe dai cuong vi. Héa hoe v6 co. Hoa hoc phan tick déng ume tro quan trong ux c6 thé noi déng vai tro séng con dai vdi si phat trién céc mén héa hoc khac cling nhw cée nganh khoa hoc khae nhau, cdc tink vue cha cong nghé, sin xudt vd doi séng xd hh. Chi can don oi mét thi du: Muén téng hop mot chat mdi rdi nghien cit ede tink chat ung nhu nhitng ing dung cia no nhdt thiét phdi sit dung cée phuong phap phan tich thich hgp dé xée dink thank phan nguyen 15, mite dé tink khiét, xée dinh edu tric cia nd, Chink vi thé Engel da Hing noi:"Khong 6 phan tich thi khéng thé: eb ting harp’ Do cé tim quan trong nhu vay nen mot loat cée chuyén ngank cra khoa hoe phan tich da ra doi va ngay cang phat trién manh nh: Phan tich moi truong, Phan tich khoang liéu, Phan tich hop kim, kim logi, Phan tich lam sing, Phén tich duoc phém, Phan tich thye phém, v.v. Khi tien hanh phon tich mot déi tugng nao dé nhés phan tieh phdi thie hign cde bude sau day: a) Chon phiong phap phan tich thich hop vis xée dinh cdc udn dé can gidt quyét. Khi thuc hién bude nay can phdi dac bidt chi $ déa tam quan trong, ¥ nghia phap Ui va kink 1é vita céng viée phan tick, chi ¥ déx do ding dén, dé lap lai va tinh khd thi eda phuong phap phan tich. 4) Chon mau dai didn ia méu 6 thank phan phén anh ding nkét cho thank phan cia déi itong phan tich. Tit mdu dai dién tién hanh chon va chudn bj mda thi nghiém la mau ding dé tién hank phan teh chat cin xée dink, Sau a6 thite hign vide bién méu nay thanh dung dich phan tick. c) Tich chit. Dé phan tich ede mdu co thanh phan phic tap thong phdi tach hoge It ede chdt Ia, ede chat ngan cin phép xdc dink chat cn phan theh hode tach riéng chet cin phan tich ra khéi hdn hop udi cde chat khée. d) Tih hank dinh ltgng chat cin phan tich, tite la thie hién cde thao téc, cae phép do dac phan tich dé xtc dinh néng dé hode ham Luong chat cin phan tich trong dung dich mdu da chudn 0} trong butée trén. e) Tink todn hét qud phan tich, dénk gid dé tin edy cita cde két qué dé, Tat cd cae brede trén du 66 tim quan trong vii lién quan mat thiét vdt nhau khong thé b6 qua var coi nhe bude néo cd. Thay thude vite ban cht clin cae phitong phap phan tick ma ngudi ta chia ching thank4 LOI MO DAU cée nhom chi yds sau: 1- Nhém cdc phuong phip hiu hoc, trong 46 ngudi ta sit dung chii yéu ede phén ting héa lige (thuong goi la céc phan ting phan tich) va nhitng dung eu thiét bi don gidn dé phan tich cde chat, Cae phuong phap hoa hoe ra doi rét sam, thuong duoc ding dé xde dink nhang luong lin, itong vita vi khong qua nhé cde chdt. Tuy vay ede phuong phap hoa hoe la ca 36 dé phat trién cée phiong phép phan tich hién dai sé duoc néi dén ngay sou day va khong bao gid thidu duoc trong bat hi phong thi nghiem phan tich nao. 2- Nhom cde phicong phap vat ti va hou lt, trong dé nguii ta sit dung cde thiét bi may moe phite tap dé do hoge ghi nhitng dgt long odt li va héa ii nhu cudng dé vach quang phd phat xq nguyen tit, cwong do phan ra phong xa hat nhan nguyen t2, dién thé can bang ctia céc dign cuc nhiing vao dung dich phan tich, cuimg dd ding hhi didn phn chdt phan tich v.v...., cée dai lugng dé hade lt dae trung cho bin ehdt phan tich hode la ham 56 ctia nong do chdt dé. Nhém cde phuong phap vet lf va hda li thuong duge coi fa cac phuong phap phan Hick cong en. Da 36 ede phuang phap thuge nhém nay la ede phuong phap hién dai, ra doi fit vai chue nam gin day nhdm dép ting nhitng yeu cau ngdy cang cao cita khoa hye, Ki thudt va doi cdng hién dai. Su ra dai vat phat trién cla ede phuong phap nay la su ket hop nhiing thank tu cia khoa hoe phan tick, nhing thank titu cia hée hoe vdi nhiing thank tu rat rue 0 cha vat ti hoc hien dai, ki nghe tin hoc, dién at va tu dong héa. Cée phuong phap nay co mot loat wu diém ndi bat nhu cha phép xdc dink mot cach tu dong hoae bin ty dong nhting liong nh6, cite nhd cde chat v6 ed ciing nhu hau co. Tvong mhidu truimg hop ede phitong phap cong cu hién dai cho phép xtc dink edu trite cde phan tit phutc tap (cdc phic chét, cde chat hit ca). Tuy udy, dé ném ving diy di nguyen li, ban chdt vd sit dung thanh thao cée phitong phap nay phai nam ving co sd li thuyét cha cae Jogi phan ting phan tich vt ede phuong php hoa hoe cia phan tich Vi nhitng li do trén ma cudn séeh nity 58 duge chia thank kai phiin chinh. Phan thi nhdt trink bay ca sé Ii thuyét eta ede phdn dng phan tich va cae phuong phap hoa hoc ste dung cae loai phan ing dé. Phitn tut hai trinh bity li thayét co sd vie cde ting dung phan tich eta cée phuong phép phan tich cong cu quan trong mhét. Cuén gido trink nay ditge bien sogn nhém phuc vu sinh vitn ve can 69 gidng day cee iruing dai hoc va. cao dang cé tham gia hoc tap va gidng day mén Hoa hoc phan tich, dua trén yéu clu vé cdi tién néi dung chitong trink cho thich hop udi hoan cdnk cia chuong trink moi lie vita cung edp cho nguei hoc nhiing kien tute ea ban truyén théng lat vita c6 nhing ign thite cép nhat dé ném duac ban chét eta che phuog phap phan tich vita phat huy duoc de te duy héa hoe vit vita biel edch dp dung sing tuo cdc quy trink phan tich vao vide gidi quyét tot cée you ett thue fién cia nude ta va thu duge ket qua tét trong nghién eu khoa hoc, nhanh chong hoa nhap duge vdi nén hoa hoe ngay cing phat trign hien nay. Tham vong thi lin nlutng thoi gian va trink dé cd han nén chée chén cwdn sdch khong thé tranh khéi sai sét. Ching toi s? rét biet on khi nhén duge nnitng § hién déng gop cia céc ban ding nghigp ve anh chi em sink vién. Moi ¥ kidn dong gop xin giti ve. NHA XUAT BAN KHOA HOC VA KY THUAT, 70 TRAN HUNG DAO, HA NOL Cae tae giaMuc Luc ‘Trang Lai mé dau 3 PHAN THU NHAT CO SO Li THUYET CUA CAC PHUONG PHAP PHAN TICH HOA HOC Chwong 1. Can bang héa hoc va hoat do 15 Chwong 2. Dai cutong vé phan tich khéi lugng va phan tich thé tich 2.1. Nguyén tic chung ciia cde phuong phép phan tich khéi lvong 19 2.2. Yeu cau cia dang ket tia va dang can 20 2.3 Cach tinh két qué trong phan tich khéi lang 21 2.4. Nguyén tae cla phutong phap phan tich thé tich 22 2.5. Phan ting ding trong phan tich thé ich 22 2.6. Phan loai vic phusng phap phan tich thé tieh 22 2.7. Cac phuong phip chudn do 28 2.8. Nong do 23 2.9. Cach tinh két qué trong phan tich thé tich 27 2.10, Cach diéu ché cic dung dich : 29 Chuong 3. Axit va bazg - Phan ting trao déi proton 3.1. Dinh nghia al 3.2. Phucng tinh bao toan proton 3a 3.3. pH elia dung dich hé don axit - bazo trong ave 36 3.3.1. pH eda cae dung dich axit manh 36 8.3.2. pH cla eae dung dich baze nanh aT 3.8.3, pH cla ede dung dich don axit yéu 38 3.3.4. pH oda cde dung dich bazo yéu 40 3.4. pH ctta dung dich hén hop axit vA baze lién hop. Dém nang 41 3.5, pH eda dung dich hén hgp axit-bazo khéng lién hop 45 3.6. Da thj logarit nong do ca dung dich axit you HA 46 8.7, Dung dich da axit 50 3.7.1. Da thi logarit nong do cua dung dich da axit a1 3.7.2. pH eda dung dich da axit 53 3.7. 3. pH cua cae dung dich mudi tan cua cdc da axit 54 38. Cac axit va bazo trong dung méi khae nude 56 3.8.1. Phan loai dung moi 566 MUC LUC 3.8.2. Anh hyéng cla dung moi dén tinh chat cia cdc axit va bazo Chuong 4, Phuong.phap chudn 46 axit bazo - Phuong phép trung hda 4.1, Chat chi thi axit - baze 4.2, Dung dinh phén 4.2.1. Duang dinh phan khi chudn do axit manh bang bazs manh 4.2.2. Dugng dinh phan khi chuiin do bazo meh bang axit manh 4.2.3, Chun dé dan axit yéu bang bazd manh hoae don bazo yeu bing axit manh 4.2.4, Cae thi du khic vé chudn dO don axit yéu hoac dun baza yeu 4.2.5. Duong dinh phan chun d9 da axit bing bazd manh 4.2.6. Dinh phan da bazo bing don axit manh 42.7. Dinh phan hén hgp axit va hén hop bazo Chuong 5. Phite chat trong dung dich 5.1, Dinh nghia. Danh phaip 52, Hang s6 ben va hang s6 khong ben cia phic chat 5.3. Tinh ndng dé can bang otia cic clu Hf trong cae dung dich phe chat 5.4. Anh huang etia pH va etia céc chat tao phe phy dén néng dd cin bang cia phic, Hang ad khong bén va hing 56 bén dieu kien 5.5. Pinic chat. cita cdc ion kim logi véi axit etilendiamin tetranxetic Chuong 6, Phuong phap chuin do tao phitc 6.1, Phuong phap chun dé complexon G.1.L. Chat chi thi trong phuong phap complexon 6.1.2. Duang dink phin trong phuong phap complexon 6.1.3, Mot. 36 chat chi thj quan trong ding trong cc phuong phaip chudn do tgo phic 6.2. Phuong phap bac. Chuan dd xianua 6.3. Phuong phiip thay ngan. Chuan do cae halogenua Chuong 7. Phan wing két tia 7.1. Digu kién tao thinh két tha, Quy ludt tich sé tan 7.2. Quan hé gitta tich 36 tan va do tan 7.3. Nhing yéu td Anh huéng den de tan 7.3.1. Anh hudng cua cae ion chung: 7.3.2. Anh hudng cia pH va cia chat tao phic 7.3.3, Anh hudng eta nhiet do 7.3.4. Anh hudng eita kich thuée hat ket tia 7A, Cong két va ket tia theo 7.5. Két tia phan doan 7.6. Kat tia keo 57 61 65 65 69 70 WT 79 87 389 101 105 110 1G 112 116 119 122 123 124 126 126 127 136 136 is7 140 141CO SO HOA HOC PHAN TICH 7 Chuong & Phuong phap chuan dé két tia 8.1, Nguyen td chung eda phueng php 143 8.2. Phung trinh dugng chudn do cée halogenua 144 8.3. Duong dink phan 145 8.4. Sai s6 chudn do 146 8.5. Chuan do hin hgp 147 8.6. Cac chat chi thi ding trong phuong phap bac 148 Chuong 9. Chat oxi hoa khtt - Phan tng trao déi electron 9.1. Dinh nghia 151 9.2. Curing dO chit oxi héa va chat kbd 153 9.3. Nhiing yeu t6 Anh hudng dén thé oxi hda - khit. Thé oxi hda - khit tieu chuan didu kien 156 9.3.1. Anh hudng eta dé axit 156 9.3.2. Anh hudng cia phan Ung tao phic 157 9.3.3. Anh huéng cia phan ting két tua 159 9.4. Bang thé oxi héa kh tidu chudin 159 95. Thé oxi hda khis cba dung dich chat oxi hda va chat kin tien hap 163, 9.6. Thé oxi hea eiia dung dich chat oxi hda va chat kht khong lién hyp 164 9.7. Hang sé ean bang eda phan tg oxi hea - khit 168 9.8. Chat oxi héa va chit khir da bac 169 9.9. Téc d6 ciia phan ting oxi hoa - khit 170 Chuong 10, Phuong phép chudn do oxi héa - khit 10.1. Chait chi thi oxi hoa - khir 175 10.2. Dang dinh phan 177 10.3. Sai sd chi thi 182 10.4. Chudn do ehiit da oxi hoa ~ khiy 183 10.5. Mot s6 tng dung phé bién va dién hinh cia phuong phap chudn dé oxi hda - khir 185 10.5.1. Cae chat oxi hea hé trg 185 10.5.2, Cae chat. khit phit tra. CAc loai cot kbit 186 10.5.3. Mot 36 ung dung cia eae phutong phap oxi hda - khir 187 Chuang 11. Sai sé trong phan tich xi ly u thuc nghiém theo théng ké todn hoc 111. Dinh nghia cde khai niém 191 11.2. Cée dai lugng trung binh 193 11.3, Cée dai lugng dae trung cho dé phan tan 194 11.4, Cée loai phan bé 195 11.5, Bién gidi tin cay 197 11.6. Kiém tra théng ké eac dit kién thye nghiém 198s MUC LUC 11.7. Dah gid két qué phan tich theo théng ké 200 PHAN THU HAL CAC PHUONG PHAP CONG CU Chuang 12. Phuong phdp do d6 d&n dign 12.1. Dac diém eka phugng phap do dé dan dién 205 12.2. Do dain din riéng va dé dain dién duang hsong 206 12.2.1, Dé din dien rieng 208 12.2.2. Do dan dién duong huong 206 12.2.3. Chat dien li trong trudng dong cao tan 208 12.3. C&c thiét bj eda phugng phap do do din dien 208 12.4. Cac phutung phap phan tich do dé din dién 208 12.4.1. Phuang phap do truc tip 208 12.4.2. Phuong phap chudn do do dan dién 209 12.4.3. Dinh phan voi dong cao tin B12 12.5, Ung dung cia phuang phap chudn do dé din dien 213 Chuong 13. Phuong php phan tich do dign thé 13.1, Dae diém chung eda phiteng phip phan tich do dién thé 215 13.2. Thé dién cue 216 13.2.1. Dién ce chi thi 217 13.2.2. Dién cue so sinh 217 13.3. Phuang phap do thé di¢n cue 219 13.8.1. Nguyen tie 219 13.3.2. Thiét bi do site dien dong cia pin galvanic 219 13.3.3. Dien thé khugeh tan 220 13.4. Phutong php do dign thé truc tigp 221 18.4.1. Do pil 221 13.4.2. Dién eye chon loc ion vA phvong php do trye tigp néng dd ion 223 13.5, Phucng phap chudin do dién thé 224 13.5.1. Trudng hop dinh phan theo phuong phap axit-bazo 225 13.5.2. Trg hop dinh phan bing phan tng oxi hia - khit 226 13.5.3. Tring hop dinh phan bang phdn dng tuo kei tan 226 13.5.4. Truéng hop dinh phan bang phan ting tao complexon 226 13.6, Ung dung cla phvang phap do dién the 227 Chuang 14, Phitong phdp phan tich von - ampe 14.1. Cu sé cia phuang phap 229 14.1.1. Dac diém chung 229 14.1.2. Qua trink xAy ra tren dién cuc giot thay ngan 230 14.1.3. Dién thé nita song va phiong trinh sdng cue pho 283 14.1.4, Cue dai trén séng cue phd 234CO 86 HOA HOC PHAN TICH 9 14.1.5. Phuong trinh Inkoviteh 234 14.2. So dd thiét bi phan tieh cue phd 235 14.8. Céc phuong phap von - ampe trye tiép 236 14.3.1. Dién thé nia song va phan tich eve phé dinh tinh 236 14.3.2, Phuong phap cule phd dong mot chidu 236 14.3.3, Phuong phap do vi phan 237 14.3.4. Cue phé dong xoay chiou 239 14.3.5, Cute pho xung 240 14.3.6. Phuong phap von - ampe quét thé nhanh 242 14.3.7. Phuong php von - ampe nguge 244 14.3.8, Phan tich hgp chat hiru eo 246 14.4. Phuong phap chudn ampe 246 14.4.1, Dang dink phan chudn ampe 246 14.4.2. Cac phan ting ding trong chun ampe 247 14.4.8. Dinh phan voi hai dién cue chi thi 248 14.5. Ung dung cia phuang phap von - ampe 249 Chuong 15. Phuong phép dién phan va do dién lugng 16.1, Dinh luat ve sv dign phan 251 15.2. Dign thé phan hay va qua the 262 15.8. Phuong phap phan tich bang qua trink din phan 254 15.3.1. So dé thiét bj dién phan 254 15.8.2. Tach bang phuong phap dién phan 205 15.3.3. Dign phan véi catot thay ngan 258 15.8.4. Phuong phap noi dién phan 258 15.4. Phuong phap do dién lvong 259 15.4.1. Phan tich do dién lugng voi viée kiém tra dign thé 259 15.4.2. Phan tich do dién lugng khi kiém tra dong 261 15.5. Ung dung cia phuong ph4p dién phan va do dién luong 262 Chuang 16. Ma dau vé cdc phuong phép phan tich do quang 16.1. Dac tinh eta biic xa dién tic 265 16.2. Phé dign tir 267 16.3. So dé dai cuong eda cde thiét bi do quang 267 Chuong 17. Ly thuyét chung vé ede phuong phép phé hip thu phan ti 17.1, Dinh lugt Bouguer - Lambert - Beer 269 17.2. Ung dung cia dink luat Beer a7 17.2.1. Déi vdi mot chat nghién citu a7 17.2.2. DSi vai hén hep chat nghién ctu 274 17.3. Nhitng sai léch déi vai dinh luat Beer 2761 MUC LUC Chuong 19, Cée ting dung céa phuong phap hap thu phan tr 18.1, So dd thiét bi do dé h4p thu quang 18.1.1. Nguén sang 18.1.2, Bo loc song 18.1.3. Ngan dung mau do 18.1.4, Cac detects 18.2, Céu tao ela mot may do dd hap thu quang 18.8. Cae ing dung 18.4.1. Ung dung trong cong nghiép 18.3.2. Ung dung trong méi trudng 18.3.3. Cae ting dung khée Chuong 19. Phuong phdp phé hujnh quang phan tit 19.1, Dai evting vé phuong phap phé huynh quang phan tu 19.2. Nguyen tae chung 49.3. Cong cu trong phvong phap hujnh quang phan ti 19.3.1. Nguén kich thich 19.3.2. Bo phan chon séng 19.3.3. Ngan dung mau 19.3.4. May thu tin higu - Detects 19.4, Ung dung cia phifong phap phd huynh quang phan tit 19.4.1. Ung dung trong phan tich dink tinh 19.4.2. Ung dung trong phan tich dinh Ivong Chuong 20. Phung phip phé phat xa nguyén tt 20.1. Dac diém cia phtong phap 20.2. Su tao thanh phé phat xa nguyén tir 20.2.1. Ngudn géc phé phat xa nguyén tit 20.2.2. $8 hang quang phd 20.2.3. Su kich thich phat vach quang phé 20.2.4. Cac dac trung cla cdc vach quang phd 20.3, Cac thiét bj chinh trong phan tich quang phé 20.3.1. Dae didém chung eta ede thiét bi quang phd 20.3.2. He thong chiéu sing 20.3.3. May quang pho 20.3.4. Thiét bi ghi phd 20.4. Phuong phap quang phé dinh tinh 20.5. Phuong phap quang phd phat xa dink lang 20.5.1. Dae diém chung céa phuong php 20.5.2. Phan tich quang phé ban dinh Iuong * 20.5.3. Phuong phap quang phé dinh Iugng bang kinh anh 20.5.4. Phung phap quang dién 279 280 280 285 285 286 288 288 289 290 293 204 295 295, 296 296 296 297 297 297 301 301 301 302 304 304 306 306 307 310 313 315 317 317 318 319 3820CO SO HOA HOC PHAN TICK 20.5.5. Phuong phap hea quang pho 20.6. Ung dung cia phuong phap quang phé phat xa Chuong 21, Phé hap thy nguyen tw 21.1. Dae diém chia phuong phap 21.2. Dibu kién tao thanh phd hap thy nguyén tit 21.2.1. Qua trinh nguyén tit hoa 21.2.2. Su hap thu bie xa cong hirang 21.3. Cac thiét bi cla phuong phap pho hap thu nguyén tit 21.8.1, Nguén phat bic xa cong huéng 21.3.2, Thiét bi nguyen ti héa 21.2.3. May phat tia dan sdc 21.3.4, Thiét bi ghi phé 21.4. Phuong phap phan tich phé hap thu nguyen tt 21.5, Ung dung cia phuong phap phé hap thu nguyén ti Chuong 22. Phuang phap chiét 22.1. Dae didm cita qua trinh chiét 22.1.1. Dac diém chung cia phuong phap 22.1.2. Phan loai qua trinh chist 22.2. Cac diac trung dinh Ivgng cla qua trinh chiét 22.2.1. Dinh luat phan bé Nernst 22.2.2. He s6 phan bd 22.2.3. Do chiat R 22.2.4. Hé 36 tach va hé 3d lam giau 22.3, Chiét hap chat noi phite 22.3.1. Dac diém chung cilia qué trinh chiét hgp chat noi phde 22.3.2, Gidi thigu mOt 96 qué trinh chiét hyp chat noi phite 22.4, Chit ede tap hyp ion 22.5, Téc do qua trink chist 22.6. Ung dung cia qua trinh chiét Chuong 23. Phuong phdp sac ki 23.1, Cae vain dé chung cia phuong phap séc ki 23.1.1. Dae diém chung ctia phuong phdp ade ki 23.1.2. Co sé cada phuong phap séc ki 23.1.3. Phan loai cée phwong phap sAc ki 23.1.4. Cae cach tién hanh phan tich sde ki 23.2. Pic se ki va cde dac trung cla qua trink ria gidi 23.3. Co 86 If thuyét ciia phuong phap sdc ki 23.3.1. Li thuyét dia 23.3.2. Li thuyét dong hoc 23.4. Cée thiét bj ding trong phuong phip sic ki 321 321 323 324 324 324 325 325 325 326 326 327 328 329 329 329 330 330 330 331 333 335 335 336 337 338 339 341 341 341 342 343 344 347 347 348 349,12 MUC LUC 28.5. Sde ki léng dang cot 350 23.5.1, Dac diém chung cia sfe ki ling dang cot 350 23.5.2. Sde ki léng - ran 353 23.6. Sac ki trao déi ion 354 23.6.1. Cac loai nhya trao déi ion 355 23.6.2. Can bang trao déi ion 357 23.6.3. Ung dung ca sac ki ion 359 23.7, Sde ki lang - léng trén cot 361 23.8, Sac ki lép mong 362 23.8.1. Dae diém chung cla phuong phap 362 23.8.2. Che dae tring cg ban cba sde ki lop mong 362 28.8.3. Ky thuat sdc ki lop mong 363 23.8.4, Sde ki lép méng trong phan tich dinh tinh 364 28.8.5, Se ki lop méng trong phan tich dink lugng 365 23.8.6. Ung dung eda phuang phap sée ki lop méng 365 23.9, Phuong phap sie ki gidy 366 23.9.1. Dae diém cia phuong phap 366 23.9.2. Céc dac diém ky thuat sdc ki gidy 366 23.10. Sac ki gel 368 28.11. Phuong phap sie ki khi 369 23.11.1. Cat sde ki 369 23.11.2. Detecto . 371 28.11.38. Khi mang 372 23.114. Phan tich dinh tink 872 2.11.5, Phan tich din lugng 373 23.11.6. Ung dung eta phiong phap adc ki khi 375 23.12. Céc ting dung chung eta phuong php sdec ki 375 ‘Tai ligu tham khao 377PHAN THU NHAT CO SG Li THUYET CUA CAC PHUGNG PHAP PHAN TICH HOA HOCCHUONG 1 CAN BANG HOA HOC VA HOAT DO ‘Trong Hoa hoc phan tich ta thudng phai tink nang dé can bang cda cde chat tham gia vA duge tao thanh trong cac phan tng phn tich, tle 1a néng dé cia cde chat do khi phan ting dat t6i Lang thai can bang, Dé tinh ede néng dé can bang, ngudi ta thudng sit dung biéu thic cia hang s6 can bing duge thiét lap bang cach ding dinh luat tac dung khéi luong. GiA sit xét can bang hoa hoe: mA + nB + pO +qD +... fa), trong do A, B, C, D... 14 nhiing eu tit tham gia cin bang (a) ma ching khong tich dién. Ap dung dinh luat tac dung kh6i lugng, ta c6: (cry (ayn B]" trong do [A], [B], [C], [D]... 14 néng dé can bang ciia cic chat A, B, C, D... va K 1a hang 36 can bang,l dai lwgng chi phu thude vao nhiét 49. Néu A, B, C, D... lA nhitng ion, thi ta phai tinh dén tuong tac tinh dién oda chung, nén trong biéu thie (1.1) ta phai thay ndng do bang hoat do. Hoat 46 a cla mot chat duge xac dinh bAng hé thie: a= fc, (1.2) trong dé, C la ndng dé cia ion; fla hé $6 hoat do. Dai ltgng f phy thuge vio Ie ion eda dung dich. Lue ion « biéu thi tuang te tinh dign gitta eae ion trong dung dich. =k, ay16 CAN BANG HOA HOC VA HOAT DO Néu Z,, Z;... 1 didn tich va C,, C,... la ndng do cia dac ion trong dung dich, thi lye ion 4 duge xée dinh bang hé thite: 1 Wm 7 BIC, + BIC, +d (3) Hode dudi dang tong quat: log wa gh Ac, a3) ist Neu w gan bing khong tie la dung dich rét loang, twang tae tinh dién gitta céc ion khéng dang ké, thi f bang 1, hoat do bang ndng do. Khi « < 0,02 thi f dude tinh bang he thie: f= > ove (1.4) Thi du f: Tinh hoat 6 cia cdc ion trong dung dich hén hgp KCl 10°M, MgSO, 103M Tinh Ive ion ¢ ca dung dich: # = 0,5 (1.103 + 1.103 + 27.103 + 22.104) = 5.10% Vi = 7.107 = 0,07 Tinh hé s6 hoat dO cla cde ion log f = lg fe- = —0,05.1.0,07 = -0,035 ft =o = 92 tog f ay Pang Tinh hoat do cae ion ays = ae. = 0,92. 103 = 9,2.104 molt! Ogi = @ 0h 0,72.103 = 7,2.104 molZ? Kini 0,02 < p< 0,2 thi f duge tinh bing hé thie ot logf = -0,5 ——— (1.8) Livi -0,5.27.0,07 = -0,14 Thi du 2: Tinh hoat dQ eta cdc ion trong dung dich KCI 0,1 M. Lye ion cha dung dich « = 050701 + 17.6) = O1 fi = 0,32 Hé sé hoat d6 cia cae ion: log f+ = 18 Fer = (0,5.17.0,32)(1 + 0,82) = 0,121 f = 0,757 Hoat do cila cdc ion: gt = @ gy-= 0,757.10"! mol. + Khi 4>0,2 thi hé s6 hoat dé f duge tinh bang cng thie:©O $6 HOA HOC PHAN TICH " NR Live log f = -0,52 + hw 1.6) trong do A la hé sd thay d6i cing voi ion Néu A, B, C, D... trong hé thiic (1.1) !4 nhitng ion, tite 1A nhitng phiin tit tich didi thi biéu thie hing 0 efin bing od dang sau: « 7) ‘Trong trudng hop nay, K, duge goi 1a hAng sé can bang hoat dé hay hang s6 can “bing mhiét dong, dai lugng nay chi phu thugc vao mhiét dd (khong phu thude vao ndng 6). Thay a = fC vao bieu thie (1.7): BK, LOND FRAG Peri = K, fre (1.8) (APB RF wi trong dé, K. doe goi 1A hAng s6 can bing ndng do, dai luong nay khong nhiing phis thude vao nhiét dé ma cdn phu thuéc vao lye ion cua dung dich. Cae hang sd can bing cia ede h¢ khac nhan, thi dy hang 36 axit, hang 36 Lazo, tich 56 ion ela nude, tich s6 tan cla cdc cht kho tan, hing 26 bén va khong kén cla c: phe chat ghi trong cdc tai liéu thutng ta cdc hang sé hoat do. Trong. thie té, dé tinh toain duge don gian, khi tink néng dé ede ion trong dung dich, hing 36 can bang hi 46 thuing duge ect bang hang s6 cin bing ndng d6, tie la ta bd qua su twang tie tinh dién ctia cée ion trong dung dich va coi hé sé heat dO bang 1. Két qua tinh ton, ah vay, sé thiéu chinh xe. Nhung vi ta thudng ding cdc dung dich loang, nén sai s6 c0 thé nam trong giti han co thé chap nhan duge. ‘Trong ede chugng sau, dé don gidn hoa viée tinh to’n, hé 36 hoat dé thing duge coi Dang 1 Gia st ching ta phai xét cin bing (a) ma cdc chat A, B, C, D... trong dé edn tham gia vio cdc phan ting phu Khdc (nhu phan ting (rao d6i proton, phan dng tao phe chit, Phin dng tuo két tia) thi nény do cla ching tham gia vao cin bang a) 8% giAm di, nghia IA ede phan Ung phu d4 Anh hudng dén can bang (a) dé. Dé biéu thi anh hudng cla ede phan Ung phu dén can bing (a), ngudi ta thudng ding mot dang hing 36 gol lA hang s6 dieu kien, Got {A}, {B'], [C’], [D']... 1a tng nong dé can bang cla ec dang eda A.B, G, D... trong dung dich thi (AJ, (B], (C], [D] chi bang mét phan ctia ede nong do {A}], {B'}, (C’], [D'], tie ta: TA} = [8] «5 {B) = [B’] e, trong do «,, jy 1A ede hé 86 hd hon 1 la nhéing dai lvong biéu thi Anh hudng cits cae phan ting phu tdi nong do ca A, B,C, Du, tat do Thay clic ndng do cin bing (AJ, [B]... trén vao hé thie biéu dién hing sé can bing ndng dé cia cén bang (a), ta eo (CPD EP eR DI (CPD PR ag, TAY" [By TA)” hh TAPES et NB K (1.9) Dai lugng K’ trong hé thie (1.9) duge goi 1a hang s6 can bling diéu kién, né khong8 CAN BANG HOA HOC VA HOAT DO nhiing phu thu6c vao nhiét do, vao lve ion ela dung dich ma cdn phu thudc vao ca ndng 6 eta cde cht khde tie 1A phu thudc vao diéu kign cba dung dich trong do can bing chinh (a) duge thiét lap. Cac thi dy cu thé sé duce trinh bay trong cée chuong sau. Trong cae phuong phap ha hoc noi riéng cfing nhu trong tat cA cac phuong phdp cia phan tich ni chung, nguai ta thudng nghién ettu sit dung cdc loai can bang chinh sau day ~ Can bang axit - bazo (hoac cn bang trao déi proton). - Can bang tao phic. - Can bing két tha. - CAn bing oxi hoa khu (hoae ean bing trao déi electron) ‘Trude khi di vao xét ca sd Wi thuyét cla céc loai can bang trén va wing dung cta ching trong cac phuong php héa hoc cling nhut hda li céa chung, ching ta hay dé cap dén nguyén tac cla cac phudng phép héa hoc: phudng phap phan tich khéi Iugng va phan tich thé tich.19 CHUONG 2 DAI CUONG VE PHAN TICH KHOI LUONG VA PHAN TICH THE TICH 2.1 Nguyén tac chung cia ede phitang phap phan tich khdi lugng Phan tich khéi lugng la phitong phap dinh luong hoa hoe trong dé ngudi ta do chinh xde bing cach can khdi Iugng eda chat cin xac djnh hoge nhiing hgp phan cia no da duge tach ra d trang thai tinh khiét héa hoc hodc 1A duéi dang hyp chét co thanh phan bist trude. Thi du, dé dinh luong vang trong hop kim, ngudi ta ly mot mau dai din cho hop kim dé, dem hda tan mau nay trong mot hrong thich hop nue cvdng thay (HCl + HNO,) dé chuy@n hoan toan m4u thinh dung djch. Dem ché hoa dung dich do bang ning thude thi thich hgp, ri khit chon Ioe va dinh hang va..¢ (IID) thanh vang kim loai Au. Dem loc, rita két ta Au dé rdi sily va nung dén khdi Ivong khong déi. Cudi cing can Juang Au dé tren cn phan tich dé xéc dink khoi lugng cla nd. Ti khéi Itong nay x4c dinh ham luang vang trong mau hgp kim, Dé xdc dinh magie ngudi ta tién hanh nhu sau: Hoa tan mdu phan tich trong dung méi thich hyp dé chuyén toan bo lvong magie vao dung dich duéi dang ion Mg’*, Ché hoa dung dich bang cdc thube thit thich hgp dé két tua hein toan va chon loc ion Mg?* dudi dang hgp chat khé tan MgNH,PO,. Loe, ria két tia roi sdy va nung nd 4 nhiét 46 thich hop dé chuyén hoan ton thanh hgp chat Mg,P,0,. Cudi ciing edn dé xac dinh khéi lugng cla nd. Dua vao cong thie cia két tia va khéi lugng via can dude sé tinh duge ham Iwong cia Mg trong mau phan tich. ‘Trong thi du nay hop chat MgNH,PO,20 DAI CUONG VE PHAN TICH KHOI LUONG duge két ta dé tach dinh luong magie nén duge goi 1A dang Rét tia con Mg.P30, 1a hop chat duve tao thanh sau khi nung dung két tia va duge edn dé xée dink ham lwong cia magie nén duye goi la dang cin, Phuong phap phin tich khoi luong magie nit tren dude goi la phuong phap két ta, Phuang phap ket tia la phitong phap duae st dung phé bin nhsit trong phan tich khoi lugng. Dé xde dinh CO, trong quang cacbonat, ngu mét dung eu riéng bing axit: CaCO, + 2H + Ca? + CO, + H,0 ‘Toan bé Iwong khi CO, gidi phong va duge hap thy hét vao hén hyp CaO + NaOH dung trong mot binh riéng. Lugng CO, do duge xic dink theo do tang khéi Ivang ctia binh dung hén hap hap thu. Phuong phap xéc dinh ham lugng CO, nbu tren goi 1 phuong phap cat, ta phan hiy Ingng can mau trong 2.2. Yeu cau cua dang két tia vi dang can Dé phugng phdp phan tich khéi lugng dat duce dé chinh x4c cao, dang két tia phai théa man nhing yéu cau sau: - Két tia cn phai thyc té khong tan. Mudn vay, khi tién hanh két tua ngudi ta phai chon nhifag dieu kién thich hop nhu pH toi wu, nong d6 thude thit, nhiet do thich hop dé ket tua hinh thanh thuc té khong tan hoge, hue ngudi ta ndi, chat phan tich duce lam két tha mt céch dinh lugng, thi du ket tia tii 99,99% - Két ta thu duge can phai tinh khiét, khong h4p phu,cong ket va ndi hap cic tap ehait. Chi ed nhwvay thi dang ean moi cé thanh phan xde dink ung dhing vdi cong thie hoa hoc etia no. + Két tua cin thu duge didi dang dé loc rita dé co thé tach ra khéi dung dich mot cach nhanh ehéng va thuan loi nhat. Cae yéu cau trén cia dang két tha sé duge ban ki va sau hon trong chuong VII (muc cac yéu té Anh hudng dén sy két tha hodn toan va dO tinh khiét cba két tia) Yeu cu quan trong nhat cia phan tich kh6i Ivong IA chat rin thu duge cudi cing phai cd cong thtte xdc dink dé cd thé ti khéi lugng cia ne tinh ra duge chink xe ham luong nguyén t6 hode ion cAn dinh phan. Déi véi nhitng két tia loai BaSO, e6 cong thite xdc dinh, bén vitng @ nhiét dé cao, nén sau khi rita sach va sy kho thi tk khéi heong cha no ed thé tinh duoc Ivong ion Ba*+ hoae SO} eo trong dung dich phan tich. Nhu vay, trong trudng hdp nay dang két tha va dang can la mot hgp chat. Nhung , khong it két téa, chang han Fe(OH), va AL(OH),, thudng khong od cong thie x4c dinh, nén Khong thé chon ld dang can ma phai nung ching 4 nhiét dd cao t6i khi cd khéi lugng khong di dé chuyén chang thanh Fe,0, hoe Al,O, la nhig dang edn. Dang cin phai théa man nhiing yeu chu sau: - Phai co cong thc xae dinh, ed thanh phan khong d6i ti khi sfiy hode nung xong dén khi cain nd trén en phan tich. Thi dy, dang ean khong duge hut Am, khéng hap thu khi CO, co trong khéng khi, khong bi phan hay béi anh sing v.v.... Dé thd man yeu cu nay clin phai tién hanh phan ich theo nbiing ki thuat nhat dinh. - Dé ed duge két qua phan tich cang chinh xac, khéi htong mol cia dang can cing Jén han khéi Ivong mol cia nguyén té hoac ion can phan tich thi cng tot. Thi dy, eo thé xac dinh Cr'¥ dudi dang can 1a BaCrO, hoac Cr,0,, Gid st, sai sé tuyét déi kdCO SO HGA HOC PHAN TICH a BaCrO, va Cr,0, déu la mot mg, nhung khi can 4 dang Cr,0, thi sai si 1a 104 « 1/ 152 = 0,7 mg Cr, cn khi can d dang BaCr , thi sai s6 1a 52» 1/ 253,3 = 0,2 mg Cr ahd hon truéng hgp truée 0,7/0,2 =3,5 lan. 2.8. Cach tinh két qua trong phan tich khéi lugng @, Hé 86 chuyén ‘Thong thu’mg dang can khong phi 14 dang cin xéc dinh ham Iuong. Vi vay, tit khéi luang cita dang can phai tinh kh6i lvgng cia dang cin xée dinh ham Iugng. Do do, dé tién cho viée tinh két qua phan tich, ngudi ta dua ra khai niém hé sé chuyén. D6 1a dai lwong ma ta cin phai nhan khéi lughg cia dang can vi né dé duge khdi lugng cia dang can xic dinh. Thang thudng hé sé chuyén la ti sé —_kh6i Iugng eda mot, hai hode abiéu nguyén ti hoge phan tit hode ion cia dang can xac dinh va kh6i lugng phan tit etia dang cAn. ‘Trong trudng hyp sac dinh Si thi hé sd chuyén tit S10, (dang can), thanh Si, dang c&n xée dink ham Juang la: Si Ke= SiO, ‘Taf du khée: Néu dang cin la Mg,P,0, va dang cfn xée dinh bam lugng 1a Mg ,MgO hay MgCO, thi hé sé chuyén Hin Iuot 1a: 2Mg = = 0,2185 Mg,P,0, 2MgO Kyg Rypgcoy =~ = 07576 6, Cach tink ket qua phan tich Thong thutng nguii ta tinh két qua theo phan tram khdi luong cia chat can dinh phan trong mau Gia sit lugng can mau 1a p(g), khdi Jugng dang ean 1a q (g), K la hé 96 chuyén. Ham luong tinh theo % khéi lugng x K.q.100 2% = (24) P Néu p(g) mau chita trong V inl dung dich ma lay ra v ml dé phan tich thi: K.q.¥100 x% =—————. (2.2) pe ‘rong trudng hgp phan tich khi va hoi thi ceh tinh kh4 don gian. Thi du dé xc dinh do sm eta mau ta lay p (g) méu. Sau khi sdy Kho thi con ai p'(g). Vay do dm ctia mau la p-p % ao dm =: P10 P2 DAI CUONG VE PHAN TICH KHOI LUONG .. 2.4. Nguyén t&e eda phutang phép phan tich thé tich Phan tich thé tich IA phvong php x4c dinh ham Ivgng céc chét dya trén sy do thé tich dung dich thude thi: da biét ndng dé chinh x4c (duce goi 1a dung dich chudin) duge thém tit buret vao dung dich cla chat dink phan, vita téc dung di vdi tat ca Ivong chat dinh phan dé. Sy thém tit tit dung dich chuiin bang buret vao dung dich chat dinh phan goi lA su’ chudn d6. Thai diém da thém lvong thude thd vila du tac dung vdi todn bo chat dinh phan goi la diém twang ducng. Thdi diém tai dd ta két thc chudn d6, goi la diém cuéi. Thong thutng diém cu6i khong tring voi diém tuong duong, nghia la thé tich dung dich chudn da duge thém vao khong bing thé tich cia no tac dung vita di véi chét dink phan (thé tich dung dich chudn dng véi diém tvong dugng), vi vay sy chudn do mic sai sd. Dé nhan biét diém tuong duong, ngudi ta thudng ding nhiing chat gay ra nhiing hign tuong ma ta cd thé quan sat duge bing mat nhv sy déi mau, sy xuat hién két taa Jam duc dung dich xay ra @ rat gin diém do. Nhiing chat dé duoc goi IA chat chi thi 2.5. Phan tng ding trong phan tich thé tich Nhang phan ung hoa hoc ding trong phan tich thé tich phai théa man cac you chu sau. - Chat dinh phan phai tac dung hoan toan véi thude thir theo mot phyong trinh phan ing xée dnb, nghia Ia thea mot hé s6 ti lvang xde dinh. - Phan ing phai xAy ra rt nhanh, Di véi cdc phan dng cham, cin lam tang tée do cia ching bling céch dun ndng hode ding chat xtc tac thich hop. Phan tng phai chon loc, nghia la thude thit chi tac dung véi chat @jnk phan tich ma khong phan tng véi bat ki chat nao khde. - Phai od chat chi thi thich hop dé xac dinh diém cu6i voi sai s6 chéip nhan duge. 2.6. Phan loai céc phuong phap phan tich thé tich Nguvi ta thusng phan loai céc phvong phap phan tich thé tich theo hai cach sau day: Phan logi theo ban cht cua phan img chudn do: - Phuong phép axit-bazo (hode phutong phép trung hoa): Phuong phap nay dua trén phan ing gitia cdc axit va bazd (phan tng treng haa (Ht + OH-> H,0) dé dink Luong truc tidip hoae gidn tiép e4c axit, bazo va mudi. = Phuong phép két tia: Phuong phap nay cha yéu ding dé dinh Iuang céc ion tao duge ede hop chat khé tan. Tuy s6 luong cdc phan Ung tao thanh két tda kho tan rat lén, nhung da sé cc phan ing do xAy ra rét cham va khong cd chét chi thi thich hop, nén viée 4p dung phiong phap nay kha han ché. - Phuong phép phite chét: Phong phap nay dita trén phan ving tao cdc phe chat gitfa chat cin phan tieh vA thuéc thi.Phuong phap duge dung dé dinh Iwong hau hét céc cation kim loai va mat 36 anion. Thude thir duce si dung phé bién nhat la nhdm thude thit od tén chung 1a complexon. - Phuong phap oxi héa - khit: Phuong phap nay dua trén phan Ung oxi hda -khiy va thuting duce ding dé dink lugng true tiép cae nguyen t6 chuyén tigp vi mol. sé chat hitu co, ngoai ra ta cdn ed thé xde dinh gidn tiép mét 86 ion v6 co,CO 80 HOA HOC PHAN TICH 23 Phan Joai theo phutong phép xée dinh diém cu6i - Cae phuong phap héa hoc dua trén sy déi mau cia chat chi thi tai diém cudi. + Céc phutong phép hoa li dua tren sy bién ddi dot ngot cda mét tinh chat vat If nao dé tai diém cudi nhu cudng do mau, dién thé, do dan dign v.v, 2.7. Cée phuong phap ehudn do ‘Tuy theo trinh ty tign hanh chudn d6, ngudi ta chia thanh ede chudn do sau: - Chudin do true tigp: Thém tit tit dung dich chun tit buret vio dung dich dinh phan dung trong binh nén. Thude thi R tac dung tryc tiép vdi chét dinh phan X: R+X > Q+Y (a) Dya vao ndng d@ dung dich chuéin, thé tich ca no da tidu t6n va phuong trinh phan ing (a), ta tinh duge lugng chat X da phan tng. - Chudn dg nguge: Thétm mot thé tich chinh xSe va du dung dich chudn vao chat dinh phan. Sau dé chudn do Ivgng thude thi R cén du lai bang mot thudc thir khée R’ thich hop. Dua vao thé tich va ndng do cia cic dung dich chudn R va R’ va phuong trinh ofc phan tng, ta tinh dugc lnong chat X hoe ndng do cla né. Phuong phap chudn do nguge nay thutng duge st dung dé dinh lugng céc chat tham gia cdc phan dng xAy ra cham hoac khong cé chat chi thi thich hop dé xdc dink X bang phan ting gita R va x. + Chudn dé thay thé: Cho chat dinh phan X tée dung voi mot hop chat thick hap khae MY dé tao thanh hap chat MX va gidi phong ra Y: X+MY>MX+Y (b) Sau do ehudin dé Y bang dung dich thudc thi thich hop roi dua vao ndng do va thé tich cia no dé tinh Ivgng chat X. : - Chudn dé gién tiép: Cach chuan dé nay ding dé dink lugng chat X khong tién hanh chudn d6 truce tigp bang thude thi nao dé, Chuyén X vao mot hgp chat thich hap chita it nhat m6t nguyén t3 co thé x4c dinh true tiép duoc bang mot thude thit thich hop. -Chudn do phan doan: Trong mét s6 trudng hgp o6 thé chudin do Lan lugt eae chat X, Y, Z... trong cing mot dung dich bang mét hoae hai dung dich chudn 2.8. Nong do Nong d6 la dai lugng ding dé chi ham Iugng cia mot eu tit (phan tit, jon) trong dung dich. Sau day 1a cae céch biéu dién nong do trong héa phan tich. Nong do thé tich: Nong 40 thé tich cia mot chat tong 1A ti sé thé tich cia chat lng 46 va thé tich ctia dung moi lén (thutimg 18 nude). Thi du dung dich HCl 1: 4 18 dung h gom 1 thé tich HCI dac (ed khéi ivgng rigng d = 1,185g/ml) va 4 thé tich nude. Nong do phisn tram khéi lvong: Nong do phan tram kh6i lugng cla mot chat. trong dung dich 1 86 gam chat dé tan trong 100 g dung dich. Thi du dung dich NaOH 25% IA dung dich cha 25g NaOH trong 100g, tic 1a dung dich gém 25 g NaOH va 75 ¢ nude, TAi du 7. Can hda tan bao nhigu gam NaCl vao 100 g nude dé duce dung dich nong24 DAI CUONG Vit PHAN TICH KHOI LUONG .. do 10%. Dat a Ja s6 gam NaCl cAn hea tan, ta cd: ———.. 100 = 10; suyraa =11,111 g¢. a + 100 Thi du 2. Cé bao nhigu gam H,SO, nguyén chat trong | ml dung dich axit sunfurie dac 98% es khdi lugng ring d = 1,84 giml? Dat @ 1A sé gam H,SO, can tinh, ta es: a —— = 98; = Va 100 = 98; suy ra. a = 1,803 g. Nong do mol: Nong 4 mol cia mot chit la sé mol chat do tan trong 1! dung dich Loai ndng 46 nay duge ki higu bing chit M hoae mol/l hose mol! dat sau chit s6 chi s6 mol. Thi du: dung dich NaOH 0,1M tric la dung dich chtta 0,1 mol NaOH hoae 0,1 « 40 = 4,0 g NaOH trong 1! dung dich Néu a 1A 86 gam chat tan trong V lit dung dich va M 1a khéi htong mol cia chat tan do thi néng do mol Cy duge tinh theo cong tht: Cy = av Néu ¥ biéu thi theo ml, thi: Cys « 1000/M.V Thi du: Can Iy bao bhiéu gam H,C,0,.2H,O dé diéu ché 250 ml dung dich nong 46 mol 18 0,025M ? Dat 56 gam tinh thé ngam nuée cn ly IA a, ta co: 1000 0,025 = ———— ; suy raa = 0,7880 g 126.250 Nong do duong lwong: Trude kia trong hda hoc ngudi ta thudng dimg khdi niém dugng lang va duong lugng gam nén trong héa hoc phan tich, dac biet trong phan tich thé tich ngudi ta thuimg ding loai néng do nay. Vi d¥a theo din luat vé duong Inong: trong mét phan ting chudn dé, cée chdt phén ting vdi nhau theo cing mot 36 mol duong lugng hode cling mét sé milimol duong lwong, thi viée tinh toan két qué phan tich rat thuan Igi va dé dang. Nhung ngay nay trén thé gidi ngudi ta khong ding dén khai niem duong luong va mol dung Itong nifa nén cée nude ft dang khdi nigm ndng do duong lugng. Nong 49 ditong Ivong cia mot chit 1A sé mol duong Iugng (D) cia chat do trong mét lit dung dich hodc 86 milimol (mD) cia chat dé trong 1 ml dung dich va thutng dvae ki hidu bang chit N dat sau chi sé chi sé ndng d6. Thi dy, dung dich NaOH 0,1N 18 dung dich clita 0,1 mol duong lugng NaOH trong 1 lft dung dich cia nd, Néu a 1a sé gam chét tan trong Vf dung dich (hoac a ia 36 mg chat tan trong V ml dung dich ) vA D la khéi lugng mol duong lugng (D), dai lveng nay trudc kia dutge gol 1a duong lugng gam, thi cd thé tinh nong do duong lwong theo céng thie: @ DVCO SO HOA HOC PHAN TICH 25 Néu @ biéu dign theo gam, cdn V theo ml thi: 1000 Cy =———— N "DW Ti cOng thie dé ta suy ra Cy.V 1 sé mol duong Iuong néu V tinh theo lit va la s6 milimol dudng lugng néu V tinh theo mililit, Khoi kiong mol duong Iveng D cia indt s6 chat 1a sé gam chat dé vB mat héa hoe tuong duang vai mot nguyen ti hoa mot mol ion H* hodc OH™ hoae 1/2 mol oxi (0) Duong Iwang mol cla mot chat khong phai 18 mot hang 36 nhit khoi Iueng mol, ma thay a6i tay theo phan ving né tham gia. ‘Thi dy, trong phan ting trung hda ede don axit, dan baze, ching han: HC] + NaOH NaCl + H,0 Duong lugng mol D cia HCI hoac NaOH bang khéi lugng mol eita ede chat do. Khi chudn d9 ede da axit, ching han HPO,,bing dung dich don bazo mgnh, thi du NaOH, thi duong Ivong mol ciia da axit phu thudc vio nde chusin do. Néu chun dé hee nde thit nhat: H,PO, + NaOH + Na,HPO, + H,0 thi duong lugng mol cia HPO, bang khdi lugng mol cia n6, B = M. Néu chudn d6 theo née thit hai: HPO, + 2NaOH + NaH,PO, + 2H,0 thi duong lugng mol ela HPO, bing 1/2 khéi itgng mol cia nd vi phiin axit da duge chudin do tuong duong véi hai mol Ht: D = 0,5M. Trong cae phan tng oxi hda khit duong lugng mol eda mot cht oxi hia hose mét chat khi bang khéi Ivong mol ciia né chia cho 36 electron n mA mot phan ii hoae mot ion chat dé trao déi, Thi du, khi ta chudn do dung dich Fe bang dung dich chudn KMnO, theo phan ung: MnOj + 5Fe?* + 8H* + Mn2* + 5Fe3+ + 4H,0 thi duong lwgng mol eta Fe? (hose eta Fe hoge ca FeSO,) bang khéi lugng mol cia no D = M vd duong wong mol eta MnO; (hede cia KMnO,) bang 1/5 khoi lugng mol cia nd D = 1/5M, vi trong phan tng dé: Fe? — le = Fe3+ va MnO; + Se + 8H* = Mn? + 41,0 Dé tim khéi Iuong mol duong lugng cla mét chat trong phin dng oxi hda khit ta khong cin phai viét cd phan ting né tham gia ma chi cin viét na phan ung cla no. Thi d Nia phan ting Duong lugng mol 2 Fe?! ~ le = Fe* 28,03" — 2e = $,02- As,0}° + 5H, - 4e + 2AsO} + 10Ht De 05M. MnO; + 4H* + 9e > MnO, + 2H,0 D=MB26 DAI CUONG VE PHAN TICH KHOI LUOQNG ... MnO; + 8Ht + 5e > Mn? + 41,0 D=MS Gr,03- + Ge + 14H? + 2Cr¥ + 7H,0 D=MG ‘Thi du: Cn lay bao nhiéu gam tinh thé ngam nude H,C,0,,1,0 (M = 126) dé pha ché 260ml dung dich chun H,C,0, 0,05N ding dé xac dinh nbng do dung dich KMn0, Vi ©,03" = 2e = 200, nen dung lugng mol cua axit oxalic D = 0,5M = 63 g 0,05D = 63 x 0,05 Latong tinh thé cin can dé pha 250 ml dung dich 0,05M 1a: 63 x 0,05 x 250 = 0,788, 1000 D6 chudn 6 chudn 1a s6 gam (hoae miligam (mg) chat tan trong 1m) dung dich. Néu a la 30 gam chét tan trong V ml dung dich, thi d0 chudn T = a/V D6 chudn theo chdt dink phan Do chugn theo chat cin dinh phan 1a sé gam chat can dinh phan (ion, phan tit hoac nguyén ti) phan dng ding vdi 1 ml dung dich chudn va duse ki hiéu la Ty x trong dé R la thude thi, X la chét can dinh phan, Cach biéu dién néng d6 loai nay rét thuan tien cho viéc tinh todn két qua phan tich, dae biét khi phan tich hing loat mau tai cac phong thi nghigém nghién ctu va san xudt. Thi du: Tinh dO chudn cia dung dich chudn KMnQ, 0,02M theo sét, bhi chuén do Fe?* theo phan ting: MnOz + 5Fe% + SH* + Mn** + 5Fe3! + 41,0 ‘Theo phuang trinh phan tng chudn do trén, ta cd: 1 mol MnOj phan dng vai 5 mol Fe2*, Trong 1 m) dung dich chudn KMnO,0,02Med chia 0,02/1000 = 2. 10°5 mal MnO; va do dé 1 ml MnO; do phan wing voi 5 x 2 « 10° = 107 mol Fe?" hoac 104 x 56 = 5,6 x 103 g Fe. Do do: Terinog ao2 Mire = 00056 g Fe.ml Nong dé (hode ham Iwong) phan trigu va phiin th Déi véi che dung dich rat long hoje eae ham Iwong rat nhé ngudi ta thuding ding cdc khai niém nay Phin trién (thutng duge ki higu 1A ppm: tiéng Anh la parts per million) 1a 86 micro gam cé trong mot gam hose 1 micro gam chat tan trong 1 gam dung dich. MOt céch téng quat ta ed: Khéi lugng chat tan (g) Cc, x 10° ppm ppm Khéi lugng dung dich (g) ‘Phi du: Dung dich Au®* ndng 40 1 ppm, tile la dung dich od chia 1g Au trong 1g hoac 1 mg Au trong 1 kg dung dich. Déi vdi céc dung dich nuléc rat lodng thi cd thé coi gin ding kh6i lugng riéng ela nude bing 1g/ml hoac 1 kg/l. Do dé, 1 ppm = 1 xgiml hoge LA 1 mg/l€O SG HOA HOC PHAN TicH 27 Déi vai cde dung dich loang hon, nguai ta ding phiin tl ki hiéu ppb (parts per billion) Khéi lnong chit tan (g} ph = x 10” ppb Khdi lugng dung dich (g) C4ch tinh két qua trong phan tich thé tich Vige tinh két qua phu thuge vao cach biéu dién nbng do va cach phan tich. Nguyén tdc chung 1a dua vao dink nghia nong dé, phuong trink phan tng chugn dé hoae dinh luat ve duong lugng ma tinh két qua phan tich. Truong hop chudn do true tiép Cach tink theo ndng do mol. Dua vio thé tich, ndng 46 dung dich chudn va phuong trinh phan tng chudn do dé tinh duve lugng chat can phan tich theo s6 milimol hose 56 mel. Thi du 1: Tinh nong 4% mol cha mot dung dich NaOH biét ring khi chudn dé 20 ml dung dich dé thi phai ding vita hét 22,75 ml dung dich HCl 0,1060 M. Phan tng chudn do: NaOH + HCI + NaCl + H,0 $6 milimol NaOH bang sé mitimol HCI Cyaan x 20 = 0,1060 x 22,75 Suy raz CNaor = (0.1060 x 22,75) : 20 = 0,1206 M Thi du 2: Khi chuda do 0,2275 g Na,CO, tinh khiét dén CO, phai ding vita hét 22, 35 ml dung dich HCI. Tinh ndng do mol cia dung dich HCI de. Phan ting chudn do: Na,CO, + 2HC] > 2NaCl + CO, + H,0 $6 mol Na,CO, bing 0,5 so mol HCI S6 mol HCI = (0,2275 : 106) « 2 Nong do dung dich HCI = C,yc, = (0,2275 : 106) x 2 : 0,02235 = 0,1920 M. Céch tink theo ning do duong Itong. Khi tinh theo néng do duong luong thi cin dua vAo dinh luat vé duong htang la: $6 mili duung lugng mol cia dung dich chudn bing $6 mili duong Iuong mol chat cn xdc dinh da phan tng voi nhau. Dé tinh duce khéi luang ede chat da phan ting phai biét khoi Ivang mol duang luang ciia cite chat &6. Thi du 3: Tinh bong d9 duong Ivong cia dung dich Na,S,0,, biét rang khi them Iuang du dung dich KI tinh khiét vao 20 ml dung dich K,Cr,0, 0,05N chia axit sunfurie Jam méi trugng thi chuan dd Ivang I, thoat ra bang 19,80 ml dung dich Na,S,0, do. Mill ducng Itong mot Na,8,0, = 19,80 » Nyas.o, = $6 milimol duong luong 10130; = 20 » 0,05. Do do Naso, * (20 x 0,05) ? fo:b0 = 0,0506 N. Cach tinh theo d6 chudn echét dinh phan. Tht du 4: Tinh ham lugng phan tram sat trong quing, biét ring sau khi hoa tan 0.5170 g quang, kbit hoin toin Fe(II) thanh Fe(ID, ri chudn dé Fe(TT) bing dung dich chudn KMnO, co do chudn theo Fe la 5,820 mg/ml thi dung vita hét 57,20 ml dung dich chudn ds. ‘Theo dinh nghia thi 1 ml dung dich chusin KMnO, oxi hea duge 5,620 mg Fe?*, Vay luang Fe eo trong quang la 5,620 x 37,20 mg. Phan tram oda Fe 1a ((5,620 « 87,20) : 517] x 100 = 62.18%28 DAI CUONG VE PHAN T{CH KHOI LUOQNG ... Truong hop chudn dg nguge. Thi du 5: Dé din lugng Cr trong thép, ngudi ta phan hiy 1,075 g mau thép thanh dung dich roi oxi hda hoan toan Cr+ thanh CrO3-. Sau dé thém vo 25 ml dung dich chuéin FeSO, 0,0410 M va igng dung dich axit sunfuric loang da am moi trudng. Luong Fe(II} du duge chudn dé bang 3,70 ml dung dich KMnO, 0,0400M. Hay tink ham Itong theo % khéi lucng ciia Cr trong thép. Dé tién loi ta tinh theo nong dé duong lugng. Nong d6 dang lugng cia dung dich chun FeSO, bing néng 49 mol cia no bing 0,0410N. Nong 6 duong lugng cla dung dich KMnO, bang 0,0400 x 5 = 0,2N. 86 mili dugng lugng mol CrO3~ tac dung véi Felt la: 25 x 0,0410 — 3,7 x 0,2 S6 duong lugng mol Cr trong mdu thép bang: 25 x 0,0410 — 3,7 x 02 1000 Khéi lvdng mol duong lugng eiia Cr 1a M:3. Phan tram Cr trong thép 1a: 25 x 0,0410 - 3,7 0,2 52 100 1000 a 1,075 = 0,4595 % ‘Truong hop chudn dé gidn tiép Tht dé 6. DE dinh luong chi (Pb) trong quang nguéi ta phan hiy 1,1060 g mau quang thanh dung dich. Tir dung dich dé thyc hién quy trinh lam két tia dinh higng chi trong méu thanh PbCrO,. Sau dé hda tan PbCrO, bing dung dich hén hop HC] + NaCl du. ‘Them vao dung dich mot Itong du KI va cudi cing chudn do lugng I, thoat ra bang 24,20 mi dung dich chudn Na,S,0, 0,0962N, Tinh ham lugng chi trong quang theo % khdi Ieong, Cée phan ting chinh ca qué trinh dinh luong: CrO2- + Pb = + PbCrOy) (a) 2PbCrO, + 2Ht + BCL» 2PbCH- + Cr, OF + 4,0 tb) 1, + 28,03 — = + 8,077 (e) © Tinh theo ndng dg mol Theo cac phuong trinh phan dng (a), (b) va (o), 1 mol Pb?* phan ting voi 3 mol $,03-. $6 mo] Pb? trong miu 4a: (24,2 » 0,0962) / (100 x 3). Vay ham Iugng % khdi Iuong chi trong quang 1a: 24,2 x 0,0962 x 207,2 x 100 = 14,55%. 1000 x 3 x 1,105 « Tinh theo ndng dé dvong lugng ‘Trong trudng hop nay khong cin phai viét cae phyong trinh phan Ung dé thuc hien vide tinh két qua vi theo dinh luat v8 duong Itong, cdc chat phan ting v4i nhau theo nhung dugng lugng mol bang nhau, tic la 36 duong Itong mol eta S,0}~ bing 86 duong Juong mol cia Pb?+. Vi mot ion Ph? tao nén mét phan ti PbCrO, ma CrOF” bj chit thanh Cr voi su nhan 3 electron, nén duong lugng mol cla PbCrO, bang 1/3 khdiCO SO HOA HOC PHAN TicH 2» luang mol cba nd, vi vay céng thie tinh trang vdi cong thite dau tinh theo nbng ¢6 mol. 2.10. Cach diéu ché eée dung dich Chat géc Nhiing chat théoa man cdc diéu kién duéi day va ding dé ditu ché cdc dung dich chuan dude ggi la chat géc. a- Chat géc thude loai phan tich hode tink khigt héa hoc. Lugng tap cht trong né nhé hon 0.1%, néu lén han phai tiga hanh tinh ché lai. b- Thanh phn hoa hoe phai ting ding vai met cong thie xéc dinh ké cA nude két tinh. e- Chat g6e vA dung dich eiia no phai bén d- Khoi luong mol phan ti cia chat cang lén cng t6t dé gidm sai sé khi diéu ché dung dich chudh. Thi du. Cac chat sau day la cde chat gée: K,Cr,0;, H,C,0,. 2H,0; Cée kim loai nguyen chat Cu, Ag, Au viv... Nhigu hda chat, ching han cdc mudi kim loai két tinh ngim nuée khi nhan vé phong thi nghiém dudi dang cdc Ip duge bao quan cén than, trén nhan dé chat lugng cao nhu tinh khiét phan tich hodc tinh khiét hoa hoe nhung sau mét thai gian bj thay déi thanh phan do hut dm déu khéng phai 1a chat g6c. Diéu ché cde dung dich chudn Néu co chat g6c thi can mot lugng xde dink chat do trén can phan tich ed dé chinh xsic 0,1 hoac 0,2 mg, hoa tan dinh Iuong lwgng ean trong binh dinh mie ed dung tich thich hop rdi pha lodng bang nude ti vach muc. Thi du, dé diéu ché dung dich chudn Na,CO, 0,1M, can can 106,000 x 0,1 = 10,6000 g chat dé hda tan thanh 1? dung dich ding nuéc eft hai lin méi cat va binb dinh mic dung tich 1 [. Néu khong co cht. gée thi truéc hét didu ché dung dich c6 ndng do gin dung, sau d6 ding chat géc hoac dung dich chudn thich hop dé xdc dinh lai ndng dd, Thi du, ding dung dich chuan H,C,0, biét chinh xdc ndng do (dung dich duge didu ché tit chat goc 1a H,C,0,. 2H,0) dé xdc dinh lai ndng d9 cla dung dich NaOH méi pha co ndng do gan dung. Didu ché dung dich tic dung dich cd nong do khée ‘Trong trufing hop khong co hda chat tinh khist ma chi od dung dich ed ndng dé Ion thi es thé tién hanh diéu ché dung dich chuidn bang cach pha lofing dung dich e6 néng do dé thanh céc dung dich es ndng dé mong muén. Dé tién hanh pha loang can ding nuée edt vA cée dung cu do thé tich chink xc nhu buret, pipet va cdc binh djnh mic. Néu Cy, C, va V,, V; JA ndng dé va thé tich dung dich truge va sau khi phn loing, ta co: Cx Vy = Cyn Vy Sit dung phwong trinh nay eo thé tinh duge thé tich cde dung dich khi tién hanh pha loang. Can chd ¥ rang cac ndng do C, va C, phai ciing thi nguyén va cdc the tich V,, V clung phai cing thu nguyén Thi du: Phai lay bao nhidu ml dung dich HCI 0,1250M dé pha 1/ dung dich HCl 0,1000M Dat thé tich HCI 0,1250M cin lay 18 V, ta ed: 0,1250 x V, = 0,1 x 100030 DAIL CUONG VE PHAN TICH KHOI LUONG Suy ra V, = 800 ml. Lay 800 ml dung dich HC) 0,1250M cho vao binh dinh mde 10 rdi thém edn thin nude eft hai lin dén vach mite va lac déu dung dich trong binh ta sé duge 1! dung dich HCl 0,1000M. Néu C, va C, 1A néng do bidu thi bang % khéi long thi cin phai biét khéi hong riéng cia dung dich dé (chi ding cong thie C, x V, = C, x Vz khi cae ndng 46 1a mol/l hoac néng 46 duong Iygng hoac dé chudn). Thi du. Can lay bao nhiéu ml dung dich axit sunfuric dac 98% ed d = 1,84 gim] dé pha mét lit dung dich H,SO, 5% eo d = 1 giml. Dat thé tich dung dich axit dae cin lay la V, ta cé: V, x 1,84 x98 = 10001145 Suy ra, V, = 27,73 mi.CHUONG 3 AXIT VA BAZO “PHAN UNG TRAO DOI PROTON 3.1, Dinh nghia Dinh nghia axit va bazo cua Brinsted Co nhidu dinh nghia ve axit va bazo, Trude day ngvai ta thuang sit dung rong rai dinh nghia cua Arrhenius. Theo dinh nghla dé axit 14 chat khi hoa tan vao nue phan }i thank jon (FT*) va anion con bazg thi phan li thanh ion hidroxyl (OH) va cation. Nhung dink ngbia nay khong téng quat vi chi ap dung cho mot sé loai chit va khi dung mdi la nude. Nam 1923 nha bac hoc Dan Mach J.N. Brinsted d@ ra mot dinh nghia téng quat hon nhit sau: Axit la chat e6 kha nang cho proton va bazg la chat cé kha nang nhan proton. MOi axit sau Ikhi cho mét proton tré thanh mt bazg goi la bazo lién hgp vai axit dé. Mét cap axit - bazo lién hop duge biéu dién bing hé thitc sau: Axit == Ht + Baza Proton khéng co khé nang ton tai d trang thai ty do, vi vay mot chat chi thé hién 76 tinh axit hoae bazo trong dung mdi cd kha nang nhan hoae cho proton Nudc JA dung mi vita od kha nang cho vita cd kha nang nhan proton, nén ede bazy va axit c6 thé thé hién tinh chat cla ching trong nuéc. Bazo + H,O == Axit + OH™32 AXIT VA BAZO - PHAN UNG TRAO DGI PROTON Thidy: NH, +H,0 == NH{ + 0H” (baza,) (axit,) (axit,) (bazo,) Axit + 1,0 == Bazo + HyO* Thidy: HE + H,O = H,O* + FO (axit,) (baze,) (axit,) (baz0)) Cae thi du khde vé cap axit - bazo lién hop trong nude: NH} +H,0 == NH, + H,0° H,PO,+H,0 == H,PO; + H,0* CN +H,0 == HON + OH” CH,COO- + H,0 == CH,COOH + OH ‘Theo quan niém c6 dién thi NH}, HjPO; khong phai la cdc axit; CN”, CH,COO- khong phai 1a cdc hazo ma la cdc cation va anion cia céc mudi thiy phan. Nhung theo dinh nghia cha Bronsted thi cdc ion do 1A nhiing axit va nhiing bazo va phan ting thoy phan chinh la phan ting cia axit (NHj, H,PO;) hoge bazo (CN~, CH,COO~) véi nuée ‘Tuy theo ban chat cia dung mai, mot chat cd thé thé hign tinh axit hoac baz0. Thi du: Trong made CH,COOH La axit vi nd cho mide proton tao thanh bazg lién hep CH,COO- CH,COOH + H,0 == CH,COO” + H,0* (axit) (bazd 1h) Nhung trong hidro florua Jéng (H,F,) th) CH,COOH lai 1a bazo vi nd nbAn proton cia dung méi do dé tao thanh axit lién hop: CH,COOH + HF, = CH,COOH} + HFy (baz) faxit 1-8) Nhu vay, qua cde vi dy trén, ta thay dinh nghia axit, bazo cha Bronsted téng quat hon dinh nghia cha Arrhenius va cé uu diém lA néu r6 duc vai tro cia dung méi. ‘Trong chvung nay ching ta chi dé cAp nhiéu dén cdc phan ang axit - baza trong dung méi nuéc. * Tich 96 ion cla nude Nuéc t& mot dung mdi ty proton phan, tife JA nd vita 1A mOt axit vita la mot bazo: H,0 + H,0 =* H,0* + OH~ Hang sé can bang cia phan ting dé la: _ CHOON} ~{H,OF Nuc phan li rat {t, [HO] duge coi la hang sé, way: KI [H,0}7 = Fay om [H,0*}(OH7] (3-1) K,j,0 dutve goi 1 teh 8 fon cia nude. No la mot hang s6, chi phy thude vie mbit 4, khong phu thude vao ndng do cia ce ion H* va OH™ trong dung dich nude. 6 25°CCO SO HOA HOC PHAN TICH B tich s6 ion cla nude Ayo = 10°4. Nevai ta con thutng dang Phung = —lekio = 1M. # Cuing do ctta axit vit bazo, Hang 86 axit K, va hang s6 bazo Ky: Mot axit khi duge hoa tan vio nude s€ nhudng proton cho nuée theo phan ing: A+H,0 ==B + H,0+ fa) trong d6, A la axit, B la bazo lién hgp voi A. Cong thite H,O* chi proton bj hidrat hia va duge goi JA hidroni hoac oxoni. Axit cang manh tie la nhwéng proton cho nude cing nhidu, tic 1a hing sé can bang: B)[H,0° «= BESO] {A][H,0] eta can bang (a) dé cdng len. Nong do eta nude, H2O xép xi bang 1000/18 = 55,5 M 1a twong déi 1én so voi ndng 6 can bang cba cde ion vA phan ti khdc trong dung dich, nén ed thd cot khong adi va ta ed thé viet: (B)(H,0°) [A] K, duge goi lA hang sé axit va biéu thi cwong do eda axit, vi K, cang lon, axit cang manh. Dé tien cha vige tinh toan, ngudi ta thubng con dang pk, = —IgK, thay cho K,. Thi da: Axit axetic CH;COOH ed K, = 1,74.10, pK, = 4,76 manh hon axit xianhidvic HON e6 pK, = 62.10", pk, = 9,21 Doi véi cdc axit manh phan li hoan toan trong aude (thi du: HCl, HNOs, HCIO,...) thi K, coi nhu bang + ‘Mot baza khi duce héa tan trong nude sé nhan proton cia nuée theo phan ting: B+H,O == A+0H- (b) Bazo cing manh ttc 1a nhan proton cia nude céing nhivu, edn bang (b) chuyén ve phia phai cang nhigu, ttc la hAng s6 can bang: (AJ[OH™] Ke {B][H,0} cua nd cAng ldn. Trong cde dung dich nuéec loang ndng d6 [11,0] co thé duge coi nhit khong ddi, nén ed thé viet: K[H,0] = (2) (AIO) (B] Xi, duce goi ls hang s6 bac va biéu thj cutmg do ca baza. Ngudi ta cing diing pK, = -lgk,. Thi du: NH, cd pK, = 4,76 la baza manh han hidrazin ed pK, = 6,01. Déi véi ede bazo manh (nb KOH, NaOH...) phan li hoan toan trong nuée thi K,, vo cig lén coi nhu bang +2 C6 nhiing axit ma phan ti chia 2 hose hon 2 proton ed thé téch ra duce trong nude. Nhitng axit dé duoc goi la da axit. Trong nude phan td cia cdc da axit phan li Han lugt theo nhigu nde va méi nae cho nude mot proton. Ung véi mdi nie co mot hing (H,0] =k, a)34 AXIT VA BAZO - PHAN UNG TRAO DOI PROTON 86 axit, Thi dy: axit photphoric H,PO, phan li theo 3 ndc va cd S hang 36 axit 1 Ky, K, va K, tuong ting voi céc nac a, H,PO, + H,0==H,PO, + H,0* pK, = 2,12 H,P0; + H,O=>*HPO; + H,0* pK, = 7,21 HPO; + H,0 == PO} + H,O* pK, = 12,36 ‘Puong ty nhy trén c6 nhiing da bazg 1a nhitng bazo ma phan tit khi cho vao nuée Jan lugt nhan mét, hai, ba proton theo cdc nde khae nhau. Thi dy: PO} la mot da bazo: PO} + H,O == HPO} + OHT pK, = 1,64 HPO? + H,O5"H,PO; + OH™ PKy, = 6,79 H,PO; + H,0 ==H,PO, + OH7 PKy3 = 11,88 © Quan hé gilta hang $6 axit vi hdng 86 bazo cia mot edp axit - bazo lién hop: Gia su A la axit va B 1a bazo ign hyp vdi A, nhy CH,COOH va CH,COO~ hose NHf va NH,. Nhan cae hang s6 K, va K, voi nhau, ta co: (B][H,O*)[AVOH™] K,» Ky = = BOOK = Hn (AB) 2 hoac pK, + pK, = ph, y = 104 6 25°C Nhu vay, lich gitta hang 86. axit vA hng s6 baza cla mot cap lien hgp bang tich 36 ion eta nude. Vi lich 36 ion eta nude 1a hing sé nén hang s6 axit cing lan (axit cdng manh) thi hang 86 clia bazo lién hgp cing nhé (bazo cang yéu) va nguge lai. Biét duge mot trong hai dai lugng ta tim duoc dai lvgng kia. Thi du: biét pK, cua CH,COOH bang 4,76 thi tinh duge pK, cla CH,COO™ bang 14 ~ 4,76 = 9,24. 3.2. Phuong trinh bao toan proton Phuong trinh bao toam proton ela mét dung dich axit - bazd la phuong trinh biéu dién sv trao déi proton cla cdc axit baze cd trong dung dich dé qua cdc néng dé can bang ota cdc edu ti trong dung dich: s6 mol proton cac axit cho ludn bang s6 mol proton cae bazd abén - Sau day 1A mot s6 thi du Thi du 1: Phuong trinh bao ton proton cia nude nguyén chat, Trong c4c nguyén chat chi co mét can bang trao déi proton: H,0 + H,O == H,0* + OH 86 mol proton nuée nhan 1a [H,0*] bang s6 mol proton nude cho {OH-] vi 1 phan tit nuféc khi cho di 1 proton thi bién thanh ion OH~ nén phuong trinh bao ton proton la: (H,0°] = [OH™} Thi du 2: Xét dung dich HCI néng do C mol/lit. ‘Trong dung dich cé 2 axit 1a HCI va nude va 1 baza 1a nude. Trong dung dich do xay ra cde qua trinh sau: HCl +H,0 == HOt + Cr)CO $6 HGA HOC PHAN TiCH 35 H,0 + HO S= H,0'+0H- S6 mol proton nude nhan bang sé mol proton HCl cho va nuée cho: {H,0*] = [OH] + [cI-} (OH }+c Tht da 3: Xét dung dich hon hop HCi eM+ CH,COOH cM. Trong dung dich oo axit mgnh HCl, axit ygu CH,COOH va bazo yéu HO, axit you H,O nén xdy ra cdc qua trinh sau: HCl+H,O === H,0°+cI- fa) CH,COOH + H,0 == CH,COO- + H,Ot — () H,0 +H,0 == .H,0* + OH- () 86 mol proton niée nhan bang s6 mol proton 3 axit cho nén: (H,0°] = [OH] + [Cl-] + [CH,COO-y [OH-] + C, + [CH,cOO-] Tht du 4: Xét dung dich NH. Dé 1A dung dich eta 2 bazo (H,0, NI,) va mot axit (H,0): NH, + H,O == NH{+0H- (a) H,0 + H,0 == H,0°+ OH- (by 86 mol proton cac bazo nhan bang sé mol proton axit cho: [H,0*] + (NH}) =[0H-] Thi du 5: Xét dung dich hén hop CH,COO- va CN-. Trong dung dich ed 3 bazo va mot axit, nén xdy ra cde ean bang: CH,COO- + H,0 == CH,COOH + OH- (a) CN-+H,O == HON +0H- H,0 + H,0 = H,O° +OH- () Téng sé mol proton ma cée bazo nhan bang s6 mol proton nude cho nén phitong trink bdo toan proton 1a: (CH,COOH] + [HCN] + [H,0*] = [OH-) Thi du 6: Xét dung dich H,PO,. Dung dich gm 2 axit: da axit (H,P0,), don axit va don bazo (H,O) nén trong dung dich cd cae can bang sau == HO" 4 H,PO; f@) == H,0* + HPO? (b) == HO* + Po} rc) HO +H,0 == H,0* + oH- (a) Phuong trinh bao toan proton cia dung dich nay: (H30°] = [OH™] + [H,P0;] + 27HPO;-] + 3(PO}}36 AXIT VA BAZO - PHAN UNG TRAO DOI PROTON Thi du 7: Xét dung dich da baze COf- (Na,CO,) Cav cn bang trong dung dich nay: CO} + H,O == HCO; + OH- (a) HCO; + H,0 == H,CO, + OH™ (by H,0 +H,0 ==H,Ot + OH- © Phuong trinh bao toan proton cia dung dich: [H,0*] + [HCO;} + [1,C0,] = [OH] Thi du 8: Xét dung dich NH,CH,COO. ‘Trong dung dich nay e6 cc can bang sau: NHj + 1,0 == H,0* + NH, (a) CH,COO~ + H,0 == CH,COOH + OH”) H,O +H,0 = H,O* + OH- fc) Phuong trinh bao tan proton cia dung dich li: [H,0*] + [CH,COOH] = [OH] + [NH] 3.3. pH cia dung dich hé don axit - bazg trong nude Dé tinh ndng dé can bang cua ion H,O*, dé tinh pH cia dung dich esc hé axit - bazo trong nutde noi chung, ta cn biét cic qua trinh trao déi proton xay ra trong dung dich ri dua vao phuong trink bao toan proton, phuong trinh biéu dign cdc hang sé axit, hang s6 bazo va phuong trinh bao ton khdi lvgag cua cac edu tit trong dung dich dé thigt lap phitong trinh cho ndng do edn bang cila ion H,O*. 3.31. pH cha cée dung dich axit manh Cae axit manh thusng gap déu la dea axit nhu HCI, HNO, HBr, HI, HSCN, HCIO,... chi tric axit sunfurie I da axit (80, 05 K, = + va Ky = 10%) Gia sit ed dung dich axit manh HA ndng do C,. Trong dung dich nay ed hai qua HA +H,O —=+ H,Ot + Am H,0 + H,0 = H,0° + OH” Dé dan gian hda, tit day ta thay H,O* bing H+, nén hai qua trinh trén ed thé duoc viét nhu sau HA +Hi+A> (a) HO Ht + OH” (b) Phuong trinh bdo toan proton cia dung dich 1a: {H*] = [A7] + [OH™] © Phuong trinh dé cing chinh 1 phuong trinh trung hoa dign (trung dung dich bat ki téng dién tich duong luon lon bang téng dién tich Am), Ao ‘hay [AT] = Cy va [OH>] = 2° vao (e), ta 6: Gt)CO SO HOA HOC PHAN TICH ca a Hy + the (3-5) (Hy hone TH}? - CAE) = tyyg = 0 a5) Phuong trinh (3-5") trén ta phvong trinh téng quat dé tinh néng dé can bang ion H* cila dung dich bat ki don axit manh nao. Nhung trong thc té cd thé don gin héa phuong trinh dé trong nhiing diéu kién sau Néu C, twong d6i 1én hon 107M (thueng nhu vay) thi eo thé bé qua [OH-] canh Cq trong phuong trinh (c) va do dé: (H*] = c, (3-6) Thi du: Néu Cy = 106 va @ nhigt do 26°C ta bd qua [OH] canh Cy, thi (Ht to“ Cy = 10%, Nhu vay pH = 6 va [OH™] = 10° va viée bé qua [OH™] 1a hyp Ii vi khi 10 bé qua [OH™] canh C, thi sai s6 chi bang: 10% x 100 10% = 1% Néu Ca > 10% ma ding cong thite (3-6) thi sai s6 con nhd hon nia. Nhung néu C, xéip x1 10°? thi phai tink [H*] bang cach giai phuong trinh (3-5') vi trong trudng hop nay khong thé bé qua [OH™] canh Cy, tite JA phai ké dén su phan li cia nude. Thi du: Néu 6 25°C va Cy = 107M thi sau khi gidi phvong trinh [H*? - 107 - 194 = 0 sé tinh duge [H*] = 1,26.10°7 va pH = 6,79 Néiu 6 25°C va C, = 10M thi sau khi giai phwong trink bAc 2, ta sé tinh dude (H*] = 1069! va pH = 6,91 Néu C, nho hon 10M, thi ed thé bo qua Cy canh [OH-) va coi pH = 7, thie 1A nong do axic Khong ding ké so véi su phan li cia nuée 3.3.2. pH cita ede dung dich baze manh Gia sit e6 dung dich bazs manh (thi dy KOH, NaOH) ndng 46 Cy NaOH Nat + OH” fa) H,0 + H,0 == H,0* + OH” () Phuong trinh bao ton proton cila dung dich nay: [H'] + Cy = (OH™] (3-7) k Thay [OH~] =—22— yao (3-7), ta ev: taal (HYP + Cy] ~ Aygo = 0 (3-8) Phuong trink (3-8) 18 phuong trinh téng quat dé tinh ndng dO can bing cua ion Ht trong bat ki dung dich don bazo manh nao. Céing nhu d6i voi dung dich axit manh, trong38 AXIT VA BAZO - PHAN UNG TRAO DOI PROTON nhidu trugng hgp ta khong c&n phai giai phuong trinh bac 2 dé dé tinh pH cia dung ajeh bazo manh. Néu Cy = 10°, ta cd thé bé qua [H*] canh Cp va cd: [OH-] = Cy Reno Hy = #20 [OH] PH = physo + logcy (3-9) Thi du: - Néu 6 25°C va Cy = 105M thi: pH = 14 + logl0S = 14-5 =9 - Néu gid tri Cy xp xl 10°7 thi gidi phuong trinh (3-8) dé tink [H*] - Néu Cy = 107M thi giai phuong trinh: [H*P + 107[H"] — 10% ta sé duge [H*] = 6,28.10°%; pH = 7,21 - Néu Cy = 10° thi gidi phuong trinh: (H+? + 104[H*] - 104 = 0 ta sé dude [H*] = 9,5.10%; pH = 7,02 - Néu Cy < 10°* thi bé qua Cy canh [H*] va ta cd pH = 7 4 25°C 3.3.3. pH chu cde dung dich don axit yeu Gia sit co dung dich axit yeu HA nong dd Cy ‘Trong dung dich nay co hai can bang sau: HA == Ht+ Aq fay H,0 == H* + OH- (by Dé tinh pH etia dung dich, ta cd thé di tit phugng trinh bao ton proton: (H*] = (OH™ + [A] © Phuong trinh bao toan kh6i lvong voi HA: (HAY) + [A7] = Cy @) va phuong trinh ela hang sd axit cla axit HA: CAT "=k, fe) {HA} ‘is {HA] Ti (e) > [Ht] =x, —~ 2) ww] Te te) = [A7] = [H‘] - [OH7] fe’) "Tit (@) va (co) + [HA-] = C, - [HAT] = Thay (c’) va (g) vao (A, ta duge: C, - [Ht] + [OH x LAT Ul ] ~ [OH] '. ~ {H] + [OH] iH] (3-10)CO SO HOA HOC PHAN TICH 39 Phuong trinh (3-10) la phuong trinh téng quat dé tink [H*] cba dung dich axit yu bat ki nao, nhung lai ta phuong trinh bie 3 theo [H*], nén khong gidi duge mét eich dé dang. Trong thue té phuong trinh dé ¢6 thé duge dun gidn héa thanh phitong trinh bac 2 trong nhiing trutmg hyp co thé bd qua nhing nbng do nhé bén canh nhiing ndng dd 1én. a) Néu [OH-] << [H'], tiie 1a coi nude phan li khéng dang ké [didu nay rét thuing gep_vi ngay trong nude nguyén chat nuée da phan li rat kém((H*] = 107M) nén trong dung dich HA, su ¢6 mat cia ion [H*] ctia cn bang (a) da lam cho can bang (b) chuyén sang phia trdi, tic la lam gidm sv phan li cia nude, thi phuang trinh (3-10) s8 duge don gian hoa thanh: ‘a ~ [H'] 1H") b) Néu [H'] << C4, tiie coi HA phan li khong dang ké thi phuong trinh trén chi con lai la: (3-11) FUP = K,Cq va (H] = VEC (12) 1 1 va pH = 5 pK,- 3 1kC, (3-121) Tht du 1: Tinh pH eda dung dich axit axetic CH,COOH 0,1M. Axit nay o pK, = 4,75. ‘Trong trutng hyp nay ta 6 dé ditu kién dé ap dung cong thite (3-12") pH = 3 (4,75 ~ Ig 0,1) = 2,87. Thi dy 2: Tinh pH cia dung dich mudi amoni NH} 0,1M. Biét NH, cd pK, = 4,75. NHj Ia axit lién hop cia NH: NH] + H,0 == H,0* + NH, Kyo _ 104 Vi vay Kyat = = 10-925, Fyn, 10475 Ap dung cong thie (3-12"), ta PH = 0,5 x 9,25 - 0,5.1g0,1 = 5,13. Voi gid tri eta [H*] = 10°15 ta thay eae didu kign dé dp dung phuong trinh (3-12) déu duge théa man. Thé du 3: Tinh ndng do ion H* va pH cia dung dich axit salixilic 103M, Biét axit c6 pK, = 3. D6i vai dung dich nay, ta chi bd qua duge su phan li cla nuée chit khong bd qua duoc su phan li eta axit vi pX, etia no tuong déi Ion. Nen dé tinh pH ta 4p dung phuang trinh (8-11): 103- [Ht [H*] = 103 (H’] hoac [H*? + 10°[H*} ~ 106 =40 AXIT VA BAZO - PHAN UNG TRAO DOI PROTON Sau khi giai phuong trinh nay, ta duge: [H*] = 6,2.10-; pH = 3,21 Ching ta hay tinh biéu thc ndng do can bing cha HA va A~ trong dung dich axit HA nbong dd C,. Ta sit dyng hai phwong trinh: {HA}+ {AT] = Cy fa) Ht [AT) OPIA)L x, ©) [HA] od thé viét (b} duéi dang: Al _K, — = Cr) [HA] [H"] va od thé bién déi thanh: We [HA] + [Aq] [H*] + K, [A] K, ce +k, Tt dé suy ra: [AT] = ak (8-13) (H'] + K, [Ha] ~All (3-14) Ht + K, Theo ede biéu thiic (3-13) va (3-14), sy phan li cia HA phu thudc vao cutng do cla axit 46, duge dac trung bang dai Itong K, va ndng dd C, cla dung dich. Do dian li « cia mot dung dich axit HA duge din nghia bang ti s6 ndng dd [A-V/C,, theo (8-13) bang: x, (Ht) +k, Nhu vay, xéc dinh duge pH cia mét dung dich axit HA ndng dC, 86 tinh duge do dign li cia dung dich do. Thi du: Tinh dd dién li cia cde dung dich axit axetic e6 cde ndng dé tuong wing la 0,1M va 0,001M. Vai dung dich ndng dé 0,1M; 4p dung cong thie (3-12) tinh duge [H*] = 1077 Voi dung dich ndng ¢@ 102M ap dung phuong trinh (3-11) ta tinh duge [H*] = 107%! Ap dung phuong trinh (3-15) ta tinh duge do dign li « cia dung dich ndng d6 0,1M 1a 0,013 hoae 1,3%; cha dung dich 10°°M IA 0,126 hoac 12.6% 4.3.4. pH cla dung dich bazo yeu Nou hoa tan mét bazd yéu B vao nuée thi trong dung dich ed hai can bing: B+ H,0 == BHt + OH” fa) H,0 =2= Ht + OH- th) fHa > (3-16)CO SO HOAHOC PHAN TICH al Tuy theo gid tri cia K, va ndng dO cita dung dich (tic IA gid tr] Cy) ma ean bang (@ Anh hudng dén can bang (b) téi mite ndo. Cang nhu trudng hop dung dich axit yu HA, déi vai dung dich bazo yéu B cd hang s6 baze K,, ndng do Cy, ta cd thé thiét IAp bigu thic tinh ndng do can bing ca cde cau tu ti ede phugng trinh sau: + Phuong trinh bao toan proton: [OH-} = [BH*] + [H'] fo) - Phuong trinh bao toan khéi lugng déi vdi B: (8) + [BH'] = c, (a) ~ Phuong trinh ctia hang s6 baza: [OH-][BH*} Bi ‘Ti cdc phuong trinh do, ta rit ra duge: C, — [OH-) + [H* fou] = Hyp C8 LOH) + BE) (OH y= K, © (3-16) Phuong trinh t6ng quét trén cing 1A phuong trinh bie 3 déi véi OH nén viee gidi rat khé khan. Tuy nbién trong nhing diéu kién cy thé phuong trinh do cing co thé duge dan gidn hoa tudng ty trung hop dung dich don axit yéu. Khi K,, khong qua ton va Cy Khong qua nbd, ta e¢ thé bS qua [H*] canh [OHM}, tue 1 bé qua cn bing (a) va phugng trinh (3.16) chi can lai: Cy — [OH7] [OH] (OH"] = K, (B17) Néu bazd phan li khong dang ké, tic JA ta bd qua duge [OH] canh Cy thi phuong trinh tren duge don giin hda thank (OH? = x, va suy ra 1 1 . POH = 9 PKy~ 5 logCy (3-18 pH = 14 - pH (4 25°C) (3-19) Thi du 1: Tloh pH ei dung dich NH, 0,1M biét NH, es pK, = 4,6 sit dung cic cong tite trén, ta tinh duge pOH = 4,26 va pH = 9,94. Thi du 2: Tinh pH eta dung dich CN 0,01M, bit HCN e6 pK, = 9,21. CN- la baza lien hgp cia HCN: . CN” + H,0 == HON + OH- fa) Néen Kon” = 104 Kycy = 10479, Ap dung phyong trinh (3-18), ta tinh duge pOH = 3,4 va pH = 10,6. 44. pH eda dung dich hén hop axit va baze liga hgp. Dém ning PH eda dung dich axit va bazg lien hop HA + A~ (Phi du: CH,COOH + CH,COO-a AXIT VA BAZO - PHAN UNG TRAO DOI PROTON hoge NH{ + NH,) thay déi khong ding ké khi thém vao mot it axit manh hoac bazo manh, vi néu tang ndng dé ion H*, thi A~ sé két hop véi H* tao thank HA, ngitoc lai néu gidm nong do H+, thi HA sé ph4n li thém dé sinh thém H*. Két qua 1a sau khi can bang thiét lap thi ndng d6 eta ion H* trong dung dich sé thay déi khong dang ke Vi vay, dung dich hén hop axit yéu va bazo lién hyp vdi né dude goi la dung dich dém. Chang ta hay thiét lap cOng thie tinh pH cia dung dich hén hop axit HA ndng do C, va mudi NaA ndng dé Cy. ‘frong dung dich nay es hai can bang: HA = Ht + AW (a) HO = Ht + OH- (b) Dé tink pH ching ta c6 ede phuong trinh sau: - Phuong trinh hang s6 axit: EA] —— ©) [Ha] - Phuong trinh bao toan khéi lugng cla HA va Aq: [HA] + [A7] = Cy + Cy @ - Phuang trinh trung hda dién: [H*‘] + {Na*] =(OH-]+ {A ] Hoac [H*)+C, =[OH™}+ [A] 4) Ti (e) suy ra: [AT] = Cg + [H*} - [OH] wo Tit (d) va (f), suy ra: [HA] = C, — (H*) + [GH J tg) Thay (f) va (g) vao (c), ta suy ra: sy ~ (AI) + (OHM) * Cy + OH] - [0B] Biéu thie (3-20) cd thé thiét lap tir hé thie (c) va hai can bang {a) (b) vdi lap luan sau: Nong dd cén bang cia axit HA, [HA] bang ndng do ban dau cua no tric di nong do Ht do HA phan li ra. Nong 46 H* do bang ndng do can bang [H*] trit di ndng do H* do nutée phan li ra, tric 1a trir di (OH7) [HA] = C, — ((H*] - (OH) = €, ~ (H") + (OH) Nong dd can bang cla A~, [A7] bang ndng do ban dau ciia nd Cy, cong voi ndng do A> do HA phan li ra: (Al = Cy ~ [HY] ~ (0H) Thay cac biéu thie trén cia [HA] va [A] vao biéu thiée (c), ta suy ra ngay biéu thie (3.20). D6i véi cde dung dich dém thugng cs Ht va OH™ khong dang ké 50 vdi C, vA Cy nén phuong trinh (3.20) due don gian hda: (H’] (3-20)CO 86 HOAHOC PHAN TICH B Cs (Hy = K, @2p Ce oe Hoac pH = pK, + loge (3.22) Thi du 1: Tinh pH eta dung dich hén'hop CH,COOH 0,1M + CH,COONa 0,1M Ap dung cong thie trén, ta ed: o1 pH = 4,75 +log— = 4,75 0,1 Thi du 2: Tinh pH saw khi thém 10? mol HCI yao 1 1i¢ dung dich dém trong thi du 1 Khi them HCI vao dung dich d¢m trén thi thue té xay ra: H' + CH,COO- + CH,COOH va c6 thé coi: [CH,COOH] = 0,1 + 0,01 = 0,11 (CH,coo-] = 0,1 ~ 0,01 = 0,09 O11 Do do: HY} = 10475 jogp— (HY) fF 09 O11 pH = 4,75 -— Le = 4,75 - 0,087 = 4,66, 9, Nhu vay, khi thém 107 mol vao 1 lit dung dich dém o think phan nbw trén thi PH eda no chi gidm di 0,087 don vj pH. Nhung néu thém 102 HCI vao 1 iit nuéc cat thi pH 36 gidm tir 7 xuOng 2 ttc la 5 don vi pH. Tht du 3: Tinh pH cia dung dich hén hop NH, 0,1M + NH,Cl 0,1M. PKxuy = 14 — py, = 14 - 4,75 = 9,25 Ot PH = 9,25 - logs = 9,25 Wd Bim niing Dé bigu thi kha nang cia dung dich dém chéng lai su thay déi pH khi them axit manh hoac bazo manh vao, ngudi ta ding khai nigm dém nang. Dem nang duge dinh nghia bing s6 mol cba mot bazo mamh (hoac mot axit manh) can them vao 1 lit dung dich dém dé pH ciia né tang lén (hoac gidm di) 1 don vi. Vi dem nang thay d6i cng véi thanh phan dung dich, nén eang thay déi cing voi PH, do de dé dinh nghia duge chinh xée cin phai biéu thj dem nang # 4 dang vi phan: db de f= --—, dpH apt trong ds db va da Ian uot 1a 36 mol bazs manh va axit manh cin thém vio mot lit dung dich dim dé pH eta né tang tén hay gidm di mot lugng bang dpH. Ta hay thiét lap cong thi tinh dém nang # eta dung dich dém gdm axit yéu HA ndng do C, va mui Nad ndng do Cy. (3.28)a4 AXIT VA BAZO - PHAN UNG TRAO DO! PROTON Vi Cy + Cy = C khong thay déi, nén khi them mot axit vao Jam thay déi C, va Cy thi dCy = - dC,, Nhu vay, néu thém db mol bazg mgnh vao | it dung dich dé tang ndng dB lén mot Iwong dC, thi ndng do cia HA sé gidm di mot long bang dC, bang dC, Vi vay: Vi pH = ~log[H*], nen: ab ab aCy po = -23 = ~2,3 [H+] pH aln[H*] ate] Vi Cg = [Nat], nen ta tinh duge Cy, tit phuong trinh trung hoa dien: (Na*] + [H*] = (OH7] + [A] (3.24) CK Cy = [Na*] = {OH-] - [H*] ++ (a) (H') + Ky Tinh dao him cia Cy theo [H*]: aC, Kyo CK, a{H*] (HYP (Ht) + KF ‘Thay biéu thie trén vao phuong trigh (3.24): 1,0 OKA) = 28 (sant aa 8 (ay tT (Hy +K)e ‘rong trudng hgp H* va OH~ khong dang ké so voi C, va Cy bie Ja trong trutng. hop pH cia dung dich dém duge tinh bang cong thie don gidn (3.21) thi dem nang # duge tinh bang hé thife (3.25) duge don gidn hda: (3.25) CK,[H*} p= 2,3 —~— (3.26) c ({H*] + K,)? Thay (H*] = K, ~ vio (3.26), 86 duge: (3.27) B 88 ewe dai khi 8 sang khong, tie la kh C, aC, Doi voi ty sé CalCy khong dei, f ty Ie voi téng ndng do C. He thite (3.27) duac thiét lap véi gid thiét [H*] va {OH”] khong dang ké so voi Cy va Cy nén khong thé ap dung dude vdi cée dung dich dom qua long. Thé du: Tinh dem nang cia dung dich dem CH,COOH 0,01M + NaCH,COO 0,1M Ap dung c6ng thie (3.27) ta tinh duge: 0,01.0,01 | 6 = 2,3 ——_—" = 00115 0,02 0,5CO SO HOA HOC PHAN TicH 4s Mot cach gin dung c6 thé dink nghia dem nang la ty 56 cia higu ndng do vA hiéu pH tuang dng khi ching 6 gid tr} tuang déi ahd: AC, AC, pot 2 A (3.28) ApH ApH ‘Tir dinh nghia nay ching ta ed thé tinh dude nhétng hin hop dem can thiét Thi dui Tinh nong do cia dung dich dem CH,COOH + CH,COONa co pH bang 5 48 Khi thém 0,25 mot HCI vio 1 it dung dich d6, thi pH cia né khong gidm qua 0,5 don vj. Dem nang cia dung dich duyc tinh theo céng thite don gidn (3.28) la: 0,25 B=— = 05 Mi pH eta dung dich dem 18 5, nén ta e6 thé bé qua [H*] va [OH] canh C, va Cy Ap dung cong thtic (3.26) CAT (Ht) + Kt €.1,74, 105.105 C05 + 1,74.10°5)2 ‘Tir dé tinh duge C = 0,9M. Vi vay, khi them 0,25 mol HCI vao dung dich dém CH;COOH + NaCH,COO (pH = 5) e6 téng nbng dé 1a 0,9M (1 M) thi pH cia no khong gidm qué 0,5 don yj. B= 0,5 = 2,3 0,5 = 2,3 3.5. pH etia dung dich hén hgp axit va bazo khong lién hop Gia sit e6 hOn hep gom axit HA, ning do C, cia he HA,/Ay va baza Ay ndng do Cy cila he HA,/Ay, cae hang s6 axit cila 2 hé la Ky vA Ky Dé tinh pH eta hén hop nay ta viét phugng trinh bao toan proton xuat phat ti HA, Ay va H,O [A"] + (HA) = [OH] + (ary fa) Néu (H*] va [OH-] khong dang ké, thi: (HA) = [A7) Hoa CoH] OAR, w 2) K+ Hy Neu Cy = Cy, thi: ty 4K, K+) K+} (ec) Hoae IP = KK, [H"] = vK\R,46 AXIT VA BAZO - PHAN UNG TRAO DOI PROTON va pH = 0,5 (pK, + pK) (3.29) Thi du: Tinh pH cia dung dich NH,CN 0,1M, Biét HCN c6 pKyycy = 9.21 va NH, 6 PK yy, = 4,76. Day 1A hén hop gdm NH va CN~ co ndng do ban dau bang nhau 0,1M Kyyf = 10M10% = 1024 - Ap dung cong thite (3.29), ta ed pH = 0,5 (9,24 + 9,21) = 9,28. Néu cdc ndng do C, va Cy khong bang nhau, C, = mC, thi phai giai phutong trinh: Cul] my, K,+ OP) K+ 1) HY mK, hoae me (3.30) K,+ (0) Ky, + 4 Ta eo thé don gian hda phuong trinh nay them nia, néu ta so sdnh cdc gid tri cia [Ht] va K,, K, bing cach ding 4% thj logarit néng 46 cia dung dich don axit - bazd. 3.6. Da thi logarit néng 46 céa dung dich axit yéu HA Dd thj logarit néng d6 1 dd thi tap hyp nhig duang biéu dién sy bién thién cha logarit néng dé cdc ion va phan tit theo pH vao cing mét hé toa dé. ‘Trén true hoank ciin hé toa dS vudng gcc ta ghi gid tri pH, trén truc tung ghi gid tri logarit ndng d@ cita cdc ion va phan ti cd trong dung dich. Da thi logarit nang 4 cla axit you HA gdm bén duing bidu dién su bién thidn cla logH*], log{OH™], log[A~] va log{HA] theo pH. Vi lg(HI*] = —pH, nén dudng biéu dién Ig(H*} la dudng thang cs hé-s6 goc bang -1 Vi logiOH] = pH - phy,o, nén dung bidu dién log[OH-] la duting thang c¢ he 86 ge bang +1. Vi tich cta haf he s6 gc bing -1, nén hai dutng dé 18 hai dubng vubng géc véi nhau va c&t nhau tai diém ma toa do théa man phuong trinh: Hoae ‘Tie la diém cd heinh do pH = 0,5 phy,o a tung dO log{H*] log(OH"] = -0.5 Phyo = 14, non giao diém cia hai duimg 46 od hodnh do bing 7, tung 46 bang —7 Dé ve cde dudng log HA va log A’, ta ding cac bigu thie: (H" c.f) (HA): ow jay) —— sm 1H) +B, ary +k, ‘Méi hé anit baza tien hop due dac tring bing C, va K,, nén trén do thi diém cd hoanh dé pH = pk, va tung d6 logC, duge goi la diém he (diém x trén hinh 3.1). O ben a hé, [H*] >> K,, nén cde biéu thite (a) va (b} duge dan glan hda thanh: C.K, Hy {HA} = Cy; [Aj =CO 86 HOA HOC PHAN TICH a Do do: log{HA] = logC,; log(A~] = logC, ~ pK, + pH Nhu vay, 6 bén trai diem’ hé dung log(HA] 1a doan thing song song voi truc hoanh va tring vai duing log@ va duéng log[A~] 1a doan thang cd hé 86 gée bang +1. Hai doan thang d6 néu duge kéo dai vé phia phai sé cét nhau tai diém hé, vi toa do cia diém he nghiém dung c& phuong trinh dudng log[HA] ldn phuong trink duéng Jog[A”]. Ngoai ra duting log{A~] con song song véi dutng log{OH-] vi ca hai du od cling hé sé géc bang +1. © phia ben phai diém he, thi [H+] << K,, nén: [A-] = Cy; log(A-] = lec, e,(H* va (HA) a hoge log(HA] = IgC, — pk, — pH Vi vay, ding log{HA] trong khu vc nay 1a doan thing os hé sé géc 1a —1, nén nd song song véi dudng log[H*], cin dutmg log[A~] 1a doan thang song song véi true hoanh, tic 1a tring voi dutmg logC,. Hai doan thing nay néu duge kéo dai sé edt nhau tai diém he. © gin diém he, [H*] va K, xp x1 bing nhau, nén phai tinh (HA) vA [A-] theo ede cong thiic (a) va (b) 4 trén, Do do, sy bién thién 4 doan dudng cong cét nhau tai diém he, tai do: log{HA] = log/A7] 2 4 e @ 10 pH Mink 3.1. BB thi logartt niang 45 eiia dung djeh axit HA O,1M 6 pK, = 4,75.48, AXIT VA BAZO - PHAN UNG TRAO DOI PROTON CK, —SaKa EAA Wy +K, (Hr) + x, ‘Tite la: nghia la 4 diém 6 hoanh dO pH =pK, va tung do log/A~] = log[HA] = logC,/2 vi [HA] + [A7] = Cy. Do de giao diém cia hai dutmg log(HA] va log[A~] cd cing hoanh dé vai diém hd va d dudi diém hé 0,3 don vi logarit ndng dd, vi log 2 = 0,3. ‘Tom lai muén vé dd thi logarit wong dQ cua dung dich axit yeu HA ndng d¢ Cy thi trude két ké hai dung log[H*} va log{OH~], sau dé ghi diém hé cd hoanh do pHi va tung dé logC = IgC,. Sau dé ké hai bén diém hé hai doan thing song song véi truc hoanh va hai doan thang khac, m6t song song véi dudng log(H*], mot song song vi duimg log[OH™}, od bén doan nay cing déu hudng ve diém hé. Sau cing 4 gan diém hé, n6i doan thang cla c&p nay vai dogn thang cia cap kia bang hai doan cong cat nhau 8 duéi diém hé 0,3 don vi logarit ndng do. ‘Tren hinh 3.1 14 dé thi logarit ndng 46 ciia dung dich axit HA ndng do 0,1M, od pK, = 4,75, Bang d® thi dé ta od thé ude lugng duge ngay bing mét pH cia dung dich. Thuc vay, ta o6 thé giai phugng trinh béo ton proton bang dé thi: (H*] = (OH7] + [CH,COO~} Bang d® thi ta o6 thé théy bang mat bic tranh toan cdnh va ndng dé cia cdc cau tit trong dung dich 8 cae gid tri pH khéc nhau trong sust thang pH tir 0 dén 14, DO thi logarit nong dé ciia dung dich bazo yéu duge vé tuong bf nh cia dung dich axit yu. Thi da: D6i voi dung dich NH; 0,1M. Vi NH, 1a bazo lién hop cia NH, va vi: (NHy] + [NH{] = 0,1M, nén d& thi eda dung dich NH, 0,1M cing 1a dO thi cla dung dich NH 0,1M va cing la d6 thi cha dung dich NH, + NH{ od téng ndng dé bang 0,1M. ‘Tuong tu nhu vay, dd thi logarit ndng d6 cia dung dich CH,COOH 0,1M cing la @ thi ofa dung dich CH,COO- 0,1M hodc dd thi cia dung dich CH,;COOH + CH,COO™ ed téng ndng do bang 0,1M. Dé ve dé thi cha dung dich NH, 0,1M, ta lay diém he od hoanh do 18 pKyy¢ = 9,25 va tung do 1a logC = log 0,1 = -1. Hinh 3.2 la d3 thj cia dung dich NH, 0,1M ‘Tuy hai dung dich NH, 0,1M va NH{ 0,1M es chung mot do thi, nhung khi tim pH céa dung dich dé ta phai gidi cde phuong trinh khac"nhau D6i voi dung dich NH phuang trinh bdo toan proton 1a: (OH"] = (H*] + [NHZ] nén pH cha dung dich 14 pH tng vdi hoanh do giao diém hai dueng log[OH™) va logiNHf} : (pH khoang 10,6; diém B) Doi voi dung dich NH{ 0,1M, phuong trinh bao toan proton 1a: [H+] = (OH-] + {NH,): Va pH cia dung dich l pH ung véi giao diém cia hai duimg log{H*] va log[NH3] (diém A trén hinh 3.2) .CO 86 HOA HOC PHAN TiCH 4 bog 0 ee tag (NAST “2 4 ~é “8 -10 dung dich NILCH,COO 01M. Hinh 3.3. DO thi logarit mong 450 AXIT VA BAZO - PHAN UNG TRAO DOL PROTON ‘Trén hinh 3.3 1 do thi logarit néng dd cha dung dich NH,CH,COO 0,1M. Ding do thi nay ta dé dang gidi phuong trinh bao toan proton cia dung dich ds: [H*] + [CH,COOH) = [OH-] + [NH,j ‘That vay, theo 4B thj logarit ndng dé, tai giao diém cia hai dung log [CH,COOH] va log [NH] (diém A) thi [H+] << (CH,COOH] va (OH-] << (NH] nén phitong trinh proton trén duge don gian hda thanh: [CH,COOH] = [NH,] Va néu ding do thi thi thay ngay pH cia dung dich 14 hoanh d6 cia diém A (khoang 9). Néu muén tinh chinh xac thi ta gidi phuong trinh: [CH,COOH) = [NH] (a) [0,1[H*} 0,1.10°%25 = ———_ by 10778 4 fH] + 10°28 Vi [H*] << 10-475 va [H*] >> 10-925, nén (b) duge don gidn héa thanh: ta] 10825 102s (a) Hoac (At? = 104251025 = 104 = (Ky x Ky) {at} = 107 pH =7 3.7. Dung dich da axit Trong phan dau cua chvong ching ta da biét, da axit la axit ma phan tt phan ly Tan litot theo nhiéu n4c, ung véi mdi née ed mgt hang s6 axit riéng, Thi du: [H*}[H,PO; | H,PO, = Ht + H;POy (HPO) L610 [H,PO,] H*}[HPO2~ HP Ht + HPO} SPIE ONT _ g2.108 [H,PO;] H*}[POs- HPO?” = Ht + PO} rer 4,210 (HPO;"] Noi chung proton téch ra khéi ti€u phan cla nde trite d8 dang hon 6 nfc eau vi dign tich ion ca nde sau am hon née trutée, nén git proton cang chat hon. Do dé hang s6 phan li cla nde sau thugng nhé han cia nc trtée. Déi vdi cde axit nh H,PO,, H,$0,, H,CO, eo tat cA ede nhom OH dink vao cling mét nguyén ti, thi hang s6 phan li cia n&e sau thudng bang khoang 105 hang s6 phan li cla née truée. Thi du: D6i voi HyPO, thi Ky/K, bang 1,23.105 va K,/K, bang 1,5.105 hoac d6i véi H,SO, thi K/K, = 1,7.10°6,2.10 = 2,7.108. Déi véi cdc da axit 6 cA 2 proton trong phan tit dinh truc tiép vao mot nguyen tit thi hing s6 phan li nde thit hai edn nhé hon 105 hang sé phan Ii nde dauCO SO HOA HOC PHAN TICH st Thi du: OHS thi K\/K, bang 10° © H,Se thi K/K, bang 1,3.107 HyTe thi K/K, bang 2,3.108 Déi véi cde da axit mA cdc nhom cho proton cang cécn xa nhau, thi hang s6 axit Ung voi cdc proton dé c6 gid tri cang gin nhav. Thi du; Cac da axit ed mach cacbon dai gitta cdc hom axit thi gid tri cde hang so axit rit. gin nhau: Axit suxinic HOOC-CH,~CI1,~COOH ed K, = 1,6.10° va Ky = 2,3.10" Axit tactric HOOC—CH(OH)-CH(OH)—COOH es K, = 9.1.10+ va Ky = 4,3.10 va axit xitric HOOC-CH,~C(OH)(COOH)-CH,-COOH es K, = 7,4.10%, Ky = 1,8.105 va K, = 1.107. 1. DB thi logarit ning dé cla dung dich da axit Dé ve duge do thi logarit. néng dé cua dung dich da axit trvéc hét ta thiét lap cae bigu thie ciia néng do can bang cla cdc ion va phan tif theo néng do can bang cla ion Hi. Dé di t6i biéu thc téng quat, ta xét dung dich HyA ndng dd C, vai cdc hing sé axit Ky, K, va K,, Trong dung dich dé e6 cdc can bang sau: HA == Ht + HAT HAT == Ht + HA? HA? == Ht + A* Dé thiét lap cae phwong trinh cia cdc ndng dO can bing cac ion va phan tit ta di tir hé eae phuong trinh sau: (H*}01,47] = K,1H,A] fa) [E*]HA?) = K,[H,A7] (o) [H*j[A*] = K,[HA?] () [HA] + [H,A7] + [HAZ] + [A] = Cy id) (HAS) Tu (c) suy ra: [HAZ] = ———— te) Ky Tit (b) va (e) suy ra: H)(HA?] — (H+y?[ a3 arya) SURAT Pa © K, KK, ‘Tir (a) va (f) suy ra: TH'YE,AT] (AP TAY HA] = cae t . K, x, K, Ky ® Thay (e), (f) va (g) vao (d), ta 06: (tB *P TRY] 34 (OR PR) 8 PY Geigy aR tm +!) = ea32 AXIT VA BAZO - PHAN UNG TRAO DOL PROTON c fay = ~ mee ee (RK Kt mT) K,K,K,C. (3) = pen (331) (HP + KBP + KKH} + KKK) ‘Thay (3.31) vao (g), (f) va (e) ta sé duye biéu thie hang sé cin bang cia phan tit va cae ion trong dung dieh HA: HA Cate? (3-82) ESAS TEs BCP + RR + RR, [H,Ac] = Co? (3-33) * (HP + KAYE + KK) + KKK, C,K KH? (HA2} = aR (3-34) {HY} + Kt? + K,KpiH"] + KKK, Nhu vay, trong dung dich HA nding d6 C, thi nong do phan ti va cae ion phu thude phic tap vao pH cia dung dich vi méu s6 eta ede biéu thie trén IA phutong trinh bac 3 theo (H*]. Tuy nhién 6 nhing khong pH khae nhau thi ta c6 thé bd qua cac gid tri ndng dQ nhé ben canh cic gid tri néng dd 16n va cde phuong trink trén duoe don gidn hoa di rat nhidu. Bang sau day tdm tat cde phuong trinh (3-32), (3-33), (3-34) va (3-31) da duge don gidn héa trong nhiing khodng pH khac hau. 0 (yal UL,A] ima] 1A*) pK < pK, Ca KCl) KAR CAUA | KR KGCIIP pil = pk, Cyl2 K Cai KC a2] Kok gC Jah F px < pl < pK Cat VK Ca KCqillit] KK ACMI pH = pk, CK 32K Cal Cy KCK pK, < plc pk | Call K (Ky CAIUP YK CA “Qt pul = pk Cy KK Ky Cy PK Cyr? Cn? pil > pky CAP PUK KK, | CqiUMTEK. CALA YRS Cy j Ti nbimg ket qua cia bang tren, ta suy ra: Khi pH nhé hon pK, nbiéu, duong log(H,A] 6 trén duting thang song song véi truc hoanh, dudng log[H,A7] ¢ tren duvong thang song song vai dutmg log{OH™], dutng log[HA?] ¢ trén mot dudng thang lam voi truc hoanh mot gde cd tg bang +2 va dudng log[A*] 6 trén dudng thang lam véi (rue hoanh mét goe ed tg bang +3. Khi pK, << pH << pX;, duing log[H,A] 3 tren mot dying thang song song voiCO SOHGA HOC PHAN TiCH 33 log(H*}, duting logiH,A~] 4 trén dudng thdng song song véi true hoanh, duang log{HA?] 6 tren duéng thang song song véi duing log(OH] va duting logiA*] nam trén dudng thang lam véi true hoanh mot gée od tg bing +2 Khi pK, << pH << pK, dutng log[H,A] nam tren duang thang lam véi truc hoanh mot_gée oo tg bang ~2, dudng log(H,A-] 3 tren dang thing song song vai duong log{IT'], duimg log(HA*] 4 tren dying thing song song v6i true hoanh, dutng log[A*] 4 trén dudng thang song song v6i logiOH-]. Khi pK, << pH, dudng log{H,A] 4 trén dudng thing lam vdi true hoanh mot gée 6 tg bang —3, duung logtH,A~) nim trén duang thing lam véi true hoanh goe e6 tg bang —2, dudmg logfHA*] 6 tren duémg thing song song véi dung log(H*] va dong loglA*] 4 trén dudng thang song song véi truc hoanh. ‘Trén hink 3.4 la dd thi logarit ndng 46 eta dung dich axit HyA 0,1M 6 pK, = 2,12; pK, = 7,21 va pK, = 12,36 (axit photphoric H,P0,). lage 10 2 4 6 e 10 EP pa Hil: 3.4. DB Uh) Loy PK rit nBng a eda dung dich (HPO, 01M) 6 12s pK 2 = 7,26; pK, = 12,36, 4.7.2. pH cia dung dich da axit Dung dich da axit ed thé xem nhu dung dich ctia mgt h6n hop ede axit yéu od nong do bang nhau va hang sO axit khae nhau. Néu nhu hang s6 K, cia nde the nhat lon hon cila nae thit hai nhieu thi ed thé coi da axit hu dun axit ed ndng do Cy va hang s6 axit XK, vi H* do nde thit ahat phan li ra da cAn trd sy phan li cia ode nfe sau, Tht da; Tinh pH cia dung dich axit HyPO, 0,05M. Vi axit nay cd K, = 7,6.10°3 ldn hon rat nhiéu gia tri K, = 62.10% va Ky = 4,2.10-3 nén thye t@ trong dung dich chi e6 1 can bang:4 AXIT VA BAZO - PHAN UNG TRAO DOI PROTON H,PO, == H* + H,PO; Thay [H*} = [H,POj] va [H,PO,] = C - [H*] vao biéu thie eta Kj, ta ed: ay ———_ = 7,6.103 0,1 - {H*] Giai phuong trinh nay, ta duge [H*] = 5.1025 va pH = 1,80. 3 pH tia cée dung dich mudi tan cia ede da uxit Dé tinh pH cia cdc dung dich mu6i tan eta cac da axit ta gidi phuong trinh bio _toan proton cia cae dung dich dé va dung d® thj logarit ndng 46 dé don gian hoa viec giai Cae thi du Thé du 1: Thuh pH cia dung dich NasPO, 0,1M. Phuong trinh bao toan proton cia dung dich nay la: [OH-] = (4) + [HPO}"] + 2[H,PO;} + [H,P0,) (a) Theo dd thi logarit ndng d6 céa dung dich H,PO, 0,1M trén hinh 3.4 thi tai giao dim cia 2 dian log [OH-] va log [HPO3"] cac gis tri [H*], [H5PO,], (H,PO;] rat nho so véi [OH™], HPO} nén (a) duoc don gidn ha thanh: [OH-] = [HPO}} tb) Fink 3.5. D8 thj logarit nbng 44 cis dung dich (NIL) TPO, 01M.CO 50 HGA HOC PHAN TicH 55 1ols 0.1 Ht [H*] [HP] + 101236 hoae Sau khi gidi phuong trinh bac 2 trén, ta tinh duge: [H'] = 265.1013 pit = 12,58 Thi du 2: Tinh pH cia dung dich NaH;PO, 0,1M Phuong trinh bao toan proton cita dung dich nay xudt phat tir HjPO, va HO Ia: (H'] + (H,PO,) = {OH-} + [HPO2-1 + 2(P0F] w@w Theo dd thi logarit ndng dd (hinh 3.4) tai giao diém cla 2 dung log/H;PO,] va log [HPO}-] ta c6 thé bé qua cae ndng d6 can bang nhé (H*], [H-], va (PO}-] ben canh cac nong dg (H,PO;] va [HPO}-], nén (a) duge don gian hda con: {HPO = ([HPO}] howe QUILPOR) _ K,LH.PO;] x, 1] Tit do, suy ra: wry? = KK, [H*] = KK, pH = 0,5(K, + pK,) = 0,5(2,12 + 7,21) = 4,67. Thi du 3: Tinh pH caa dung dich Na;HPO, 01M. Cang tuong ty nhw a thi du 2, néu ding dd thi logavit néng da dé don gidn hda vide gidi phuong trinh bao toan proton eta dung dich nay la: [H*] + 2(H,P0,) + [H,PO;] = [OH™] + [PO}-] (a) ta cang di dén cong thus tinh pl eda dung dich axit va bazo khong thuge hai hé lien hop ed nbng dg bang nhau nhw trong mue 3.5. PH = 0,5(pK, + pK,) = 0,5(7,21 + 12,36) = 9,79 Thi du 4: Tinh pH cia dung dich (NIL,),HPO, 0,1M.1a [H"] + 2[H,P0,) + [H,POz] = [OH] + {NH + [POF] @ Ta cing ding d6 thi logarit ndng do dé don gidn hoa viée gidi phuong trinh a6. Dd thi ciia dung dich nay la dd thi ctia dung dich NHj 0,2M va d6 thi cia dung dich H,PO, 0,1M vé trén cing mgt hé toa do (hinh 3.5). Theo dé thi logarit ndng d6 thi tai giao diém cia 2 dutmg logiH,POz] va log [NH] ta o6 thé bd qua duge cde 86 hang [H*] va [H;PO,] trong vé trai vA cic sf hang [OH™] va [PO}-] trong vé phai ca (a) va phuong trinh dé chi con: . (H,PO;] = [NH3} ) Lai ding dd thi dé don gian hoa phuong trinh biéu dién céc ndng do can bang do, ta ditoc: 10H} 2.10°10.25 [HY] + 10721 py + 1025 Sau khi gidi phyong trinh dé, ta duoc [H+] = 1,4.10°25 pH = 8,156 AXIT VA BAZO - PHAN UNG TRAO DOI PROTON 3.8. Cie axit vi bazu trong dung m6i khée nuée ‘3.8.1. Phén leai dung méi Trong phan dau cia chuung nay, ching ta da biét ring, tinh chat axit hoac tinh chat baza cia cée chat phu thude vao tinh chat cia dung mdi trong dd cae chit duge hoa tan. Dua yao kha nang trae déi proton, cd thé chia cé¢ dung méi thanh ba loai chinh sai a) Cac dung moi ¢6 kha nang proton phan, thi du nhu nuéc, amoniac, axit axetic... 2H,0 == H,0* + OH- 2NH, == NH} + NHy 2CH,COOH == CH,COOH; + CH,COO- Cac dung méi loai nay lai co thé duge chia thanh ba phan nhom: - Nhiing dung méi cé kha nang vita cho vita nham proton. Thi du: nude va rugu etylic - Nhiing dung mdi va proton la nhimg dung moi thé hign chi yéu tinh bazg nhy amoniae léng, dimetylfomamit. - Nhitng dung mdi thé hin cha yéu tinh axit. Thi du; axit axotic, axit fomic... Bang 4.1. Phan loai cée dung mdi theo Brénsted “Thi dy Pea] Rat ring | Tinh ass inh tes? Gong tnie | ing Sdn | en sb ion aay “ mie 25°C) | 28°C) 1 + + + 11,0 783 Ko cHon 325 17 2 + + - 11580, ‘01 36 uo | 585 6%) 3 + - + HCN 360 265 4 + - - CyllgNOy 348. 5 - + + enci,cnt m3 1 6 - + - c1i,coon 6a 5 7 - - + Calg Ra Gain, Mai, NI 2 bs 8 - - - Cally 23 (20°C) b) Cac dung moi khong cd kha nang proton phan nhung ed thé nhgn proton. Thi au: pitydin, axeton. Phan tit cla dung mdi nay cha nguyen tit nita (N) hoac oxi () con c¢ cap electron ty do dé két hyp vdi proton, nén thé hign tinh bazs. ©) Cée dung mdi tro 1a nhiing dung moi khong co kha nang cho va nban proton, nén khong eo kha nang tham gia phan ung trao déi proton. Thi du: benzen, clorofom Can bang axit bazo xay ra do su phan li cla cdc phan ti axit, baza thanh ion. Do 6, kha nang ion hda cia cdc dung moi déng vai trd quan trong déi vai cée can bangCO 86 HGAHQC PHAN TiCH 37 axit - bazo. Kha nang ion héa cia dung méi due dac trung bang hang s6 dién moi cla ne Brénsted da phan loai céc dung mai dya vao ba tinh chat cia ching lA kha nang ion hoa, kha nang cho proton (tinh axit) vA khé ndng nh4n proton (tinh chét baza). Theo Brinsted eo tam loai dung m6i duge phan loai trong bang 3.1 Déi véi ede dung moi loai (a), khA nang ty proton phan duoc dic trung bang tich 36 ion cia dung moi Thi du: D6i véi regu metylic: 2CH,OH == CH,OH} + CH,O- Kegon = “cujonf * @cuy0- = 107 (8 25°C) tudng ty nhu HO ed tich sé ion bang 104 3 25°C. ‘Trong 86 cac loai dung mei thi cde dung méi es kha nang ty proton phan duge ung dung rong rai nhat dé nghién cau va tién hanh ede phan dng axit - baz. 3.8.2, Anh hiedng ciia dung moi dén tink chdt cha céc axit = buzo ‘Tinh chat axit, baza cia cdc chat phy thugc vao tinh chat cia cdc dung mdi ding dé hoa tan ching. Tht du: Naphtylamin la bazo yéu trong nude (pK, = 10,01) nhung la mét baz kha manh trong axit fomic (pK, = 0,88). Tham chi cé nhimg chat la axit trong dung moi nay nbung lai 1a bazo trong dung m6i khac. Thi du: Ure 1a baza yéu trong nue HLNCONH, + H,0 === H,NCONII} + OH™ (haze yéu) nbung lai la axit trong amoniac léng: NH,CONH, + NH, ==NH,CONH- + NH} (axit) va la bazo manh trong axit axetic: NH,CONH, + CH,COOH == NH,CONH; + CH,COO- DE dae trung cho cuong do cila axit vA baza trong cée dung moi khic nude, ngui (a cung ding céc dai Ivgng hang 36 axit va hang 66 bazo nhu d6i véi ede axit bazo trong nude. Thi du: Doi voi axit HA trong dung moi khée nude D. HA+D == DH'+A- ayy4, Ke = ZOHA CHa ‘Déi v6i bazo B trong dung mdi D: B+D == BHt + (D- H)- 8554.458 AXIT VA BAZO - PHAN UNG TRAO POI PROTON DOi véi mot cap axit baze lién bgp trong dung mdi ty proton phan, tich s6 hing s6 axit va hing sé bazd bing tich sé ion cda dung moi K, Ky = Ky pK, + p&y = pK Cang giéng nhu trong nude, trong céic dung mdi khéc nitée, mot axit hoge mot baza eang manh sé cs K, hoae Ky, cang lon. Dung moi axit JA nhiing dung mdi ¢6 kha nang cho proton cia minh, Vi vay, trong cae dung moi do o6 s6 chat thé hign tinh axit gidm, s6 chat thé hin tinh bazo tang lén Thi du: Trong CH,COOH nguyén chat thi cdc axit cacboxylie Jai hau nhu khong thé hién tinh axit vA céc axit manh trong nuéc lai 1a céc axit yéu trong dung moi nay (es pK, tit 3 dém 11). Nguyén ‘nhan cia su gidm cutng dé axit nay la tinh baza yéu vA kha nang ion héa thap cla CH,COOH. Kha nang ion hda cia dung mi anh huéng lén dén tinh axit cla cac chat. Thé du: Axit fomic HCOOH tuy cé tinh axit cao hon axit axetic nhung axit fomic lai it lam gidm eutng dé etia cdc axit vO ca hon axit axetic, vi axit fomic ed kha nang ion héa céc chat cao hn axit axetic, Bang 3.2 trinh bay cdc gi tri pK, cua cae axit khac nhau trong CH;COOH va HCOOH. Rang 3.2. Gid tej pX, eda mat sd axit trong efie dung moi khiie muse Axil pK, rong HCOOH pK, trong CH,COOH Peelorie 028 38 Brombidric 028 67 Clohidrie ag9 885 Sunfurie 085, 829 Nite gs 9,38 Nhiig chat trong nvéc thé hin tinh bazo yéu hode khong thé hién tinh baza od thé trd thanh bazo manh hode yéu trong cae dung mi axit khac nvéc. Trong cac dung méi ¢é tinh axit cao va kha nang ion héa manh thi tinh bazo eda ede chat tan trong né tang lén manh (xem bang 3.3). Bang 3.3, Cie gid tri pK, cits mot sf haze trong nuée vi ede dung mol axit khie nurée Brey pK, trong HO | pk, trong HCOOH | pK, trong pk, trong, CH,COoH CHsCOOI Preidin 885 027 445 968 Dietyhunin 3,02 058 450 954 Peotin 752 058 432 951 Prperidin 280 038 440 950 Antipinia pay 058 S10 10s7 Ure Bx2 0 690 1087 ‘Thioure 1496 10 660 1059CO 86 HGAHOC PHAN TICH 39 Anh hvdng cia cdc dung méi ed tinh bazo th) ngugc lai. Vi nhitng dung m6i nay co kha nang nh4n proton nén trong moi trudng elia ching sO eac chat thé hién tinh axit tang lén con s6 chat thé hién tinh bazo giam di. Trong céc dung moi cé tinh baza, cudng dQ ciia céc axit yéu tang len, nhiéu axit you (6 thanh axit manh. Gid trj pK, clia da s6 céc axit trong amoniac léng bién thién trong gidi han ti 2,5 dén 4,4. Dong thai voi tinh bazo, khA nang ion héa cla dung méi cing Anh hudng dén cutng do cia axit vA bazo. Tht du: hidrazin co hing 86 dién moi tvong Adi cao (52) nén cae axit trong nude os pK, nam trong khoang 3 dén 9 thi thye té phan li hoan ton trong hidrazin, cn piridin od hing s6 dién moi khong cao nén cac axit menh trong nuée nhu HClO, KCt tré thank yéu hon trong piridin (od pX, tit 3 dén 5). Con déi vdi céc dung méi luting tinh kiéu nuée thi rugu va dac biét 1A cdc rugu metylic, etylic va propylic dug nghién ettu va duge sit dung nhi8u nhat. So vdi nude thi cde rugu dé lam giam cutng dé cic axit, Thi du: trong rugu metylic thi pK, ciia cae axit cachoxylic gidm tii 4,5 + 5,5 don vi; ciia cde phenol gidm di 3 = 4 don vi; cdn cla ede axit vO co thi gidm di 2 dun vj. Trong rugu etylic cu’ng a6 cla cdc axit con gidm di nhiéu hon. Thi du: pK cia cde axit cacboxylic giam di 5 + 6 don vi, ciia céc phenol gidm dé 3 + 4 don vi. Nguyén nhan cia sy gidm cutng d6 axit, bazo la kha nang ion hoa ella cdc dung méi giam di thé hién 6 su gidm caa hAng s6 dién moi; cla nude la 78,3 con cia metanoi 1a 32,5; ca etanol 1a 24,3.61 CHUONG 4 PHUONG PHAP CHUAN DO AXIT - BAZG (PHUGNG PHAP TRUNG HOA) Phuong phép chun do axit - bazo dua trén phan ing trao d6i proton gitta dung dich chudn cia dung dich dinh phan dé xde dinh ndng 40 cia axit vA baz. Cac phan wing ding trong phuong phap nay du théa man cée yéu chu cla phan tng ding trong phén tich thé tich, Cac dung djch chudin ding trong phuong phép nay thutng IA cdc dung dich axit manh hoac bazo manh. Trong qué trink chudn dd ndng dé ctia cdc ion H' va OH™ thay déi, tite 1a pH ciia dung dich thay @6i. Vi vay, dé xc dinh diém tuang duong ngudi ta thung ding nhig chat ma mau sc cla ching thay d6i theo pH cla dung dich. Nhiing chat nay duce goi la chit chi thi axit-bazo hoac chit chi thi pH. Dutng bigu dién sw phu thuéc céa pH trong qué trinh chudn dO vao thé tich dung dich chudin thém vao hoge Iugng chat dinh phan da duge chun 40 duoc goi 1a duang dinh phan, Ngudi ta thudng dya vao dutng dinh phan dé chon chit chi thi thich hgp nbat. 4.1. Chat chi thi axit - baze Cac chat chi thj axit - bazo phiin Ién 1a cdc phim nhudm hitu cg. Chiing Ia cée axit hoae bazo hitu co yéu trong dé dang axit vA bazo lién hgp ob mau khée nhau, vi vay mau cla ching phy thuge vao pH cia dung djch. Ta kf hiéu chat chi thj la axit HInd va bazo 1a IndOH. Trong nude ode chat chi thi dé phan li nhu sau: HInd == Ht+Ind- Kyng fa)62 PHUONG PHAP CHUAN DO AXIT-BAZO IndOH S= Ind* + OH™ King ib) Trong do cc dang lién hyp tuong ting cla méi cht cé mau khée nhau. Su thay déi mau céa chat chi thj phy thuge vao pH cla dung dich duge gidi thich bang thuyét ion - nhém mang mau: Khi pH thay déi thi cdc e&n bang (a) hode (b) sé chuy6n dich vé phfa phai hoae phia trai, chat chi thi sé ton tai chi yéu duéi mét trong hai dang lién hyp, nén dung dich sé e6 mau ciia dang nao tin tai cha yéu trong dung dich. Thi dy: néu chat chi thi 1A Hind thi khi thm axit vao dung dich cia no c4n bang (a) sé chuyén vé phia trai va dung dich ed mau cia dang axit Hind. Ngwgc lai néu giam do axit cia dung dich (chang han thém kitm vao) thi can bang (a) sé chuyén sang phia phai, nén dung dich od mau ctia dang Ind (dang bazo) Khi pH eda dung dich chita chat chi thi thay déi thi cfu trae cia phan ti trong a6 ¢6 nbitng nhdém mang mau thay déi din dén su thay déi mau cla chit chi thi. ‘Vi du: Phenolphialein cd thé ton tai trong dung dich 4 cdc dang cfu tric phan ti sau day: —_—~ co Son oe Dang lacton khong miu khdog mau HO, oH HO, o- OL Th, AT oc OH coo” coo" Dang quinon mau bong khong mau Vi vay, trong méi truéng axit va trung tinh phenolphtalein ton tai chi yéu dudi dang lacton khong mau, trong méi truting bazo ton tai chi yéu dudi dang quinon mau hong, nhung trong moi trugng kiém manh lai ton tai J dang khong mau Metyl da cam c6 thé ton tai trong dung dich dudi ede dang sau:CO 86 HOA HOC PHAN TICH 63 (CHy)y nV N=N —> [OWT] nén tit (4-8) suy ra: CLV, I} =a-/ (4-9) VitV Phuong trinh trén cho ta thay ndng d6 [H*] bang ndng d6 axit chua duge chudn 46 48 bj pha loang bang V ml dung dich chuda NaOH duge thém vao. Tuy nhién, ditu nay chi dung khi con tuong déi xa diém tuong duong. Cang gan diém tuong duong ta cang phai ké dén su phan li eda nude. Tai diém tuong duong, khi F = 1, tit (4-8) ta co: (H"] = [OH™] = V2j1,9 = 107 ( 25°C) Sau va xa diém tuang duong vi du tuong déi nhitu NaOH nén [OH™] >> [H*] va. tit phuong trinh (4-8) suy ra: Ma k C, tee LF (OH-] = mm We (4-10) Sat trude va sau diém tvong dung, [H*] ~ [OH™] nén phai gidi phuong trinh (4-8) 46 tinh pHi Can cht ¥ rang, sét diém tung duong ed thé coi CV bing C,V,, tic la: Vo _ &a VotV Oot 2 22 hoge: QO = 2 (ap vo Cc Vv, Cc Thi dy 1: Vé dung dinh phan khi chun dQ 10ml dung djch HC! 0,1M bing dung dich NaOH 0,1M. ‘Ap dung ede cong thic (4-9), (4-10) két hop v6i (4-11) ta tinh duge pH khi cho nhitng thé tich NaOH khée nhau vao dung dich HCI dé chudn d6 HCI, Cac két qua duge tap hop trong bang sau: Vimy] a 0 50 0) v | 999 | 10 | or | im | 10 F 0 ar [ os | 09 | 099 ) o999 | 1 7 tom | um a pl 1 uf us | 228 | 330 | 430 | 70 | 970 | 7 | 1168 Nhdn xét v8 dubng dink phan axit manh bing bazo mank: - Trude va sau diém tuong duong, khi F nhé hon 0,99 va In hon 1,01 thi pH cia dung dich bién di rét it. Trai lai 6 vang gin diém tuong duang pH thay déi rat nhiéu, tao nén buéc nhay pH 6 sét diém tuang duong, - Doan pH ting véi thai diém con 0,1% Ivgng axit cha duge chudn d6 va 0,1% Iugng ki&m du s0 véi axit, tie 1A khong pH dng v6i F = 0,999 va 1,001 thuang dige quy ude 1A bide nhay cia duong dinh phan. Trong trudng hop nay bude nhay cla duing dink phan 1a 5,4 dun vj pH.CO SO HOA HOC PHAN TICH 67 @ “ 0 aN waa Ae aa 4st gt te 8 Hink 4.1, Bwieng diph phan dung dich HCI 0,1 M bing dung dich NaOH 01M ~ Duta vao buée nbay ciia dudng dink phan ta cd thé dé dang chon chat chi thi. Trong trudng hgp nay ta cho bat ky chat chi thi pH nao co pT ndm trong bude nhay tic la trong khodng pH tir 4,3 dén 9,7 ta déu co thé nhan ra diém tuong duong véi sai 56 khong vigt qué 0,1%. ~ Nong dO axit cAng lén thi bude nhay cang dai. ‘Ta hay tinh pH cia bude nhay. Khi chudin do thidu 0,1%; tue la: Vi+¥ F-1= -0,001 = ((OH7] - [Hp Gia sir C= C va gan diéin twong duong, nén V gan bang V, ngoai ra cd thé bé qua OH™ canh Ht, nén phuong trinh trén duge don gidn thanh ©, -103 = -[H*} —* 2.103 (HT ¢, pH = -le(H*] = - Khi chudn d6 thita 0,1%, tic la: ~ 0,3 - IgC, = -3,3 - IgC, (a) vitV F-1= +0,001 = (OH7) - [H*p ——— Vi sau diém tudng duong nén ta bé qua [H+] canh (OH™] va co thé coi V bang V,, nén phuong trinh trén duge don gidn héa thanh: 2 104 + 0,001 = [OH-] — = : cy eC, 268 PHUONG PHAP CHUAN DO AXIT-BAZO wy 102 a") C, pH = —log(H*] = 11 — 0,3 + logC, = 10,7 + logc, ob) Bude nhay bing higu sé hai gia tri pH trén ApH. ApH = 10,7 + logC, - 3,3 + IgC, = 7,4 + 2logC, ©) Thi du 2: Tinh pH cia bude nhay trong cdc trudng hop sau: Chuan do dung dich HCI eo ndng do bang: a) 1M; b) 0,1M; ¢) 0,01M va d) 0,005M bang dung dich HCI cing ndng do. Sau khi ap dyng cong thitc (c) trén va tap hop cde két qua trong mot bang ta <6: Nong 45 1 1 opt 0.005 0001 Buse nhiy 74 dvpHt SA vp 34 depHi 28 dvpll 14 dvplt ‘Ta thay ngay rang buéc nhay pH tai diém tuong dvong khi chudn dO axit manh bang bazo manh cing ndng do cang Ién khi ndng d6 cang lon. Sui s6 cht tht ‘Trong phan tich thé tich noi chung va phuong phap chudn 46 axit - baza noi riéng, ngoai sai sO thé tich do dung cu va sir dung dung cu (buret, pipet, binh dinh mtic) gay nén cdn hai loai sai sé quan trong khéc la sai s6 do pT cia chat chi thi khéng tring voi PH 4 diém tuong duong goi tét 1a sai 66 chi thi va sai sé do x4c dinh sai p7 cia chat chi thi tue IA xac din pH & diém cudi dutge goi la sai s6 diém cudi, Sai s6 chi thj: la sai sd do diém cuéi dude nhén ra bang chat chi thi co pT khong tring véi diém tuong duong. Ta hay thiét lap phvong trinh tinh sai s6 dé dudi dang sai 86 tuong déi S. Theo dinh nghia: hoac dudi dang phan tram: S% = (F - 1).100 Khi F nhé hon 1 thi $ 1a phan axit cha duge chudin d va co ddu am. Khi F lén hon 1, 5 1a phan axit tuong duong véi lvong bazo dt va cd déu dvong. Dua vao phyong trinh dudng dinh phan, ta lap duge phuong trinh sai s6 chi thi theo pH 4 diém cui hie la theo pT eda chat chi thi. Déi véi tru’ng hop chudin dg axit manh bang bazv manh tit phuong trinh (4-8), ta od: Vi+¥ S=F,- 15 (OH7}, -[ Ht} — (4-12) CY, trong do: ¢ la chit viét tdt cha chit ew thi: Néu két thiic chudn d6 4 gin diém tuong duang V,+V C,+e QV, * CW nen = Vv. Cc (4-13)O86 HOA HOC PHAN TICH 69 Truée diém tuong duang, néu Ht >> (OH-] thi: Yat ¥ S = -(H*),——. (4-14) CW Sau diém tuong dueng, néu {OH-], >> [H*),, thi: Yet V S = [OHJ, ——— (4-15) CY, Néu sat didm tvong dugng thi dimg phuong trinh (4-13) Thi du I: Tinh sai s6 chudn 49 dung dich HCI 0,1M bing dung dich HCl 0,1M néu két thie chudn d6 J a) pH, = 5,0 va b) pH, = 10,0 ‘Trung hop a, ta dp dung (4-14): 01 + 0,1 A= ~105 = —0,0002 tue la -0,02% 0,1 x OL ‘Truang hop b, ta ap dung (4-15): 01+ 01 A= 104 ——. = 0,002 tie 1a 0.2% Ol x 01 Thi du 2: Néu chudn do dung dich HC] 0,1M bang dung dich NaOH 0,1M thi cin két thie trong khodang pH nao dé sai sé chi thi khong qua 0,1% Déi véi sai sé —0,1% tie la S = -0,001; nghfa 1 luong NaOH thém vao chua du. Ap dung cong thife (4-14), ta ed: 0,1 + 01 = 0,001 = (H*), ——_—— 01x01 [H*] = 5.105 + pH = 4,3 Doi véi sai sé +0,1%, te la S = +0,001; nghla 1A Iugng NaOH them vao du; ta dung (4-15): . 0,1 + 0,1 +0,001 = [OH~], ———. 01x 01 19M Ht), = = 5.10" ~ pH = 9,7 (#"), [oH p Nhu vay, muén sai s6 chi thi khong vuot qué 0,1%, ta phai két thc chudn dé trong khoang pH tit 4,3 va 9,7 hay ni cach khac 1A dig ede chat chi thi cd pT nam trong Khoang 4,3 + 9,7. 4.2.2. Duirny dink phan khi chudn dé haze manh biing axit manh Khi chudn d@ axit manh (thi du: HC) bing dung dich chudin bazo manh (thf du: NaOH hose KOH) pH cia dung dich tang din trong qua trinh chuan dO va tai diém tuong duong c¢ sv tang dot ngOt pH tao nén bude nhay tang pH tren duong dink phan Khi chun a6 dung dich bazd manh kiéu NaOH hoc KOH bing dung dich axit_ manh (thi du: HCI thi sy thay déi pH trong qué trink chudn dé cing xay ra tuong ty nhung70, PHUONG PHAP CHUAN DO AXIT-BAZO. chi khac la pH gidm trong qua trinh chudn 46. Phong trinh dudng dinh phan cing duce thiét lap tuong tu, ta co thé hon vi phetong trinh dudng dinh phan cia trutng hap trude bang cach thay [Ht] bing [OH] cho dung dink phan cia tring hyp nay. ‘Thi du: Chudn do Vmi dung dich bazo manh bang dung dich axit manh ning dé C. Phuong trinh bdo toan proton cia dung dich trong qué trinh chudn dé: cv oe {H*] - ——— = (0n-]-—"~_ (4.16) Vi +¥ Vi+¥ cv . Dua F = vao phuang trinh trén ta duge: CoM tv F-1 = (OH7] - [H*) (417) CY, ‘Trude va tuang d6i xa digm tuong duong, tic la khi [OH] lén hon [H*] nhiéu, ta bé qua (H*) canh (OH"], nén (4-17) dude dan gian hoa thanh: k Cy, {oH"] a =F DE oe (4.18) *) yt ‘Tai diém tuong duong: [H*] = [OH] = ayo = 107 Sau va xa diém tuong ducng, ta bo qua [OH™] canh [H*), nén: ‘Mo [’]} == Vy + ¥ (4-19) ‘Trong tring hop nay dvéng dinh phan cing ed dac tinh nhv trudng hop trén, chi khac la pH gidm trong qué trinh chudn 46 Dudng dinh phan dung dich NaOH bAng dung dich HCl 0,1M la duing déi xing hoan toan véi dung dinh phan dung dich HCI 0,1M bang dung dich NaOH 0,1M. Vi vay vide tinh bude nhay cia dutng dinh phan va sai s6 chi thi dé chon chat chi thi cing hoan toin gidng nbau, ta dé dang suy ra duge, 6 day khong lap lai nia. 4.2.3. Chudn dj don axit yéu bang bazo mank hodc don bazo yéu bang axit mank « Phuong trinh dung dinh phan bhi chudn dé axit yéu HA bang bazo manh Gia sit chudn dg V, ml dung dich axit yéu HA hang s6 K, bang dung dich chuan NaOH ndng d6 € (mol/lit). Phan ung chudn dd: HA + NaOH = NaA + 1,0 HA + OH” = Av + HO Phuong trinh bao toan proton cia dung dich trong qua trinh chudn do xudt phat tir sn phim cia phan ding 14 A~ va 1,0: (H*] + fa] - Mo cv =[OH7] - Vi +V Vi+¥CO $6 HGA HOC PHAN TICH 1 ow ‘Ta cing dat F = 0 va dua F vao phucng trinh trén, ta duoc: CMe ev - Cv, yt [Hy F-1=-——*? = (on) - pp 2 - = (4-20) CM Cw, ] + x, Phuong trinh trén la phugng trinh bac 3 theo [H*] nhwng trong cac giai doan cla qua trinh chudn d6 no co thé duge don gidn hoa. - Khi chya chudn 40 F = 0, V = 0 trong dung djeh axit ndng 46 C, ta bé qua ndng 49 ion OH”, phuong trinh (4-20) duge don gian hoa thanh: kK, o (By) = 4-21) K, + (H*] va néu (H*] >> K, thi [H'? = K,c, (4-22) Ta 6 céng thite quen thudc tinh pH cua dung dich axit yéu vA tit cong thie dé dé dang suy ra pH = 0,5pK, - 0,51gC, (4-23) - Sau khi them V ml NaOH vao nhung con xa diém tuong duong, thi [H*] va {OH"] thudng ahd hon [Na*] va [A-] nhiéu nén c6 thé bé qua sé hang ([OH™]- [H*]) Vi+V do d6 phuong trinh (4-20) tré thanh: CMe (H] F-1=-——_ (4-24) (H") + K, tit (4-24) suy ra duge: [H*] = (4-28) ‘Trong phuong trinh (4-25), 1 — F ig véi phan axit HA cdn lai chua duge chudn do, con F ting véi phan axit da duge chudn dé 4é sinh ra bazd Aq lien hgp voi n6. Vi vay, phutong trinh dé chinh la phugng trinh Unh pH cia dung dich dém goin axit HA va bazo lién hop Av. Tai diém tuong dong F = 1, ta cd dung dich A~, nén [OH7] >> [H*], va phuong trinh (4-20) tra thank: ow] f Oe one K, + (H‘) Cc hone Hy igo So + © K,+(H*) (H*) Gc Néu axit khong qué yéu thi K, >> {H*], nén ta cé thé bd qua (H*) canh K, va phuong trinh’trén chi don glam thanh: c,+e HP oy ae 10%,R PHUONG PHAP CHUAN DO AXIT-BAZO Ce, +e (Ht) (4-26) c,c Day chinh 1a cong thic tinh pH cha dung dich A~ cd ké dén su pha loang. Sau va tuong déi xa diém tuung duong F > 1 ta ed dung dich baza yéu A~ va bazo manh NaOH du, nén (OH~] >> [H*} va néu tH) viotV Vi +¥ ——— = (A) << (OH-] ~—— K, + H] CMe Ys tie 1a [HA] << [OH™] thi phuong trinh (4-20) chi cbn ia: vi tV F-1=(OH} CuMy oot aan hoa OH} = F - 4. fe (OH v,+¥ 6 ving sat diém tuong ting voi 0,999 < F < 1,001 chi bé qua duge [H*] canh [OH™] va thudng khong bé qua duge s6 hang nao trong hai sé hang: eee Yt ¥ -———— «a [0H] K, + [A] viv ta phai gidi phuong trinh: at Kino Vo + ¥ pope __ Bie Ye 47 (4-28) K,+ (3) (H') 6.Y, pit w 90 6 6 4 92 Os 1 45 F Hinh 4.2 Dureng dint phin chute 9 CHCOOIT 0,1M bing NaOH 01MCO 86 HOA HOC PHAN TICH 3B Thi du: Ve dudng dinh phan chudn do 100 ml dung dich CH,COOH 0,1M co px, = 4,75 bing dung dich chudn NaOH 0,1M. Ap dung eae phugng trinh (4-23), (4-25), (4-26), (4-27) va (4-28) ta tinh duge pH tai cdc diém khée nhau eta qua trinh chudn dé va tap hop két qua vo bang sau ven] 0 20 | so { 9a | 99 | vs | qo | oor | wr ] uo | ise F 0 a2 | 05 | og | a9 | og99 | 40 [1001 [aor | an 1s pH | 288 | 24 | 47s | sso | 6s [78 | az4 f 97 [o7 | aw | ms Nhén xét ve duong chudn do trong truang hop chudn do axit yéu bang bazo manh - Cling gidng nhu trong chudn do don axit manh bang bazg manh, true vA sau diém tuong duong trong chuan d6 don axit you bing bazo manh pH it bién déi theo F, nhung ¢ sat diém tuong duong pH tang dot ngot theo F tao nén bude nhay cla dung dinh phan. Néu cing quy w6c bude nhdy pH 1a tng véi su chudn dé thita va thiéu 0,1% lugng axit thi trong truéng hop nay bude nhay ngén hon truding hop chudn do axit manh bang baza manh (1,9 don vi pH so vai 5,4 don vi pH). - Khée véi trvang hop chuén do axit manh, khi chudin d@ axit yéu pH tai diém twang duong khong bang 7,0 ma lan hon 7 vi san phdm cia phan dng chudn d6 IA haze you CH,COO- - Bude nhay cia dutng dinh phan phu thude vio cudng d6 axit. Axit cang yéu thi bude nhay pH 6 ving diém tuang duong cang ngdn. Ta hay gid sit chudn 0 cdc dung dich axit HA nodng do 0,1M bang dung dich chun NaOH 0,1M. Cae axit dé cd pK, 1an lugt 1a 3; 4; 5; 7 va 9, Trong trudng nay ta sé tinh pH tai diém tuong duong va bude nhay 1a gid tri ApH khi chudn dé thiéu va thita 0,2%. Dé tinh cae gia tri pH 6 diém tuong dugng va gid tri ApH, ta sé gidi phuong trinh: W+¥ Ot] F-1 = (OH (atp ——— - —— 1 @ CV, (H+ K, Khi tinh pH tai diém tuong duong ta thay F — 1 va trong cfc trutng hop ta bé qua [H*] canh [OH] va bé qua [ H*] eanh K, trong bén triting hyp dau, Ngoai ra, vi C, = C nén khi F = 1 va F = + 0,002, ta od Vi+V 2 CY, =O, pH tai diém tuong duong duge tink bang phuong trink sau. 204 BBg * (Phia30 + PK, — Toe). zr = 7 + O.5pK, - 0,15 + 0,51g0,1 = 6,35 + 0,5pK, Khi gidi phuong trinh (a) vdi F — 1 = +0,002, déi vdi cde axit o6 pk, nhé hon hay bang 7 co thé bd qua fH") canh [OH™] va bé qua sé hang thi hai cba phuong trinh (a), tite 1A sé qua su thy phan eda AW va chi ké tdi sy du ion OH™ sau diém tuang duong. Khi axit cd pK, = 9 khi tinh pH chi bé qua (H*] canh (OH™] trong phuong trinh (a) Voi cde gid thiét trén, sau khi gidi phuong trinh (a) da duge don gian hoa trong tingTh PHUONG PHAP CHUAN DO AXIT-BAZO truting hgp, ta duge cde két qua trong bang sau: 6 hop; Cursrng 6 anit (pK) pH wong dong Bucke ahiy pH ‘ApH 30 185 57+ 100 43 av 40 835 67 = 00 3a dv 59 870 77 = wo 23 dv 79 985 97 + 103 043 av 99 1085 10,84 + 10.91 0,06 oy Qua cae két qua trén ta thay, cdc dung dich axit cing ndng dé nhung co pK, khac nhau thi véi axit cang yéu, twie co pK, cng lén thi pH tai diém tuong duong cdng !én hon 7 nhidu va bude nhay pH tai diém tuong dugng cang ngiin. Khi pK, bang 9 thi thyc té khong cd bude nhay. Déi véi axit e6 pK, bang 7 buGe nhay pH chua dat duge 0,5 don vi pH; nén khé chon duge chat chi thj dé ed thé phan biét duge sy déi mau bang mat thung. Doi véi axit co pK, bang 8 hose 9 thi khong thé chudn do duge vi khong thé chon duge chat chi thi, Bude nhay cia duéng dinh phan cdn phy thudc vao ndng 46 ciia axit can chudn do va ndng do cla dung dich chudn bazo manh. Ta hay tinh bude nhay dung dinh phan khi chudn do cae dung dich CH;,COOH pK, 4,75 c6 cae ndng dé 1A 1,0; 0,1; 0,01; 0,001M bang cae dung dich chuéin NaOH cing néng d6. Trong truéng hop nay gid sit bude nhay ting vGi F - 1 = £0,002; tic la chudin do thiéu va thita 0.2% Iugng axit cin chudn dé. Sau khi giai phuong trinh (a), ta duce cée két qua @ bang sau: Nong d CHyCOOH va Nal pH bute hay Apli 100 M 745 = 10 355 dy pil 0M 145 + 100 2.55 dv pl oot 744 + 90 180 dv pH 001M 137 + 78 043 dv pH Qua cac vi du trén ta thay bude nhay cAng ngén néu ndng d@ axit edng nbd. Cac dung dich ndng d@ nhd hon 0,001 M gin nhu khong cd bude nhay, nén néu chusin do sé mic sai $6 chi thi rét ldn hoae khong thé chon duge chat chi thi. « Phuong trink tinh sai 6 chi thi hi chudn dO axit yeu bing bazo manh ‘Tit phuang trinh duong dinh phan ta rot ra phusng trinh tinh sai s6 chat chi thi: uy], vi tv S=F,-1-——*— + ((OH7], - [H*]) (4-29) K, + DP), CM Néu diém cudi gin diém tuong duong thi: tH), c+ € , $= F,-1-——+— + (OW), - [H4]9 {— (4-30) K, + (H], CC Tuy theo pT cua chat chi thi, ta cd thé don gidn hda duge cic phtong trinh trén them nita,CO 86 HOA HOC PHAN TICH 1B Thi du I: Tinh sai 36 chi thi, khi chudn d@ dung dich CH,COOH 0,1M bang dung dich NaQH 0,1M ding céc chat chi thi ed pT hing: a) 4,0; b) 8,0; c) 9,0. ‘Trudc hét tinh pH tai diém tuang duong theo (4-26) a) Trting hyp pH Vi (H*] = 10 va [OH] = 101 nén es thé bé qua sé hang thi hai trong phuong trinh (4-29) dé tinh sai 66: -104 ——— = - 0.85 tic la 85% 10475 + 10-4 Nhu vay la sai sd am rat 16n: 85% luang axit chua duge chudn dé. b) Trudng hop pH = 8: ‘Ta kot thiic chun do truée diém tuang duong nén vn bé qua sé hang thit hai trong phutong trinh (4-29) dé tinh sai sé: ~108 -10# 104 + 108 19-475 = 10325 = 0,00056 hoac -0,056%., Sai s6 kha nbé vi chi con 0,056% Iugng axit chia bi chun do. ©) Trutng hyp pH = 9: Ta két thiic chudn d9 sau diém tuong dugng khi da du lugng nhé kiém cia dung dich chudn, Trong trutng hyp nay ta bé qua #6 hang thi nhét trong phuong trinh (4-29) 4@ tinh S: 10-4(0,1 + 0,1) 10? x 01x 0,1 Sai 96 rét nhé vi chi chudn thiia 0,02% Itong axit Thé du 2: Tinh sai s6 chuén dé dung dich CH,;COOH 10M bang dung dich NaOH cing ndng dé va két thic chudn 46 khi pH = 7,5. Ap dung phuong trinh (4-26) dé tinh pH diém twong duong: = +0,0002 hoac +0,02% 2 PH = 0,5pKy,9 + 0,5pK, ~ 0,51g —~ C, = T+ 2,38 — 0,18 + 051g 0,001 = 7,73 Khi két thie chudn do 4 pH = 7,5 tiie Ia sat truse diém tuong dugng, ta tinh sai 36 theo phvong trink (4-30); 1078 2 + (065 — 10°75) ____ = _0,0026 § = 10-475 4 1975 0,061 fhe 18 —0,26%., Sai sé nay chap nhan duge. » Phuong trinh duong dinh phan bazo yeu bang axit manh ‘Tat ca cde Lap Indn déi véi truéng hop chun do axit yéu bing bazo manh cing dingI PHUONG PHAP CHUAN DO AXIT-BAZO duge cho trusng hgp chuéin d@ don baza yéu bang axit manh. Vi vay, chi cin hodn vi H* cho OH™ va thay K, bang K, trong phuong trinh (4-20) ta sé duge phyong trink duéng dinh phan dung dich don bazo ydu bang dung dich don axit manh. vVj+Vv [oH] F- 1 = (H‘)- (OH) —— - ———_ 431) CY K, + (OH) Phuong trink dé biu thi F — 1 theo [H*] va [OH™] va K,, Nhung ta cing od thé thigt lap phong trinh duang chudn dé theo cach tuong tu va biéu thi F - 1 theo (H*], [OH-] va K, la hang 86 axit cua axit yéu Han hgp véi baza. Phuong trinh dé nhu sau: VitV K, — (4-32) CY, I) + K, DE vé dudng dinh phan hoac tinh sai s6 chi thj ta co thé diing phuong trinh (4-31) hoac (4-82) véi cung mot két qua. Cung twong ty nhu duing dinh phan don axit yéu bing don bazo manh, dudng dink phan don bazo yéu bang don axit mank, (thi dy: chudn do dung dich NH, bang dung dich chugn HCI) co nhitng tinh chét twong tu nhau. Déi voi trudng hop nay, pH 4 diém tuang duong khéng phai la 7,0 ma nhé hon 7 vA phy thuge vao ndng do dung dich baze can dinh phan vi dung dich ¢ diém tuong duong 1A dung dich don axit lién hap voi bazo e&n dinh phan. Dutng dinh phan cing co bude phy pH 4 ving diém tuong duong va buée nhay nay ngdn hon buée nhay eda dung dink phan don axit manh cing ndng do bang dan bazg manh. Buéc nhay dai hay ngan cin phu thudc vao cong do bazo va ndng 46 ca nd. Baza cang yeu (pK, cang ln) thi buée nhay cang ngén. Nong d6 bazo can dinh phan cang nhé thi bude nhay cing cdng ngén. Ta hay ding phuong trinh (4-32) dé tinh pH tai diém tuang duong va pH bude nhay (vai quy uée chudn 46 thiéu va thita 0,2% Itong bazo) khi chudn dé dung dich NH, ed ndng dO khac nhau 1M, 0,01M va 0,001M bang dung dich HCI cing ndng dd. ‘Tai diém tuong duong tic 18 khi F = 1, phuang trinh (4-32) duge don gidn héa khi F-1= ({H*) - (OH-) vit ¥ bo qua (H*] canh [OHM], K, = Ryyj.10 canh [H*] va C, = C nén khi dé Gy tra thamh 2/C, va ta 6 ‘Mo 2 10-925 F-1=0nen —[H')= c, i] var te pP pH = 0,5pK, + 0,5 log2 — 0,5 log, = 4,68 + 0,15 — 0,5 logC, = 4,78 — 0,5 log, Khi gidi phuong trinh (4-82) voi F — 1 = —0,002; tie 1a dau bude nhay ta co thé bd Vat¥ 2 qua (OH™] canh (H'] va Kyy¢ canh [H*] dong thoi thay CV. ~ Cy Khi gidi phuong trinh (4-32) vai F — 1 = +0,002 tie la cudi bude nhay khi da du 0,2% lugng axit cin dé trung hoa NH, ta bé qua sO hang thit hai trong phuong trinhCO $0 HOA HOC PHAN TICH 7 d6 va dong thai bé qua [OH] canh [H+] 8 sé hang thi nh4t. Voi sy don gidn hoa dé, sau khi giai ta duoc cdc ket qua 6 bang sau: Nang 6 dung dich NH, (molt) PA F =) pH bude nhay (F - 1= 20,002) 100 478 655 + 300 6.10 $28 655 + 400 om 578 656 = 500 oor 628 7.16 + 5.97 Dé tinh sai s6 chi thi truée hét ta cing tinh pH tai diém tuong duong dé dan gian héa vige giai phuong trinh: Vi,+V S= F~ 1 = (HY), ~ (OH) 2 - + cy, + K, Tht du: Tinh sai 96 khi chudn dé dung dich NH, 0,1M bang dung dich HCI 0,1M dang chat chi thi cs pF bang a} 5; b) 4,0 a) Truong hop két thie chudn d0 khi pH = 5. Ta tinh pH tai diém tuong duang: PH, = 4,78 — 0,51g0,1 = 5,28 Khi pH = 6,0 tdc la [H*] = 10% nén e6 thé bd qua [OH] canh [H*] va bd qua Kun canh [H*], Vi pH nay gin pH tai diém twang duong va vi C, = C nen thay Yt 9 CMe 2 10-925 Ss (10s a7 = 2.105 - 10425 = +1,44,10 hose +0,0144%, x 10°5 ») Truing hop két thie chudn dé bhi pH = 4,0, pH nay twang d6i xa pH diém tuong duong, nén ta bé qua s6 hang thit hai trong phwong trinh tinh sai s6, bd qua [OH”] canh (H*] trong sé hang thi nhat. 2 S104. ut +2.103 hoac +0,2% 1 4.24. Céc vi du khde v8 chudn d6 don axit yén hotic don buze you Thi du J: Can thém bao nhiéu ml dung dich NaOH 0,1M vao 50m] dung dich CH,COOH 0,2M dé pH cia dung dich cudi cing bang a) 4,0; va b) 7,0 Goi thé tich dung dich NaOH 0,1M cin them vao 1a Viml). Dé tinh V ta ding phvong trink duong dinh phan: cv yiotv [H+] ~ 1 = (OH-] - (x+y) S$ -—_ CMy CM, [H*] + K, a) Trung hop pH = 4; thay vao (a) C = 0,1, C, = 0,2; V, = 50; [H*] = 10-4; (OH-] = 10°, K, = 10-475 rot thyc hién cic phép tinh ta duge V = 15,18 ml. b) Trudmg hop pH = 7,0: ta cng thay nhu trén chi khée trong tring hop b nay fa)Bw PHUONG PHAP CHUAN DO AXIT-BAZO thay [H*] = 10-7, (OH™] = 10°7 roi thye hién cae phép tinh, ta duoc V = 99,44 ml. Neu chun 9 60ml dung dich CH,COOH 0,2M bing dung dich chudn NaOH 0,1M thi dé dat duge diém twong dung cin thém vao: 50.0,2 = V.0,1 suy ra Vig = ‘Theo tinh toan ciia vi dy trén, khi thém vao 99,44 ml NaOH 0,1M thi pH cia dung dich cudi cing bang 7,0. Nhu vay, néu ding chat chi thi ed pT bang 7,0 dé xde dinh diém tuong dutong thi sé mac sai 36 1a: 99,44 — 100 = — 0,0056 tte la -0,56% 100 Thi du 2: Can 1,25g axit yéu HA, hoa tan trong nuéc cat thanh 50,00 ml dung dich A. Dung dung dich chudn NaOH 0,09M dé chun do dung dich A 46. Biét rang khi them vao A 8,24 ml NaOH thi pl ca dung dich bing 4,30 va khi thém vao 41,20 ml NaOH thi dat duge diém tuong duong. Hay tinh khéi lvgng phan ti cia HA va hing s6 axit pk, ciia axit dé, Dat M 1a khoi tong phan ti oda HA va K, 1a hang 86 axit cla né Khi chugn do 50 ml dung dich HA bang dung dich NaOH 0,09M thi thé tich NaOH ung véi diém tuang duong Ia 41,2 ml. Vay ta ed: Cyia50 = 0,09.41,2 fy Theo dau bai,ndng d Cjjq ea dung dich A 12: ca, ee 1000 o = © Ha Mx 50 Tir (b) va (c), suy ra M = 387,11. Thay C, = (0,09.41,2)/50 = 0,07416; V, = 50; C = 0,09; V = 8,24; [H*] = Lo; {OH7] = 10-97 vao phuong trinh: cv - CV, vi+¥ {H4) 2 = (on) - (tp — _ - ———_ CMa OM GH) +K, Oi giai phuung trinh dé dé tinh K, thi tim duge K, = 1,26.105. Thi du 3: Gia st chudn dé axit you HA 0,1M bang dung dich chudn NaOH 0,1M vai chat chi thi c6 pT = 7,0, Néu muén sai sé khéng vugt qué 0,1% thi hing 96 axit pK, cia né phai od gid tri nhu thé nao? pH 6 diém tong duong JA pH cia dung dich chi e6 Aq phai lén hon 7,0 ma ta két thie chudn d6 4 pH = 7 tic IA trude diém tuong dvong. ‘Theo thé thiic tinh sai s6: 107 S$ =- ——_ =-0,001 K, + 107 Dé tinh K,, ta gidi bat phuong trinh: 103K, + 101 > 107 > K, > 104.CO SO HOA HOC PHAN TicH 9 Nhu vay néu K, lén han 10-4 thi co thé chudn d6 vai chat chi thi ed pT = 7,0 dé sai sO khong vugt qua 0,1%, 4.2.5, Duong dink phin chudn d6 da axit bing bazo mank Ts hay thiét Ip phuong trinh dung dinh phan khi chudin d@ dung dich da axit HA nong do mol la C, bing dung dich chudn bazd manh NaOH néng d6 mol C. Su chun dQ nay duce tién hanh theo 2 née: H,A + OH™ > H,0 + HA- fa HA- + OHO + 1,0 + a2 @) ‘Trong tring hyp nay ta cing biéu thi mic chutn do bang dai htgng F véi dinh nghia: cv “Oy, tic la phiin axit da duge chudn do, Xhi chudn do theo nic thi nhét, tue 1a tién hanh chudn dd theo phan ung (a) thi tai diém tuong duong thd nhat, ia oé F = 1. Khi chuan 6 theo nie thit (2), tue la tiép theo phan ting (b), thuc hién tigp phan ting (b), tai diém tuong dugng thit hai, ta co F =2 ‘Trong trudng hop chudn do da axit nay ta cing co F, - 1 1a sai s6 khi chudn do theo nac thi nhat va F, ~ 2 1a sai s6 chi thi theo née thd hai ‘Ta hay thiét lap phuong trinh dvéng dink phan theo nae thtt nhat. Ta viet phuong trinh bao ton proton xwit phat tir sn phdm phan tng (a), tie la tir HA~ va HO khi eo mat HA va da them vio V ml NaOH: Mg ov OH) + [HA] - = [oH] - ——— + fay tv vi+V CH= OM one 2 = fon) = pet) + (a2) — a vav [OH] - [H+] + [A] - [HA] ~ CMa KK, - [W'P = (OH™) - [H*} +. —_ Vo+¥ [WYP + KY) + KK, vit¥ Nhan hai vé cia phuong trinh trén voi ay dita: Vo cv - GY, vi+¥ KK, ~ (HP Day 7 > vqoH) - jay S—— 4-2 aga vi+V CY, [HYP + KH) + KK, Phuong trinh trén 1a phyong trinh bac cao theo [H*] nhung e6 thé duge dun gidn hoa trong timg giai doan cia qu trinh chudn a6. Khi chua chan dV = 0, # = 0 ta bo qua duge (OH™] va [A] eanh [HA] nen (4-88) duoc don gidn héa thanh: ay (4-34)80 PHUONG PHAP CHUAN DO AXIT-BAZO Khi moi chutin 46, cdn xa diém tuong duong tht nbét, [H+], (OH] va [A*] khong dang ké so voi [Hj] va [HAT], phugng trinh (4-33) duge don gian hoa thanh: (H*] i) +, 1-F IH] = K, (4-35) Nhu vay, khi K, >> Ky va thuong nbu vay nén ta co thé coi HyA nhur 1a don axit yéu ndng dé C, vA cé K, = K, va ta oo phuang trinh tinh pH eda dung dich dém cia hg HA va HA. Sat diém twong duong thd nbat (bude nhay pH thd nhdt cia dudng dink phan) ta thudng bé qua dude [OH™] va hai s6 hang [H']? (tuong tng véi phan HA rat nhé chia duge chuéin 9) va K,K, (twang tng vai lugng A? cing rt nhé do HA~ phan li ra) trong vé phai cia (4-33) nén phuong trinh dé duge don gién hda thanh: Vat ¥ Rik ~ HP CY, KH) F- 1 =-{84] (4-86) ‘Tai diém tung duang thi nhat, khi F - thanh: . = 0, CV = C,V, phuong trinh (4-36) trd C,+C KK, - (HP 5+ moe Ki (H"] (4-37) e,c Néu @-7G lon hon Ky nhitu thi ob thé bd qua K, trong méu $6 biéu thie trong can eda (4-87) va (4-87) tré thanh: {H'] = VK,K, (4-38) Dé lap phuang trinh dutng dinh phan cho nic thit 2, ta viét phugng trinh bao toAn proton cia dung dich xuét phat tir cde sin phém cia phyong trinh chudn dQ nic dé la A® va HO: Ht [HAT 2[H,A] - 2 CoN [OH (a+ 0 | + AUDA] ~ Vi+V =i ray = 200¥o jon” fH) HAT 2[H,A) Tory CORD HY HAT ~ 208) cy, ‘Ky{H* a(n? = jones — ey — Coe _H) + 2) Vi +V (Ht? + &[H*] + KK,CO 86 HOA HOC PHAN TICH 81 Vit ¥ Nhan hai vé cia phuong trinh trén vdi CV ta duge: Vo+¥ KH] + 2(H+ F-2= (OH) - [1p - 4:39) CoM, (HY + KEY) + KK, Phuong trinh (4-39) tren cing la phwang trinh bge 3 theo [H*] nhung trong giai doan cua qua trinh chudn dé no cd thé duge don gian hoa. Khi dang chudn 48 née thit hai, cdn xa diém tuong duong thi hai, ta co thé bo qua duge (H*], (OH-j, [A?] va [HA] nén (4-39) duge dun gian héa thanh: Ht poy- tH") + K, my= x, 20" (4-40 va suy ra Hy = -40) y (HE) toa Phuong trinh (4-40) chinh la phyong trinh tinh pH ctl dung dich he dém HA va AX, Trong bigu thitc(4-40;, 2 — F ting véi nong 9 HA~ con lai chua bi trong ha, con F ~ 1 dng voi néng do phan HA~ bi trong hda thanh [A2}. © sat diém tuong duong thd hai ta od thé bé qua duge (OH™], HA}, [HA] nén phuong trinh dudag dink phan con la: Yot¥ (A) F-2-=(O0H7] -— aay CM, [HY] + x, 2C,+C ‘Tai diém tuong duong thi hai, F = 2. CV = 2C,V,, = nen: 2c, +¢ (HY (OH-] = —__ (4-42) cc, (H) + K, Tuy theo gid tri ca.K, s0 voi ndng do ion H* didm tuang duong (gid tri [H*] thuang Jén hon 107 kha nhiéu) ma phuong trink trén con ed thé diye don gidn héa nia. Sau diém tuong ducng ngoai buée nhay, khi du OH™, ta bd qua sy thay phan cia A?, tte la bd qua sO hang thd hai vé phai phuong trinh (4-83), nén phuong trinh dd chi con: vi+¥ 10M Vie cM, (H} GV, Thi du: Ve duéng dinh phan chudn dd dung dich H;C,0, 0,1M bang dung dich NaOH 0,1M. H,C,0, ¢6 pK, = 1,25 va pK, = 4,27. Dé ve dung dinh phan hay tinh pH khi F = 0,5; 0,9; 1,0; 1,1; 1,5; 1,996; 2,00; 2,004 va 2,5. Ap dung cac cong thie trén day, tinh pH tai céc diém ofa dudng dinh phan, ta duge ede két qua & bang sau: Fe = [OH-] (4-43)82 PHUONG PHAP CHUAN DQ AXIT-BAZO F as a9 100 110 150 ie | 200°] 2,004 25 pil 15 22 276 | 332 | 427 667 | 835 yet] 16 Nhén xét: Axit oxalic cé pK, kha nhé tite la K, kha lin, K, va K, khong I6n hon nhaw nhiéu nén khi chudn d@ buée nhay 6 diém tuong duong thi nhat hau nby khong c6, chi ed bude nhay 6 diém tuong duong tht hai nhu khi chudn dé axit axctic cing néng dd. Vi vay, khi chudn d@ axit oxalic ta chi chudn dé theo née thit hai va co thé ding cdc chat chi thi co pT’ nim trong khoang pH tit 7,0 dén khodng gin 10, thi du: 6 thé ding phenolphtalein ¢hinh 4.3) "ron fo 7 15 2 25F Hink 4.3, During dint phan dung dich 130, 01M bing dung dich chun NaOH 01M. « Duong dink phan dung dich axit photphoric HyPO, bang dung dich chudn NaOH Gia sit phai chun dV, ml dung dich HPO, ndng do mol C, bang dung dich chudin NaOH ndng do mol la C. Cae phuong trinh phan dng chudn dé dung dich H,PO,: H,PO, + OH” = H,POz + H,O née thu nhat HPO; + OH~ = HPO} + H,O née thit hai HPO} + OH” = PO} + H,0 nae thi ba ‘rong trang hop nay phvong trinh duéng dinh phan cing duoc thiét lap nhu & trutmg hop dinh phan dung dich HA bang dung dich chudn NaOH, Ta cing dat F la phan axit duge chugn d6 vai F = CV/C,V, khi chudn dé theo nic thi nhat ta cd F - 1 ‘Tai diém tuong duang thé nhat CV = C,V,, nén F = 1. Dé thiét lap phuong trinh dutngCO 80 HOA HOC PHAN TiCH 33 dinh phan néc thd nhat ta cing viét phugng trinh bao toan proton ciia dung dich xuat phat tir phan tng chuda dg nde dé 1a HPOy va H,0: Mo - wv - 3 (H*] + [H,PO,) - a {OH} - wav? [HPO}-) + 2[P03-] ov - CN, va (O1H7] ~ [H%) + [HPO}"] + 2[P0}] - fH,P0,] Dua F vao phitsng trink trén bang odch nhan hai vé véi V, + VIC.V,, thay cde gia tr] nbng do ean bang céc ion cua axit photphoric, ta dude phuong trinh dudng dinh phan. Vi + K,K,[H"] + 2K\K,K, - (H*P P= 1 = (Onn) - grep 2 YARD + OK GK (DP CM, (NP + KH + KIN) + KKK, Phuong trinh trén lA phvang trinh bac 3 theo [H*] nhung no cé thé duge dun gian hea trong timg giai doan ctia qué trinh chudn do. Khi cha chugn 46 F = 0, ta bd qua duge [OH], [HPO}-}, [PO}-] nen phuong trinh (4-44) duoc dun gidn hoa thanh (4-44) Kieu [ty =e (4-45) K, + (H] Kni thém V mol NaOH vao nhung'cdn xa diém tuong duong thi nhdt thi ta od thé ba qua [H*], [(OH-}, (HPO}-] va [PO}-] nén (4-44) dee don gidn hoa con: ) “Ky + Py suy ra: (4-46) Phuong trinh trén la phuong trinh biéu dién ndng 46 can bing ion [H*] cia he dém H,PO;/HPO}-, vi 1 — F sing voi phan ndng d6 HPO, chua bj chudn dé bai NaOH con F la phan ndng do HPO, 44 bj chudn do thanh H,PO;. O sat diém tuong duong thit nhat, khi F nim trong khodng 0,998 dén 1,002 ta chi bé qua duge (OH™] canh [H*], 2K,K,K, (tng véi PO}-) 6 tit 86 cia phuong trinh (4-44) va"bé qua duoc [H*}, K,K,[H*] va K,K,K, (tuong ding vai [H,PO,], (HPO}-] va [PO}-)) & mau 6 eda phuong trinh dé. Phuong trinh (4-44) duge dan gian hoa thanh: Cot © | KKH") - [HP ee Ky KK, ~ (HP yom KH] Tai diém tuong duong thi nhat F = 1, (4-47) duge don gidn hda thanh: (4-47) aad (4-48)84 PHUONG PHAP CHUAN DO AXIT-BAZO ce, C,+e Phuong trinh dudng dinh phan theo née thit hai, duoc biéu dién theo F — 2, duoc viét tit phudng trinh F — 2 = F - 1- | hoac viét phuong trinh bao toan proton cha dung dich khi them V ml NaOH xudt phat tit cdc sin pham cila phan ting chudn d6 1a HPO; va H,0: va néu Jon hon K, nhiéu thi (4-48) dugc don in héa thanh [H*] = (K,K,)° YotV KK, ~ KH"? ~ 21"? CY, FD + KP + KKH") + K\KK, Khi dang chuan do nac thit hai, con tuong déi xa diém twang duong thi hai, phuang trinh (4-49) duge don gin héa thanh: F 2 = (OH7]-[H*)). (4-49) (H‘] K, + (H*) - . 2-F hoac WH] = Ky (4.50) © sat diém tuong duang thi hai, khi 1,998 = F < 1,002 ta cd phuong trinh: 2C,+C — K,K,K, ~ K,[H*? F - 2 = (OH-] —2— 4 AGI ~ IAT (4-51) Coe EK IH) ‘Tai diém tuong dung thi hai, khi ¥ = 2, ta cé phuong trinh tinh [H*] sau khi duco don gian hda: 2C,+C TH] = (KK, + hy.ofSe-) (4-52) Déi véi née chun d6 thé ba, phuong trinh dung dinh phan edng duge thiét lap theo cach tuong tu hoe theo F ~ 3 = F ~ 2 — 1 hode viét, phuong trinh bao toan proton cua dung dich xudt phat tir PO} va H,0: Vi+tV KKH’) + 2K [H'? + 3p = ((OH-} ~ [Hy + CY, (H*P + KH]? + K,K,[H*] + K\KK, Fo (4-53) Khi dang chudn 49 nae thi ba cin xa diém tung duong ta es thé bé qua (H*), (H;PO,], [HPOz] ben canh {HPO}-], (PO}-] va [OH] nén phuong trinh (4-53) duge don gian héa thanh: vy +V (8*) = (OH™} - {H*) = (4-54) CM 3 + TH] {H') + (] ‘Tai sat diém twong duong tht ba, khi CV = 3C,V, ta ed thé coi: F- hose: (4-55) 3c, Vv BC,+ C0 Vi+V ee hoae 2 c V,€O SO HOA HOC PHAN TICH 85 ac, +c (Ht) nén F- 3 = (OH-] ~—— -~——_ (4-56) ce f+ Ky ‘Tai diém tuang duong thi ba, khi F = 3; CV = 3C,V, thi: ac, +c [H+] [oH-] —— = ——_ (4-57) cc [HY] + Ky Kha xa diém tuong duong thit ba, ta vin khong bd qua dude su thiy phn ca PO}, van phai ding (4-56) dé tink pH ctia dung dich. Thi du: Vé duéng dinh phan khi chun do dung dich H,PO, 0,1M bang dung dich chuéin NaOH 0,1M. HPO, cd pK, = 2,12; pK, = 7,21 va pK, = 12,36. Ap dung cde cng thc va cde phwong trinh (4-45), (4-46), (4-47), (4-48), (4-50), (4-51), (4-52), (4-54), (4-56) va (4-57) ta tinh duge pH tai cde diém cia qué tink chudn do nhut sau; F 0 as | 09 | 099 [og | soon | wor ] us wo | i999 pH | ist | 23 | 307 | 4i2 | aor | 471 | 478 | 721 | 920 | 961 FB zou; 2001 | 201 | 250 | 299 | 2999 | 3000 | som | am | 350 all | 96s | 977 | 1037 | at ] Ras | pax | as Peay | as | 27 Hink 44, Duong dink phan chubn 49 dung dich It3P0, 0,1M bing dung dich chohn NaOH 01M, Dudng dinh phan chi eo hai buéc nhay d diém tuong duong tht nhat va diém tung duong thd hai. Diém tvong duong thi ba hoan toan khéng eé bude nhay va hing a6 axit, cia nde thf ba rat bé: 10°12.36, Bude nhay pH thit nhat nim trong khoang déi mau cia metyl dé, buge nhay thi hai ndm trong khoang déi mau cia phenclphtalein,

Co So Hoa Hoc Phan Tich Hoang Minh Chau Tu Van Mac Tu Vong Nghi

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Co So Hoa Hoc Phan Tich Hoang Minh Chau Tu Van Mac Tu Vong Nghi

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