P N PHN I CNG V V C BNG A

OLYMPIC HA HC CC TRNG I HC VIT NAM NM 2004

Cu 1:
1) Nng lng lin kt 1e vi b mt mng tinh th bc c k hiu l (
V c lin h: EMBED Equation.3
(: Tn s nh sng n. Ch : EMBED Equation.3
v: Vn tc trung bnh ca e khi b bt khi b mt
m: Khi lng e
Ta c:
EMBED Equation.3
Cn EMBED Equation.3 = 256,21875.10-21J
Nh vy ta tnh c ( = 7,1343979.10-19J = 4,45 eV
2) Tnh nng lng:
Biu thc gn ng Slater: En = EMBED Equaon.3
n
1
2
3
4
n*
1
2
3,7
Hng s chn b c ly theo quy tc Slater
a) Tnh nng lng e ca oxy (Z = 8) ( 1s22s22p4.
E1: 1s2
E1 = -13,6.(8,0 0,3)2.2 = -1312,688 eV
E2: 2s22p4
E(2s2) = -140,777 eV
E(2p4) = -281,5%4 eV
E2 = -422,331 eV
Vy nng lng electron ton nguyn t s l; E = E1 + E2 = -2035,619 eV
b) Tnh nng lng ion ha:
C s: Theo nh ngha: I = - E (E l nng lng 1e trng thi c bn)
M I = -E = - EMBED Equation.3
k: s e cn li n ht v cng ch th t e nu c Ik.
k = 1 ( N. Vi N l tng s e ca nguyn t:
C th ta c kt qa tnh nng lng ion ha nh sau:
Nng lng ion haI1I2I3I4I5I6I7I8Ga tr
(eV)14,16133,14654,97879,135105,799134,946742,288870,400Cu II:
a) 5 ng phn hnh hc ca phc cht l:
EMBED ChemDraw.Document.6.0
Trong 5 ng phn hnh hc trn th B c hai ng phn quang hc c cu to B1, B2 nh sau:
EMBED ChemDraw.Document.6.0
b) Gii thch hnh dng bt din u:
Cr3+ c cu hnh e: {[Ar]3d2}3+:
Thuyt lai ha Pauling:
Cr c lai ha d2sp3. V cc phi t NH3, Br, H2O u khng mnh: do khng cn/khng xy
ra s sp xp li e trong 10 d.
Vy 2AO 3d trng s tham gia lai ha vi 1AO 4s v 3AO 4p. l lai ha trong d2sp3
Hnh bt din u c tm l Cr, 6 nh chnh l 6 nh ca 6 AO d2sp3.
Thuyt trng phi t:
C s tch mc nng lng AO-d ca Cr3+ trong 6 phi t:
eg

t2g
V 6 phi t u c phn b trn 3 trc to nn 2AO: EMBED Equation.3 b y ln
mc eg cn 3AO dxy; dxz v dyz mc t2g thp. Kt qa ion phc [Cr(H2O)2(NH3)2Br2]+ c hnh
bt din u nh quan st c.
a) H3 hnh tam gic u nn c nh thc th k nh sau:
(-E (
(
( (-E (
= 0 (1)
(
( (-E
(: Tch phn Coulomb
(: Tch phn trao i.
E: Nng lng MO tng ng.
b) Khai trin (1) ta thu c biu thc: ( ( - E - ()( ( - E + 2()( ( - E - () = 0
Vy E1 = ( + 2(; E2 = E3 = ( - (
Do ta s c gin nng lng nh sau:

c) Xt cu hnh e tng ng v tnh E:

H32+:1e ( ( ( E = E1 = ( + 2(
H3+: 2e ( (( ( E = 2E1 = 2( + 4(
(
H3: 3e
( E = 2E1 + E2 = 3( + 2(
((
(
H3-: 4e
( E = 2E1 + E2 + E3 = 4( + 2(
((
Cu III:
C=Rq+( +2=311+2=3
S 3 cho bit: T, P v t l N2 : H2 nh hng n cn bng.
Trong cng nghip: T ( 500oC; P ( 300atm, cht xc tc st: T l s mol N2 : H2 = 1 : 3.
P cao ph hp vi nguyn l Le Chartelier, H < 0 nn P cao cn bng chuyn dch v pha to
ra NH3. T cao nn cn bng chuyn dch theo chiu ngc li v H < 0, khng ph hp vi
nguyn l Le Chartelier nhng v tc phn ng qa b nhit thp nn cn tng nht
v dng cht xc tc. T l s mol N2 : H2 l 1 : 3 s chuyn ha ca N2 v H2 thnh NH3
l ln nht.
a)
PNH3 = a.P; PH2 = 3PN2; P = 4PN2 + aP
EMBED Equation.3
P = 300atm ( a = 0,226; P = 600atm ( a = 0,334
N2
+
3H2
2NH3
CB: 1 - (
3 3(
2( ( (n = (4 - 2() mol
EMBED Equation.3
P tng ( ( tng ph hp vi nguyn l Le Chartelier, nhng P qa cao khng m bo sn xut
an ton lu di. Mt khc trong qa trnh sn xut NH3 c ngng t tch khi mi trng

phn ng.
Cu IV:
Ta c:
EMBED Equation.3 nm
4Au + O2 + 8CN- + 2H2O 4[Au(CN)2]- + 4OHPhn ng cha hai cp oxi ha kh [Au(CN)2]-/Au v O2/H2O:
Xt cp [Au(CN)2]-/Au:
[Au(CN)2]- + e
Au + 2CNAu+ + 2CN- + e
G = G 1 + Go2
EMBED Equation.3
Xt cp O2/H2O:
EMBED Equation.3
Vy th kh ca cp [Au(CN)2]-/Au b hn so vi cp O2/H2O nn phn ng ho tan vng
trn xy ra c
o

Cu V:
Cl2(k) + 3I- 2Cl- + I3Go = -2.96500.(1,36 0,54) = -158260J
KP = 5,5.1027
Cu2+ cn tr s nh phn v xy ra phn ng:
2Cu2+ + 5I- 2CuI(r) + I3Chng minh: Phn ng xy ra do hai cp oxy ha - kh: Cu2+/CuI v I3-/ICu2+ + e + ICuI(r)
Cu+ + IG = Go1 + Go2 EMBED Equation.3
V th kh ca cp Cu2+/CuI ln hn so vi cp I3-/I2 (0,54V) nn phn ng trn xy ra
Cu2+ + e + I- CuI(r)
EMBED Equation.3
2Cu2+ + 5I
2CuI(r)
+ I3-5
Ncb: 10 2x
1 5x
x
o
G = -2.96500.(0,87 0,54) = -8,314.298lnK
( K = 1,46.1011
V K rt ln cho nn ta co 2x = 10-5 ( [Cu2+] = ( v x = 5.10-6M
[I-] = 1 25.10-6M = 1M:
EMBED Equation.3

OLYMPIC HA HC CC TRNG I HC VIT NAM LN TH HAI ,2004

THI PHN HA HC C S, BNG B
180 pht lm bi, khng c dng ti liu ngoi bng h thng tun hon, my tnh c nhn b ti
Cu I:
1) Tng ozon l l chn bo v tri t trnh bc x nng lng cao ca mt tri.
a) Hy vit phng trnh ha hc xc nhn vai tr ca ozon.
b) Tnh nng lng theo kJ do 1m3 ozon hps th t tia mt tri c di sng 3400 :
Bit hiu sut hp th nng lng l 100% t to = 300oC.
Cho h = 6,626.10-34J.s; c 3.108m.s-1
2) C14 ng v km bn, phng x ta, c chu k bn hu 5700 nm.
a) Hy vit phng trnh phng x ca C14.
b) Tnh tui c vt c t l C14/C12 l 0,125.
c) Tnh phng x ca mt ngi nng 80,0kg: Bit rng trong c th ngi ocs
1(% khi lng l cacbon, phng x ca c th sng l 0,277Bq tnh theo 1,0 gam
cacbon tng s.

3) St l nguyn t ha hc rt ph bin v quan trng.

a) Hy trnh by chi tit v kt qa vit cu hnh electron ng ca Fe (c dng lng
t).
b) Vit phng trnh phn ng gii thch l cu hnh electron ca Feo (c gii
thch chi tit).
Cu II:
1) Nhm nguyn t ha hc M trong bng h thng tun hon c s oxy ha khng i to
c ba loi oxit theo t l s mol M : O ln lt l 2 : 1; 1: 1 v 1 : 2. Hy vit cng thc v
gi tn tng oxit ca tng nguyn t trong nhm (ghi kt qa thnh bng).
2) Thc nghim cho bit ion PO43- c hnh t din u. Ion ny c th c nhng cng thc cu
to Lewis no? Hy trnh by c th.
3) NO c electron c thn nn c vai tr quan trng trong cc c th sng. Hy gii thch cc
lin kt ha hc trong NO theo thuyt obitan phn t.
Cu III:
SO2 phn ng vi O2 theo phng trnh:
2SO2(k) + O2(k) 2SO3(k)
1) Da vo quy tc pha ca Gibbs tnh bc t do (bin ) ca h cn bng trn. Ga tr thu
c cho ta bit nhng thng tin g v h cn bng? Gii thch.
2) Trong cng nghip ngi ta dng oxy khng kh d thc hin phn ng nhit
khong 700K v c cht xc tc p sut thng. Nhng iu kin phn ng ny c ph
hp vi nguyn l Le Chartelier khng? Gii thch.
3) Khi cn bng p sut 1 atm v 700K thu c hn hp kh gm 0,21mol SO2; 5,37 mol O2;
10,30 mol SO3 v 84,12 mol N2. Hy tnh:
a) Hng s cn bng KP.
b) S mol ban u ca SO2; O2 v N2.
c) T l chuyn ha ca SO2 thnh SO3.
Nu trong hn hp ban u khng c N2 (ngha l dng O2 tinh khit cho phn ng) nhng
vn gi s mol ban u ca SO2 v O2 nh trn th t l chuyn ha ca SO2 thnh SO3 l bao
nhiu? p sut lc cn bng vn gi 1atm.
So snh trong hai trng hp v gii thch ti o trong thc t ngi ta dn O2 khng
kh m khng dng O2 tinh khit.
Cu IV:
1) Cc ion CN- c mt trong mt s loi nc thi cng nghip. C th loi cht c ny bng
phn ng sau 25oC:
CN- + H2O2 NCO- + H2O
a) Tnh hng c cn bng ca phn ng.
b) Trong nc thi c nng CN- l 10-3mol.L-1. Nu dng dung dch H2O2 0,1M (th
tch khng i) nng CN- cn li sau phn ng l bao nhiu? Rt ra kt lun.
Cho Eo(H2O2/H2O) = 1,77V v Eo(NCO-/CN-) = -0,14V
2) Nu thm t t dung dch NaOH vo dung dch Al3+ u tin thy kt ta Al(OH)3, sau kt
ta ny tan do to thnh Al(OH)4- pH = 10,9. Tnh nng ban u ca Al3+ v nng cc
ion OH-, Al3+ v Al(OH)4- khi cn bng.
Cho bit tch s tan ca Al(OH)3 l 10-32 v:
Al(OH)4- Al(OH)3 + OHK = 1/40
Cho F = 96500C/mol; R = 8,314J.K-1.mol-1.
Cu V:
Trong dung dch axit, khi c mt cht xc tc H2O2 phn hy theo phn ng:
H2O2 H2O + 1/2O2

1) Tc phn ng tun theo cng thc:

-d[H2O2]/dt = k[H2O2]. Nng ban u ca H2O2 l 1,000mol.L-1
25oC hng s tc k = 7.689.10-3ph-1. Tnh nng H2O2 cn li sau 30 pht v thi gian
m mt na H2O2 b phn hy (t1/2).
2) 50oC, hng s k = 0,129ph-1, tnh nng lng hot ha Ea ca phn ng.