He So Chuyen Doi

TRNG THPT CHUYN TIN GIANG.
TI LIU BI DNG HC SINH GII THPT Cc h s chuyn i, phng trnh v hng s c bn
n v khi lng nguyn t S Avogadro Hng s Boltzmann in tch ca electron Hng s Faraday Khi lng electron Khi lng neutron Khi lng proton Hng s Planck Tc nh sng
1u = 1.6605 10-27 kg k = 1.38065 10-23 J K -1 e = 1.6022 10-19 C F = 9.6485 104 C mol -1 me = 9.11 10-31 kg mn = 1.67492716 10-27 kg mp = 1.67262158 10-27 kg
N = 6.02 1023 mol-1
h = 6.63 10-34 J s c = 3 108 m s-1 E = E (0.0592 / n) log K ln P = - Hvap / RT + B
Phng trnh Nernst (T = 298 K) Phng trnh Clausius-Clapeyron Phng trnh kh l tng H thc De Broglie Nng lng t do Phng trnh Arrhenius E = hv U = q + w G = G + RT ln Q w = - PV Standard atmosphere = 101325 Pa RT ti 298.15 K = 2.4790 kJ mol-1 Pi ( ) = 3.1415927 1 A = 10-10 m 1 J = 1 kg m2 s-2 1 Pa = 1 kg m-1 s-2 = 1 N m-2 1 eV / mol = 96.4853 kJ mol-1
o
PV = nRT
G = H - TS k = Ae-Ea/RT
= h / mv
G = - nFE
1 W = 1 J s-1 1 cal = 4.184 J 1 bar = 105 Pa
1 atm = 1.01325 105 Pa = 760 mmHg (torr) CC N V O LNG K t nm 1960 ti hi ngh quc t v cn o, ngi ta xut h thng quc t v cc n v, vit tt l h SI (Systme International dunits). GV:TRNG CHU THNH. Ti liu lu hnh ni b 1
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT By n v c bn ca h SI i lng c bn chiu di khi lng thi gian cng dng in nhit lng cht cng sng Tn n v met kilogam giy Ampe Kenvin mol Candela K hiu m kg s A K mol cd
Cc n v dn xut ca h SI i lng p sut Nng lng Cng sut in lng in th Tn s Lc n v Pascal Joule Watt Coulomb Volt Hertz Newton K hiu Pa J W C V Hz N nh ngha Kg/m2 hay N/m2 Kgm2/s2 Kgm2/s3 tc J/s A.s J/A.s tc J/C s-1 Kgm/s2
1. Chiu di : Trong h SI n v chiu di l met (m). i vi cc ht vi m (nguyn t, phn t, ion ..) 0 th kch thc cc ht ny thng o bng n v : nanomet (nm), angstron ( A ), picomet (pm) 1 nm = 10-9 m 1 A = 10-10 m 1 pm = 10-12 m 2. Khi lng : l thc o lng vt cht trong mt vt. Trong h SI n v khi lng l kilogam (kg). Trong ha hc n v khi lng thng dng l gam. 1 kg = 1000 gam 3. Khi lng ring : khi lng ring l khi lng ca mt n v th tch. m d= Trong h SI khi lng ring c n v l : kg/m3. Trong thc t th hay s dng V n v ca d l g/cm3 hay g/ml. Khi lng ring cht kh thng dng l g/l 1 g/ml = 1000 kg/m3 1 g/l = 0,001 g/ml 4. Nhit : thang nhit bch phn (gi l thang Celcius) 0C, chia khong nhit t 00C (nhit nng chy ca nc) n 1000C (nhit si ca nc) thnh 100 phn bng nhau. Nhit bch phn khng phi l n v ca h SI. Kenvin l n v nhit ca h SI (k hiu l K). Nm 1848 nh khoa hc ngi Scotland tn l Lord Kelvin ch ra rng : 273,150C l nhit l thuyt thp nht c th t c v ng gi l 0 tuyt i. Vi 0 tuyt i lm im xut pht, ng thit lp thang nhit tuyt i m ngy nay gi l thang Kenvin. Nhit tuyt i khng c du ( 0 ) T (K) = t (0C) + 273,15 (0C) 5. p sut : l lc tc dng ln mt n v din tch. Trong h SI p sut c n v l Pascal (Pa) 1 atm = 1,013 105 Pa = 760 mmHg = 760 torr (Torricelli) 1 torr = 1 mmHg 1 bar = 105 Pa 1Pa = 1 N/m2 6. Nng lng : Joule (J) l n v nng lng dn xut ca h SI. Joule l cng m lc 1N sn ra khi di chuyn trn qung ng 1 mt. 1 J = 0,239 calo = 107 erg 1 calo = 4,184 J 1 eV = 1,602 10-19 J 7. Mol : l n v lng cht v l mt n v c bn ca h SI. 1 mol = 6,023 1023 ht vi m (nguyn t, phn t, ion ) 1 mol nguyn t c cha 6,023 1023 nguyn t. GV:TRNG CHU THNH. Ti liu lu hnh ni b 2
0
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT 1 mol phn t c cha 6,023 1023 phn t. 1 mol ion c cha 6,023 1023 ion. (6,023 1023 = N cn gi l s Avogadro) PV 8. Hng s kh R : Theo phng trnh trng thi kh l tng : PV = nRT R = nT R : l hng s kh. Tr s ca R ph thuc vo n v ca P v V Xt trong 1 mol kh (n = 1), t phng trnh trng thi ta c : PV PV = RT R = T kc (00C, 1 atm) Khi P = atm , V = lt , T (K) ta c P = 1 atm, V = 22,4 lt (th tch 1 mol), T = 273 K (00C) 22,4 R= 0,082 (l.atm.mol-1.K-1) 273 Khi P = mmHg, V = ml, T (K) ta c : P = 760 mmHg, V = 22400 ml, T = 273 (K) 760 22400 R= 62400 (mmHg.ml.mol-1.K-1) 273 Tnh theo h SI : P = Pa (Pascal), V = m3, T (K) ta c : P = 1,013 105 Pa, V = 22,4 10-3 m3, T = 273 (K) 1,013 10 5 22,4 10 3 R= = 8,314 (J.mol-1.K-1) hay R = 1,98 (cal.mol-1.K-1) 273 Cc tip u ng dng trong h SI Tip u ng Tera Giga Mega kilo deci centi mili micro nano pico K hiu T G M k d c m n p ngha 1012 109 106 103 10-1 10-2 10-3 10-6 10-9 10-12
Tng quan gia mt s n v nng lng J cal eV cm-1 J 1 4,18 1,6.10-19 11,96 cal 0,239 1 3,82.10-2 2,859 eV 6,25.1018 2,62.1019 1 1,24.10-3 cm-1 5,034.1022 2,105.1023 8,067.103 1
p dng : 1. Kc = Kp.(RT) n 3. Kp = Kc(RT)n 5. MOMEN LNG CC a2 = b2 + c2 2bc. cos A )
2. Kx = Kp. P n 4. G0 = RTlnKp 6. G = RTlnK 1 N0 v t = ln k Nt 7. G = H T. S * ln K P (T1 ) H 1 1 = K P (T2 ) RT T2 T1 3
ln 2 8. * Hng s phng x: k = t 1
2
GV:TRNG CHU THNH. Ti liu lu hnh ni b
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT * Hng s kh: R = 8,314 J.K-1.mol-1; p = 1atm = 1,013. 105 Pa ; NA = 6,022. 1023 10.Theo G = A + PV hay G = A + PV = A + n.RT 0 th A 300 > 0 phn ng xy ra theo chiu nghch. 11.Cc hng s R = 8.314 J/mol.K C = 2.998 108 m/s Cng thc: F = 96485 A.s/mol h = 6.62 10-34 J.s NL = 6.023 1023 mol-1 p = 1 bar
dp S = dT V
H = U + pV = U + nRT
ln p 2 HV 1 1 = T T p1 R 1 2 ln
G = G + RT ln Q = RT ln K + RT ln Q
k(T2 ) E A 1 1 = T T k( T1 ) R 1 2 ln
K P ( T2 ) HR 1 1 = T T K P (T1 ) R 1 2
K P = K C (RT )n = K Xp n
KS = c0
c A = c 0 k.t A p i = p i0 .x i
T2
v0 =
v max .[ S] K M + [ S]
2 1
1 1 = 0 + k.t cA cA
k = A.e
EA RT
c A = c 0 .e k.t A
G = z.F.E
p i = p g .x i
TG =
2 RTG M1 m* 2 H S
TG =
T2
2 RTS M1 m* 2 H V
H(T2 ) = H(T1 ) + C P dT
T1
1 1 = RH 2 2 n 1 n2
= eq 0
S(T2 ) = S(T1 ) +
l A.R
eq =
c.n e
CP T dT T1
eq = 0 k. c
mag = B . n( n + 2)
1.IN HA HC
S pin : (-) Zn(r) 2+(aq) (C) Cu2+(aq) (C) (r) (+) Zn Cu (C) nng dung dich mui Cu2+ va Zn2+ Qui c : - Vach thng ng chi ranh gii gia 2 pha : pha rn (kim loai) va pha long (dd) - Hai vach thng ng chi ranh gii gia 2 pha long lin h vi nhau bng mt cu ni 0,059 [oxh] lg n [kh] * Ap dung cng thc Nerst cho tng loai in cc cu th : a/ in cc kim loai : (in cc loai 1) Mn+ + ne M 0,059 lg[M n + ] E = E0 + n b/ in cc loai 2 : TD : in cc calomen : Hg2Cl2 + 2e 2Hg + 2ClHay Hg22+ + 2e 2Hg 0,059 2 lg[ Hg 2 + ] E = E0 + 2 Cng th Nerst: E = E0 + GV:TRNG CHU THNH. Ti liu lu hnh ni b 4
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Do Hg2Cl2 la mui it tan nn trong dung dich co cn bng : Hg2Cl2 Hg22+ + 2ClT(tan) Ta co tich s tan : T(tan) = [Hg22+][Cl-]2 [Hg22+] = [Cl ] 2 T(tan) 0,059 lg Thay vao phng trinh trn ta co : E(cal) = E0 + 2 [Cl ] 2 0,059 0,059 lg THg 2Cl2 lg[Cl ] 2 Vi T(tan) la mt hng s nn thun tin ta vit : E(cal) = E0 + 2 2 0,059 lg THg 2Cl2 (la mt hng s nhit xac inh) t E0(cal) = E0 + 2 Ta co : E(cal) = E0(cal) - 0,059lg[Cl-] Vy th cua in cc calomen chi phu thuc vao nng Cl- trong dung dich. kc thi E0(cal) = + 0,268 v c/ in cc oxi hoa kh : Gm thanh kim loai tr hay graphit nhung trong dung dich cha ng thi dang oxi hoa va dang kh cua cp oxi hoa kh TD : in cc Fe3+, Fe2+ Pt Sn4+, Sn2+ Pt Phan ng in cc : Fe3+ + 1e Fe2+ ; Sn4+ + 2e Sn2+ [ Fe 3+ ] 0 E = E + 0,059lg [ Fe 2+ ] TD : i vi in cc : MnO4- , H+, Mn2+ Pt + Phan ng in cc : MnO4 + 8H + 5e Mn2+ + 4H2O 0,059 [ MnO4 ][ H + ]8 0 lg E = E + 5 [ Mn 2+ ] d/ in cc khi : Gm mt thanh kim loai tr hay graphit ong vai tro vt dn in ng thi la vt mang cac phn t khi c nhung trong dung dich cha ion tng ng va c bao hoa bng khi tng ng. TD : in cc hidro : H3O+ + e H2 + H2O [ H 3O] + 0 Th cua in cc : E = E + 0,059lg vi E0 = 0 va thng thng P = 1 atm nn pt co dang : PH 2 E = 0,059lg[H3O]+ Ta co : pH = - lg[H3O]+ nn O2, OH- Pt Phan ng in cc : O2 + 2H2O + 4e E = E0 +
PO2 0,059 lg 4 [OH ]4
E = - 0,059pH 4OH-
Ta co : E 0 O2 + 2 H 2O / 4OH = + 0,401 v nn : PO2 0,059 lg E = 0,401 + nu ta gi cho PO2 = 1 atm thi : 4 [OH ] 4 E = 0,401 - 0,059lg[OH-] Mi quan h gia G0p , E0pin va hng s cn bng cua phan ng : K nE 0 E pin Ta co : G0 = - nFE0 mt khac thi G0 = - RTlnK lnK = RT Thay F = 96500 C ; R = 8,314 J ; T = 298 K ri chuyn sang lg ta co : lgK = GV:TRNG CHU THNH. Ti liu lu hnh ni b
0 nE pin
0,059 5
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT K= 10
nE 0 0 , 059
(n la s electron trao i trong phan ng oxi hoa kh)
2.NHIT NG LC HC
Nhit ca mt s qu trnh quan trng : 1/ Nhit to thnh ca cc cht : H(tt) (hay sinh nhit) Nhit to thnh ca 1 hp cht ha hc l hiu ng nhit ca phn ng to thnh 1 mol cht t nhng n cht trng thi chun. Trng thi chun ca 1 cht l trng thi bn nht ca cht p sut 1 atm v 250C (hay 298,15K) TD : phn ng : N2 + 3H2 2NH3 H = - 92,22 KJ H pu 92,22 Nhit to thnh ca NH3 = = = - 46,11 KJ/mol 2 2 C(r) + O2(k) CO2(k) H = - 393 KJ/mol Nhit to thnh CO2 = H(p) = - 393 KJ/mol Nhit to thnh ca cc n cht iu kin chun c qui c bng 0. Khi phn ng xy ra m tt c cc cht (n cht v hp cht to thnh) u iu kin chun th ta c 0 nhit to thnh chun. K hiu tt 2/ Nhit phn hy : Nhit phn hy ca 1 hp cht l hiu ng nhit ca phn ng phn hy 1 mol cht to thnh cc n cht. 0 TD : H2O(l) H2(k) + O2(k) 298 = + 285,84 KJ Nhit phn hy H2O kc = + 285,84 KJ/mol 3/ Nhit t chy (hay thiu nhit) H(tn) Nhit t chy ca 1 cht l nhit ta ra khi t chy hon ton 1 mol cht trong oxi. TD : C(graphit) + O2(k) CO2(k) H = - 393 KJ/mol Nhit t chy ca C = - 393 KJ/mol 2C2H5OH + 3O2 4CO2(k) + 6H2O(k) H = - 2736 KJ H pu 2736 Nhit t chy C2H5OH = = = - 1368 KJ/mol 2 2 nh lut Lavoisier Laplace : Nhit to thnh v nhit phn hy ca mt hp cht bng nhau v tr s nhng ngc nhau v du 4/ Nhit phn li : Nhit phn li ca mt cht l nng lng cn thit phn hy 1 mol phn t ca cht ( th kh) thnh cc nguyn t th kh. TD : H2(k) 2H(k) H = 104,2 kcal/mol O2(k) 2O(k) H = 117 kcal/mol CH4(k) C(k) + 4H(k) H = 398 kcal/mol 5/ Nng lng ca lin kt ha hc : Nng lng ca mt lin kt ha hc l nng lng cn thit ph v lin kt to thnh cc nguyn t th kh. Xc nh nhit ca cc phn ng ha hc : nh lut Hess. y l mt nh lut c bn ca nhit ha hc do vin s Nga H.I. Hess (1802 1850) tm ra ln u tin, c ni dung nh sau : Trong trng hp p sut khng i hoc th tch khng i, hiu ng nhit ca phn ng ha hc ch ph thuc vo dng v trng thi ca cc cht u v cc sn phm cui, khng ph thuc vo cch tin hnh phn ng C th minh ha ngha nh lut Hess trong th d sau : Vic oxi ha than bng oxi to thnh kh CO2 c th tin hnh theo 2 cch : Cch 1 : t chy trc tip than thnh CO2 Pt : C(graphit) + O2(k) CO2(k) H (hiu ng nhit ca phn ng) GV:TRNG CHU THNH. Ti liu lu hnh ni b 6
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Cch 2 : tin hnh qua 2 giai on : C(graphit) + O2(k) CO(k) H1 CO(k) + O2(k) CO2(k) H2 C th biu din hai cch tin hnh trn bng s sau : C(graphit) CO2(k)
+ O2
H1
CO(k)
H2
Nu cc qu trnh trn tha mn iu kin : Nhit v p sut ban u bng nhit v p sut cui ta c : H = H1 + H2 Vi h qu ca nh lut Hess : 1/ H qu 1 : Hiu ng nhit ca phn ng bng tng nhit to thnh ca cc sn phm tr tng nhit to thnh cc tc cht (c k cc h s hp thc ca phng trnh phn ng)
0 0 0 = tt ( sf ) tt (tc) 298
TD : Tnh hiu ng nhit ca phn ng : 0 = ? CaCO3(r) CaO(r) + CO2(k) 298 0 Bit tt - 1206,9 - 635,6 - 393,5 (KJ) Gii : 0 Ta c : 298 = (- 635,6) + (- 393,5) (-1206,9) = + 177,8 KJ 2/ H qu 2 : Hiu ng nhit ca phn ng bng tng nhit t chy ca cc tc cht tr tng nhit t chy ca cc sn phm (c k cc h s hp thc ca phng trnh phn ng)
0 = 0 (tc) 0 ( sf ) 298 dc dc TD : Tnh hiu ng nhit ca phn ng : 0 = ? CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l) 298 0 Bit H(c) - 871,69 - 1366,91 - 2284,05 0 Gii : Hiu ng nhit ca phn ng : 0 0 = 0 (tc ) tt ( sf ) 0 = (-871,69) + (-1366,91) (-2284,05) = 45,45 KJ 298 dc 298
3/ H qu 3 : Hiu ng nhit ca phn ng bng tng nng lng lin kt c trong cc cht tham gia (tc cht) tr tng nng lng lin kt c trong cc cht sn phm.
0 0 0 = lk (tc) lk ( sf ) 298
TD : Xc nh nng lng trung bnh ca cc lin kt O H trong phn t nc, bit rng nng lng lin kt H H v O = O tng ng bng 435,9 KJ v 498,7 KJ, khi t chy ng p 2 mol H2 ta ra 483,68 KJ. Gii : Pt : 2H2(k) + O2(k) 2H2O(k) H = - 483,68 KJ Da vo h qu th 3 ca nh lut Hess ta c : 0 0 0 = lk (tc) lk ( sf ) - 483,68 = 2(435,9) + (498,7) - 2 0 2O 298 H
0 0 2O = + 927,09 KJ lk (O H) = H
+ 927,09 = + 463,545 KJ (do 1 phn t H2O c 2 lk O-H) 2
4/ Chu trnh nhit ha hc hay chu trnh Born Haber (Booc Habe) GV:TRNG CHU THNH. Ti liu lu hnh ni b 7
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Mt phng php ng dng ca nh lut Hess thng c dng tnh hiu ng nhit ca cc qu trnh (nng lng mng tinh th, nhit hidrat ha, nhit ha hi ) l lp nhng chu trnh nhit ha hc trong qu trnh m chng ta quan tm l mt giai on ca chu trnh, khi tt nhin phi bit hiu ng nhit ca cc giai an khc trong chu trnh. Sau y l mt vi th d : TD : Tnh nng lng mng li ca tinh th NaCl. Nng lng mng li ca tinh th NaCl l hiu ng nng lng ca qu trnh : Na+ + Cl- NaCl (tt) E NaCl Lp chu trnh nhit ha hi nh sau : Hth Na DCl2 Na(r) + Cl2 (k) Na(k) Cl(k)
H(tt) NaCl INa ACl ENaCl
NaCl(tinh th)
Na+ (k) + Cl-(k)
Trong bit hiu ng nhit ca cc qu trnh sau : - Nhit thng hoa ca Na : Hth Na = 25,9 kcal/mol - Nhit phn ly ca Cl2 thnh nguyn t : DCl2 = 57,2 kcal/mol - Nng lng ion ha ca Na : INa = 117,8 kcal/mol - Ai lc electron ca Clo : ACl = - 88,0 kcal/ngtg - Nhit to thnh ca mui NaCl tinh th (t cc n cht) : H(tt) NaCl = 98,2 kcal/mol T theo nh lut Hess ta c th tnh c nng lng mng li ca NaCl : ENaCl = H(tt NaCl) (Htn Na + DCl2 + INa + ACl) Thay cc gi tr vo ta c : ENaCl = - 182,5 kcal/mol TD : Tnh nng lng lin kt Hlk HCl gia cc nguyn t H v Cl trong phn t HCl, ngha l nng lng c gii phng khi to thnh phn t HCl t cc nguyn t H v Cl. Bit Nhit phn ly Cl2 v H2 thnh nguyn t : DH2 = 103,4 kcal/mol ; DCl2 = 57,2 kcal/mol. Nhit to thnh kh HCl : HHCl = - 22,1 kcal/mol. Ta lp chu trnh nhit ha sau : H2 + Cl2
HHCl DCl2 DH2
H(k)
- Hlk HCl
+ Cl(k)
HCl(k) T chu trnh trn khi p dng nh lut Hess ta c : Hlk HCl + HHCl = DH2 + DCl2 Hlk HCl = HHCl ( DH2 + DCl2 ) (103,4 + 57,2) Hlk HCl = - 22,1 = - 102,4 kcal/mol 2 Nhit dung : Nhit dung l nhit lng cn thit un nng mt lng cht nht nh ln 10 bch phn (10C) Nhit dung ring l nhit lng cn thit nng nhit 1 gam cht ln 10 bch phn. Nhit dung mol l nhit lng cn thit nng 1 mol cht ln 10 bch phn
3.TC PHN NG
1. nh ngha Tc phn ng l bin thin nng ca mt cht cho (cht u hoc cht cui) trong mt n v thi gian. 2. Biu thc tnh tc phn ng nhit khng i, gi s c phn ng ha hc din ra theo s : Phng trnh phn ng (I) gi l phng trnh t lng. biu din tc phn ng ngi ta c th chn bt k cht no trong phn ng (A, B, X, Y), nhng trong thc t, ngi ta thng chn cht no d theo di, d xc nh c lng ca chng cc thi im khc nhau. y, ta chn cht A, X kho st v c nh th tch ca h kho st (V = const).
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Gi s thi im t, nng cht A l CA, cn cht X l CX v thi im t + t , nng tng ng ca chng l: CA + CA, CX + CX. Tc trung bnh V ca phn ng c biu th nh sau: C A +CX V= V = t t
III. NH LUT TC DNG KHI LNG i vi phn ng tng qut (II) T = const Guldberg v Waage thit lp biu thc lin h gia tc phn ng vi nng cht phn ng. l biu thc ca nh lut tc dng khi lng. Biu thc (1.6) biu din nh lut c bn ca ng ha hc, n m t nh hng ca nng ln tc phn ng. Theo cch m t trn, nhit khng i, tc phn ng l mt hm s nng ca mt hoc mt s cht phn ng. i vi cc loi phn ng khc nhau dng ng cong biu din s ph thuc ny l khc nhau. k trong phng trnh (1.6) l mt hng s nhit khng i, n c trng ng hc cho phn ng cho trc. Nu ta thu xp cch biu din nng lm sao cho [A] = [B] = 1 mol/l th v = k, vy: Hng s tc phn ng l tc phn ng khi nng cc cht phn ng bng nhau v bng n v (= 1). Th nguyn (n v biu din) ca hng s tc ty thuc vo loi (bc) ca phn ng (xem bng 2.1). phng trnh (1.6) c gi l phng trnh tc hay phng trnh ng hc ca phn ng ha hc. So snh (1.4) v (1.6) phng trnh tc cn c biu th:
Biu thc ny cho bit mi lin h gia tc phn ng vi nng . Dng ca ng biu din ny cng khc nhau. IV. PHN LOI NG HC CA PHN NG V phng din ng ha hc, ngi ta c th chia cc phn ng ha hc theo phn t s v bc phn ng. 1. Phn t s phn ng Phn t s phn ng l s phn t tng tc ng thi vi nhau trc tip gy ra bin ha hc trong mt phn ng c bn. Cn phn ng c bn (hay phn ng s cp) l phn ng ch mt giai on duy nht, GV:TRNG CHU THNH. Ti liu lu hnh ni b 9
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT cht phn ng tng tc vi nhau trc tip cho sn phm phn ng. Da vo khi nim phn t s phn ng, chng ta c th phn bit ba loi phn ng: phn ng n phn t, lng phn t v tam phn t.
Khi cc phn t tng tc vi nhau, khng phi tt c cc va chm gia chng u dn n bin ha ha hc, m ch mt phn nh va chm trong cc va chm dn n bin ha ha hc, va chm gi l va chm c hiu qu hay va chm hiu dng. Khi phn ng ha hc din ra, m bo cho cc phn t va chm ng thi dn n bin i ha hc, th phn ng cng nhiu phn t tham gia cng kh thc hin iu kin trn. Ngi ta tnh xc sut v chm, th xc sut va chm ba l b nht, c ngha phn ng tam phn t rt him, trong thc t ngi ta cha tm thy phn ng c phn t s cao hn 3.
Theo ngha ca phn t s mun cho phn t trn din ra phi do s va chm ng thi ca 13 phn t. iu ny khng bao gi gp nh va ni trn, cha gp phn ng c phn t s l 4, hung chi l 13. Mt khc nghin cu phn ng bng thc nghim cho bit phn ng trn l phn ng phc tp (bc ba). S phn tch trn cho thy khi nim phn t s khng p dng trit cho nhiu phn ng ha hc. iu dn n s ra i mt khi nim khc mi thay th cho khi nim phn t s, l bc phn ng. 2. Bc phn ng
T dn n nh ngha bc phn ng: "Bc phn ng i vi mt cht cho trc l s m nng ca cht y trong phng trnh ng hc ca phn ng".
10
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT
Ngoi cc bc k trn, c th c phn ng bc phn s hoc bc m na. iu chng ta cn lu l: trong trng hp chung l h s t lng trong phng trnh (II), khi phn ng l phn ng n gin (c bn) th hai i lng trng nhau. 3. So snh phn t s v bc phn ng -Bc phn ng c th l s nguyn dng, v cng c th l m, khng hoc phn s na, cn phn t s c gi tr nguyn, dng. Tr s cao nht ca bc phn ng v phn t s l ba. - Khi nim phn t s ch c p dng cho phn ng c bn (1 giai on) khng p dng cho phn ng phc tp bao gm nhiu giai on (phn ng c bn), cn bc phn ng ch c xc nh bng thc nghim. 4. Phn ng bc gi i vi phn ng phc tp, tc phn ng l mt hm s ca nng ca mt vi cht phn ng. S ph thuc phc tp ny gy kh khn cho vic nghin cu thc nghim. lm cho s ph thuc phc tp ni trn n gin hn, ngi ta s dng khi nim bc gi. Ni dung c bn ca vn l tm cch chuyn cho tc phn ng l mt hm s ch i vi nng cht nghin cu. Trong thc t, ngi ta thc hin nh sau:
11
y, nng HCl l cht xc tc, nn nng ca n khng thay i trong phn ng. Cn nc l dung mi, lng ca n ln nn lng nc thay i trong phn ng l khng ng k, do thc t nng ca nc cng khng thay i, ngha l:
5. Mt s nhn xt a) Ta c hai loi phng trnh: phng trnh t lng (phng trnh hp thc) v phng trnh tc (phng trnh ng hc). Phng trnh t lng ca phn ng ch m t trng thi u v cui ca phn ng, khng phn nh s din bin ca phn ng. Cn phng trnh ng hc c th phn nh c ch phn ng mt cch chung nht. Cc h s t lng trong phng trnh c a vo lc cn bng phng trnh, tri li cc s ly tha (s m) ca nng trong phng trnh ng hc c xc nh bng thc nghim, ngha l phng trnh ng hc c xc lp bng thc nghim, sau khi bit r c ch phn ng. T s phn tch trn, chng ta cn lu rng khng th da vo phng trnh t lng m rt ra phng trnh ng hc mt cch my mc, lm nh vy s mc sai lm, v d i vi hai phn ng di y:
12
4.DUNG DCH CHT IN LI

Hng s axit v hng s baz : 1/ Hng s axit : Ka Lc axit ( mnh yu ca axit) trong dung dch nc c xc nh bi mc din bin ca cn bng sau : HA + H2O H3O+ + AGV:TRNG CHU THNH. Ti liu lu hnh ni b 13
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT [ H 3O] + [ A ] Hng s cn bng : K = v [H2O] thay i khng ng k nn c th gp vo hng s [ HA][ H 2 O] [ H 3O] + [ A ] [ H + ][ A ] hoc c th vit n gin l Ka = [ HA] [ HA] Ka c trng nh lng cho s phn ly ca axit. Ka c gi l hng s axit. mt nhit nht nh, Ka cng ln th axit cng mnh. Cc axit mnh hn H3O+ phn ly hu nh hon ton trong nc. Cc axit yu thng phn ng rt t vi nc, trong dung dch nng H3O+ v A- nh, nng HA ln nn Ka nh. Ngoi Ka ngi ta cn dng pKa : pKa = - lgKa. i vi axit a chc qu trnh phn ly mi nc s tng ng vi mt gi tr Ka nht nh v Ka1 > Ka2 > Ka3 > Kan TD : Dd H2S H2S + H2O H3O+ + HSKa1 = 1,0 10-7 HS+ H2O H3O+ + S2Ka2 = 3,0 10-13 2/ Hng s baz : Kb Mt baz yu B trong dung dch c cn bng : B + H2O BH+ + OH[ BH + ][OH ] Hng s cn bng : K = Trong dung dch long [H2O] coi nh khng i nn c [ B ][ H 2 O] K thnh Ka : Ka = [ BH + ][OH ] Hng s Kb thng nh, nn thun tin ngi ta [ B] dng i lng pKb : pKb = - lgKb mt nhit nht nh Kb cng ln (pKb cng nh) th baz cng mnh Trong dung dch nc ng vi cp axit/baz lin hp ta c : Ka Kb = 10-14 hay th gp vo hng s K c : Kb = pKa + pKb = 14 TD : xt axit yu HA ng vi cp axit/baz lin hp : HA/A[ H + ][ A ] HA H+ + A- c Ka = [ HA] A
-
H2O
HA
OH
c Kb =
[ HA][OH ] [ A ]
[ H + ][ A ] [ HA][OH ] = [H+][OH-] = 10-14 pKa +pKb = 14 [ HA] [ A ] nh hng ca dung mi n lc axit baz : Cc axit mnh nh HCl, HNO3, HClO4 khng th tn ti trong nc, chng nhng proton hon ton cho nc : HCl + H2O H3O+ + ClHNO3 + H2O H3O+ + NO3Dung dch HCl cha cc ion H3O+ v Cl- v khng tn ti phn t HCl. Dung dch HNO3 ch cha cc ion H3O+ v NO3- v khng tn ti cc phn t HNO3. Ngi ta ni rng nc lm cho lc cc axit mnh bng nhau, axit mnh nht c th tn ti trong nc l H3O+. Tt c cc axit mnh hn H3O+ khng th tn ti trong nc v b ion ha hon ton. Cng tng t nh vy, baz mnh nht c th tn ti trong nc l OH-. Ngi ta ni rng nc lm cho lc cc baz mnh bng nhau khng phn bit c mnh tng i ca chng. Tnh cht ca dung mi lm san bng lc axit th hin cng mnh khi dung mi c tnh baz cng mnh. TD : Trong nc th axit benzoic l mt axit yu nhng trong amoniac lng th n tr thnh mt axit rt mnh bi v tnh baz ca NH3 mnh hn tnh baz ca nc lm cn bng chuyn dch mnh v bn phi :
Ta c : Ka Kb =
14
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT C6H5COOH + NH3 C6H5COONH4 Mun xc nh lc axit tng i ca cc axit mnh cn khc phc hiu ng san bng ca dung mi. iu c thc hin bng cch dng mt dung mi c tnh cht axit mnh hn nc nh CH3COOH khan, H2SO4 hay dng mt dung mi khng nhn proton nh benzen. V nguyn tc trong c hai trng hp u xy ra s thay i lc tng i ca cc axit. Trong cc dung mi axit ngi ta xc nh c th t thay i lc ca nhiu axit nh sau : HClO4 > HBr > H2SO4 > HCl > HNO3 Qui lut bin i mnh cc axit : 1/ Cc hidraxit : HX Trong cc hidraxit proton lin kt trc tip vi nguyn t trung tm. mnh ca axit HX ph thuc ch yu vo 2 yu t : - Nu lin kt H X cng phn cc th trong dung mi phn cc (nh nc) th cng d tch proton. - Nng lng lin kt H X cng km b th cng d tch proton. TD : i vi H F v H I. Mc d lin kt H F phn cc hn lin kt H I nhng nng lng lin kt ca H F l 569 kJ/mol trong khi nng lng lin kt ca H I ch bng 297 kJ/mol do vy trong nc lc axit HF < HI. Trong nc lc axit ca cc axit halogenhidric tng dn theo th t : HF < HCl < HBr < HI 2/ Cc oxaxit : Cc oxaxit l nhng axit to nn t nguyn t trung tm kt hp vi cc nguyn t oxi v nhm hidroxit OHTD :
H O Cl
O
H O Cl
H O Cl
H O Cl O
H O H O S
O O
C vi qui tc gip ta xc nh gn ng mnh cc oxaxit : Qui tc 1 : Hng s in ly nc th nht (K1) ca cc oxaxit c xc nh theo gi tr ca m trong cng thc XOm(OH)n : Nu m = 0 (khng c nguyn t oxi d so vi nguyn t hidro nh B(OH)3, HClO, HbrO, HIO) l nhng axit rt yu, c K < 10-7 Nu m = 1 (nh HClO2, H2SO3 (SO(OH)2) l axit yu c K 10-2 Nu m = 2 (XO2(OH)n hay HnXOn + 2 : HClO3, H2SO4, H2SeO4 l nhng axit mnh Nu m = 3 (XO3(OH)n hay HnXOn + 3 : HClO4, HMnO4 ) l nhng axit rt mnh Nguyn nhn ca hin tng trn : mnh ca axit ph thuc vo in tch v bn knh ca nguyn t trung tm. ng vi tr s m cng ln th in tch ca nguyn t trung tm cng ln, phn t axit cng d tch proton cho nn tnh axit cng mnh. Qui tc 2 : Hng s in ly ca cc nc ni tip nhau K1, K2, K3 t l vi nhau theo t l gn ng l: 1:10-5:10-10 pH ca dung dch : Trong nc nguyn cht lun c tn ti cn bng phn ly t ion ha thnh H+ v OH-. H2O + H2O H3O+ + OHHay vit n gin : H2O H+ + OH(1) + [ H ][OH ] Hng s in ly ca nc : K = = 1,8.10-16 ( 250C) [ H 2 O] 1000 55,55 M [H+][OH-] = 1,8.10-16[H2O] = 1,8.10V 1 lt nc nng 1000 gam nn [H2O] = 18 16 .55,55 [H+][OH-] = 10-14 i lng ny hu nh khng thay i trong dung dch bt k no c dung mi l nc v c gi l tch s ion ca nc. GV:TRNG CHU THNH. Ti liu lu hnh ni b 15
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Trong nc nguyn cht : [H+] = [OH-] = 10-7 M. Ta thy nng H+ trong nc nguyn cht rt nh, cho nn tin s dng ngi ta nh gi axit hay baz ca dung dch bng i lng pH. pH = - lg[H+] [H+] = 10-pH
Trong mi trng trung tnh : [H+] = [OH-] = 10-7 pH = 7 Trong mi trng axit : [H+] > [OH-] pH < 7 Trong mi trng baz : [H+] < [OH-] pH > 7 Tng t nh cch tnh pH ta c : pOH = - lg[OH-] [OH-] = 10-pOH
Trong dung dch ta c : pH + pOH = 14. Cch tnh pH ca dung dch : 1/ Tnh pH ca dung dch cha axit mnh : Cc axit mnh thng gp u l n axit nh : HNO3, HCl, HBr, HI, HClO4, HSCN, H2SO4 ( nc 1) TD : Dung dch X cha dung dch HA c nng Ca. Tnh pH ca dung dch X. Pt in ly : HCl H+ + A- (1) Ca Ca Ca + H2O H + OH(2) Ap dng nh lut bo ton in tch ta c : [H+] = [A-] + [OH-] (*) Kw Kw [H+]2 = [H+]Ca + Kw Thay [A-] = Ca v [OH-] = vo (*) ta c : [H+] = Ca + + [H ] [H + ] [H+]2 - [H+]Ca - Kw = 0 (**) Phng trnh (**) l phng trnh tng qut tnh nng cn bng ca ion H+ trong dung dch n axit mnh bt k no. Tuy nhin trong thc t c th n gin ha phng trnh (**) trong nhng iu kin sau * Nu Ca 10-6M, ta c th b qua [OH-] cnh Ca trong phng trnh (*) [H+] = Ca pH = - lgCa -8 * Nu 10 M < Ca < 10-6 M th phi gii phng trnh (**) tnh [H+] v suy ra pH, v trong trng hp ny phi xt n s phn ly ca nc. * Nu Ca 10-8M th c th b qua Ca cnh [OH-] [H+] = [OH-] = 10-7 pH = 7, khi coi nh nng axit khng ng k so vi s phn ly ca nc. 2/ Tnh pH ca dung dch baz mnh : TD : Dung dch X cha NaOH c nng Cb. Tnh pH ca dung dch X. Pt in ly : NaOH Na+ + OH(1) Cb Cb Cb H2O H+ + OH- (2) Theo nh lut bo ton in tch ta c : [Na+] + [H+] = [OH-] (*) Kw Kw [H+].Cb + [H+]2 = Kw Thay [Na+] = Cb v [OH-] = vo (*) ta c : Cb + [H+] = + [H ] [H + ] [H+]2 + Cb.[H+] - Kw = 0 (**) Phng trnh (**) l phng trnh tng qut tnh nng cn bng ca ion H+ trong dung dch bt k cha n baz mnh no. Tng t nh vi dd axit mnh ta c th n gin ha phng trnh (**) trong nhng trng hp sau : Kw K = w Nu Cb 10-6M ta c th b qua [H+] cnh Cb ta c : [OH-] = Cb [H+] = [OH ] C b pH = pKw + lgCb = 14 + lgCb 3/ Tnh pH ca dung dch n axit yu : TD : C dung dch cha n axit yu HA c nng Ca. Hng s in ly ca axit l Ka. Tnh pH ca dung dch. GV:TRNG CHU THNH. Ti liu lu hnh ni b 16
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Trong dung dch c cc cn bng sau : HA H+ + A(1) Ka H2O H+ + OH(2) Kw + Theo nh lut bo ton in tch ta c : [H ] = [A ] + [OH ] (*) Phng trnh bo ton nng : [HA] + [A-] = Ca (**) [ HA] [ H + ][ A ] Ta c : K = [ HA] [H+] = K [ A ] T (*) [A ] = [H+] - [OH-]
a a
T (**) [HA] = Ca - [A ] [HA] = Ca - [H+] + [OH-] Thay vo hng s cn bng Ka ta c :

-
C a [ H + ] + [OH ] [H ] = K a [ H + ] [OH ]
+
y l phng trnh tng qut tnh [H+] ca dung dch n axit yu bt k no. Trong thc t ta c th n gin ha phng trnh trn thnh phng trnh bc 2 trong nhng trng hp c th b qua nhng nng nh bn cnh nhng nng ln. Nu [OH-] << [H+] tc l coi s phn ly ca nc khng ng k (iu ny thng gp v nc l cht phn ly rt yu [H+] = 10-7M nn trong dung dch HA s c mt ca H+ do axit in ly ra cng lm cn bng (2) chuyn dch mnh sang tri, ta c : Ca [H + ] [H+] = K a [H + ] * Nu [H+] << Ca tc coi HA phn ly khng ng k, ta b qua [H+] cnh Ca th ta c : Ca 1 [H+]2 = Ka.Ca [H+] = K a .C a pH = (pKa - lgCa) [H+] = K a + [H ] 2 4/ Tnh pH ca dung dch n baz yu : TD : C dung dch cha n baz yu B c nng Cb. Hng s cn bng Kb. Tnh pH ca dung dch. Trong dung dch c cn bng : B + H2O BH+ + OH(1) Kb + H2O H + OH (2) Kw + + Theo nh lut bo ton in tch ta c : [OH ] = [BH ] + [H ] Phng trnh bo ton nng : Cb = [B] + [BH+] [ B] [OH ][ BH + ] [OH-] = K b Ta c : Kb = [ BH + ] [ B] T [OH-] = [BH+] + [H+] [BH+] = [OH-] [H+] T Cb = [B] + [BH+] [B] = Cb [BH+] [B] = Cb - [OH-] + [H+] T ta c : C b [OH ] + [ H + ] + [OH-] = K [OH ] [ H ]
b
Phng trnh ny l phng trnh bc 3 i vi [OH-] nn vic gii s gp kh khn. Tuy nhin trong nhng trng hp c th c th c n gii ha tr thnh phng trnh bc 2 khi b qua nhng nng nh bn cnh nhng nng ln. Khi Kb khng qu ln v Cb khng qu nh, ta c th b qua [H+] cnh [OH-], tc b qua qu trnh C b [OH ] in ly ca nc khi ta c : [OH-] = K [OH ]
b
* Nu baz phn ly khng ng k tc b qua [OH-] cnh Cb khi ta c : Cb K b Cb [OH-] = K [OH ] [OH-]2 = K .C [OH-] =
b b b
17
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT 1 pH = 14 - (pKb - lgCb) 2 5/ Tnh pH ca dung dch a axit yu : C th coi cc a axit nh l hn hp ca nhiu n axit. Trong a s cc trng hp, nht l i vi cc axit v c th s phn ly ca cc a axit xy ra mnh nht nc u v sau gim dn cc nc tip theo. Cc hng s in ly : K1 > K2 > K3 > Kn. TD : Axit photphoric H3PO4 c K1 = 10-2,23 ; K2 = 10-7,21 ; K3 = 10-12,32 i vi cc a axit m hai nc phn ly cch nhau rt xa (t 104 tr ln) th c th coi s phn ly ca nc th nht ng vai tr quyt nh v ta c th tnh nng ion H+ da vo cn bng in ly ca nc th nht nh trng hp i vi n axit. TD : Tnh nng cn bng cc ion trong dung dch bo ha kh cacbonic nhit thng v pH ca dung dch, bit rng trong dung dch bo ha nhit thng nng kh cacbonic l 3.10-2 mol/l. Trong dung dch c cc cn bng : H2CO3 H+ + HCO3(1) K1 = 10-6,35 HCO3- H+ + CO32(2) K2 = 10-10,23 H2O H+ + OH(3) Kw = 10-14 Do K1 >> K2 >> Kw nn trong dung dch cn bng (1) l cn bng ch yu. H2CO3 H+ + HCO3(1) K1 = 10-6,35 -2 B 3.10 [] 3.10-2 x x x [ H + ][ HCO3 ] x2 = = 10-6,35 2 [ H 2 CO3 ] 3.10 x -2 -2 3.10-2 x2 = 3.10-2 10-6,35 x = 1,16.10-4 Vi x << 3.10 3.10 x [H+] = [HCO3-] = 1,16.10-4 pH = 3,9 tnh nng ion CO32- cn da vo cn bng (2) HCO3 H+ + CO32(2) K2 = 10-10,23 B 1,16.10-4 1,16.10-4 -4 [ ] 1,16.10 y y + 1,16.10-4 y Ta c : K1 = [ H + ][CO32 ] ( y + 1,16.10 4 ) y K2 = = = 10-10,23 [ HCO3 ] (1,16.10 4 y ) Do y << 1,16.10-4 (y + 1,16.10-4) = 1,16.10-4 v (1,16.10-4 y) = 1,16.10-4 y = 10-10,23 10 14 [CO32-] = 10-10,23 [OH-] = = 8,6.10-11 1,16.10 4 Dung dch m Tnh pH ca dung dch n axit yu v baz lin hp vi n : TD : C dung dch X gm axit yu HA c nng Ca v mui NaA c nng Cm. Tnh pH ca dung dch X bit axit HA c hng s axit l Ka Trong dung dch c cc qu trnh : NaA Na+ + A(1) + HA H + A (2) Ka H2O H+ + OH- (3) Kw + Trong dung dch thng th [H ] v [OH ] khng ng k so vi Ca v Cm v HA v A- c sn trong dung dch lm cn tr qu trnh sinh ra H+ v OHHA H+ + AA- + H2O HA + OHThng th Ka >> Kw nn c th b qua qu trnh (3), theo cc qu trnh : NaA Na+ + A(1) GV:TRNG CHU THNH. Ti liu lu hnh ni b 18
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Cm Cm + HA H + A(2) Ka B Ca Cm x x x + Cm [ ] Ca x x (Cm + x) ta c : [ H + ][ A ] x(C m + x) = Ka = Do x << C Cm + x Cm v Ca x Ca [ HA] (C a x ) Ka = C C C [ H + ]C m [H+] = K a a - lg[H+] = - lg K a a = - lgKa + lg m Cm Cm Ca Ca pH = pKa + lg Cm Ca (*)
biu thc ny thng ng dng tnh pH ca dung dch gm 1 n axit yu v baz lin hp vi n TD : Tnh pH ca dung dch X gm CH3COOH 0,1M v CH3COONa 0,1M, bit Ka = 1,778.10-5 0,1 pH = 4,75 p dng (*) ta c : pH = pKa + lg 0,1 Nu thm 0,005 mol KOH vo 1 lt nc nguyn cht th nng OH- tng t 10-7 M n 5.10-3M, do pH tng t 7 ln 11,69 ngha l tng ti 4,69 n v. Nhng nu thm 0,005 mol KOH vo 1 lt dung dch X trn th pH ca dung dch thay i khng ng k. Trong dung dch xy ra cc qu trnh sau : KOH K+ + OH0,005 0,005 CH3COOH + OH- CH3COO- + H2O 0,005 0,005 0,005 [ ] (0,1 0,005) (0,1 + 0,005) Cm 0,105 pH = 4,75 + lg pH = pKa + lg = 4,79 Ca 0,095 Nh vy khi thm 0,005 mol KOH vo 1 lt dung dch X th pH ca dung dch tng ln khng ng k (4,79 4,75) = 0,04 n v Tng t khi thm 0,005 mol HCl vo 1 lt dung dch X. Trong dung dch c cc qu trnh : HCl H+ + Cl0,005 0,005 CH3COO- + H+ CH3COOH 0,005 0,005 0,005 [ ] (0,1 0,005) (0,1 + 0,005) Cm 0,095 pH = 4,75 + lg ta c : pH = 4,75 + lg = 4,71 Ca 0,105 Nh vy khi thm 0,005 mol HCl vo 1 lt dung dch X th pH ca dung dch gim i khng ng k (4,75 4,71) = 0,04 n v. Nhng dung dch loi ny c gi l dung dch m. Nh vy dung dch m l nhng dung dch c pH thay i khng ng k khi thm vo dung dch mt lng nh axit mnh hoc baz mnh. Dung dch m c vai tr quan trng trong cng nghip ha hc, n c kh nng duy tr pH ca dung dch n nh thc hin cc phn ng c bit cc phn ng ln men v nhiu phn ng khc. Trong c th ca ng vt cao cp, c bit l ngi, pH trong dch t bo, trong mu v trong nhng dch khc dao ng trong mt khong rt hp l nh cc h m : Axit cacbonic v mui bicacbonat : MHCO3 (M l Na, K) Mononatri photphat NaH2PO4 v dinatriphotphat Na2HPO4 Protein v natri proteinat GV:TRNG CHU THNH. Ti liu lu hnh ni b 19
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Hemoglopin v kali hemoglobinat Axit hu c v mui ca axit hu c. Tnh pH ca dung dch n baz yu v axit lin hp vi n : TD : Cho dung dch X gm 1 n baz yu B c nng Cb v axit lin hp vi n BH+ c nng Cm. Tnh pH ca dung dch bit baz B c hng s cn bng l Kb Tng t nh trn ta c : Cb pH = 14 pKb + lg Cm TD : Tnh pH ca dung dch X gm NH3 0,1M v NH4Cl 0,1M, bit KNH3 = 10-4,76 Ap dng cng thc (**) ta c : 0,1 pH = 14 pKb + lg = 14 4,76 = 9,24 0,1
5. CN BNG HA HC TRONG DUNG DCH

1. Cn bng axit-baz trong dung dch nc Nc l dung mi quan trng nht hin nay. S sng ca chng ta da trn cc phn ng ha hc xy ra trong dung dch nc trong t bo. Nhiu phn ng ha hc quan trng trong cng nghip, cng nh cc phn ng ha hc trong t nhin xy ra trong dung mi nc. Do y ch yu ch kho st cn bng ca cc loi phn ng, ca cc loi cht khc nhau trong dung mi nc. Kt qu thu c t vic kho st cc phn ng xy ra trong dung mi nc cng c th p dng tng t cho cc dung mi phn cc khc. a. S ion ha ca nc Nc l mt cht in ly rt yu, t phn ly to ra mt lng rt nh, nhng bng nhau ca ion H+ v OH-. Phng trnh: H2O + H2O H3O+ + OHS ion ha ny ng mt vai tr quan trng trong cc phn ng axit-baz xy ra trong nc Do qu trnh l cn bng, p dng nh lut tc dng khi lng ta c:
i vi cc dung dch long nng ca nc tinh cht xem nh khng i (vi khi lng ring l 1, 00g/ml, nn nng ca nc tinh cht c gi tr khong 55, 6 mol/l), do ta c th vit. [H3O+][OH-] = K[H2O]2 = Kw Kw gi l tch s ion ca nc. 250C Kw c gi tr l 1,0.10-14 (mol/l)2. Qu trnh ion ha ca nc tng theo nhit . 1000C gi tr Kw = 10-12 (mol/l)2, gp 100 ln 250C. Nc tinh cht phn ly to ra mt lng bng nhau ion H+ v ion OH- nn 250C ta c: [H+][OH-] = 10-14. Tt c cc dung dch nc u c ion . Nu thm axit vo nc 250C, [H3O+] s ln hn 10-7v [OH-] < 10-7M v ngc li khi thm baz vo nc 250C th [OH-] > 10-7M v [H+] < 10-7M. Tch s ca nng ion H+ v OH nhit xc nh lun lun l hng s, v do khi nng ion ny tng ln, th nng ion kia gim xung nhng khng bao gi bng 0. Ion H+ trong dung dch nc thc s tn ti di dng ion H3O+, nhng trong a s trng hp, tin cho cc tnh ton, ngi ta n gin ha bng cch dng H+. Do qu trnh phn ly ca nc c th biu din bng phng trnh: H2O H+ + OH- Kw = [H+][OH-] = 1,0.10-14 250C b. Thuyt axit-baz ca Bronsted v Lowry Ngi u tin a ra cc nh ngha v axit v baz l Svate Arrhenius. Da trn cc kho st thc nghim v cht in ly, ng cho rng: Axit l cht phn ly choH+khi ha tan vo nc. Baz l cht phn ly choOH- khi ha tan vo nc. Vo thi im , y l mt bc tin quan trng trong vic nh lng axit-baz. Nhng thuyt ny b gii hn ch ch p dng c cho dung dch nc v cho mt loi baz duy nht l hydroxit. Mt nh ngha tng qut hn c ngh bi nh ha hc an Mch: Jonhannes K. Bronsted v nh ha hc ngi Anh: Thomas Lowry. GV:TRNG CHU THNH. Ti liu lu hnh ni b 20
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Theo thuyt ny: Axit l cht cho H+. Baz l cht nhnH+ TD: Khi ha tan kh HCl vo nc, mi phn t HCl s cho mt proton H+cho phn t nc, v do HCl l axit, nc l baz. HCl + H2O H3O+ + ClNguyn t oxy ca phn t nc cn hai i electron cha gp chung, mt i electron c th to mt lin kt cng ha tr vi proton H+. Ion H3O+c gi l ion hydronium. Phng trnh tng qut ca mt axit khi ha tan vo nc c vit nh sau: HA + H2O H3O+ + APhn ng ny cho thy vai tr ca phn t nc phn cc l ko proton H+ ra khi axit. Phn cn li ca axit sau khi cho proton H+ c gi l baz lin hp ca axit, ngc li H3O+ c gi l axit lin hp ca nc. Ni cch khc mt cp axit-baz lin hp biu th hai cht vi mi quan h l mt cht cho H+ v mt cht nhn H+. Phng trnh trn cng c trng cho kh nng phn ng ca 2 baz: nc v A-. Nu H2O l baz mnh hn A- tc i lc i vi H+mnh hn A- th cn bng dch chuyn mnh sang phi, ngc li, nu A- c i lc i vi H+ mnh hn H2O th cn bng dch chuyn mnh sang tri. p dng nh lut tc dng khi lng cho cn bng trn ta c:
Biu thc khng c s hin din ca H2O v trong dung dch long, chng ta c th quan nim nng ca nc s khng thay i khi ha tan axit vo, bn cnh , trong a s trng hp H3O+ c thay th bng H+, nn phng trnh c vit rt gn l: HA H+ + A[ H + ][ A ] Ka = [ HA] Ka c gi l hng s phn ly ca axit. Mc d vit nh th, nhng chng ta khng c php qun vai tr quan trng ca nc trong vic ha tan axit. Thuyt axit-baz ca Bronsted v Lowry c th m rng ra cho cc dung mi khc nc cng nh cho cc phn ng xy ra trng thi kh. TD: NH3 (k) + HCl (k) NH4Cl (r) Trong phn ng ny NH3 l cht nhn H+, HCl l cht cho H+ v do NH3 l baz, HCl l axit. Da trn cc lp lun tng t, khi ha tan mt baz vo nc phn ng gia baz vi nc c th biu din bng phn ng tng qut: B + H2O BH+ + OH[ BH + ][OH ] Kb = Kb l hng s baz [ B] c. Thuyt axit-baz ca Lewis Mt thuyt tng qut hn na v axit-baz c G.N.Lewis a ra vo nhng nm 20. Theo thuyt Lewis: Axit l cht c th nhn mt i electron hnh thnh mt lin kt cng ha tr. Baz l cht c mt i electron c th hnh thnh mt lin kt cng ha tr. Do mt axit Lewis phi c mt obitan ha tr trng nhn mt i electron, cn mt baz Lewis phi c mt i electron ha tr cha to ni. T y ta thy nh ngha axit-baz ca Lewis bao hm nh ngha ca Bronsted v Lowry. TD: NH3 + H+ NH4+ Trong phn ng ny NH3 l baz v l cht cho mt i elactron, H+ l axit v nhn mt i electron. Tng t cho phn gia proton H+ v ion OH-, H+ l axit v l cht nhn mt i electron, cn OH- l baz v l cht cho mt i electron, gia chng s hnh thnh c mt lin kt cng ha tr. Gi tr ca thuyt Lewis v axit-baz l ch gii thch c cc phn ng axit-baz theo quan im ca Bronsted v Lowry, hn th na cn gii thch c mt s phn ng axit-baz m thuyt Bronted v Lowry khng gii thch c. TD: Phn ng gia Trifluorua bor v amoniac: BF3 + NH3 F3B-NH3
21
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT BF3 l phn t thiu electron, xung quanh nguyn t B ch mi c 6 electron, khi phn ng vi NH3, nguyn t B s t c c cu 8 electron. BF3 l mt cht c i lc mnh vi cc cht cho electron v do l mt axit Lewis mnh. Thuyt axit-baz ca Lewis cng gii thch thnh cng qu trnh hydrat ha ca ion kim loi. TD: Al3+ + 6H2O Al(H2O)63+ 3+ Al l cht nhn electron t nguyn t oxy ca nc l axit v nc l baz. Rng ra hn na phn ng gia mt oxit axit v nc, theo thuyt Lewis cng l mt phn ng axit-baz, trong oxit axit l cht nhn mt i electron nn l axit, nc l cht cho mt i electron nn l baz. d. Thang pH v pOH Do nng H+trong dung dch nc thng l nh, nn ngi ta a ra nh ngha pH v pOH nh gi tnh axit-baz ca mt mt dung dch cho tin li. pH v pOH ca mt dung dch c nh ngha nh sau: pH = - lg[H+] [H+] = 10-pH. pOH = - lg[OH-] [OH-] = 10-pOH Tng t nh th ngi ta nh ngha : pK = -lgK Vi K l hng s phn ly ca cc cht. TD: H2O H+ + OH- c Kw = 1,0.10-14 pKw = -lgKw = -lg(1,0.10-14) = 14 [H+][OH-] = Kw = 10-14 pH + pOH = 14 i vi dung dch trung tnh: [H+] = [OH-] = 10-7 pH = 7 Vi dung dch axit th [H+] > 10-7 pH < 7 Vi dung dch baz th [H+] < 10-7 pH > 7 Gi tr pH ca mt dung dch c th c xc nh bng my o pH hay giy o pH. e. mnh ca axit- baz Khi ha tan axit vo nc xy ra qu trnh. HA H+ + AQu trnh phn ly c c trng bng hng s phn ly Ka Bng 5.8. Quan h gia nng [ H+] v [OH- ], gia pH v pOH v gi tr pH ca mt s cht ph bin 25oC [H+ ] pH Dung dch mu -14 10 14 -13 10 13 10-12 12 10-11 11 -10 10 10 Dung dch NaOH 1M 10-9 9 Dung dch NH3, cc cht ty ra. 10-8 8 Mu 10-7 7 Nc nguyn cht 10-6 6 Sa 10-5 5 Gim 10-4 4 Axit bao t 10-3 3 Dung dch HCl 1M 10-2 2 -1 10 1 100 0 Mt axit c gi l mnh khi cn bng phn ly b dch chuyn mnh sang phi, ngha l hu ht cc phn t HA u b phn ly to ra baz yu lin hp A- khi qu trnh phn ly t cn bng. Ngc li mt axit c gi l yu khi cn bng phn ly b dch chuyn mnh sang tri, ngha l hu ht phn t HA tan vo nc u hin din di dng HA khi qu trnh phn ly t cn bng. Da vo gi tr Ka ta c th bit c axit mnh hay yu. Ka c gi tr cng ln tng ng vi axit cng mnh, Ka c gi tr cng b tng ng vi axit cng yu. Cc axit thng dng nh H2SO4, HCl, HNO3, HClO4 u l axit mnh. Cn ch rng H2SO4 l mt axit mnh, phn ly ha ton khi ha tan vo nc: H2SO4 H+ + HSO4Nhng HSO4- l mt axit yu, phn ly theo phn ng cn bng: HSO4- H+ + SO42GV:TRNG CHU THNH. Ti liu lu hnh ni b 22
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Mt s axit yu nh H3PO4, HNO2, HClO , cc axit hu c, khi ha tan vo nc chng s phn ly theo phn ng cn bng: HNO2 H+ + NO2HClO H+ + ClOCH3COOH H+ + CH3COOGi tr Ka ca mt s axit yu ph bin Cng thc Tn gi Ka Ion hydro sunfat 1, 2. 10-2 HClO2 ClCH2COOH HF HNO2 CH3COOH HClO HCN Axit Clor Axit monocloro acetic Axit flohidric Axit nitr Axit acetic Axit hypoclor Axit cianhydric Ion amonium 1, 2. 10-2 1, 35. 10-3 7, 2. 10-4 4, 0. 10-4 1, 8. 10-5 3, 5. 10-8 6, 2. 10-10 5, 6. 10-10
C6H5OH Axit phenic 1, 6. 10-10 i vi axit yu a chc, qu trnh phn ly xy ra tng nc, c trng cho tng qu trnh phn ly ta c hng s phn ly tng nc. V d Axit cacbonic l axit hai chc, phn ly nh sau: H2CO3 H+ + HCO3- Ka1 = 4,3.10-7 HCO3- H+ + CO32- Ka2 = 5,6.10-11 Axit photphoric l axit yu 3 chc, phn ly nh sau:
Thng thng bao ta cng c Ka1 >> Ka2 >> Ka3 . . . . Ngha l kh nng phn ly proton H+ th 2, th 3 bao gi cng km hn proton th 1, iu ny d gii thch v in tch m ca axit cng gia tng th kh nng phn ly cho proton (in tch dng) cng kh. Cc gi tr hng s phn ly tng nc ca mt axit yu Cng thc Tn Ka1 Ka2 Ka3 -3 -8 H3PO4 Axit photphoric 7, 5. 10 6, 2. 10 4, 8. 10-13 -3 -8 H3AsO4 Axit arsenic 5. 10 8. 10 6. 10-10 -7 -11 H2CO3 Axit cacbonic 4, 7. 10 5, 6. 10 H2SO3 Axit sunfuar 1, 5. 10-2 1, 0. 10-7 -7 H2S Axit sunfuahydric 1, 0. 10 1, 3. 10-13 H2C2O4 Axit oxalic 6, 5. 10-2 6, 1. 10-5 -5 H2C6H6O6 Axit ascorbic 7, 9. 10 1, 6. 10-12 i vi baz, mnh ca baz c t trng bng hng s kt hp proton Kb. Gi tr Kb cng ln baz cng mnh v ngc li. Gi tr Kb ca mt s baz Cng thc Tn Axit lin hp Kb + NH3 Amoniac NH4 1,8. 10-5 CH3NH2 Metyl amin CH3- NH3+ 4,38. 10-4 + C2H5NH2 Etyl amin C2H5- NH3 5,6. 10-4 C6H5NH2 Anilin C6H5- NH3+ 3,8. 10-10 + C5H5N Pyridin C5H5- NH3 1,7. 10-9 f) Tnh ton cn bng trong cc dung dch axit-baz GV:TRNG CHU THNH. Ti liu lu hnh ni b 23
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Phn trn chng ta trnh by tt c cc nh ngha c lin quan n dung dch axit- baz. By gi chng ta s p dng m t nh lng cc qu trnh axit baz xy ra trong dung dch . Tnh pH ca dung dch axit mnh. TD: Tnh pH ca dung dch HNO3 0,10M V HNO3 l axit mnh, nn phn ly hon ton thnh ion: HNO3 H+ + NO3Ngoi ra trong dung dch cn c qu trnh phn ly ca nc H2O H+ + OH- Kw = 10-14 + Do [H ] do nc phn ly rt b so vi [H+] do HNO3 phn ly nn qu trnh chnh xy ra trong dung dch c chn l qu trnh phn ly ca HNO3, c th b qua qu trnh phn ly ca nc . Do [H+] = 0,10M pH = -lg[H+] = - lg(0,10) = 1 V d: Tnh pH ca dung dch HCl 1.0.10-10M y mc d l axit mnh, phn ly hon ton thnh ion, nhng lng H+ do HCl phn ly b 10-10 nh hn 1000 ln so vi lng H+ do nc phn ly, nn qu trnh chnh xy ra trong dung dch l qu trnh phn ly ca nc. H2O H+ + OHDo [H+] = 10-7 pH = 7 Tnh pH ca dung dch ca axit yu TD: Tnh pH ca dung dch HF 1,00M bit Ka = 7,2.10-4 Trong dung dch c hai qu trnh phn ly cho H+ l: HF H+ + F- (1) Ka = 7,2.10-4 H2O H+ + OH- (2) Kw = 10-14 So snh gi tr Ka v Kw ta thy qu trnh (1) l ch yu
x l nng ca HF b phn ly.
Do HF l axit yu, phn ly khng ng k, nn mt cch gn ng c th chp nhn
C s ca php tnh gn ng y da trn yu cu mc chnh xc cn c. Thng l gi tr . [HA]0 Nu chp nhn [HA]0 x Nu sai s trong phm vi 5% th hon ton c th chp nhn c. x 2,7 10 2 100 = 100 u tin ta s tnh gn ng x K a [HA]0 = 2,7.10-2 Sau lp t s: [ HA]0 1,00 = 2,7% < 5% Do gi tr x = 2,7.10-2 l chp nhn c. V d Tnh pH ca dung dch axit HClO 0,100M bit Ka = 3,5.10-6 Trong dung dch c 2 cn bng phn ly phng thch proton:
Do HClO phn ly mnh hn nc ng k, nn qu trnh phn ly chnh c chn l ca HClO.
x l nng HClO b phn ly GV:TRNG CHU THNH. Ti liu lu hnh ni b 24
Kim tra tr li gi thuyt gn ng:
Do kt qu chp nhn c. pH = -logx = -log5,9.10-5 = 4,23 Tnh pH ca dung dch hn hp cc axit yu. TD: Tnh pH ca dung dch hn hp cha HCN 1,00M c Ka = 6,2.10-10 v HNO2 5,00M c Ka = 4,0.10-4. Tnh nng cn bng ca ion CN- trong dung dch. Trong dung dch c 3 qu trnh phn ly cho proton H+ HCN H+ + CN(1) Ka = 6,2.10-10 + 2HNO2 H + NO (2) Ka = 4,0.10-4 H2O H+ + OH(3) Kw = 1,00.10-14 Do s hin din ng thi ca 3 axit lm cho vn thm phc tp. Tuy nhin, nu so snh cc gi tr hng s phn ly ta thy HNO2 tuy l axit yu nhng vn mnh hn rt nhiu so vi HCN v H2O, v do qu trnh phn ly cho H+ ch yu c s dng y l ca HNO2. Qu trnh (2) HNO2 H+ + NO2Ka = 4,0.10-4 B 5,00 ly x [] 5,00 x x x
Kim tra li kt qu ta c:
Kt qu ny chp nhn c, do : pH = -log x = -log 4,5.10-2 = 1,35 tnh nng cn bng ca CN- ta p dng biu thc:
Do HCN phn ly rt t nn ta c th chp nhn [HCN] = [HCN]0 Do : Tnh thnh phn phn trm ca axit b phn ly. xc nh % axit b phn ly ta dng cng thc:
V d Tnh % axit acetic b phn ly trong 2 trng hp: a. Dung dch CH3COOH 1,00M b. Dung dch CH3COOH 0,100M p dng phng php nh trnh by trn ta c: Trng hp a: [H+] = 4,2.10-3M GV:TRNG CHU THNH. Ti liu lu hnh ni b 25
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Do mt phn t CH3COOH khi phn ly ch to ra mt ion H+ nn nng axit b phn ly chnh bng nng H+, do :
Trng hp b: 1,3.10 3 100 =1,3% 0,100 T v d ny ta nhn thy, i vi dung dch axit yu, nu nng axit cng long th % axit b phn ly cng ln, hay ngc li nu nng axit cng ln th % axit b phn ly cng b. Gi tr % axit b phn ly c s dng xc nh hng s phn ly Ka ca cc axit yu. TD: Tnh Ka ca axit lactic bit trong dung dch 0,100M, c 3,7 % axit b phn ly. Ta c cn bng phn ly ca axit lactic [H+] = 1,3.10-3 M %axit b phn ly =
Tnh pH ca dung dch axit yu a chc V d Tnh pH ca dung dch H3PO4 5,0M v nng cn bng ca cc tiu phn khc trong dung dch. H3PO4 l mt axit yu 3 chc, xy ra qu trng phn ly tng nc nh sau: H3PO4 H+ + H2PO4(1) K1= 7,3.10-3 H2PO4- H+ + HPO42(2) K2 = 6,2.10-6 2+ 3HPO4 H + PO4 (3) K3 = 4,8.10-13 So snh cc gi tr Ka, r rng ta thy mnh ca cc axit nh sau: iu ny c ngha l qu trnh ch yu phn ly cho H+ trong dung dch l qu trnh phn ly nc th nht: H3PO4 H+ + H2PO4K1 = 7,3.10-3 Ban u: [] 5, 00M 5, 0 - x x x
Mt cch gn ng, ta chp nhn 5,0 x 5,0 x = 1,9.10-1 Kim tra li mc gn ng ta c:
Nn kt qu trn l chp nhn c: pH =-log[ H+ ] = - log x = 0, 72 T y ta xc nh c:
Nng ca cc cu t cn li c tnh da vo gi tr Ka tng ng: GV:TRNG CHU THNH. Ti liu lu hnh ni b 26
Cc kt qu tnh ton cho thy qu trnh phn ly ca nc 2 v nc 3 to ra mt lng H+ hon ton khng ng k. Tnh pH ca dung dch baz mnh. V d 5.31. Tnh pH ca dung dch NaOH 5,0.10-2 M Do l baz mnh nn NaOH phn ly hon ton thnh ion khi tan vo nc to ra OH-. Bn cnh cng c qu trnh phn ly to OH- ca nc. Lng OH- do nc phn ly ra khng ng k nn qu trnh to OH- ch yu l ca NaOH NaOH Na+ + OH(1) 14 10 Theo (1) [OH-] = 5,0.10-2 [H+] = = 2,0.10-13 pH = - lg(2,0.10-13) = 12,7 [OH ] Tnh pH ca dung dch baz yu. Vic tnh pH ca mt dung dch baz yu hon ton tng t nh tnh pH ca dung dch axit yu. TD: Tnh pH ca dung dch NH3 15,0M Bit Kb = 1,8.10-5 Trong dung dch xy ra 2 cn bng phn ly cho OH-
Do s ng gp OH- ca nc l khng ng k v Kb >> Kw nn c th b qua cn bng phn ly ca nc. Ban u: 15,0 [ ]: 15,0 - x x x l nng NH3 b proton ha
Mt cch gn ng ta c:
Kt qu ny chp nhn c. Vy: pH = 12,20 Cc lp lun tnh pH ca dung dch baz yu hoc dung dch hn hp cha cc baz yu cng hon ton tng t nh tnh pH ca dung dch axit yu v dung dch hn hp axit yu. Tnh pH ca dung dch mui c tnh axit, hoc baz. Mui chng qua l tn gi n gin ca cc hp cht ion. Khi ha tan mui vo nc, mui s phn ly thnh ion. Trong mt s trng hp cc ion ny c th ng vai tr nh mt axit hoc baz. V d 5.33. Tnh pH ca dung dch NaCl 1M. Trong dung dch NaCl phn ly hon ton thnh ion NaCl Na+ + Cl+ Cc ion Na v Cl- khng nh hng g n nng H+ v OH- ca dung dch, do lng H+ v OHtrong dung dch do cn bng phn ly ca nc to ra khng c g thay i v c gi tr l 10-7 M, nn pH dung dch bng 7 TD: Tnh pH ca dung dch NaF 0,3M, cho Ka ca HF = 7,2.10-4. Khi ha tan vo nc NaF phn ly hon ton thnh ion NaF Na+ + FDo F l baz lin hp ca axit yu HF nn F- s tham gia cn bng kt hp proton ca nc GV:TRNG CHU THNH. Ti liu lu hnh ni b 27
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT F- + H2O HF + OH- Kb [ HF ][OH ] 10 14 10 14 Kb = ta c: Ka.Kb = 10-14 Kb = = = 1,4.10-11 Ka [F ] 7,2.10 4 T gi tr Kb bit, ta tnh c pH ca dung dch nh sau: F- + H2O HF + OHBan u: 0, 3 [] 0, 3 - x x x x2 ta c: Kb = = 1,4.10-11 (0,3 x) Nu coi nh x << 0,3 0,3 x 0,3 x = 2,049.10-6 = [OH-] pOH = 5,7 pH = 14 5,7 = 8,3 TD: Tnh pH ca dung dch NH4Cl 0,1M. Bit Kb ca NH3 = 1,8.10-5 Trong dung dch NH4Cl phn ly hon ton thnh ion NH4Cl NH4+ + ClNH4+ l axit lin hp ca baz NH3. Do l mt axit nn NH4+ nhng H+ theo cn bng NH4+ + H2O NH3 + H3O+ Ka 14 14 10 10 Ta c: Ka.Kb = 10-14 Ka = = = 5,6.10-10 Kb 1,8.10 5 Ban u: [] 0,10 0,10-x ta c: Ka = x = 7,5.10-6
x
2
x = 5,6.10-10 Nu coi x << 0,10 0,10 x 0,10 x2 = 5,6.10-11 0,10 x
x 7,5.10 6 100 = Kim tra mc gn ng, ta c: < 5% + 0,1 [ NH 4 ] Kt qu ny chp nhn c. Do [H+] = 7,5.10-6 pH = 5,1 T cc v d trn, v nhiu kho st thc nghim khc, ngi ta i n kt lun: Dung dch mui c cha cation ca baz mnh v anion ca axit mnh (tc mui ca axit mnh v baz mnh) c pH = 7. Dung dch mui cha anion l baz lin hp ca axit yu ( tc mui ca mt axit yu v mt baz mnh ) c tnh baz. Dung dch mui cha cation l axit lin hp ca baz yu ( tc mui ca axit mnh v baz yu) c tnh axit. Mt s mui khc, v d: CH3COONH4 khi ha tan vo nc phn ly hon ton thnh ion: CH3COONH4 CH3COO- + NH4+ C 2 ion u nh hng n pH ca dung dch. Ion NH4+ b proton phn ly lm tng H+ ca dung dch, tc gim pH. Ngc li CH3COO- b proton ha lm gim H+ ca dung dch, tc tng pH. Ni chung cc qu trng xy ra y rt phc tp, do chng ta ch kho st nh tnh axit- baz ca dung dch: Nu Ka > Kb: dung dch s c tnh axit pH < 7 Nu Ka = Kb: dung dch trung tnh pH = 7 Nu Ka < Kb: dung dch c tnh baz pH > 7 g) Hiu ng ion chung Trong phn trc chng ta kho st cch tnh pH ca cc dung dch axit, baz cng nh dung dch mui. By gi chng ta kho st mt h tng i phc tp hn, l dung dch axit hay baz c cha mui tan ca chng. V d Tnh % axit b phn ly trong dung dch hn hp gm: HF 1,0M (Ka = 7,2.10-4) v NaF 1,0M Trong dung dch mui NaF b phn ly hon ton thnh ion. NaF Na+ + FGV:TRNG CHU THNH. Ti liu lu hnh ni b 28
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Bn cnh xy ra qu trnh proton phn ca HF v H2O HF H+ + FKa = 7,2. 10-4 + H2O H + OH Kw = 1,0.10-14 H2O l mt axit rt yu so vi HF, nn H+ ca nc khng nh hng quan trng n s thay i pH ca dung dch, v do c th b qua qu trnh phn ly ca nc. Ta s dng cn bng phn ly ca HF tnh pH ca dung dch, c iu khc vi trc y nng u ca F- khng phi bng 0 m l 1,0M. HF H+ + FBan u: 1,0 1 [ ]: 1,0-x x 1,0+x
S hin din ca F- s dch chuyn cn bng sang tri, v do kh nng phn ly ca HF s gim, nn c th xem . Kim tra gn ng ta c:
Gi tr tm c hon ton c th chp nhn. Nu so snh vi trng hp khng c NaF , % axt b phn ly l 2,7% . s khc bit ln ny cho thy Fc nh hng mnh v lm gim kh nng phn ly ca HF. Hon ton tng t nh vy trong dung dch NH3 nu c s hin din mui NH4Cl, ion NH4+ to ra t mui nh hng mnh lm gim kh nng proton ha ca NH3. Ngoi ra hiu ng ion chung cng nh hng rt mnh v lm gim kh nng ho tan ca mui. h) Dung dch im - m nng ng dng quan trng nht ca dung dch axit-baz c cha ion chung l dng m. Dung dch m c nh ngha l dung dch c kh nng chng li s thay i ca pH khi thm vo dung dch mt lng nh H+ hay OH-. V d thc tin quan trng nht v dung dch m l mu. Mu c th hp thu axit hoc baz to ra t cc phn ng sinh ha gi pH khng i. Mt dung dch m cha mt axt yu v mui ca n (v d: CH3COOH v CH3COONa) hoc mt baz yu vi mui ca n (v d NH3 v NH4Cl).Bng cch chn nng ca cc cht thch hp c th to ra dung dch m c pH xc nh. Cch tnh ton cn bng trong dung dch m hon ton tng t nh trnh by trc y. Nhng hiu r tc dng m ca dung dch m ta xem xt cc v d sau: V d 5.37 1/ Tnh pH ca dung dch m gm (CH3COOH 0,50M v CH3COONa 0,50M) bit Ka = 1,8.10-5 2/Tnh thay i pH khi thm 0,010 mol NaOH rn vo 1 lt dung dch m trn. So snh vi trng hp thm vo 0,010 mol NaOH rn vo 1 lt nc nguyn cht. Gii 1/ Bng php tnh v lp lun tng t nh trnh by. Ta xc nh c pH ca dung dch: pH = 4,74 2/ Khi thm vo 0,010mol NaOH vo 1 lt nc nguyn cht, ta thu c dung dch NaOH 0,010M. p dng phng php tnh pH ca dung dch baz mnh ta tnh c: pH=12,00. Ngha l khi thm 0,010mol NaOH rn vo nc nguyn cht, pH thay i 5 n v. Khi thm 0,01mol NaOH vo dung dch m, 0,010mol NaOH s trung ha c 0,010 mol CH3COOH to ra mt lng mui tng ng. Do thnh phn dung dch thu c l: CH3COOH 0,49M v CH3COONa 0,51M. p dng cch tnh pH ta tnh c: pH = 4,76 So vi ban u ch thay i 0,02 n v pH.
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Khi thm OH- vo th OH- s tc dng vi HA v lm gim nng HA, lm tng nng A- , t s [ HA] s gim. Tuy nhin nu lng HA v A- trong dung dch rt ln so vi lng OH- thm vo th s [ A ] [ HA] [ HA] 0,5 thay i t s l khng ng k, v do pH hu nh s khng i. = =1 [A ] [A ] 0,5 [ HA] 0,49 Sau khi thm 0,01 mol NaOH vo th = = 0,96 [A ] 0,51 Ngc li khi thm mt lng axit mnh, v d 0,010 mol HCl vo, s to ra thm mt lng HA tng [ HA] 0,51 ng l 0,010 mol v gim mt lng mui NaA 0,010 mol. = = 1,04 [A ] 0,49 T s thay i khng ng k v do pH cng s thay i khng ng k. Trong a s trng hp ta c th p dng phng trnh Henderson - Hasselbalch tnh pH ca dung dch m.
Phng trnh ny cho ta mt kt lun quan trng l cng mt h m, nu t l trn ca chng u bng 1 th chng c cng mt gi tr pH, tuy nhin kh nng m ca chng khc nhau. Kh nng m ca mt dung dch m c nh ngha l s lng ion H+ hay ion OH- m dung dch c th hp th nhng khng to ra mt thay i ng k ca gi tr pH. T nh ngha ny ta thy nu nng ca cht tham gia to nn h m cng ln th kh nng m cng ln. V d Tnh thay i ca pH ca dung dch khi thm 0,010 mol kh HCl vo dung dch trong 2 trng hp: Dung dch A: gm CH3COOH 5,00M v CH3COONa 5,00M Dung dch B gm: CH3COOH 0,050M v CH3COONa 0,050M. Cho Ka = 1,8.10-5
Khi thm 0,010 mol HCl vo dung dch A, s lm tng nng ca CH3COOH ln 5,01M, lm gim nng ca CH3COO- cn 4,99M, do pH dung dch A sau khi thm HCl vo l:
pH = 4,74 - 0,0017 = 4,74. Ngha l pH dung dch A khng i. Khi thm 0,010mol HCl vo dung dch B, lm tng nng CH3COOH ln 0,060M, lm gim nng 0,040 CH3COOH cn 0,040M nn: pH = 4,74 + lg = 4,74 - 0,18 = 4,56 0,060 Mc d s thay i pH ca dung dch B l nh, nhng s thay i vn xy ra. Nguyn nhn dn n kt qu trn l do dung dch A cha lng cc cht to nn h m nhiu hn dung dch B v do kh nng m ln hn. Mt kt lun quan trng khc cng c th nhn thy t phng trnh tnh pH ca dung dch m l khi t [ A ] s nng cng t b nh hng bi s thm H+ hay OH- th kh nng thay i pH cng nh. iu [ HA] [ A ] = 1 lc ny pH ca dung dch m c gi tr bng pKa cu axit to nn h m. s xy ra khi [ HA]
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TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Tm li mun to nn mt h m c kh nng m ln (m nng ln) mt gi tr pH no ta chn axt no c gi tr pKa cng gn vi gi tr pH cng tt v nng ca cc cht to nn h m bng nhau v cng ln th cng tt. 2. Cn bng trong dung dch cha cht in ly t tan a/ Vai tr ca qu trnh ha tan Ha tan cc cht l mt qu trnh quan trng. Do tan c trong nc nn ng v mui c th c dng to mi v cho thc phm, do t tan trong nc nng nn CaSO4 s tch t trn thnh cc thit b dng un, nu v do lm gim kh nng hp th nhit. Bnh su rng xy ra do men rng b ha tan bi cc axt to nn t thc n cn b ng li cc k rng. Men rng cha cht khong c tn hydroxy apatit [Ca5(PO4)3OH], cht ny tan tt trong axt. Khi nc hay kem nh rng c b sung F-, F- s thay th OH- to nn fluoro apatit Ca5(PO4)3F, cht ny khng b ho tan trong axt v do ngn chn c bnh su rng. BaSO4 tan rt km trong nc cng nh axt, c dng lm cht cn quang khi chp X-quang rut, mc d Ba2+ rt c... T mt s v d thc t trn cho thy tm hiu cn bng ha tan cc cht l vic rt cn thit. b/ Tch s tan Ksp Khi ha tan CaF2 rn vo nc khng c ion Ca2+ v F-, do qu trnh ha tan nng ca Ca2+ v F- tng, lc ny xy ra s kt hp tr li gia Ca2+ v F- to CaF2 rn. Ni cch khc khi trong dung dch c Ca2+ v F- th s xy ra mt qu trnh ngc li to CaF2. Ca2+(aq) + 2F- (aq) CaF2 (r) Sau mt thi gian, vn tc hai qu trnh bng nhau, cn bng ha tan CaF2 c thit lp: CaF2 (r) Ca2+ (aq) + 2F- (aq) p dng nh lut tc dng khi lng, biu thc m t cn bng ha tan c dng nh sau: Ksp = [Ca2+][F-]2 Ksp: c gi l tch s tan ca CaF2 Nh trnh by i vi cc cn bng d th trong biu thc ca hng s cn bng khng c mt ca cc cht rn nguyn cht, nn trong biu thc ca Ksp khng c mt CaF2 Cn phn bit r gia tan v tch s tan. Tch s tan l mt hng s cn bng m t cn bng ha tan ca mt cht tan, do mt nhit xc nh, mt cht tan c th ch c mt gi tr xc nh ca tch s tan. Ngc li tan l mt v tr cn bng, nn mt nhit xc nh, ty nng cc cht c mt trong dung dch, m c th c gi tr tan khc nhau. Tuy nhin gia chng c mi quan h. mt nhit xc nh v mt iu kin thc nghim xc nh bit Ksp c th tm c tan v ngc li.Cc bc kho xc cn bng ha tan tng t nh cn bng axit-baz. TD: 250C CuBr c tan l 2,0.10-4 mol/l. Tnh Ksp CuBr(r) Cu+ + Br + Ksp = [Cu ][Br ] = S2= (2,0.10-4)2= 4,00.10-8 mol2/l2 TD: Cho Ksp ca Cu(IO3)2 250C l 1,4.10-7. Tnh tan ca Cu(IO3)2
Mt vn cn c lu khi dng gi tr Ksp. Nh bit gi tr Ksp cho chng ta thng tin v kh nng ha tan ca mt cht. Ksp cng ln cht tan cng tt, Ksp cng nh cht cng t tan. Tuy nhin khi dng gi tr Ksp so snh tan gia cc cht phi thn trng. TD: CuS c Ksp = 8,5.10-45 v Bi2S3 c Ksp = 1,1.10-79 iu ny khng c ngha l Bi2S3 c tan km hn CuS. Tht vy ta c tan ca CuS c/ nh hng ca ion chung n tan ca mui Tng t nh khi kho st cn bng axit-baz, hiu ng ion chung lm gim kh nng phn ly ca axit-baz rt r rt. Trong cn bng ha tan , hiu ng ion chung lm gim tan ca cht tan, v c ng dng nhiu trong phn tch. V d 5.42 Tnh tan ca Ag2CrO4 trong dung dch AgNO3 0,100 M GV:TRNG CHU THNH. Ti liu lu hnh ni b 31
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT v trong nc nguyn cht. Cho Ag2CrO4 c Ksp = 9,0.10-12 Gii. Do AgNO3 phn ly hon ton ion trong dung dch nn
Trong nc nguyn cht Ksp = (2S2)2 (S) = 4S3 = 9,0 .10-12 S = 1,3 .10-4 mol/l So snh 2 trng hp ta thy d tan ca Ag2CrO4 gim mnh khi trong dung dch c ion Ag+ d/ nh hng ca pH n tan ca mui Trong trng hp cc ion ca cht tan c th kt hp vi H+ hoc OH- th tan ca cht tan b nh hng bi axit hay baz ca dung dch. Ni cch khc pH ca dung dch nh hng n tan ca cht tan. Vd 5.43. Xt cn bng ho tan Mg(OH)2 Mg(OH)2 (r ) Mg2+ (dd) + 2OH- (dd) Khi thm OH vo dung dch, tc lm tng pH ca dung dch, hiu ng ion chung s lm cn bng ha tan chuyn mnh sang tri, lm gim tan ca Mg(OH)2 Ngc li khi thm H+ vo dung dch, tc lm gim pH, OH- ca Mg(OH)2 s b trung ho bi H+, nng ca OH- gim, cn bng s dch chuyn sang phi, Mg(OH)2 s b ha tan nhiu hn. y cng l l do ti sao Mg(OH)2 c dng loi b axit trong bao t. Mt v d khc minh ho nh hng ca pH n tan l Ag3PO4 tan trong axit tt hn trong nc nguyn cht
Phn ng ny lm gim nng PO43- nn s lm cn bng ha tan Ag3PO4 dch chuyn sang phi tc tng tan ca Ag3PO4 Ngc li AgCl c tan nh nhau trong nc nguyn cht v trong dung dch axit l do Cl- l mt baz yu khng th kt hp c vi H+, H+ khng lm thay i nng Cl-, v do khng lm thay i tan ca AgCl. T cc v d chng ta c th c kt thnh qui lut nh sau: Nu anion X- l mt baz mnh ng k , tc axit lin hp HX l axt yu, th mui MX s tan tt trong dung dch axt hn trong nc nguyn cht. Cc anion l baz mnh thng gp l:OH-, S2-, CO32-, CrO42- Mt kt qu th v do nh hng axt dung dch n tan ca mui l s hnh thnh cc hang ng vi. CO2 ha tan trong nc lm cho nc c tnh axt , v do lm gia tng kh nng ha tan mui cabonat vo nc, theo thi gian do cacbonat b ha tan s to ra cc hang ng. Ngc li, s thot CO2 khi cc git nc lm pH ca nc tng, cc mui cabonat s kt ta to ra cc lun thch nh v chung thch nh. e/ Tnh ton cn bng to kt ta-ng dng trong phn tch Phn trn chng ta cp n qu trnh ha tan ca cc cht v cc yu t nh hng n tan ca cc cht. By gi chng ta kho st qu trnh ngc li, tc l qu trnh to kt ta t dung dch.
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TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Khi c s trn ln cc dung dch vo nhau, d on xem c kt ta to ra hay khng, ta dng gi tr tch s ion Q. Tch s ion Q c biu thc tng t nh tch s tan Ksp nhng thay nng cn bng bng nng u ca cc ion trong dung dch sau khi trn ln. TD: Biu thc tch s ion ca CaF2 c dng:
V d 5.45. Kt ta Ce(IO3)3 c to ra hay khng khi trn ln 750 ml dd Ce(NO3)3 4,0.10-3M vi 300 ml dd KIO3 2,0.10-2M? Cho Ce(IO3)3 c Ksp = 1,9.10-10 0,75 4,0.10 3 Ta c [Ce3+]0 = = 2,86.10-3M 1,050 2,0.10 2 0,3 [IO3-]0 = = 5,71.10-3M 1,050 [Ce3+]0[IO3-]3 = (2,86.10-3) (5,71.10-3)3 = 5,32.10 -10 > Ksp = 1,9.10 -10 Vy c kt ta Ce(IO3)3 to thnh khi trn ln 2 dung dch vo nhau. D nhin, mc ch ca chng ta khng ch n gin l d on c kt ta to ra hay khng khi trn ln cc dung dch vo nhau, m xa hn na, l phi tnh c nng ca cc cu t trong dung dch khi cc qu trnh t n cn bng. TD: Tnh nng cn bng ca cc ion trong dung dch thu c khi trn ln 200,0ml dung dch NaI 0,100M vi 100,0ml dung dch Pb(NO3)2 0,05M. Cho Ksp ca PbI2 = 1,4.10-6 Gii Trc ht chng ta tin on xem c kt ta to ra hay khng.
Vy s c kt ta PbI2 c hnh thnh. tin cho vic tnh ton nng cn bng ca cc ion trong dung dch sau khi pha trn, trc tin ta gi thit rng qu trnh to kt ta gia Pb2+ v I- xy ra hon ton.
T y kt lun bng ha tan ca PbI2 trong cc iu kin nh sau:
. Bi ton by gi l tnh cn
ng dng quan trng nht ca kho st cn bng to kt ta l la chn iu kin tch kt ta cc ion trong dung dch bng mt thuc th thch hp. GV:TRNG CHU THNH. Ti liu lu hnh ni b 33
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT V d 5.47 Mt dung dch cha - Khi thm I vo dung dch cation no s kt ta trc. - Tnh nng I cn kt ta mi cation. Cho Gii: i vi PbI2 ta c : ca
Do nng
l :
Tng t nng I- cn kt ta CuI l
So snh 2 trng hp ta thy khi thm I- vo dung dch th kt ta CuI s to ra trc tin, ngha l c th dng I- tch Cu+ ra khi dung dch hn hp gm Cu+ v Pb2+. Do cc mui sunfua kim loi c tan khc bit nhau ln nn ion S2- thng c s dng kt ta chn lc cc ion kim loi. Do S2- l mt baz, nng ca S2- c th c kim sot bng cch iu chnh pH ca dung dch. H2S l mt axit yu nh thc, phn ly theo 2 nc: H2S H+ + HSKa 1 = 1,0.10 -7 HSH+ + S2Ka 2 = 1,3.10-13 Gi tr nh ca l mt baz mnh, trong mi trng axit nng ca S2- s nh, ngc li trong mi trng baz nng ca S2- ln. iu ny c ngha l i vi cc mui rt t tan nh CuS c th kt ta trong mi trng axit v ch cn mt lng nh S2-. Ngc li trong iu kin cc mui nh MnS , s kt ta c Mn2+ v Ni2+ bng cch chnh cho mi trng hi baz. Quy trnh kt ta ion kim loi bng S2- l mt quy trnh quan trng trong phn tch nh tnh cc cation. Gi tr Ksp ca cc cht in ly t tan 250C Cht Ksp Cht Ksp -5 PbCl2 1,6 x 10 Ba(OH)2 5,0 x 10-3 AgCl 1,6 x 10-5 Ba(OH)2 1,3 x 10-3 Hg2Cl2 1,1 x 10-18 Fe(OH)2 1,8 x 10-15 PbI2 1,4 x 10-8 Fe(OH)3 4 x 10-38 AgI 1,5 x 10-16 Cu(OH)2 1,6 x 10-19 Hg2I2 4,5 x 10-29 Mg(OH)2 8,9 x 10-12 CaSO4 6,1 x 10-5 Ag3PO4 1,8 x 10-18 Ag2SO4 1,2 x 10-5 Ca3( PO4)2 1,3 x 10-32 SrSO4 3,2 x 10-7 Ag2CrO4 9,0 x 10-12 PbSO4 1,3 x 10-8 PbCrO4 2 x 10-16 BaSO4 1,5 x 10-9 BaCrO4 8,5 x 10-11 3. Cn bng to phc trong dung dch a) Tnh nng ca cc cu t trong cn bng to phc Ion phc l cc cu t c mang in tch c cu to bi ion kim loi bao quanh bi cc phi t .Cc phi t n gin l cc baz Lewis-tc l phn t hay ion c mt i in t c th cho orbital GV:TRNG CHU THNH. Ti liu lu hnh ni b 34
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT trng ca ion kim loi hnh thnh mt lin kt cng ho tr. Mt s phi t ph bin nh H2O, NH3, Cl-, CN-... S lng phi t c th to ni vi ion kim loi c gi l s phi tr. S phi tr thng gp l 2,4 v 6. Vd 5.48
Qu trnh to phc gia ion kim loi vi phi t c th xy ra tng nc v c c trng bng hng s to phc tng nc hay hng s bn tng nc.V d : Khi trn ln dung dch Ag+ vi dung dch NH3 xy ra qu trnh to phc tng nc
Vic tnh nng ca cc cu t trong kho st cn bng to phc rt phc tp, do c cc qu trnh to phc tng nc. Tuy nhin trong a s trng hp nng ca phi t ln hn rt nhiu so vi ion kim loi, do phng php gn ng cho php ta n gin cc php tnh rt nhiu. V d 5.49. Kho st dung dch to ra bng cc trn ln 100,0ml dung dch. Trc khi xy ra cc phn ng th [Ag+]0 =5,0.10-4M [NH3]0 =1,0M s to phc tng nc vi NH3
Do hng s to phc tng nc ln, v do lng d ca NH3 rt ln nn c th gi thit ton b , do :
Trong thc t, s c mt lng nh rt t bng phn ly ca tnh nng cn bng ca
v NH3, tuy nhin do . Ta dng cn
By gi ta s dng cn bng phn ly ca
Kt qu tnh ton cho thy: GV:TRNG CHU THNH. Ti liu lu hnh ni b 35
Kt qu ny ph hp vi gi thit V do hon ton chp nhn c. V d 5.50 Tnh nng cn bng ca pha trn 150,0ml dung dch nc l Gii Nng u ca trong dung dch to ra do s . Cho hng s to phc tng
Do ln nn ta gi thit cc phn ng to phc tng nc u xy ra hon ton. Hai qu trnh to phc tng nc c th gom thnh mt qu trnh tng nh sau:
xc nh nng cn bng ca
ta dng cn bng phn ly phc:
Kt qu tnh cho thy: Kt qu ny hon ton ph hp gi thit v do chp nhn c. b). nh hng ca s to phc n tan Trong phn trc y chng ta trnh by ng dng ca phn ng to kt ta l kt ta chn lc nhm cc ion kim loi trong phn tch nh tnh. Bc tip theo l phi ha tan cc kt ta ny tch cc ion kim loi trong tng nhm. C th ta c hn hp rn gm , lm th no ho tan hn hp kt ta ny v tch ring bit cc cation . Mt trong cc phng php quan trng l dng cn bng to phc tc ng n cn bng ha tan. Xt cn bng ha tan ca AgCl: AgCl ( r) Ag+ + Cl- , Ksp = 1,6.10-10 Ta bit Ag+ to c phc bn vi NH3
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TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Khi c s hin din ca NH3 s to ra qu trnh to phc gia Ag+ v NH3. Qu trnh ny lm gim nng ca Ag+ do cn bng ho tan s dch chuyn sang phi. Nu lng NH3 d th ton b Ag+ s chuyn ht vo phc v kt qu l AgCl b ho tan hon ton. Ta c th biu din cn bng ho tan AgCl khi c mt NH3 nh sau : y l cn bng tng ca 3 cn bng trn, nn hng s cn bng K c xc nh nh sau:
S dng cn bng ny chng ta s th tnh tan ca AgCl trong dung dch NH3 10,0M. Gi x l tan ca AgCl trong dung dch NH3 10,0M
So snh vi tan ca AgCl trong nc , ta thy trong dung dch NH3 10,0M AgCl tan rt nhiu do nh hng ca s to phc. n y ta c 2 phng php hiu qu ho tan cc cht rn t tan . Nu anion ca cht rn l mt baz mnh, ta c th ho tan cht rn bng dung dch axit. Trong trng hp anion khng phi l baz mnh ta c th ho tan cht rn trong dung dch c cha phi t to c phc bn vi cation ca cht rn. Tuy nhin trong mt s trng hp phi cn n s phi hp ca nhiu phng php, nhiu phn ng ho hc ho tan cht rn kh tan. V d: HgS l mt cht rn kh tan hp axit HCl v HNO3 m c ( gi l nc cng thy) mi ha tan c HgS, to phc vi , phi dng hn
v do lm dch chuyn cn bng ho tan ca HgS sang phi. Mt khc, tan ca cc mui ph thuc vo nhit v thng lm tng theo nhit , do , i vi mt s mui ta c th ho tan chng bng cch n gin l un nng dung dch. i vi PbCl2, c th ho tan PbCl2 bng cch un si dung dch. Lc ny AgCl v Hg2Cl2 vn dng kt ta v tan ca chng trong nc khng ng k. Dung dch NH3 s c dng ho tan hnh thnh hn hp gm Hg v HgNH2Cl. Nh vy, ta tch ring c hn hp gm ng kim chng pht hin s c mt ca cc cation kim loi. v c th thc hin cc phn
TM LC Khi cht tan ho tan vo dung mi to nn mt h ng nht ca cc nguyn t, hoc phn t, hoc ion ta c mt dung dch.Cht tan c th l cht rn, cht lng, hoc cht kh cn dung mi thng l cht lng. Cc cht khi tan to ra dung dch cha cc ion, dn in gi l cht in ly. Cht khng in ly l cht khi tan to ra dung dch phn t v khng dn in c. Kh nng ho tan mt cht kh vo dung mi lng ph thuc vo p sut ca kh trong iu kin kh khng phn ng vi dung mi v thng gim theo tng nhit . Cc cht lng phn cc thng GV:TRNG CHU THNH. Ti liu lu hnh ni b 37
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT tan trong nc, ngc li cht lng khng phn cc thng t tan hoc khng tan trong nc.Thng thng kh nng ho tan ca cht rn trong nc tng theo nhit , tuy nhin vn c nhng ngoi l. Cc dung dch tun theo nh lut Raoult gi l dung dch l tng, hnh thnh khi lc tng tc gia cc phn t cht tan v dung mi c gi tr tng ng vi lc tng tc gia cc phn t cht tan cng nh gia cc phn t dung mi. Qu trnh xy ra t nhin v c s gia tng xo trn ca cc phn t cht tan v dung mi khi hnh thnh dung dch. S gia tng mc tng tc gia phn t cht tan v dung mi hng ti qu trnh hnh thnh dung dch mt cch t nhin Lng tng i ca cht tan v dung mi trong dung dch c th c m t nh lng bng nng ca dung dch. C cc loi nng nh: nng %, nng mol, phn mol, nng ng lng, nng molan. Cc tnh cht ca dung dch ph thuc vo nng ca cht tan c gi l cc tnh cht nng , bao gm cc thay i nh: p sut hi, nhit si, nhit ng c ca dung mi trong dung dch. ln ca cc tnh cht ny ch ph thuc vo nng ca cc cu t trong dung dch m khng ph thuc vo loi cu t. Nng ca cc cu t cn nh hng n p sut thm thu, l p sut cn phi p t ngn chn s khuych tn ca cc phn t dung mi nguyn cht xuyn qua mng bn thm vo dung dch. Cht keo l cc ht khng tan, l lng, thng c kch thc ln hn phn t nhng vn nh c th tn ti trong mi trng trong mt thi gian di.
6.CN BNG HA HC
Phn ng A + B C + D c gi l phn ng cn bng hay thun nghch khi n xy ra theo hai chiu ngc nhau trong cng mt iu kin. Do , phn ng cn bng xy ra khng hon ton, ngha l sau phn ng khng nhng thu c sn phm (C,D) m cn c c cc tc cht (A, B). Th d: Vi phn ng este ha gia acid acetic CH3-COOH vi ru etilic C2H5OH CH3-COOH + CH3-CH2-OH CH3-COO-CH2-CH3 + H2O Nu ly 1mol CH3COOH cho tc dng vi 1mol CH3-CH2-OH th sau khi phn ng t mc cn bng (coi nh phn ng xong), ta thu c 2/3 mol ester CH3COOC2H5, 2/3 mol nc, 1/3 mol acid CH3COOH, 1/3 mol ru C2H5OH Phn ng thun nghch A + B C + D c gi l t trng thi cn bng khi trong cng mt n v thi gian nu c bao nhiu phn t tc cht (A, B) mt i do tham gia phn ng thun to sn phm (C, D) th cng c by nhiu phn t tc cht (A, B) c to tr li t phn ng nghch, lc vn tc phn ng thun v vn tc phn ng nghch bng nhau, lc ny nng cc cht trong phn ng khng thay i na. Cn bng ha hc c gi l cn bng ng v thc ra lun lun c phn ng thun v nghch xy ra nhng do lng cc cht trong h phn ng khng thay i khi phn ng t trng thi cn bng nn phn ng c coi nh xong. Hn na, c th lm thay i trng thi cn bng ca phn ng bng cch thay i cc yu t nh : nng cc cht, nhit , p sut. I. NH LUT TC DNG KHI LNG nh lut ny do Gulberg Waage (Na Uy) a ra nm 1864, nhm xc nh trng thi cn bng ca mt phn ng cn bng. 1. Trng hp cn bng gia cc kh c th xem nh kh l tng a. Hng s cn bng KC Xt phn ng cn bng: kt A(k) + B(k) C(k) + D(k) kn Gi kt v kn ln lt l hng s vn tc ca phn ng thun v nghch. Gi s phn ng thun cng nh phn ng nghch u thuc loi n gin (ngha l phn ng ch xy ra trong mt giai on, bc phn ng ring phn ca mi tc cht bng h s t lng nguyn ti gin ng trc mi tc cht trong phn ng). Vn tc phn ng thun l : Vt = kt[A][B] Vn tc phn ng nghch l : Vn = k n[C][D] GV:TRNG CHU THNH. Ti liu lu hnh ni b 38
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Gi s lc bt u phn ng, ch c A, B hin din. Vn tc phn ng thun Vt lc u rt ln, vn tc phn ng nghch Vn bng khng. Phn ng cng xy ra lu, nng cc tc cht A, B cng gim ([A] , [B]), nng cc sn phm C, D cng tng ([C][D]). , Nh vy, Vt gim dn theo thi gian, cn Vn tng dn theo thi gian. Sau mt thi gian vn tc phn ng thun Vt s bng vn tc phn ng nghch Vn, lc ny phn ng t trng thi cn bng, phn ng c coi nh xong. Vt = Vn k [C ][ D] kt[A][B] = kn[C][D] t = k n [ A][ B ] V kt, kn l cc hng s vn tc phn ng, ch ty thuc nhit (v ty thuc bn cht ca phn ng), cho nn ng vi mt nhit xc nh (v mt phn ng xc nh), ta c: k t [C ][ D] = KC = k n [ A][ B ] cb: cn bng, ch nng cc cht C, D, A, B lc t trng thi cn bng. Kc c gi l hng s cn bng ca phn ng lin h n nng (mol/l). Kc ch ph thuc nhit v bn cht ca phn ng, m khng ph thuc vo nng cc cht trong phn ng. H thc trn biu din s lin h gia nng ha cht (tc khi lng ca ha cht) lc cn bng, chnh l ni dung ca nh lut tc dng khi lng. C th pht biu nh lut ny nh sau: Khi mt phn ng ng th t trng thi cn bng th t s tch s nng sn phm vi tch s nng tc cht l mt hng s mt nhit xc nh. Tng qut vi phn ng: mA + nB pC + qD ngi ta ch rng : k [C ] p [ D] q KC = t = k n [ A] m [ B ] n Vi [A], [B], [C], [D] l nng ca A, B, C, D lc cn bng. Th d: vi phn ng : 2NOCl(k) 2NO(k) + Cl2(k) [ NO]2 [Cl 2 ] th KC = [ NOCl ]2
b. Hng s cn bng Kp Hng s cn bng ny lin h n p sut ring phn ca ha cht th kh lc cn bng (lc t trng thi cn bng). [p sut ring phn ca mi cu t ca hn hp c th tch chung l V l p sut m cu t y c khi n ng ring mt mnh v cng chim th tch V ca hn hp cng nhit ]. Xt phn ng: mA(k) + nB(k) pC(k) + pD(k) Gi PA, PB, PC, PD ln lt l p sut ring phn ca cc kh A, B, C, D c th xem nh kh l tng lc cn bng nA, nB, nC, nD ln lt l s mol ca A, B, C, D hin din trong th tch V ca h phn ng (bnh phn ng) lc cn bng nhit T (K). T n P PAV = nART PA = A RT = [ A]RT [A] = A V RT nB P RT = [ B ]RT [B] = B PBV = nBRT PB = V RT n P PCV = nCRT PC = C RT = [C ]RT [C] = C V RT n P PDV = nDRT PD = D RT = [ D]RT [D] = D V RT Thay [A], [B], [C], [D] vo biu thc ca hng s cn bng KC : GV:TRNG CHU THNH. Ti liu lu hnh ni b 39
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT p q PC PD ( PC ) p ( PD ) q [C ] p [ D] q RT RT (m + n) (p + q) KC = = ( 4 3) m n = m n (RT) [ A] m [ B ] n ( PA ) ( PB ) PA PB RT RT ( PC ) P ( PD ) q t KP = (4-4) (PC, PD, PA, PB ln lt l p sut ring phn ca C, D, A, B lc cn bng). ( PA ) m ( PB ) n KC = KP(RT)(m + n) (p + q) T (4 3) KP = KC(RT)(p + q) (m + n) t n = (p + q) (m + n) ( n l tng h s mol kh sn phm - tng s mol kh tc cht) (4 -5) Ta c Kp = KC(RT) n (4-6) Do KC ch ph thuc nhit T nn Kp cng ch ph thuc nhit T. c. Hng s cn bng Kx Hng s cn bng ny lin h n phn s mol (phn mol, phn mol) ca cc cht trong phn ng. Phn s mol (phn mol hay phn mol) x ca cu t i trong hn hp gm nhiu cu t l t s gia s mol ca i vi tng s mol ca cc cu t c trong hn hp. ni xi = 0 xi 1 xi = 1 ni Xt phn ng: mA + nB pC + qD Gi P l p sut ca hn hp kh lc cn bng; A, B, C, D ln lt l phn s mol ca A, B, C, D lc cn bng. nB nC nA nD n ; C = n ; D = n vi n = nA + nB + nC + nD l tng s mol hn hp gm A = n ; B = cc kh A, B, C, D lc cn bng. nA n n RT = A nRT RT = A P = A P PA = A P PAV = nART PA = V n P Tng t : PB = B P PC = C P PD = D P Th PA, PB, PC, PD vo biu thc Kp ca phn ng: ( PC ) P ( PD ) q ( C P ) P ( D P ) q ( C ) P ( D ) q ( P + q ) ( m + n ) = = P KP = ( PA ) m ( PB ) n ( A P ) m ( B P ) n ( A ) m ( B ) n (C ) P ( D )q KP = KxP ( A )m ( B )n = (p + q) (m + n) : (Tng h s mol kh sn phm) (Tng h s mol kh tc cht) Nh vy hng s cn bng Kx ph thuc vo nhit T v p sut tng qut P ca hn hp kh lc cn bng. Nu = 0 (p + q) (m + n) = 0 (p + q) = (m + n) => Tng h s mol kh bn sn phm = Tng h s mol kh bn tc cht. Th t KP = K C ( RT ) = K ( P ) (4 9) KP = KC = K (4 10) t Kx = Ch thch: - Ngi ta ch rng trong biu thc ca cc hng s cn bng lin h n kh nu trn, ta khng ch n cc cht lng v cht rn. Th d: GV:TRNG CHU THNH. Ti liu lu hnh ni b 40
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT CaCO3(r) CaO(r) + CO2(k) Kp = PCO2 NH4Cl(r) HCl(k) + NH3(k) Kp = PHCl.PNH3 HCl(k) + NH3(k) NH4Cl(r) Kp = - Hng s cn bng K cng ln, phn ng cng thin v chiu thun, hng s cn bng K cng nh phn ng cng thin v chiu nghch (0 K < ) - Ty theo h s ca phn ng m hng s cn bng ca cng mt phn ng c th khc nhau. Th d: vi phn ng 2 PSO3 2SO2 (k) + O2 (k) 2SO3 (k) th KP = 2 PSO2 PO2 Vi phn ng : SO2 (k) +
1 O 2 2 (k)
SO3 (k)
th KP =
PSO3 PSO2 ( PO2 )

1 2
2. Trng hp cn bng trong dung dch lng Trong trng hp ny, thng hng s cn bng KC c p dng cho dung dch long. Vi phn ng: mA(dd) + nB(dd) pC(dd) + qD(dd) Ngi ta cng ch rng: [C ] p [ D ] q KC = [ A] m [ B ] n Vi [C], [D], [A], [B] ln lt l nng ca C, D, A, B trong dung dch lc phn ng t trng thi cn bng. Trong trng hp dung dch lng nu trong h phn ng c hin din cht rn th ta khng ch n cht rn. Th d: 1 Ag+(dd) + Cl-(dd) AgCl(r) KC = + [ Ag ][Cl ] Vi [Ag+], [Cl-] l nng ca ion Ag+ v Cl- trong dung dch c cn bng vi pha rn AgCl. 3. S lin h gia hng s cn bng K vi bin i nng lng t do G ca phn ng Xem phn ng cn bng ca cc ha cht th kh: mA(k) + nB(k) pC(k) + qD(k) Bin i nng lng t do G ca phn ng l: G = (p G C + qG D ) (mG A nG B ) Vi kh c th xem nh kh l tng, iu kin ng nhit, s ph thuc ca hm s nng lng t do G theo p sut P l: Trong l tr s nng lng t do ca 1 mol i 1atm, ng vi nhit T.
41
(4-13) Khi phn ng t trng thi cn bng p sut P, nhit T th: G = 0 ( PC ) p ( PD ) q G 0 = K P G0 = - RTlnKP lnKP = Ta c : ( PA ) m ( PB ) n RT 0 G l bin i nng lng t do iu kin chun thc (p sut P = 1 atm, nhit T xc nh). G0 ph thuc vo nhit T. H thc trn cho bit c th tnh c hng s cn bng da vo cc i lng nhit ng hc ca ha cht. Theo trn: - Nu G0 < 0 KP > 1 v KP cng tng nu G0 cng m Do , vi nhng phn ng cn bng tng ng vi G0 rt m c khuynh hng xy ra gn trn vn, mc cn bng, nng sn phm rt ln. - Nu G0 > 0 KP < 1 v KP cng nh nu G0 cng dng Vy nhng phn ng cn bng ng vi G0 cng dng th cng xy ra khng trn vn, mc cn bng, nng sn phm tng ng rt nh. Vi trng hp dung dch lng v long vi phn ng: mA(dd) + nB(dd) pC(dd) + qD(dd) trng thi chun thc thch hp, ngi ta cng chng minh c h thc: [C ] P [ D] q 0 0 G i = G i + RT ln C i G = G + RT ln [ A] m [ B ] n Lc phn ng t trng thi cn bng, ta c: G = 0 cho nn G0 = - RTlnKC II. NH LUT DI I MC CN BNG LE CHTELIER "Trong mt phn ng cn bng, s thay i mt yu t lm xo trn mc cn bng s lm cn bng di i theo chiu chng li s thay i y". Chng ta s xt mt s yu t c th lm thay i mc cn bng : 1. nh hng ca nng S thay i nng ca mt cht s lm cn bng di i theo chiu chng li s thay i y. Ngha l nu lm tng nng mt cht th cn bng s dch chuyn theo chiu lm gim nng ca cht ny xung, tc l chiu cht ny tham gia phn ng; cn nu lm gim nng ca mt cht (nh ly bt cht ny ra khi h phn ng) th cn bng s dch chuyn theo chiu lm tng nng cht ny ln, tc l chiu phn ng to ra thm cht ny. Xem phn ng cn bng: A + B C + D Khi phn ng t trng thi cn bng, ta c:
Nu lc by gi, thm cht A vo h phn ng th [A]mi > [A] cb c KC vn gi nguyn tr s c (khng i) th [A] mi phi gim v [C], [D] mi phi tng, nn phn ng cn bng s di i theo chiu lm gim nng ca A, to ra thm C, D cho n khi no cc nng mi t c tr s nh th no cho:
Tng t, sau khi phn ng t c trng thi cn bng, by gi nu ta ly bt C hoc D ra khi mi trng phn ng, th cn bng s b ph v v cn bng mi s c thit lp theo hng to ra thm C, D. Ni chung mun phn ng cn bng: GV:TRNG CHU THNH. Ti liu lu hnh ni b 42
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT A + B C + D Cho ra nhiu sn phm C, D th ngi ta c th: - Lm tng nng tc cht A, B. - Hay lm gim nng sn phm C, D. 2. nh hng ca p sut Trong mt phn ng cn bng c lin h n kh, khi lm tng p sut th mc cn bng s di i theo chiu chng li s tng p sut, tc l chiu lm gim s mol kh, cn khi lm gim p sut th mc cn bng s di i theo chiu lm tng p sut ln, tc l chiu to ra nhiu s mol kh hn.
(4-16)
Vi * Nu
tng s h s mol kh sn phm - tng s h s mol kh tc cht. => s mol kh bn sn phm < s mol kh bn tc cht.
TM TT L THUYT V CU TO NGUYN T
I. Cu to nguyn t : Lp v : gm 1 hay nhiu electron proton Ht nhn ntron ( ngoi tr 1H1 ). -19 qe = - 1,602.10 C = -eo = 1- . me = 9,1.10-31 kg. qp = + 1,602.10-19 C = + eo = 1+. qn = 0. mp = 1,00728 u (v.C). mn = 1,00866 u. II. Nng lng ca electron trong nguyn t : 1) Nng lng ca electron trong nguyn t H v cc ion tng t nguyn t H (cc ion c 1 electron): 2 2Z2m e4 (erg) En = n2 h2 Nguyn t trong : n: s lng t chnh. Z: s in tch ca ht nhn. m: khi lng electron = 9,1.10-28 g. GV:TRNG CHU THNH. Ti liu lu hnh ni b 43
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT e: in tch ca electron = 4,8.10-10 CGSE. h: hng s Planck = 6,626.10-27 erg.s. Hoc: k2 2 2Z2m e4 (J) En = n2 h2 trong : k: hng s tng tc tnh in = 9.109 J.m.C-2. m = 9,1.10-31 kg. e = 1,6.10-19 C. h = 6,626.10-34 J.s. Thay cc gi tr vo, ta c: En = - 13,6 Z2 / n2 (eV) (eV = 1,602.10-19 J)
2) Tng qut (theo Slater): En,l = -13,6 Z*2 / n*2 (eV). trong : Z*: s in tch hiu dng = ( Z - b ), vi b l hng s chn. n*: s lng t hiu dng. a) S lng t hiu dng Ty thuc vo s lng t chnh n, n* c xc nh nh sau: n 1 2 3 4 5 6 * n 1 2 3 3,7 4,0 4,2 b) Hng s chn tnh b, ngi ta chia cc AO thnh cc nhm sau: (1s); (2s,2p); (3s,3p); (3d); (4s,4p); (4d); (4f).... * Cc electron thuc lp ngoi AO ang xt ng gp mt hp phn bng 0. * Cc electron trn cc AO cng nhm vi AO ang xt gp mt hp phn bng 0,35. Ring i vi nhm (1s), hp phn tnh l 0,3. * Nu electron ang xt trn AO s hoc p th mi electron trn cc lp k trong (c s lng t chnh n nh hn lp ang xt 1 n v) gp mt hp phn bng 0,85. Mi electron trn cc lp su hn ng gp mt hp phn bng 1. * Nu electron ang xt trn AO d hay f th mi electron trn cc nhm pha trong (ngay c khi cng lp n) gp mt hp phn bng 1. VD: Xt nguyn t C: 1s22s22p2 i vi electron trn obitan 1s: b = 0,3; Z* = 6 - 0,3 = 5,7. i vi electron trn obitan 2s hoc 2p : b = 3. 0,35 + 2.0,85 = 2,75; Z* = 3,25. Nng lng : E1s = -13,6.(5,7)2 = -441,8 (eV) E2s = E2p = -13,6.(3,25)2 / 4 = -35,9 (eV) Tng nng lng cc electron trong nguyn t C: EC = 2E1s + 2E2s + 2E2p = -1027,2 eV.
III. S phng x
1) Tnh phng x t nhin Tnh phng x t nhin l kh nng ca cc cht cha cc nguyn t xc nh khng cn tc ng bn ngoi t pht ra cc bc x khng nhn thy vi thnh phn phc tp. 2) Thnh phn ca tia phng x Xt tc dng ca t trng ln tia phng x, ngi ta phn bit 3 loi tia phng x: a) Tia : gm nhng vi t l ht nhn nguyn t He (He2+) GV:TRNG CHU THNH. Ti liu lu hnh ni b 44
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT b) Tia : gm nhng vi t l negatron (hay electron) (k hiu - hay -1e0) hoc nhng vi t l positron (k hiu + hay 1e0). c) Tia : gm nhng vi t trung ha, thc cht l cc dng photon (tia c cng bn cht vi nh sng). 3) nh lut phn r phng x a) nh lut: N = No.e-kt (1) No : s ht nhn phng x c ti thi im u (t = 0) N : s ht nhn cn li thi im t ang xt k : hng s phn r phng x. b) Chu k bn hy (t1/2): t1/2 = ln2 / k = 0,693 / k (2)
4) phng x (hot phng x) * phng x A ca mt mu phng x l mt i lng bng s phn r trong mt n v thi gian. A = - dN / dt = k.N (3) n v phng x c o bng Curi (Ci). 1Ci = 3,7.1010 phn r / giy = 3,7.1010 Bq (Becquerel). * Ngi ta xc nh c rng: trong kh quyn, trong mi c th ng thc vt ang sng, c 1 giy, trong 1 gam cacbon c 15,3 phn r 14C. Khi c th ny cht i, tc phn hy gim dn vi chu k bn hy 5730 nm. T (1) , (2) , (3) suy ra: t = (t1/2 / 0,693).ln(No / N) = (t1/2 / 0,693).ln(Ro / R) trong : Ro : 15,3 phn r 14C trong 1 giy trong 1 gam cacbon R : s phn r 14C trong 1 giy trong 1 gam cacbon thi im t. IV. Mt s h thc ca Einstein 1) E = h = hc / trong : E: nng lng ca photon : tn s ca nh sng hay bc x ni chung h: hng s Planck c: vn tc nh sng = 3.108 m/s : bc sng nh sng (bc x). 2) H thc lin h gia khi lng m v nng lng E: E = m.c2 E = m.c2 V. Nng lng lin kt ht nhn - Phn ng ht nhn 1) Nng lng lin kt ht nhn (E) E = m.c2 trong , m = (Z.mp + N.mn ) - mhat nhan E / (Z + N) : nng lng lin kt ring hay nng lng lin kt trung bnh ca 1 nucleon. 2) Phn ng ht nhn S tng tc ca hai hay nhiu ht dn n to thnh nguyn t mi (v c th c thm phn khc) c gi l phn ng ht nhn. tnh nng lng ca phn ng ht nhn, ta dng cng thc: E = m.c2. GV:TRNG CHU THNH. Ti liu lu hnh ni b 45
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Trong phn ng ht nhn, s khi v in tch c bo ton. 7.HIN TNG PHNG X V PHN NG HT NHN 1. Cc loi ht: Proton 1 1 H (p) 2. S phng x: a) Cc ht nhn nng khng bn (U, Th, Pu, Po, Ra...) lin tc t pht ra cc tia khng nhn thy gi l tia 4 0 phng x: ( 2 He); ( 1 e); (bc x)
4 0 V d: 83 Bi 84 Po + 1 e v 84 Po 82 Pb + 2 He b) nh lut chuyn dch phng x (cc nh lut bo ton s khi v nh lut bo ton proton): A A 4 4 A A 0 v Z X Z 2 Y + 2 He Z X Z +1 Y + 1 e 210 210 210 206
Electron 0 1 e (e hay )
Ntron 1 (n) 0n
Phn electron 0 () +1 e
anpha 4 2 He ()
Phng x khng lm thay i nguyn t 2. Cc loi phn ng ht nhn: a) Phn ng n gin: V d: phn ng Rutherford
4 2
He +
14 7
N 8 O + 1 p (th nghim tm ra proton) 1

12 1
17
phn ng Chadwick 4 He + 9 Be 6 C + 0 n (th nghim tm ra ntron) 2 4 b) Phn ng phn hch: 1 235 V d: 0 n + 92 U X + Y + 3n (Bom nguyn t, nguyn tc l phn ng ht nhn) c) Phn ng nhit hch: 2 2 V d: 1 H + 1 H 4 He (Nguyn tc bom hidro) 2 3. ng hc qu trnh phng x: dN = k.N (k l hng s phng x, N l s nguyn t ti thi im xt) dt ln 2 0, 693 b/ Hng s phng x: k = t = t 1 1 a/ Tc phng x: v =
2 2
c/ Chu k bn hy (t1/2): l thi gian lng cht ban u mt i mt na (a/2 hay N0/2) N0 1 Quan h: k = ln (N0 l s ht nhn phng x ti thi im ban u, Nt l s ht nhn cn Nt t li ti thi im t ang xt, t l thi gian phng x) 0, 693 t1 2,303 t 1 N0 N0 2 2 lg Thay k = t cho t = . ln hay t = Nt Nt 1 0, 693 0, 693 2
8.Thuyt lai ha orbital :

Cc kiu lai ha AO : Lai ha sp : 1 AO s trn ln vi 1 AO p to ra 2 AO lai ha nm thng hng vi nhau to thnh gc 1800
s p 2 AO lai hoa sp - Lai hoa sp2 : 1 AO s tron lan vi 2 AO p tao ra 3 AO lai hoa sp2 nam trong cung mat phang tao vi nhau nhng goc bang nhau va bang 1200
46
s 2 AO p 3 AO lai ha sp2 3 - Lai ha sp : 1 AO s trn ln vi 3 AO p to thnh 4 AO lai ha hng theo 4 nh ca hnh t din u, cc gc HCH bng nhau v bng 109028
3 AO p 4 AO lai ha sp3 2 Ngoi cc kiu lai ha trn cn cc kiu lai ha khc nh : dsp (hnh vung) sp3d2 (hnh bt din u) iu kin lai ha bn : - Nng lng cc orbital tham gia lai ha phi xp x nhau. - Mt electron ca AO tham gia lai ha phi ln - Mt xen ph ca cc AO lai ha vi cc AO ca cc nguyn t khc tham gia lin kt phi ln to thnh lin kt bn. c im AO lai ha - S lng AO lai ha thu c bng tng s AO tham gia lai ha - Cc AO lai ha c cng mc nng lng - Mi AO lai ha gm 2 phn: phn n rng v phn thu hp; hai phn ny cch nhau mt nt ti ht nhn nguyn t (phn n rng thng c du +, phn thu hp thng c du -) - Mi AO lai ha c phn b trn mt trc xc nh i qua ht nhn nguyn t (c th trng hoc khng trng vi trc ta ecac). Ngi ta ni AO lai ha c tnh i xng trc T cc iu kin trn ta c th thy : Trong mt chu k hiu nng lng ca AO s vi AO p tng ln khi i t u n cui chu k nn kh nng tham gia lai ha gim xung. Khi tng kch thc nguyn t, kh nng lai ha ca cc AO ha tr gim xung. * Lin kt xich ma lin kt pi : a. Lin kt xich ma : L lin kt cng ha tr hnh thnh do s xen ph 2 orbital dc theo trc ni 2 ht nhn nguyn t. Do mt xen ph cc orbital ln nn lin kt xich ma bn (c nng lng lin kt ln) b. Lin kt pi : L lin kt hnh thnh do s xen ph cc orbital p, vng xen ph cc orbital p vung gc vi trc ni 2 ht nhn nguyn t. S xen ph ny gi l s xen ph bn. Do mt xen ph cc orbital p thp nn lin kt pi km bn hn lin kt xich ma. Cc kiu xen ph trc ca lin kt xich ma : Xen ph s s : TD : phn t H2 Xen ph s p : TD : phn t HCl, HF, HI Xen ph p p : TD : phn t Cl2, Br2 Cc kiu xen ph bn to lin kt pi :
M hnh cc phn t : CH4, C2H6, C2H4, C2H2
47
Nguyn t C lai ha sp3 Nguyn t C lai ha sp2
Nguyn t C lai ha sp 3/ Cu trc hnh hc ca phn t : Cng thc nguyn ca mt cht cho ta bit tng qut s nguyn t m n c. Bit cng thc ny l cn thit nhng r rng l khng tin on nhng tnh cht ca n, v nhiu tnh cht l suy trc tip t cc c trng hnh hc ca phn t. TD : Cc phn t H2O, H2S c dng gc, cho nn trng thi lng chng l dung mi tt i vi cc cht ion, trong khi cc cht tng t chng nh CO2, CS2 c dng thng v ch lm dung mi cho cc phn t cng ha tr, Trong thc t, bit s m nguyn t X kt ho vi nguyn t trung tm A cha xc nh cu trc phn t AXm, v vhnh s electron ha tr tng cng mi ng vai tr quyt nh. Ci tin m hnh Lewis, thuyt VSEPR (Valen Shell Electronic Pair Repulsions) da trn s y cc cp electron ca nhng lp ha tr cho php xc nh cu trc hnh hc ca phn t. L thuyt VSEPR : Xut pht t tng a ra ln u bi N. Sidgwick v H.Powel l : cc cp electron ha tr ca mt nguyn t lun y ln nhau. R.J. Gillespie a ra qui tc tin on s nh hng cc lin kt xung quanh 1 nguyn t gi l nguyn t trung tm ca phn t hoc ion. M hnh Gillespie l mt qu trnh suy lun n gin v hiu qu trn c s sau : Mi cp electron lin kt v khng lin kt v c khi l electron c thn lp ngoi u c tr mt cch thng k cng mt khong cch xc nh so vi ht nhn, nh l chng c xp trn b mt hnh cu m nhn mm tm. Cc electron tng ng y ln nhau v nh v nhng v tr lm cc tiu lc y electron. V l do i xng, cc cp electron lp ngoi ca nguyn t trung tm to ra nhng m hnh hnh hc u m ty trng hp l ni tip trong vng trn hay trong hnh cu. Trong m hnh VSEPR mt cp electron t do (hay 1 electron c thn) cng c coi nh l nhng lin kt gia cc nguyn t. V trc lin kt khng ph thuc vo lin kt l n hay bi, nn ch cn bit tng s nguyn t lin kt vi nguyn t trung tm m khng cn bit n bn cht ca lin kt ny. - Nguyn t cn nhiu electron hn to octet c gi l nguyn t trung tm A - Phi t c hai loi: * Nguyn t lin kt ha hc vi A c k hiu l phi t X Ta c cng thc AXm (m 1, nguyn). TD: CO2, BeH2 thuc dng AX2, BH3 thuc dng AX3 * i electron cha tham gia lin kt ca nguyn t trung tm (nu c) c gi l phi t E Trong cc iu kin nh trn cng thc VSEPR ca hp cht biu th bng cch vit : AXmEn trong : m l s nguyn t X lin kt vi nguyn t trung tm A. n : l s thc th khng lin kt (i electron t do v electron c thn) m n c Tng s : (m + n) quyt nh cu trc hnh hc ca phn t C mt s phng php khc nhau gii thch cu trc hnh hc ca phn t nh : Phng php m hnh s y gia cc i electron v ha tr VSEPR, phng php m hnh lin kt b un cong hoc phng php m hnh lai ha orbital nguyn t. Sau y ta xt cu trc hnh hc ca phn t trn c s m hnh lai ha orbital nguyn t. TD : Dng AX2E0 c (m + n) = 2 c cu trc thng, nguyn t trung tm c kiu lai ha sp nh phn t : BeH2, CO2, ZnCl2 Cu trc thng
Dng AX3E0 c (m + n) = 3 c cu trc tam gic, nguyn t trung tm c kiu lai ha sp2 nh phn t BF3, SO3, CO32- Cu trc tam gic Cu trc t din
48
Dng AX4E0 c (m + n) = 4 c cu trc t din, nguyn t trung tm c kiu lai ha sp3 nh : CH4, CF4, SO42-, NH4+ Dng AX5E0 c (m + n) = 5 c cu trc dng lng thp tam gic, nguyn t trung tm c dng lai ha sp3d nh: PCl5, PF5
49
Di y l mt s m hnh cu trc hnh hc ca phn t : AXnEm Dng cng thc AX2E0 AX3E0 Tng (m + n) 2 3 S cp e khng lk 0 0 Kiu lai ha sp sp2 Tam gic phng AX2E1 3 1 sp2 Gc AX4E0 4 0 sp3 T din AX3E1 4 1 sp3 Chp thp AX2E2 4 2 sp3 Gc H2O, H2S, SF2, SCl2, F2O NH3, PH3, AsCl3 CH4, NH3, NH4+, SO42-, CCl4, ClO4-, PO43-
Cu trc hnh hc
Cc cht minh ha
ng thng
CO2, C2H2, BeH2, BeCl2, ZnCl2 SO3, BF3, AlCl3, O3, NO2, C2H4, CO32-, NO3SO2, O3
AX5E0
sp3d lng chp
PCl5, PF5
AX6E0
Sp3d2 Bt din
SF6, AlF63-, SiF62-
9.CC TINH TH
1. Chng minh c kht ca mng tinh th lp phng tm khi l 0,68. Xt 1 n v mng li tinh th lp phng tm khi c cnh = a V mng tt = a3. 1 S nguyn t kim loi c trong 1 mng c s = . 8 + 1 = 2 (nguyn t) 8 Cc nguyn t kim loi xp st nhau. Xt theo ng cho ca khi lp phng: a 3 4R = a 3 R = R R R R 4 Th tch chon ch ca 2 nguyn t kim loi: 4 VKL = 2 . 3 a 3 4
3
A
3
4 a 3 VKl 2. . Vy c kht ca mng tinh th = = 3 4 = 0,68 Vt t 3 a
50
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT 4 4 a 3 V . R3 2. . c a 3 Hoc: c kht P = N. = 2. 3 vi R = nn P = 3 4 = 0,68 V tb 4 3 a a3 (N : s nguyn t trong c trong 1 mng c s tinh th Vc : Th tch 1 nguyn t dng qu cu Vtt : Th tch ton b t bo tinh th ) 2. Chng minh c kht ca mng tinh th lp phng tm din l 0,74. Xt 1 n v mng li tinh th lp phng tm khi c cnh = a V mng tt = a3. 1 1 S nguyn t kim loi c trong 1 mng c s = . 8 + . 6 = 4 (nguyn t) 8 2 Cc nguyn t kim loi xp st nhau. Xt theo ng cho ca mt hnh vung: a 2 4R = a 2 R = R R R R 4 Th tch chon ch ca 4 nguyn t kim loi: 4 VKL = 4 . 3 a 2 4
3 3
A
3
4 a 2 VKl 4. . Vy c kht ca mng tinh th = = 3 4 = 0,74 Vt t 3 a 4 4 a 2 V . R3 4. . c a 2 Hoc: c kht P = N. = 4. 3 vi R = nn P = 3 4 = 0,74 V tb 4 3 a 3 a 3. Cu trc su phng c kht Cc kim loi Zn, Be, Mg, Cd, Co, Sc, Y, La, Ti, Zr, Hf... c cu trc ny. S phi tr l 12 v s nguyn t kim loi trong mt t bo c s l 2. Cc nguyn t kim loi chim khong 74% th tch tinh th .
3
Cu trc tinh th nguyn t

Trong mng tinh th ny, n v cu trc l cc nguyn t . Lin kt trong mng tinh th nguyn t l lin kt cng ha tr nh hng. Lc lin kt cng ha tr ln nn cc tinh th nguyn t kh cng, kh nng chy, kh bay hi. VD: Cu trc tinh th kim cng v than ch. 4. TINH TH KIM CNG a) Hy v s m t cu trc ca mt t bo s ng ca kim cng. b) Bit hng s mng a = 3,5 , hy tnh khong cch gia mt nguyn t C v mt nguyn t C lng ging gn nht. Mi nguyn t C nh vy c bao quanh bi my nguyn t khong cch ? c) Hy tnh s nguyn t C trong mt t bo s ng v khi lng ring ca kim cng. a) nguyn t C chim v tr: - cc nh ca t bo s ng -tm ca cc mt -tm ca 4 trong 8 hnh lp phng nh cnh a/2. b) BD2 = BC2 + CD2 = (a/2)2 + (a/2)2 = a2/2 v AD2 = AB2 + BD2 = (a/2)2+ a2/2 = 3a2/4
51
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT AD 3 3 AD = a IA = =a = 1,52 . l khong cch ngn nht gia hai nguyn t C (ng 2 2 4 vi khong cch C C trong farafin). Nguyn t I chng hn c bao quanh bi 4 nguyn t A, C, E, G vi IA = IC = IE = IG = 1,52 . Mi nguyn t C nh vy c bao quanh t din bi 4 nguyn t C khc vi khong cch ngn nht. 1 1 c) S nguyn t C trong mt t bo s ng n = 8. + 6. +4=8 8 2 8.12 Khi lng mi t bo m = gam 6,023.1023 8.12 m 3 Khi lng ring d = = 8 3 23 = 3,7 g/cm . V (3,8.10 ) .6,023.10
Cu trc ca mt s tinh th ion:

1. Tinh th CsCl: Mi loi ion Cs+ hoc Cl- to thnh mt mng li lp phng n gin. 8 ion cng loi to thnh mt t bo c s. Mi ion c bao quanh bi 8 ion khc du. Nh vy s phi tr l 8. V mi ion nh thuc 8 t bo c s nn ng vi mi t bo c s c : 8.1/8=1 ion Cs+ cng nh 1 ion Cl-. Mt s hp cht khc cng c mng tinh th nh CsCl l: CsBr, CsI, TlCl, TlBr, TlI, NH4Cl... v cc hp kim Cu - Pd, Li - Hg, Be - Cu, Al - Ni.... 2. Tinh th NaCl: Mi loi ion to thnh mng li lp phng mt tm. 8 nh ca t bo c s l 8 ion cng loi. Mi ion c bao quanh bi 6 ion khc du gn nht. Nh vy s phi tr l 6. V mi ion nh thuc chung cho 8 t bo c s v mi ion nm tm mi mt thuc 2 t bo c s nn ng vi mi t bo c s c: 8.1/8 + 6.1/2 = 4 ion cng loi. Mt s hp cht khc cng c mng tinh th nh NaCl l: NaF, KCl, CaO, MgO, FeO....
Cu trc tinh th phn t

Trong tinh th phn t , mng li khng gian c to thnh bi cc phn t . Lc lin kt gia cc phn t trong tinh th l lc Van Der Waal. Lc lin kt Van Der Waal l l lin kt yu nn tinh th phn t c nng lng mng li nh, Do cc tinh th phn t d nng chy, mm. VD: Tinh th phn t CO2 rn.
10.LIN KT THEO PHNG PHP MO Gin 1:
1s 1s*2s 2s* z x=y x*=y* Gin 1 p dng i vi nguyn t cui chu k t O n Ne

Gin :2
1s 1s*2s 2s* x=y z x*=y* Gin 2 p dng i vi nguyn t u chu k t Li n N Nlk = ( n - n* ) : 2 vi n l tng s e trong MO lin kt vi n* l tng s e trong MO phn lin kt
p dng 1. Vit cu hnh electron ca cc ion v phn t : O2, O2,O22, O2+ theo thuyt MO. Tnh s lin kt, so snh di lin kt trong cc phn t v cho bit cht no thun t, cht no nghch t. p n Cu hnh electron : S lin kt : 2 * 2 2 2 2 * 1 * 1 O2 16e: 2s 2s z x y x y (8-4)/2 = 2 GV:TRNG CHU THNH. Ti liu lu hnh ni b 52
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT O2 17e :2s2 *2s2 z2 x2 y2 *x2 *y1 (8-5)/2 = 1,5 2 2 * 2 2 2 2 * 2 * 2 O2 18e:2s 2s z x y x y (8-6)/2 = 1 + 2 * 2 2 2 2 * 1 O2 15e:2s 2s z x y x (8-3)/2 = 2,5 S lin kt gim, di lin kt tng theo th t O22> O2> O2> O2+ O2, O2 v O2+ u c electron c thn => c tnh thun t. O22 khng c electron c thn => c tnh nghch t + 2. Hy gii thch ti sao kh F2 mt mt electron thnh F2 th bn lin kt tng; kh N2 chuyn thnh N + th bn lin kt gim. 2 p n F2 : [KK] ( x Y ) ( ) Bc ni: (8 6) : 2 = 1
2 S *2 S 2 Z 4 * x * 4 y 2 F2+ : [KK] S*2 2 ( x y )4 *2 *1 S Z x y + 2
Bc ni: (8 5) : 2 = 1,5
+ V bc lin kt trong F ln hn trong F2 nn F2 c bn lin kt ln hn. 2 *2 4 2 N2 : [KK] s s ( x y ) z
Bc ni: (8 2) : 2 = 3 Bc ni (7 2) : 2 = 2,5
2 *2 4 1 N + : [KK] s s ( x y ) z 2
+ + V bc lin kt trong N 2 nh hn trong N2 nn lin kt trong N 2 km bn hn. Phn t hai nguyn t AB:
Cn ch y v s ph hp tnh i xng khi t hp tuyn tnh cc AO thnh MO.
Cc phn t AB ng e vi cc phn t A2:

Trc tin xem xt cc phn t AB c tng s e nh phn t A2. im cn lu l trong gin nng lng cc MO nguyn t no c m in ln hn th AO ca n c v tr thp hn so vi AO tng ng ca nguyn t kia. Xt phn t CO. T cu hnh e ca nguyn t: C:1s22s22p2, O: 1s22s22p4. Vy CO c 14 e nh N2 (cn ni CO ng e vi N2). S lng AO ho tr v do s lng cc MO ca hai phn t ny nh nhau. Cn lu O c m in ln hn C. T kt qu
2 *2 2 *2 2 2 2 ta c cu hnh e ca CO l 1s 2 s 2 s 2 s x y z
Vy trong CO c lin kt ba gm 1 lin kt v hai lin kt . Kt lun hon ton tng t kt lun v N2.
Mt s phn t AB khc
tham kho thm v vic p dng MO gii thch lin kt ha hc trong phn t AB c ch n i xng, ta xt phn t HF. Cu hnh H 1s1. Vy 1H c 1 AO v 1e. Cu hnh F 1s22s22p5. V nguyn tc F c 4AO ha tr vi 7e km theo (khng k 1s2 bn trong). F c m in bng 4,0 ln hn hn m in ca H. Do AO-2s ca F c nng lng cch xa AO-1s nn AO-2s ny c coi l khng tham gia t hp vi AO-1s. Trong 3 AO-2p, AO-2px s t hp vi AO-1s to ra 2 MO- ; 2 AO-2px, 2py c trc vung gc vi nhau v vung gc vi trc AO-2pz nn 2 AO ny khng tham gia c vo t hp trn v khng ph hp v GV:TRNG CHU THNH. Ti liu lu hnh ni b 53
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT 0 0 i xng. 2 AO-2px, 2py chuyn thnh cc MO khng lin kt, c k hiu l x , y . Vy cu hnh e
2 o2 o2 ca HF l [1s22s2] z x y Mt s phn c t 3 nguyn t tr ln V nguyn tc, thuyt MO gii thch c lin kt ha hc trong nhiu phn t. Ta xt tip mt trng hp na l phn t c t 3 nguyn t tr ln dang ABn (n 3). C hai vn cn lu : + Cc yu t i xng (tm, trc, mt phng) + S t hp cc AO ca n nguyn t B t to ra c cc MO thch hp vi AO ca A. Di y xem mt s trng hp thng thng a. H2O H2O l phn t c gc. S phn b trong khng gian cc nguyn t trong H2O c hnh thnh nh sau: O trn trc z, 2H nm trong mt phng yz. 2H c 2AO-1s, chng ta to ra t hp + v -. O c 4 AO ha tr l 2s, 2px, 2py, 2pz. gii thch c tr s gc, lin kt do thc nghim xc nh c (104o28'), gi thit rng nguyn t O trong H2O c lai ha sp3. Hai t hp ca 2AO-1s ca 2H t hp vi 2 trong 4 AO-sp3 ny to ra 4MO- gm 2 MO lin kt, hai MO phn lin kt. Hai AO-sp3 cn li chuyn thnh MO tng ng. Ta c cu hnh ca H2O l [1s2]2122te23te24.Vy trong H2O c 2 lin kt b.CO2 CO2 l mt phn t thng, c lin kt khng nh c. gii thch gc thc nghim OCO = 180o, ngi ta gi thit rng C c lai ha sp. Nh vy trong C c 2 AO -sp di1, di2 v c 2 AO -p nguyn cht x v y. O c m in ln hn C, nn AO-2p c nng lng thp, s khng tham gia t hp tuyn tnh vi C to MO. Mi O c 3 AO-p tham gia t hp. Tng cp 2 AO-2p tng ng ca 2O: x v x, y v y, z vi z t hp + v -. ta c 6 t hp. Hai t hp ca 2AO-2pz s t hp vi 2 AO-sp ca C v chng ph hp nhau v trc i xng, to ra 4 MO- : 2 MO lin kt l 1, 2 v 2 MO phn lin kt *1, *2. Mt t hp cng ca 2 AO-2px nguyn cht ca C, to ra 2MO-x: x lin kt v *x phn lin kt Mt t hp cng ca 2 AO-2py nguyn cht ca C, to ra 2MO-y: y lin kt v *y phn lin kt 2 t hp - ca AO-x v AO-y s chuyn thnh 2 MO- khng lin kt ox v oy. Gin nng lng v kt qu s in e vo cc MO ca CO2 c trnh by trn hnh 12 2 2 2 2 o2 o2 Ta c cu hnh e ca CO2 l [1s 2 2s 2 ] 1 2 x y x y Vy trong CO2 gia 2 nguyn t O v nguyn t C c 2 lin kt v 2 lin kt ng lu l 2 lin kt ny c gii ta, ngha l 2 lin kt ny dng nh chung cho c 3 nguyn t. Do ta c th biu din cng thc cu to ca CO2 nh sau: O C O
11.PHC CHT I. Khi nim phc cht:

Nm 1967, nh bc hc ngi Nga Iaximirski a ra nh ngha v phc cht nh sau: Phc cht l hp cht to c cc nhm ring bit t cc nguyn t, ion hoc phn t vi nhng c trng sau: - C mt s phi tr. - Khng phn ly hon ton trong dung dch. - C thnh phn phc tp. Trong phn t phc cht thng gm hai phn: ion phc hay cn gi l cu ni v cc ion tri du vi ion phc gi l cu ngoi. Cu ni c to thnh bi nguyn t hoc ion kim loi, gi l ion trung GV:TRNG CHU THNH. Ti liu lu hnh ni b 54
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT tm lin kt trc tip vi cc phn t trung ha trung ha hoc ion bao xung quanh n. Cc ion hoc phn t trung ha ny gi l phi t, s phi t bao quanh ion trung tm gi l s phi tr. V d: K3[Fe(CN)6] th Fe(CN)63- l cu ni, K+ l cu ngoi, CN- l phi t v s phi tr l 6. II. Phn loi phc cht: Da vo in tch ca ion phc, ngi ta chia phc cht thnh 3 loi: 1) Phc cht cation:Cc phc cht cation thng c to thnh khi cc phn t trung ha phi tr xung quanh cation. VD: [Zn(NH3)4]Cl2; [Cr(H2O)6]Cl3. 2) Phc cht anion: Cc phc cht anion thng c to thnh khi cc anion phi tr xung quanh cation. VD: K2[BeF4]; Na3[AlF6]. 3) Phc cht trung ha: Cc phc cht ny c to thnh khi cc phi t trung ha v cc phi t tch in m phi tr xung cation. cc phc cht trung ha khng c cu ngoi. VD: [Co(NH3)3Cl3; [Pt(NH3)4Cl2]. III. Danh php quc t: - Trt t gi cc ion: cation ri n anion. - Tt c cc phi t anion tn cng bng ch "o", cc phi t trung ha gi nguyn tn, ring NH 3 gi amin, H2O gi aqu. Nu phi t l cation th thm ui "ium". -Trt t gi tn phi t : gi phi t mang in tch m trc, sau n phi t trung ha ri n phi t dng. Trc tn gi phi t t ch i, tri, tetra, penta, hexa... ch c 2, 3, 4, 5, 6... phi t . - Sau khi gi tn cc phi t th n gi tn nguyn t trung tm. * i vi phc anion: thm ui "at" vo sau tn anion v (s oxi ha ca ion trung tm). VD: Ca2[Fe(CN)6] : Canxi hexaciano ferat (II). Na[Co(CO)4] : Natri tetracacbonyl cobantat (-I) K4[Ni(CN)4] : Kali tetraciano nikelat (0). * i vi phc cation: khng thm ui "at" vo sau tn nguyn t trung tm, ch ghi s oxi ha ca ion trung tm trong du ngoc n. VD: [Pt(NH3)4Cl2]Cl2 :icloro tetraamin platin (IV) clorua. * i vi phc khng in ly: Khng thm ui "at" hoc s oxi ha ca ion trung tm. VD: [Pt(NH3)2Cl2] : icloro iamin platin. * Ch : Tn mt s kim loi theo ting La tinh: Ag: Argentum; Au: Aurum; Co:Cobaltum; Cr:Chromium; Cu: Cuprum; Fe:Ferrum; Pb: Plumbum; Sn: Stannum; Zn: zincum. IV. Cu to phc cht theo thuyt VB: Cc ni dung c bn: 1) Lin kt ho hc trong phc cht bao gm cc lin kt 2 electron, cc phi t c 2 electron khng phn chia ng vai tr cht cho electron, cc ion trung tm c cc obitan trng ng vai tr cht nhn electron, gia ion trung tm v phi t to thnh lin kt cho-nhn v phn ng to phc c xem nh phn ng axit-baz. 2) S xen ph cng ln th lin kt cng bn. Mun vy, trc khi to thnh lin kt, cc obitan trng ca ion trung tm lai ha vi nhau to thnh cc obitan lai ha tng ng v s phi tr ca ion trung tm bng s obitan lai ha. Kiu lai ha ph thuc vo cu to electron ca ion trung tm v trong mt s trng hp ph thuc vo bn cht ca phi t. Ty thuc vo kiu lai ha ca ion trung tm m phc cht c cu trc ny hay cu trc khc. 3) Khi c obitan d ca ion trung tm tham gia lai ha, trong mt s trng hp, vic lai ha ngoi hay trong ph thuc vo s tng tc gia ion trung tm v phi t: phi t tng tc yu s to ra lai ha ngoi, phi t tng tc mnh s to ra lai ha trong. Mc tng tc gia phi t v ion trung tm gim dn nh sau: CO, CN- > NH3 > SCN- > H2O > OH- > F- > Cl- > Br- > I-. Mnh Trung bnh Yu GV:TRNG CHU THNH. Ti liu lu hnh ni b 55
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Phc cht c s lai ha ngoi th bn phc km bn hn phc cht c s lai ha trong v khi lai ha ngoi th mc nng lng ca cc obitan tham gia lai ha (ns, np, nd) khc nhau nhiu hn so vi khi lai ha trong ((n-1)d, ns, np). * c trng cho mc thun t ca mt cht, ngi ta dng mt i lng l momen t . Momen t lin h vi s electron c thn theo h thc: = [n(n + 2)]1/2 B (manheton Bo) trong , n: s electron c thn. VD: Xt s to thnh lin kt trong cc phc: [Cr(NH 3)6]3+ ; [NiCl4]2- ( t din); [Ni(NH)6]2+; [Ni(CN)4]2- (vung phng); [FeF6]4- ; [Fe(CN)6]4-.
12.PHN TCH V NHN BIT CATION

Da trn s khc nhau v tan ca cc hiroxit kim loi trong axit v baz kim nh NaOH, NH3 ; ngi ta chia cc cation thnh 6 nhm (cc cation thng gp) : - Nhm I : Cc kim loi kim Li+, Na+, K+, Rb+, Cr+, (Fr+) (v NH4+) - Nhm II : Cc kim loi kim th : Ca2+. Sr2+, Ba2+ (v Ra2+) - Nhm III : Cc cation to c mui clorua t tan : Ag+, Pb2+, Hg22+, Cu+, Au+ - Nhm IV : Cc cation to c hiroxit tan trong kim d : Be2+, Al3+, Cr3+, Zn2+, Sn2+, Sn2+, Sn4+. - Nhm V : Cc cation c hiroxit tan trong dung dch NH3 hoc dung dch hn hp NH3 + NH4Cl do to phc amin : Cu2+, Hg 2+, Ni2+, Cd2+, Co2+. - Nhm VI : Cc cation to c cc hiroxit t tan trong nc, tan trong axit : Fe3+, Fe2+, Mg2+, Mn2+. A. Cc cation kim loi kim (Nhm I) : Li+, Na+, K+, NH4+ I. Tnh cht chung : Cc cation nhm I u khng mu. - Hiroxit kim loi kim l baz mnh, - Ion kim loi kim : trung tnh - Ion NH4+ c tnh axit yu : NH4+ NH3 + H+ K = 10-9,24 II. Phng php nhn bit : 1. Da vo vo ngn la : Ly 1 dy Pt, tm HCl. t nng ngn la n kh cho n sch (mu ngn la khng i). Nhng u dy Pt vo dung dch th ri a vo ngn la : Li+: chi; Na+ : mu vng; K+ : mu tm Rb+, Cs+ : tm hng 2. Nhn bit NH4+ : Dng dung dch NaOH v qu tm () m. B. Cc cation kim loi kim th : Ca2+. Sr2+, Ba2+ I. Tnh cht chung : - Cc cation kim loi nhm II cng khng mu v c tnh axit yu M2+ + H20 MOH+ + H+ (K : rt b) - Cc mui cacbonat, sunfat u t tan, CaSO4 tan nhiu nht, mun hon ton ion Ca2+ di dng CaSO4 thng phi thm t ru etylic. II. S phn tch : D2 phn tch (3 git) + (D2 H2SO4 + Ru etylic) sunfat nhm II B
+ D2 Na2CO3 bo ho, t0 (nhiu ln) B cacbonat nhm II + D2 CH3COOH c (n tan) GV:TRNG CHU THNH. Ti liu lu hnh ni b 56
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT + D2 K2Cr2O7 BaCrO4 (vng) + D2 CaSO4 bo ho SrSO4 trng Sn2+, Ca2+ + D2 (NH4)2SO4 bo ho + D2 (NH4)2C2O4 CaC2O4 trng C. Cc cation kim loi to c mui clorua t tan (nhm III) : Ag+, Pb2+, (Hg22+) I. Tnh cht chung :Ion Ag+, Pb2+ : khng mu Ion Ag+c tnh axt rt yu, ion Pb2+ c tnh axit yu Ag+ + H2O AgOH + H+, K= 10-11,7; pH dung dch 0,01M 6,7 Pb2+ + H2O PbOH+ + H+, K= 10-6,18; pH dung dch 0,01M 4 II. S phn tch : D2 phn tch + D2 HCl 2M clorua nhm III + Nc, un nng Pb2+ + D2 KI PbI2 vng + D2 K2CrO4 AgCl (+ Hg2Cl2) + D2 NH3 2M Cc cation khc SrSO4
Ag(NH3)2Cl Hg + HgNH2Cl PbCrO4 vng + D2 HNO3 (en) Tan trong OHAgCl trng D. Cc cation kim loi to c hiroxit tan trong OH- d (Nhm IV) : Al3+, Cr3+, Zn2+ S phn tch : + Clorua nhm III D2 phn tch D2 HCl 2M + D2 H2SO4 1M (+ C2H5OH) Sunfat nhm II
+ D2 NaOH 2M d (n c) + 3 - 5 git H2O2, t0 + 1/4 V d2 NaOH 2M + NH4Cl rn, t0 Zn(NH3)42+, CrO42(C cn cn V) + D2 AgNO3 (+ vi git d2 HNO3)
Hiroxit cc nhm khc Al(OH)3 trng keo + D2 HNO3 1M + D2 Na2S 57
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Ag2CrO4 gch ZnS trng 2+ E. Cation to c hiroxit tan trong NH3 d (Nhm V) : Cu (Ag+, Zn2+) NH3 to vi Cu2+ phc mu xanh m bn, rt c trng (Phn ng dng pht hin ion Cu2+) Cu2+ + 4NH3 Cu(NH3)42+ 4 = 1012,03 2+ Phc Cu(NH3)4 d b phn hu bi axit v di tc dng ca ion S2- to t tan: Cu(NH3)2+ + 4H+ Cu2+ + 4NH4+ Cu(NH3)2+ + S2CuS + 4NH3 F. Cc cation to hiroxit t tan trong kim d v trong dung dch NH3 (Nhm VI): Fe3+, Fe2+, Mg2+, Mn2+. S phn tch: D2 phn tch (nhm VI) + D2 NaOH 2M + H2O2, to Mg(OH)2, Fe(OH)3, MnO(OH)2 + D2 HNO3 2M, t0 MnO(OH)2 + (PbO2 + HNO3 c), t0 MnO4-, tm B Mg2+, Fe3+ + D2 NH3 2M Fe(OH)3 nu Mg2+ + D2 Na2HPO4
MgNH4PO4 trng Ch : Cc ion Fe2+ v Fe3+ phi c pht hin t dung dch u v trong qu trnh phn tch, ho tr ca chng thay i. * Phn ng pht hin Fe2+ : Dng K3[Fe(CN)6] Fe2+ + Fe(CN)63Fe3[Fe(CN)6]2 (Xanh tuc bin) Phi thc hin pH < 7, khng c mt cht oxi ho Fe2+ khng b oxi ho. (Thuc th khng to vi Fe3+) * Phn ng pht hin Fe3+: c 2 phng php: 1. Fe3+ + Fe(CN)64Fe4[Fe(CN)6]3 (xanh ph) Phi thc hin pH < 7, khng c mt cht kh Fe3+ khng b kh thnh Fe2+ 2. Fe3+ + nSCNFe(SCN)n(3-n)+ (n = 1 5) (Mu mu) Phi thc hin mi trng axit mnh v pH = 2 c Fe(OH)3 lm ph hu phc.
58
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT PHN TCH V NHN BIT ANION Bng tnh tan ca mt s mui thng gp Mui NO3SO42ClBrIFCH3COOH2PO4HPO42PO43HCO3CO23SO32S2S2O32T/c chung Tan Tan Tan Tan Tan Khng tan Tan Tan Khng tan Khng tan Tan Khng tan Khng tan Khng tan Tan Ngoi tr Khng BaSO4, SrSO4, PbSO4, CaSO4 (I), AgSO4 (I) AgCl, HgCl, CuCl, PbCl2 (I) AgBr, HgBr, CuBr, PbBr, PbBr2, HgBr2 (I) AgI, CuI, PbI2, HgI2 Mui kim loi kim, NH4+, Ag+, Hg2+, Sn2+, Be2+, Al3+ Mui ca KL kim, NH4+ Mui ca KL kim, NH4+ (Li3PO4 khng tan) Mui ca KL kim, NH4+ (Li2CO3 t tan) Mui ca KL kim, NH4+ Mui ca KL kim, NH4+, Ca2+, Sr2+, Ba2+ BaS2O3, CaS2O3 PbS2O3, Hg2S2O3, Ag2S2O3
* Ch : Cc mui CO32-, SO32- v S2- ca nhng ion Al3+, Fe3+ v Cr3+ khng tn ti trong dung dch (ngoi tr Fe2S3 c tn ti v khng tan trong nc). I. Anion halogenua : 1. Phn ng pht hin ion FKhi c mt F- th phc cht st (III) thioxinat mt mu do chuyn thnh phc cht khng mu VD : Fe(SCN)3 + 3FFeF3 + 3SCN- , K = 105,66 2. Phn ng pht hin ion Cl-, Br-, I- trong dung dch hn hp c cha cc anion : * Pht hin ion Cl-: Dng dung dch AgNO3 : to c kt ta (AgCl (mu trng), AgBr : (trng ng), AgI: (mu vng nht)). Lc ly kt ta, ho tan trong dung dch NH3 long, AgCl b ho tan: AgCl + 2NH3 Ag(NH3)2+ + ClLc b kt ta, ly dung dch nc lc cho vo vi git dung dch HNO3, xut hin kt ta trng, suy ra trong dung dch ban u c ion ClAg(NH3)2+ + 2H+ Ag+ + 2NH4+ Ag+ + ClAgCl * Pht hin ion Br v I : - Cho vi git h tinh bt v vi git CCl4 vo dung dch mu th. - Cho t t dung dch nc clo n d vo, lc u, dung dch chuyn thnh mu xanh, sau mt mu, ng thi lp dung mi hu c c mu vng, suy ra trong dung dch ban u c ion I- v BrCl2 + 2I2Cl- + I2 Cl2 + 2Br 2Cl- + Br2 5Cl2 + I2 + 6H2O 10Cl- + 2IO3- + 12H+ (Cl2 d khng oxi ho c Br2) II. Anion ca lu hunh 1. Phn ng pht hn ion S2- : * Phn ng vi dung dch HCl : dung dch HCl phn ng vi cc dung dch mui sunfua cho H 2S bay ra, ho en giy tm dung dch Pb(CH3COO)2 (hoc dung dch Pb(NO3)2). * Phn ng vi d2 AgNO3 : Khi c KCN th khng to thnh cc mui kh tan khc ca Ag+, trong khi th c Ag2S mu en to thnh (v Ag2S rt t tan, Tt (Ag2S) = 10-49,2) 2. Phn ng pht hin ion SO32-: GV:TRNG CHU THNH. Ti liu lu hnh ni b 59
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Cc axit mnh tc dng vi SO32- cho kh SO2 bay ra, nhn bit SO2 bng giy tm dung dch Br2 hoc dung dch KMnO4 (mt mu). SO2 + Br2 + 2H2O H2SO4 + 2HBr 5SO2 + 2KMnO4 + 2H2O K2SO4 + 2MnSO4 + 2H2SO4 Cng c th cho kh bay ra li vo dung dch Ba2+ c HCl v H2O2. Khi SO2 b oxi ho thnh H2SO4 v ta c BaSO4 * Ch : Cc ion S2-, S2O32- cho phn ng tng t 3. Phn ng pht hin ion SO42-- : Trong mi trng axit, ion Ba2+ to vi ion SO42- kt ta trng * Ch : Mt s cht kh nh S2-, SO32-, S2O32- b oxi ho trong mi trng axit, trung tnh hoc kim cho ion SO42-. 4. Phn ng pht hin ion thiosunfat S2O32* Phn ng vi dung dch AgNO3 2Ag+ + S2O32- Ag2S2O3 vng Ag2S2O3 b phn hu khi un nng to thnh Ag2S mu en. Ag2S2O3 + H2O Ag2S + H2SO4 * Phn ng vi dung dch hn hp I3- v h tinh bt D2 mu xanh ca iot - h tinh bt (I2 + KI + h tinh bt) b mt mu khi tc dng vi dung dch S2O32- pH 7 do I3- b S2O32- kh: I3- + 2S2O323I- + S4O62III. Anion ca nit, photpho 1. Phn ng pht hin ion NO2* Ion MnO4- b mt mu khi tc dng vi dung dch NO2- trong mi trng axit v b kh thnh Mn2+: 5HNO2 + 2MnO4- + H+ 5NO3- + 2Mn2+ + 3H2O * Ion NO2 trong mi trng axit oxi ho ion I- thnh ion I3- mu nu nht hoc ho xanh trong dung dch h tinh bt : 2HNO2 + 3I2NO + I3- + 2H2O Ch : Nhiu cht oxi ho cho phn ng tng t 2. Phn ng pht hin ion NO3-: Phn ng vi Cu v dung dch H2SO4 3Cu + 2NO3- + 8H+ 3Cu2+ + 2NO + 4H2O Kh NO bay ra ho nu trong khng kh : NO + 1/2O2 NO2 (mu nu) 3. Phn ng pht hin ion PO43-: 3Ag+ + PO43Ag3PO4 (vng) 2- * Ch : Cc ion CO3 , I cho phn ng tng t IV. Anion ca cacbon, silic 1. Phn ng pht hin ion CO32- : Phn ng vi dung dch axit mnh. Axit mnh tc dng vi ion CO32- gii phng CO2. nhn bit CO2 c th dng nc vi trong hoc nc barit (dung dch Ba(OH)2) : dung dch ho c nu CO2 d th tr li trong sut. * Ch : Cc ion SO32-, S2O32- cho phn ng tng t. 2. Phn ng pht hin ion CH3COO-: * To phc vi Fe3+: Ion CH3COO- to phc mu ch vi ion Fe3+ : Fe3+ + nCH3COOFe(CH3COO)n(3-n)+ (n : 1-3) Khi un nng xut hin nu Fe(OH)2CH3COO. * Phn ng CH3COOC2H5 : Khi c H2SO4 c : CH3COOH + C2H5OH CH3COOC2H5 + H2O CH3COOC2H5 c mi c trng GV:TRNG CHU THNH. Ti liu lu hnh ni b 60
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Tc phn ng tng nhanh khi un nng v c mt t AgNO3 hoc Ag2SO4 xc tc cho phn ng. 3. Phn ng pht hin ion oxalat C2O42-: * Phn ng vi dung dch KMnO4: Trong dung dch H2SO4, ion CO42- lm mt mu dung dch KMnO4 khi un nng v cho kh CO2 bay ra : 5C2O42- + 2MnO4- + 16H+ 10CO2 + 2Mn2+ + 8H2O * Phn ng vi mui Ca2+: Ca2+ + C2O42CaC2)4 (trng) CaC2O4 khng tan trong CH3COOH nhng tan trong dung dch axit v c mnh. 4. Phn ng pht hin ion SiO32- : Khi axit ho dung dch SiO32- th to thnh trng keo (hoc dung dch keo) 2H+ + SiO32- + nH2O H2SiO3. nH2O BI TP Bi 1 (Cu I.3 HSG QG 2000 2001): C cc dung dch (b mt nhn): a) BaCl2; b) NH4Cl; c) K2S; d) Al2(SO4)3; e) MgSO4; g) KCl; h) ZnCl2. c dng thm dung dch phenolphtalein (khong pH chuyn mu t 8 10) hoc metyl da cam (khong pH chuyn mu t 3,1 4,4). Hy nhn bit mi dung dch trn, vit cc phng trnh ion (nu c) gii thch. Bi 2 (Cu I.2 HSG QG 2002 2003): Trong phng th nghim c cc dung dch b mt nhn: AlCl3, NaCl, KOH, Mg(NO3)2, Pb(NO3)2, Zn(NO3)2, AgNO3. Dng thm mt thuc th, hy nhn bit mi dung dch. Vit cc phng trnh phn ng (nu c). Bi 3 Trnh by phng php nhn bit cc ion trong dung dch c cha cc ion: a) Na+, Ca2+, Sr2+, Ba2+ b) Ca2+, Sr2+, Ba2+, Fe3+, Mg2+ c) Ag+, Pb2+, Fe3+, Mg2+, Al3+, Cr3+ d) Ag+, Cu2+, Zn2+, Al3+, Fe3+ - 2e) F , Cl , I , SO4 f) NO3-, SO42-, SO32-, CO32g) NO2-, NO3-, PO43-, CO32h) S2O32-, NO2-, CO32-, SO42-. BI GII Bi 1: Dng phenolphtalein nhn ra K2S S2+ H2O = HS + OH pH > 10 dung dch phenolphtalein c mu Dng K2S lm thuc th. Cho K2S vo cc dung dch cn li: to - Vi NH4Cl : S-2 + NH4+ = NH3 - Vi Al2(SO4)3 : Al3+ Mg2+ + + Cho kt ta keo trng Al(OH)3 3 H2O 2 H2O = = = Al(OH)3 Mg(OH)2 ZnS + 3 HS-
HS-
Nhn ra NH3 nh mi khai, hoc ho giy lc tm phenolphtalein ( v NH3 c pH > 9 ). 3 S2- + 2 S2- +
- Vi MgSO4 : Cho kt ta trng Mg(OH)2 + 2 HS- Vi ZnCl2 : Cho kt ta trng ZnS Zn2+ + 2 S2-
61
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Dng NH4Cl nhn ra MgSO4: kt ta Mg(OH)2 tan c trong NH4Cl ; trong khi cc kt ta Al(OH)3 v ZnS khng tan. Mg(OH)2 + 2 NH4+ = to Mg2+ + 2 NH3
H2O
Dng MgSO4 nhn ra BaCl2: Ba2++ SO42= Dng BaCl2 nhn ra Al2(SO4)3 : BaSO4 trng BaSO4 trng
Cn li l KCl. Ba2++ SO42= (Hoc dng metyl da cam lm thuc th: Nhn ra Al2(SO4)3 Al2(SO4)3 Al3+ + 2 Al3+ H2O = AlOH2+ + +
3 SO42H+
Dung dch c phn ng rt axit ( pH < 4 ) lm cho metyl da cam c mu da cam hoc hng. Cc dung dch cn li u c pH > 4,4 nn metyl da cam c mu vng. Dng Al2(SO4)3 lm thuc th: - Vi BaCl2 cho kt ta trng tinh th - Vi K2S cho kt ta keo trng Al(OH)3 Al3+ + 3 S2- + 3 H2O = to Al(OH)3 + 3 HSDng K2S lm thuc th: Ba2+ + SO42= BaSO4 trng
- Vi NH4Cl : S2+ NH4+ = NH3 + Nhn ra NH3 nh mi khai, hoc ho giy lc tm phenolphtalein. - Vi MgSO4 : Cho kt ta trng Mg(OH)2 Mg2+ + 2 S2- + 2 H2O = = Mg(OH)2 ZnS
HS-
2 HS-
- Vi ZnCl2 : Cho kt ta trng ZnS Zn2+ + 2 S2-
- Vi KCl khng c du hiu g. phn bit MgSO4 vi ZnCl2 , cho NH4Cl vo 2 kt ta Mg(OH)2 v ZnS th ch c kt ta Mg(OH)2 tan trong NH4Cl khi un nng to + Mg(OH)2 + 2 NH4 = Mg2+ + 2 NH3 + H2O (cn ZnS khng tan.) Bi 2: C th dng thm phenolphtalein nhn bit cc dung dch AlCl3, NaCl, KOH, Mg(NO3)2, Pb(NO3)2, Zn(NO3)2, AgNO3. * Ln lt nh vi git phenolphtalein vo tng dung dch. - Nhn ra dung dch KOH do xut hin mu ta. * Ln lt cho dung dch KOH vo mi dung dch cn li: - Dung dch AgNO3 c kt ta mu nu Ag+ + OH AgOH ; (hoc 2Ag+ + 2OH Ag2O + H2O) - Dung dch Mg(NO3)2 c kt ta trng, keo Mg2+ + 2OH Mg(OH)2 - Cc dung dch AlCl3, Pb(NO3)2, Zn(NO3)2 u c chung hin tng to ra kt ta trng, tan trong dung dch KOH (d). GV:TRNG CHU THNH. Ti liu lu hnh ni b 62
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Al3+ + 3OH Al(OH)3 ; Al(OH)3 + OH AlO2 + 2H2O Pb2+ + 2OH Pb(OH)2 ; Pb(OH)2 + OH PbO2 + 2H2O Zn2+ + 2OH Zn(OH)2 ; Zn(OH)2 + OH ZnO2 + 2H2O - Dung dch Nacl khng c hin tng g - Dng dung dch AgNO3 nhn ra dung dch AlCl3 do to ra kt ta trng Ag+ + Cl AgCl - Dng dung dch NaCl nhn ra dung dch Pb(NO3)2 do to ra kt ta trng Pb2+ + 2 Cl PbCl2 - cn li l dung dch Zn(NO3)2.
13.CACBOHIDRAT
I. nh ngha: Gluxit hay ng l nhng thut ng ch cc hp cht hu c khng mu, t nhiu c v ngt, d tan trong nc, d kt tinh, c tm thy trong ng vt v thc vt, v a s c cng thc chung Cn(H2O)m. Do vy chng cng c gi l cacbohidrat mc d kh nhiu cacbohidrat cn c c N, S v khng c v ngt nh cc gluxit. Ngi ta cn gi cc cacbohidrat l saccarit (ting Hy lp: ng). Tn gi ca cc ng ring bit c kt thc bng ui oz II. Phn loi: Da vo thnh phn v tnh cht, cc cacbohidrat c phn loi thnh: 1. Cacbohidrat n gin (hay monosaccarit) l nhng hp cht khng th thy phn c. Chng thng tan trong nc. TD: glucoz, fructoz 2. Cacbohidrat phc tp l nhng hp cht m khi thy phn hon ton cho monosaccarit. Gluxit phc tp gm: a. Oligosaccarit l nhng hp cht to nn t 2 10 phn t monosaccarit. TD: Disaccarit nh saccaroz, mantoz, lactoz. Trisaccarit nh rafinoz. Tetrasaccarit nh stachioz b. Polisaccarit (glycan) l nhng hp cht c to nn t > 10 n hng vn phn t monosaccarit. TD: Tinh bt, xenluloz, glycozen . MONOSACCARIT Monosaccarit l hp cht thuc loi polihidroxicacbonyl, tc l phn t ca chng c cha nhm C=O v nhiu nhm OH cc nguyn t cacbon k nhau TD: Glucoz: CH2 CH CH CH CH CH=O Fructoz CH2 CH CH CH C CH2 OH OH OH OH OH OH OH OH OH OH O I. Phn loi: 1. Phn loi theo nhm C=O Nu nhm cacbonyl trong phn t l andehit (nh glucoz) th gluxit c gi l anoz, cn nu nhm cacbonyl l xeton (nh fructoz) th gluxit c gi l xetoz 2. Phn loi theo s cacbon: Phn t c 2C gi l bioz, 3C gi l trioz, 4C gi l tetroz, 5C gi l pentoz, 6C gi l hexoz, 7C gi l heptoz, Andoz: c 2C nh glycoandehit HOCH2-CHO, andotrioz (c 3C) nh HOCH2-CHOH-CHO (glyxerandehit), andotetroz (c 4C) nh erythroz v threoz, andopentoz (c 5C) nh riboz, andohexoz (c 6C) nh glucoz, fructoz, mannoz, galactoz Cc ng phn lp th ca monosaccarit Trong phn t monosaccarit c n nguyn t cacbon bt i th s c 2n ng phn quang hc CH2 CH CH=O (glixerandehit) c 1 cacbon bt i nn c 2 ng phn quang hc OH OH H CH=O OH HO CH=O H
TD:
CH2OH CH2OH (D-Glixerandehit) (L-Glixerandehit) TD: CH2 CH CH CH=O OH OH CHU THNH. Ti liu lu hnh ni b GV:TRNG OH
63
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT andotetroz c 2 cacbon bt i nn c 22 = 4 ng phn quang hc (hay 2 cp i quang) CH=O H H OH HO H HO H H H H OH HO HO H CH2OH CH2OH CH2OH CH2OH D(-)-Erythroz L-(+)-Erythroz D(-)-Threoz L (+)-Threoz CH CH CH=O Andopentoz c 3 cacbon bt i nn c 23 = 8 ng phn quang hc (hay CH2 CH 4 cp i quang) OH OH OH OH CH=O H OH H OH H OH CH2OH D-Riboz CH=O HO H HO H OH H CH2OH D-Lixoz CH2 CH CH OH OH OH CH=O CH=O CH=O CH=O CH=O H OH H OH HO HO H HO H H HO H H HO HO H OH H H OH HO H H OH OH HO H H HO H CH2OH CH2OH CH2OH CH2OH CH2OH L-Riboz D-Arabinoz L-Arabinoz D-Xiloz L-Xiloz CH=O H OH H OH H HO CH2OH L-Lixoz CH CH CH=O Andohexoz c 4 cacbon bt i nn c 24 = 16 ng phn quang hc (hay 8 cp i quang) OH OH CH=O OH OH CH=O CH=O
CH=O CH=O CH=O CH=O CH=O CH=O H OH H OH H H OH HO H HO H HO H H H OH HO H HO H HO H OH OH H H H H HO OH HO H OH HO H OH H H H H OH HO OH HO H H OH HO CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH D-Anloz L-Anloz D-Antroz L-Antroz D-Glucoz L-Glucoz CH=O CH=O CH=O CH=O CH=O CH=O H H OH H OH H H H HO HO HO OH H H HO H OH OH H HO HO H OH H H H OH OH H HO H HO H HO H OH H OH H H OH HO HO H OH HO H H CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH D-Mannoz L-Mannoz D-Guloz L-Guloz D-Idoz L-Idoz CH=O CH=O CH=O CH=O H HO H HO H H OH OH HO OH HO H H H H OH HO H H HO H OH H OH H H H OH HO OH HO H CH2OH CH2OH CH2OH CH2OH D-Galactoz L-Galactoz D-Taloz L-Taloz Cng thc chiu Fischer ca cc xetohexoz
64
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH C O H OH OH CH2OH D-Fructoz CH2OH HO H H C O H HO HO H H OH CH2OH D-Tagatoz H HO HO C O OH H H CH2OH L-Fructoz CH2OH C O OH OH H CH2OH L-Tagatoz H H H C O OH OH OH CH2OH D-Pxicoz HO HO HO C O H H H CH2OH L-Pxicoz H HO H C O OH H OH CH2OH D-Soboz HO H HO C O H OH H CH2OH L-Soboz
H H HO
65
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT * ng phn i quang: Cc cp ng phn D v L i xng vi nhau nh vt v nh qua gng, nhng khng th lng kht vo nhau gi l ng phn i quang hay enantiomer (hoc antipode) TD: CH=O CH=O CH=O CH=O H OH H H HO H HO OH H OH HO OH HO H H H H HO HO H H H OH OH H H OH H H HO OH HO CH2OH CH2OH CH2OH CH2OH D (+)-Glucoz L (-)-Glucoz D (+)-Galactoz L (-)-Galactoz Khi trn ln hai ng phn ca mt cp i quang vi t l ng phn t th s to ra bin th raxemic. Bin th raxemic khng hot ng quang hc v c s b tr nng sut quay cc sang phi v sang tri. * ng phn quang hc thng (hay ng phn dia) (diastereomer) ng phn quang hc thng l ng phn quang hc ca nhau nhng khng i quang. TD: trong 16 ng phn quang hc ca andohexoz c 8 cp i quang, mi cp i quang c 14 ng phn cn li l ng phn dia ca chng * ng phn epime Hai monoz l ng phn epime ca nhau khi chng ch khc nhau v cu hnh 1 nguyn t cacbon bt i, cn cu hnh ca cc nguyn t cacbon khc hon ton ging nhau CH=O CH=O H OH (2) HO H H H OH OH H OH H OH H H OH OH CH2OH CH2OH D-(+)-Anloz D-(+)-Antroz
Hai epime ch khc nhau cacbon bt i s 2

Cu hnh dng vng ca cc monoz Cu trc dng mch h ca cc monoz khng gii tch c nhng hin tng v cc phn ng ca n sau y: - Nh chng ta xc lp c cu to ha hc ca D-Glucoz, n l mt pentahidroxiandehit. Mc d c nhm chc andehit nhng D-Glucoz li khng tham gia phn ng cng vi natri bisunfit NaHSO3 v khng lm hng thuc th Ship - Nhm OH hemiaxetat Khi cho D- Glucoz un nng vi ancol metylic c hidroclorua khan xc tc th ch c 1 nhm OH c metyl ha to ra sn phm metyl glucozit c tnh cht tng t axetal. Metyl glucozit l mt ete, khng cho phn ng ca nhm andehit nhng d b thy phn trong dung dch axit cho li sn phm u. Nu tip tc cho metyl glucozit tc dng vi metyl iodua CH3I v AgOH th 4 nhm OH cn li c metyl ha cho sn phm l tetrametyl glucozit. Khi thy phn sn phm ny bng axit v c long, ch c 1 nhm CH3 lc u tch thnh ancol metylic, cn 4 nhm CH3 metyl ha sau vn tn ti cho sn phm l tetrametyl glucoz, c tnh cht c trng ca nhm andehit nh glucoz. Nh vy, D-(+)-glucoz c mt nhm OH c bit khc vi 4 nhm OH cn li. Ngi ta gi nhm OH c bit ny l OH hemiaxetal (hay OH bn axetal) D-(+)-glucoz c hin tng quay h bin (hay s i quay). Khi ha tan D-(+)-glucoz tinh th, c nhit nng chy 1460C vo nc th nng sut quay cc lc u ca dung dch l +1120, nhng dn dn gim xung cn +52,70. Mt khc, nu ha tan tinh th D(+)-glucoz, c im nng chy 1500C vo nc th nng sut quay cc ca dung dch lc u l +190, dn dn tng ln +52,70 GV:TRNG CHU THNH. Ti liu lu hnh ni b 66
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT - Andohexoz dng mch h c 16 ng phn quang hc, cn xetohexoz c 8 ng phn quang hc, nhng thc t s ng phn quang hc ca chng l rt nhiu Tt c cc mu thun trn c th c gii p dc trn c s cu trc dng mch vng ca Dglucoz Cng thc cu hnh dng vng theo Haworth ca mt s andohexoz CH2OH CH2OH CH2OH H H H O OH O OH O H H H H H OH H OH HO H HO H HO OH OH OH OH H -D-Anlopiranoz -D-Antropiranoz CH2OH CH2OH H O OH HO O H H H H H OH OH HO H H OH H OH -D-Glucopiranoz CH2OH H O H H OH OH HO OH H OH -D-Glucopiranoz CH2OH HO O OH H H OH H H H OH -Galactopiranoz
H OH -D-Galactopiranoz CH2OH H O OH H OH OH HO H
H H H H -D-Mannopiranoz -Mannopiranoz Xt s to vng ca D-Glucoz S vng ha ca D-glucoz xy ra do s tng tc ca nhm C=O (C1) vi nhm OH C4 hac C5 tng t s hnh thnh hemiaxetal khi cho andehit tc dng vi ancol H OR ROH C H R O H CH C OR H 2O OR O OH Hemiaxetal CH2OH H C OH O 5 H CH C1 CH
3 6
axetal
HO
CH
2
HO
OH
67
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT CH2OH CH2OH H H O H O OH H H H H OH OH HO OH HO H H OH H OH -D-Glucopiranoz -D-Glucopiranoz Dng v ca D-(+)-glucoz khng phi l i quang ca nhau, n l 2 ng phn dia v gi l ng phn anome. Hau ng phn anome c th chuyn ha ln nhau trong dung dch. Hin tng quay h bin l do s d dng m v ng vng ca cc dng hemiaxetal ca D-(+)-Glucoz S metyl ha bng ancol metylic khi c mt hidroclorua khan hnh thnh 2 dng ng phn v -metyl glucozit l do nhm OH hemiaxetal linh ng hn cc nhm OH khc trong phn t v d metoxi ha hn. CH2OH CH2OH H H O H O H H CH3OH H H H2 O H HO OH HCl HO OCH3 HO OH H OH -D-Glucopiranoz CH2OH H H OH HO O H H OH CH3OH HCl OH H -metyl glucozit CH2OH H H HO HO O H H OCH3 H2 O
OH H OH H -D-Glucopiranoz -metyl glucozit Cc metyl glucozit c th coi nh tng ng vi axetal hon ton, chng khng c hin tng quay h bin v khng c tnh kh nh glucoz. Chng kh bn trong nc cng nh trong dung dch baz. Chng b thy phn trong dung dch axit khi un nng v ti to li dng hemiaxetal ban u. Cc monoz khc tng t nh D-(+)-Glucoz cng tn ti di dng ng phn anome, cho quay h bin v tham gia phn ng metyl ha nh cho glicozit ring Nhm OH cacbon s 4 hoc s 5 tng tc vi nhm cacbonyl cacbon s 1 to vng 5 hoc 6 cnh. Nu to vng 5 cnh gi l furanoz cn vng 6 cnh gi l piranoz Cng thc Haworth Cng thc Tollen Cng thc Haworth CH2OH CH2OH 1 1 H OH HO 2 O H H 2 O H OH OH H H 3 3 H O HO O HO HO H HO 4 4 OH OH HO OH HO OH 5 5 OH 6 CH OH H 6 CH OH OH 2 2 H -D-Glucopiranoz -D-Glucopiranoz
68
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT CH=O H HO H H OH H 4 OH 5 OH 6 CH OH 2 D- Glucoz
3 2 1
-D-Glucopuranoz
CH2OH
1
CH OH OH H H
O H
H HO OH OH
2 3 4
OH OH
HO O HO
1 2 3 4 5 CH OH 6 CH
-D-Glucofuranoz CH2OH
OH CH OH O H H OH O H H OH OH
5 CH OH 6 CH
-D-Glucofuranoz -D-Glucofuranoz Cc xetohexoz cng c cu trc dng vng nh vy. TD: vi fructoz
HOCH2
5 6
2OH
2OH
O HO
3
CH2OH
2
H
4
OH
OH
HOCH2 C OH 3 HO H 4 OH O 6 5 HOCH2 H
HOCH2 C CH2OH 3 HO H 4 O OH 5 HOCH2 H
HOCH2
5
O HO
OH
2
H
4
H OH
3 1
CH2OH
-D-Fructofuranoz
CH2OH
2C 1
-D-Fructofuranoz
HO H H HOCH2
5 6
3 4 5 6 CH
O H OH OH
2OH
O HO
3
CH2OH
2
HOCH2
5
O HO
OH
2
H
4
OH
H
4
OH
3 1
CH2OH
-D-Fructofuranoz II. L tnh ca cc monoz Cc monoz l nhng cht rn kt tinh, khng mu, d tan trong nc, kh tan trong ancol, khng tan trong ete, clorofom v cc hidrocacbon. Khi un nng cc monoz d b phn hy Cc dung dch monoz c tnh cht trung tnh v c v ngt khc nhau. Nh D-fructoz ngt gp 3 ln D-glucoz. Cc dung dch monoz u c tnh quang hot v c nng sut quay cc khc nhau. Chng u c hin tng quay h bin gia cc ng phn anome v III. Ha tnh: Xt v mt cu to th cc monoz l cc polihidroxiandehit hay polihidroxixeton nn ha tnh ca chng ch yu l tp trung vo 2 nhm chc ny 1/ Phn ng ca nhm cacbonyl:
GV:TRNG CHU THNH. Ti liu lu hnh ni b 69
H OH -D-Fructofuranoz
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Phn ng oxi ha: - Tc dng vi thuc th Tollens (phn ng trng gng) t0 HOCH2-(CHOH-)4CHO + 2[Ag(NH3)2]OH HOCH2-(CHOH-)4COONH4 + 3NH3 + H2O + 2Ag - Tc dng vi thuc th Felinh HOCH2-(CHOH-)4CHO HOCH2-(CHOH-)4COONa + Cu2O + gch Thuc th Felinh l phc ng vi mui natrikali tactrat c mu xanh thm trong mi trng kim Thuc th Felinh c iu ch t dung dch CuSO4 v dung dch mui kp natrikali tactrat trong NaOH. Khi trn 2 dd vi nhau c cc phn ng: CuSO4 + 2NaOH Na2SO4 + Cu(OH)2 Cu(OH)2 to ra tc dng vi mui natrikali tactrat do to phc tan mu xanh thm bn trong mi trng baz COONa COONa COONa H CHOH CH O 2 Cu(OH)2 Cu O CH 2 H2 O CHOH CH O O CH H COOK COOK COOK
NaOOC[CHOH]2COOK Cu(OH)2, NaOH
Thuc th Felinh tc dnng vi hp cht hu c cha nhm CHO to kt ta gch Cu2O COONa COONa H CH O CHOH R CH=O 2 Cu O CH NaOH H2O R COONa 4 CH O O CH CHOH H COOK COOK COOK Khi cho D-glucoz tc dng thuc th Felinh c th vit theo phng trnh sau: COONa CHO H HO H H OH H OH OH 2 Cu(OH)2 NaOH t
o
COONa
Cu2O
H HO H H
OH H OH OH
Cu2O
3 H2 O
CH2OH CH2OH Hai phn ng trn khng dng phn bit andoz v xetoz. Cc xetoz nh D-fructoz mc d trong phn t khng c nhm andehit nhng vn kh c cc ion Ag+ hoc Cu2+ v 2 phn ng ny u tin hnh trong mi trng kim, cc monoz c s ng phn ha qua dng endiol -Tc dng vi nc brm: Cc anoz b oxi ha thnh axit anonic HOCH2-(CHOH-)4CHO + Br2 + H2O HOCH2-(CHOH-)4COOH + 2HBr O Trong mi trng axit cc axit anonic d bin thnh lacton
C
HOCH2-(CHOH-)4COOH
-H2O
H HO H
OH H O OH CH2OH
( -D-Gluconolacton)
Phn ng vi dd Br2 khng xy ra vi xetoz v dd Br2 c tnh axit khng gy ra s ng phn ha nh kim. C th dng phn ng vi dd Br2 phn bit anoz v xetoz
70
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT CH OH CHO CHO HO C OH H H OH HO H HO HO H OH OH H OH OH H OH H H OH H OH OH H CH2OH CH2OH CH2OH
(D-Glucoz) (Dng endiol)
OH CH2OH C O H HO OH H OH H CH2OH
(D-Mannoz)
(D-Fructoz)
Kh ha thnh ancol ng: Nhm cacbonyl ca monosaccarit b kh ha thnh polyancol bi natri bohidrit hay bi hidro ha xc tc
CHO H HO H H OH H OH OH CH2OH D-Glucoz

CHO HO H H OH H HO H HO CH2OH
CH2OH H2 Ni t
o
H HO H H
OH H OH OH CH2OH
D-Sorbitol
CH2OH H2 Ni to H HO H H OH H OH OH CH2OH
L-Glucoz D-Sorbitol Khi nhm oxo trong xetoz b kh th mt tm bt i mi c to thnh v c mt i ng phn dia TD: D-sorbitol v D-mannitol nhn c t D-fructoz CH2OH CH2OH CH2OH C O H OH HO H HO H H HO HO H H2 H2 H OH o OH H OH H Ni to Ni t H OH H OH OH H CH2OH D-mannitol Phn ng to osazon Cc anoz c nhm CH2OH D-fructoz CH2OH D-Sorbitol
CH CH=O khi tc dng vi hidrazin hay phenylhidrazin (c s mol OH
gp 3 ln) cho sn phm bis-1,2-hidrazon gi l osazon. Osazon thng l nhng sn phm kt tinh, d tch ra khi hn hp phn ng GV:TRNG CHU THNH. Ti liu lu hnh ni b 71
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT CH=O CHOH [CHOH ] n CH2OH CH N NH CHOH [CHOH ] n CH2OH CH N NH C6H5 C O [CHOH ] n CH N NH CHOH [CHOH ] n CH2OH CH N NH C O [CHOH ] n CH2OH CH N NH C6H5 C N NH C6H5 [CHOH ] n
NH NH2
H2 O
NH NH2
NH2
NH3
C6H5 NH NH2
H 2O
CH2OH CH2OH osazon S hnh thnh osazon khng ch gii hn i vi cacbohidrat m rt c trng i vi cc hp cht hidroxicacbonyl. S loi b cc nhm phenylhidrazin trong phn t osazon s to ra hp cht dicacbonyl v c gi l oson. TD: CH N NH C6H5 C N NH C6H5 2 H
+
CHO
CHO C O 2 CH N NH
osazon Cc xetoz cng to ra osazon CH2OH C O [CHOH ] n CH2OH 3 C6H5 NH NH2 C6H5 NH2 NH3 H2O
Phenylhidrazon CH N NH C6H5 C N NH C6H5 [CHOH ] n
CH2OH S to thnh osazon ch lin quan n cacbon s 1 v cacbon s 2 ca monoz, v vy cc anoz v xetoz c cu hnh t cacbon s 3 tr i ging nhau s cho cng mt osazon CHO CHO CH N NH C6H5 OH H H HO C N NH C6H5 HO H HO H H 3C6H5NHNH2 3C6H5NHNH2 HO H OH H OH H OH H OH CH3COOH H OH CH3COOH H OH CH2OH CH2OH CH2OH osazon CH3COOH 3 C6H5NHNH2
CH2OH C O HO H H OH H OH CH2OH D-fructoz GV:TRNG CHU THNH. Ti liu lu hnh ni b 72
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Phn ng to osazon rt quan trng trong vic nghin cu cc gluxit, n khng nhng dng nhn bit, tch bit v chuyn ha m cn dng thit lp cu hnh ca gluxit. Phn ng osazon ch to ra bishidrazon cn cc nhm OH sau khng phn ng tip na v osazon l sn phm bn do to phc vng cng (chelat) v lin kt hidro gia hidro vi oxi v nit C 6H 5 N CH C HC C 3H 7O 3 O H N H N N H C 6H 5
2/ Phn ng ca nhm hidroxyl V cu to monoz l polihidroxicacbonyl nn cc nhm hidroxyl v c bn ging tnh cht ca ru nhiu ln ru a/ Tc dng vi Cu(OH)2 Cc monoz tc dng vi Cu(OH)2 trong mi trng kim s cho phc mu xanh do tnh cht ca poliol. S to phc vng cng chelat vi ion Cu2+ l do 2 nhm hidroxi gn nhau (dng cis) to nn. Hai nhm hidroxi ny lin kt (e-e) hay lin kt (a-e) th c kh nng to phc, cn nu C1 v C2 dng trans lin kt (a-a) khng to phc c. Cc monoz v c nhiu nhm hidroxi nn khng ch to mt phc, v vy ngi ta t vit cc phc c th. Chng hn c nhiu kh nng to phc nh sau: hai nhm hidroxi ca D- -glucoz v tr cacbon s 3 v s 4
2 HO HO CH2OH O Cu(OH)2 HO OH OH
1
OH
2
H
3 5
O
4
O Cu O O H
CH2OH
5 3 2
O
1
2 H2O
HOCH2
6
HO
OH
-D-Glucopiranoz b/ Phn ng to ete Nhm OH hemiaxetal ca cc monoz c kh nng phn ng cao, c th metyl ha bng tc nhn CH3OH/HCl khan thu c hp cht glucozit CH2OH CH2OH O O HCl khan H2O CH3OH OH OH OH OCH3 HO HO OH OH -D-Glucopiranoz -D-Glucopiranoz metylMetyl ha cc nhm OH ancol thnh nhm ete c thc hin vi CH3I v Ag2O hoc vi dimetylsunfat (CH3)2SO4 trong kim
CH2OH O OH HO OH OCH3 2(CH3)2SO4 4NaOH CH3O CH2OCH3 O OCH3 OCH3 OCH3 2 Na2SO4 4H2O
Metyl- -2,3,4,6-tetra-O-metyl-D-Glucopiranozit
73
HO HO CH2OH O HO HO CH3OH OH HCl khan HO CH2OH O HO CH3O (CH3)2SO4 CH3O OCH3 NaOH CH2OCH3 O OCH3 CH3O
Metyl- -2,3,4,6-tetra-O-metyl-D-Glucopiranozit Metylglycozit khng th m vng c nn khng kh c AgNO3/NH3, n bn trong mi trng kim nhng d b thy phn trong mi trng axit. Trong iu kin ny cc nhm ete v tr khc kh bn CH2OCH3 CH2OCH3 O O H CH3OH H2O OCH3 OCH3 OCH3 CH3O OH CH3O OCH3 OCH3
3.Phn ng oxy ho: Phn ng ny c a vo th nghim cho php nh gi tnh cht ca cc ng kh. Trong mi trng kim, cc andoz (v cc xtoz chuyn ho thnh andoz) c bit kh cc mui kim loi thnh bc oxy ha thp hn. S tch nc trong mi trng axit c nng: Cc andopentoz, xetopentoz b tch nc trong mi trng axit c nng dn ti s hnh thnh fucfural (trng hp pentoz) v hydroxymetyl fucfural (trng hp hexoz). Trong trng hp andohexoz, phn ng nh sau:
HO OH CHO OH HO
H2SO4
HOH2C O
+
CHO
3H2O
HOH2C
- Cho bit cc sn phm to thnh khi cho HIO4 tc dng vi
74
HIO4 ng vai tr mt tc nhn oxi ha : (i) -CHO, >CHOH chuyn thnh HCOOH v -CH 2OH chuyn thnh H2C=O, vy sn phm l : 5HCOOH + H2C=O, (ii) >C=O chuyn thnh CO2, vy sn phm l : 2H2C=O + 3HCOOH + CO2. -P CA GLICOZIT CNG CH XY RA LK: -CH-CH-
+2HIO4
O=CH O=CH
+ HCOOH + 2HIO3 + 2H2O
O=CH +2HIO4 O=CHO=CH
+ HCH=O + 2HIO3 + 2H2O
- PHN NG TO AXTAN V XTAN VNG(chng ch p v tr syn(cis))

OH OH + O=CH-R
H+ -H2O
O C O axetal O C O xetal
R H R H
OH OH + O=C
R1 R2
H+ -H2O
VD:
H2SO4 -2H2O
CH3 O + CH3-CO-CH3 D-Glactopiranozo, CH3 O CH3 O
CH3 1,2,3,4-di-O-isopropyliden - -D-glactopiranozit
-P TO LACTON VNG 5,6 CNH BN VD:

COOH hay OH
OH H
GV:TRNG axit D-gluconic Ti liu lu hnh ni b CHU THNH.
-Lacton
75
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT -PHN NG KH BI H2 HOC NaBO4
NaBH4
NaBH4
, D-glucozo
D-gluxitol (hay sobitol)
, D- fructozo
- PHN NG TNG MCH CACBON

CN +H2O/H+ CH=O + HCN CH2OH D(+)aribiozo, CH2OH CN +H2O/H
+
COOH
O=C -H2O P2O5 Na/Hg CH2OH O=C Na/Hg
CH=O
CH2OH COOH -H2O P2O5 CH2OH
CH2OH , D-glucozo CHO
CH2OH
CH2OH
CH2OH , D-manozo
-THOI PHN Ruff

CH=O 1. Br2, H2O 2. Ca(OH)2 CH2OH , D-glucozo CHO 1. Br2, H2O 2. Ca(OH)2 CH2OH , D-manozo CH2OH , D-manozo CH2OH , D-glucozo COO-)2Ca H2O2, Fe3+ -CO2 COO-)2Ca CH=O
CH2OH D(+)aribiozo,
-THOI PHN Woht

CH=NOH C N
+H2NOH -H2O
+4Ac2O -4CH3COOH -H2O CH3ONa CHCl3

C N
CH3ONa -NaCN -CH3OH L-erythro
76
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT -P WERMAN CHO +NH3 CH2OH , D-manozo
NH2C=O
NH2CH-OH
CH=O +H+ -NH3
+(Cl2 +H2O) -CO2 CH2OH CH2OH
CH2OH D(+)aribiozo,
- Khi thy phn tinh bt bng men amilaza th thu c hai isaccarit l mantoz v iso-mantoz. amilaza 2(C6H10O5)n + nH2O x C12H22O11 + (n x) C12H22O11 (mantoz ) Cng thc cu to : (isomantoz)
CH2OH O OH OH
CH2OH O OH OH OH
mantoz
CH2OH O OH O OH OH
OH
O CH2 OH OH
isomantoz
O OH OH
AMINO AXIT
TNG HP AMINO AXIT Cc aminoaxit c tng hp thu nhng nguyn liu u dng tng hp peptit hay s dng b sung trong thc phm gia sc v thc phm con ngi. V cc aminoaxit trong c th u thuc dy L, nn nu tng hp cc amino axit khng chn lc lp th i hi phi tch bit cc ng phn lp th. 1. TNG HP STRECKER
Tng hp ny khng chn lc lp th. Gm phn ng un nng mt andehyt vi xyanua amoni:

NH4Cl + NaCN NH4CN +NaCl R-CHO +NH3 NH4CN +NaCl NH3
+
HCN
NH2-CH-OH R-CH NH R H2O, H+ H N-CH-COOH R-CH NH +HCN H2N-CH-CN 2 GV:TRNG CHU THNH. Ti liu lu hnh ni b R R
77
2. Tng hp Hell-Vollhard-Zelinski:
R H2C COOH + PCl3,Cl2

Tng hp ny khng c tnh lp th
HC COOH Cl NaN3 R
NH3 d-
HC COOH N3
H2, Pt
HC COOH NH2
3. CAC TINH CHT VT LY CUA AMINO AXIT 1. ng phn quang hc: Ngoi tr glyxin, cc amino axit c cacbon bt i u c hai dng ng phn hnh hc. C hai cch xc nh cu hnh lp th:
Cu hnh tng i: So snh vi cu hnh ca glyxerandehyt
L-Glyxeraldehyt
D - Glyxeraldehyt
L - Xerin
D - Xerin
Cu hnh tuyt i: S dng quy tc Cahn, Ingold v Preglog xc nh cu hnh tuyt i ca cacbon bt i R hoc S. Ngoi tr xystein, cc aminoaxit cu to t protein u c cu hnh S. Khng c mt s tng quan no gia hai h thng cu hnh tng i v tuyt i.
2. Hp ph ph t ngoi: Cc amino axit c s hp th chnh di sng nh hn 230 nm (2300A0); mt s amino axit hp th gia 250-300nm do s c mt trong gc R cc gc phenyl ( Tyr) hoc nhn indol ( Trp). Nh vy c th nh lng protein bi quang ph.
3. S ion ho:
Cc amino axit c hai nhm chc c kh nng ion ho: nhm cacboxyl v nhm amino, nhm cacboxyl c kh nng nhng proton to thnh anion RCOOH RNH2 + H + RCOO R - NH3 + + H+ v nhm amino c kh nng nhn proton to thnh mt cation
Ta c th m t hai hng s phn ly K1 v K2 tng ng vi hai cn bng trn nh sau: GV:TRNG CHU THNH. Ti liu lu hnh ni b 78
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT K1 = [ R-COO-] [ H+] 2 = [ R-NH2][ H+] [ R-COOH] [ R-NH3 +] Khi nng ion H+ bng K1, ta thy: [R-COOH] = [ R-COO-] : s anion bng phn t trung ha. Tng t khi nng ion H+ bng K2, ta thy: [ R-NH2]= [ R-NH3 +] Khi mt dung dch aminoaxit thay i t pH thp ln pH cao, ta thy chng thay i nh sau:
H3N - H+ H+
CH COOH R
H R ng vi pH, phn t amino axit R dng mt ion lng cc, m ti phn t trung ho c
H3N
CH COO
- H+
+
H2N
CH COO
v in, l im ng in ca amino axit. pH ny, tan ca amino axit l cc tiu, v nu t trong mt in trng th , pH ca im ng in l trung bnh ca hai gi tr pKa. y l tnh cht ring ca amino axit. Nhng nhm chc chng hn thiol, phenol, amin hay axit cacboxylic mang mch nhnh nh hng n gi tr ca im ng in. 4. Tnh cht ho hc ca aminoaxit Cc amino axit c cc tnh cht ha hc do cc nhm cacboxyl, nhm amin v cc nhm cu trc c trong gc R, chng ta ch cp n cc tnh cht quan trng nht v nht l cc tnh cht m chng ta s cp phn peptid v protein. 1. Phn ng do s c mt ca nhm cacboxyl a. S to thnh mui Khi c mt cc baz mnh nhm axit chuyn thnh mui. Tnh cht ny c th c s dng chit cc amino axit, nhng do kh nng phn ly yu ca nhm cacboxyl nn phn ng xy ra hon ton i hi phi tin hnh pH cao ( chng 11 hoc 12). Khi c mt xc tc amino axit c th phn ng vi cc ancol to thnh cc este. b. Phn ng decacboxyl ha Phn ng di cc cht xc tc trong cc t bo sng trong qu trnh chuyn ha cc cht m. 2. Phn ng do s c mt ca nhm amin a. To thnh amit Nhm amin bc mt phn ng vi cc clorua hay anhydrit axit to thnh amit.
H2N-CH-COOH 1/ R-COCl R R 2/ R P-HN-CH-COOH + H2N-CH-COOP 1/ DCC DCC: C6H11-N=C=N-C6H11

b. Tc dng ca axit nitr
R-CONH-CH-COOH R H2N-CH-CONH-CH-COOH R R + C6H11-NH-CO-NH-C6H11
79
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT Axit nitric phn ng vi cc nhm NH2 gii phng nit. y chnh l nguyn tc chnh ca phng php Van Slyke xc nh nhm NH2 t do ca amino axit, ca peptit hay cc peptit hay nh lng amino axit trong hn hp.
H2N-CH-COOH + HNO2 R
H+
HO-CH-COOH + N2 + H2o R
Phn ng qua s to thnh mui diazoni aliphatic, km bn, mui ny b thy phn to thnh ancol v nit. COOH R-CH NaNO2 NH2 HCl COOH R-CH N2 Cl
+ -
H2O
R-CH
COOH + N2 + HCl OH
c. N-ankyl ha v N-aryl ha Hydro ca nhm NH2 c th c thay th bi cc gc: gc no m n gin nht l CH3; ta c th thu c cc dn xut N-metyl; N, N - dimetyl v mui amoni bc bn. Gc thm, m cc dn xut dinitrophenyl (DNP) m ta s dng xc nh N -amino axit tn ca cc protein (phng php Sauger). VI .1.4. 2. d. Phn ng vi isoxyanat
R-CH COOR + CH3-N=C=O

NH2
R-CH-COOR
NH-CO-NH-CH3
Phn ng ca cc nhm chc amin ca amino axit vi cc nhm isoxyanat hay axit isoxyanic (HN=C=O) c dng cha tr mt s bnh ung th. Isoxyanat c gii phng ngay cc t bo. Phn ng xy ra nhm NH2 cc amino tn cng ca peptit. 3. Phn ng do c mt ng thi nhm cacboxyl v nhm amin v tr a. Phn ng vi ninhydrin
Ninhydrin l mt cht oxy ha mnh. Phn ng ny c th nh lng cc amino axit bng cch so mu. Tuy nhin lu rng prolin v hydroxyprolin khng to thnh cht mu tm.
Sn phm mu xanh tm GV:TRNG CHU THNH. Ti liu lu hnh ni b 80
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT VI .1.4.3. b. Lin kt amit th gia hai amino axit
Lin kt amit th hoc lin kt peptit (-CO-NH-) c th to thnh gia phn t hai amino axit, -COOH ca phn t ny lin kt vi nhm -NH2 ca phn t khc. Ngi ta nhn thy lin kt ny kt hp cc amino axit trong peptit v protein. Nu lin kt mt nhm COOH hay mt nhm NH 2 t trong v tr khc (?-COOH, ?-COOH, ?-NH2 ).
Cc axit v -amin cho phn ng ni tng t phn ng bin i cc cc axit v -ancol thnh lacton, dn xut vng y gi l lactam.
Cc lactam ca axit -amino v -amino tng ng vi cc vng 3 hay 4 cnh km bn nn khng th d dng tng hp; tuy nhin ngi ta ghi nhn s c mt ca mt vng -lactam trong cng thc ca penecillin.
Tnh cht protein gn nh ton b nhm -COOH v nhm -NH2 u nm lin kt peptit, iu ny chng t cc gc R c cc tnh cht ha hc ring. Kh nng phn ng ca cc gc ny thng gim do kch thc khng gian hoc bi s tham gia vo cu hnh ba chiu ca protein, tuy nhin chng ta cng cn bit cc tnh cht ca chnh ca cc mch bn ny. photphoric . thyroit. Cc nhm thiol xystein c th b oxy ha v h thng xystein / xystin (2R-SH ( R-S-S-R) c th tin hnh nh l cho hoc nhn hydro. Cu disulfua rt quan trng trong cu trc khng gian ba chiu ca protein. Ngoi ra s oxy ha xystein cn c th ko di n giai on to thnh R-SO3H, sn Nhm ancol v phenol (OH ca tyrosin) c th tham gia phn ng este ha bi axit Nhn thm tham gia cc phn ng th. V d: cc dn xut iot c trong cc hormon
81
TRNG THPT CHUYN TIN GIANG.TI LIU BI DNG HC SINH GII THPT phm ny b decacboxyl ha cho taurin NH2-CH2-CH2- SO3H. Axit sulfonic l mt axit mnh, taurin c tm thy di dng mt ion lng cc: NH3+-CH2-CH2-SO3-.
PEPTIT Phn loi:

Cc peptit t nhin c hnh thnh t cc amino axit khc nhau, nhng c th tng hp c t cc homo-peptit (triglyxin, poliphenylalanin...). ta gp cc peptit c trong cc cu trc khc nhau: Peptit hnh di c nhm NH2 t do mt u cn nhm COOH u kia.
Peptit phn nhnh mt hay nhiu amino axit trn mt mch peptit di do bi nhm cacboxyl ca mt amino axit dicacboxylic hoc do bi nhm -amino ca lysin. Peptit vng khng c NH2 tn cng cng nh khng c COOH tn cng. Peptit na vng ch c mt cc, hoc ch cha NH2 tn cng khi nhm -COOH ca amino axit cui cng lin kt vi -NH2 ca mt lysin endopeptidic; hoc ngc li ch cha COOH tn cng khi nhm -NH2 ca amino axit u tin lin kt vi nhm -COOH ca mt amino axit endopeptidic. - Thy phn B nh enzim cacboxipeptidaza thu c alanin => amino axit u C l Ala v nh vy tripeptit B c cu to theo trt t : GluGluAla. - B khng phn ng vi 2,4initroflobenzen v B ch c mt nhm cacboxyl t do => Nhm NH2 ca amino axit N-u mch to lactam vi nhm cacboxyl ca Glu th nht.
- Khi thy phn hon ton 1 mol tripeptit B thu c 1 mol NH3 => nhm cacboxyl ca Glu th hai tn ti dng amit CONH2.
82

He So Chuyen Doi

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He So Chuyen Doi

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TRNG THPT CHUYN TIN GIANG.

TI LIU BI DNG HC SINH GII THPT Cc h s chuyn i, phng trnh v hng s c bn

N = 6.02 1023 mol-1

h = 6.63 10-34 J s c = 3 108 m s-1 E = E (0.0592 / n) log K ln P = - Hvap / RT + B

1 W = 1 J s-1 1 cal = 4.184 J 1 bar = 105 Pa

p dng : 1. Kc = Kp.(RT) n 3. Kp = Kc(RT)n 5. MOMEN LNG CC a2 = b2 + c2 2bc. cos A )

2. Kx = Kp. P n 4. G0 = RTlnKp 6. G = RTlnK 1 N0 v t = ln k Nt 7. G = H T. S * ln K P (T1 ) H 1 1 = K P (T2 ) RT T2 T1 3

GV:TRNG CHU THNH. Ti liu lu hnh ni b

(n la s electron trao i trong phan ng oxi hoa kh)

+ 927,09 = + 463,545 KJ (do 1 phn t H2O c 2 lk O-H) 2

Na+ (k) + Cl-(k)

GV:TRNG CHU THNH. Ti liu lu hnh ni b

GV:TRNG CHU THNH. Ti liu lu hnh ni b

GV:TRNG CHU THNH. Ti liu lu hnh ni b

GV:TRNG CHU THNH. Ti liu lu hnh ni b

4.DUNG DCH CHT IN LI

GV:TRNG CHU THNH. Ti liu lu hnh ni b

T (**) [HA] = Ca - [A ] [HA] = Ca - [H+] + [OH-] Thay vo hng s cn bng Ka ta c :

GV:TRNG CHU THNH. Ti liu lu hnh ni b

5. CN BNG HA HC TRONG DUNG DCH

GV:TRNG CHU THNH. Ti liu lu hnh ni b

x l nng ca HF b phn ly.

Do HF l axit yu, phn ly khng ng k, nn mt cch gn ng c th chp nhn

Do HClO phn ly mnh hn nc ng k, nn qu trnh phn ly chnh c chn l ca HClO.

x l nng HClO b phn ly GV:TRNG CHU THNH. Ti liu lu hnh ni b 24

Kim tra tr li gi thuyt gn ng:

Mt cch gn ng, ta chp nhn 5,0 x 5,0 x = 1,9.10-1 Kim tra li mc gn ng ta c:

Nn kt qu trn l chp nhn c: pH =-log[ H+ ] = - log x = 0, 72 T y ta xc nh c:

Nng ca cc cu t cn li c tnh da vo gi tr Ka tng ng: GV:TRNG CHU THNH. Ti liu lu hnh ni b 26

x = 5,6.10-10 Nu coi x << 0,10 0,10 x 0,10 x2 = 5,6.10-11 0,10 x

GV:TRNG CHU THNH. Ti liu lu hnh ni b

GV:TRNG CHU THNH. Ti liu lu hnh ni b

GV:TRNG CHU THNH. Ti liu lu hnh ni b

T y kt lun bng ha tan ca PbI2 trong cc iu kin nh sau:

Tng t nng I- cn kt ta CuI l

Do hng s to phc tng nc ln, v do lng d ca NH3 rt ln nn c th gi thit ton b , do :

Trong thc t, s c mt lng nh rt t bng phn ly ca tnh nng cn bng ca

v NH3, tuy nhin do . Ta dng cn

By gi ta s dng cn bng phn ly ca

Kt qu tnh ton cho thy: GV:TRNG CHU THNH. Ti liu lu hnh ni b 35

ta dng cn bng phn ly phc:

GV:TRNG CHU THNH. Ti liu lu hnh ni b

PSO3 PSO2 ( PO2 )

GV:TRNG CHU THNH. Ti liu lu hnh ni b

N 8 O + 1 p (th nghim tm ra proton) 1

8.Thuyt lai ha orbital :

GV:TRNG CHU THNH. Ti liu lu hnh ni b

M hnh cc phn t : CH4, C2H6, C2H4, C2H2

GV:TRNG CHU THNH. Ti liu lu hnh ni b

GV:TRNG CHU THNH. Ti liu lu hnh ni b

GV:TRNG CHU THNH. Ti liu lu hnh ni b

sp3d lng chp

SF6, AlF63-, SiF62-

4 a 3 VKl 2. . Vy c kht ca mng tinh th = = 3 4 = 0,68 Vt t 3 a

GV:TRNG CHU THNH. Ti liu lu hnh ni b

Cu trc tinh th nguyn t

GV:TRNG CHU THNH. Ti liu lu hnh ni b

Cu trc ca mt s tinh th ion:

Cu trc tinh th phn t

10.LIN KT THEO PHNG PHP MO Gin 1:

1s 1s*2s 2s* z x=y x*=y* Gin 1 p dng i vi nguyn t cui chu k t O n Ne

+ V bc lin kt trong F ln hn trong F2 nn F2 c bn lin kt ln hn. 2 *2 4 2 N2 : [KK] s s ( x y ) z

Cn ch y v s ph hp tnh i xng khi t hp tuyn tnh cc AO thnh MO.

1s 1s2s 2s z x=y x=y Gin 1 p dng i vi nguyn t cui chu k t O n Ne