B GIO DC V O TO K THI CHN I TUYN OLYMPIC NM 2012

---------------------------------
HNG DN CHM THI CHNH THC
Mn: HO HC

Ngy thi th nht: 16/4/2012

Cu 1 (3,0 im)
1.1 (6/4 im).
a) Cng thc Lewis ca XeF2 v XeF4:

b) Trong XeF2 c 5 cp electron xung quanh Xe, trong 2 cp lin kt v 3 cp khng lin kt, cng
thc VSEPR l XeB2L3 (hoc XeF2L3).
Trong XeF4 c 6 i electron xung quanh Xe, trong 4 cp lin kt v 2 cp khng lin kt, cng
thc VSEPR l XeB4L2 (hoc XeF4L2).
c) Theo thuyt VSEPR XeF2L3 c dng hnh hc electron lng thp tam gic.Vi dng hnh hc ny
3 nguyn t lin kt nm thng hng lm cho 3 cp electron khng lin kt to thnh cc gc 120 0 vi
nhau, gim thiu lc y gia cc i electron khng lin kt. V th dng hnh hc phn t tuyn tnh
(thng) c u tin hn.

FXeF
F Xe F

E E
Hnh hc phn t XeF2
Hnh hc electron XeF2
Theo thuyt VSEPR tiu phn dng XeF4L2 c dng hnh hc electron bt din:
E
F
F F
Xe
F Xe F
F F

E F
Hnh hc electron XeF4 Hnh hc phn t XeF4

Hnh hc electron dng bt din trong cc nguyn t nm trn hnh vung phng lm cho cc
gc y gia cc cp electron khng lin kt vi nhau, gia cc cp electron khng lin kt vi cc cp
electron lin kt cng nh gia cc cp e lin kt u khng nh hn 90 O, gim ti a lc y gia cc
cp electron v c u tin hn.
d) F lun c s oxi ha l 1. V vy, cc s oxi ha tng ng ca Xe l +2 (XeF 2) v +4 (XeF4).
Cc tiu phn ny l nhng tc nhn oxi ha rt mnh!

Trang 1/9
1.2 (2/4 im).
B qua s sai khc v mc nng lng cc AO ca H v He, ta c th v cc gin MO sau:

s*

1s (H+)

1s (He)

T cc gin ny, c th thy rng trong HeH+ bc lin kt l 1.

1.3 (4/4 im).
a) Trong khong t Li n Ar , cc nguyn t nhm II c nng lng ion ha th hai kh thp (v Be +
Be2+ hoc Mg+ Mg2+ to mt lp ngoi cng bo ha, c cu hnh kh him 1s2 hay 1s2 2s2
2p6). Do 2 nguyn t c kh nng nht hnh thnh XNe2+ l Be v Mg.
b) Hai nguyn t km c kh nng nht cho s hnh thnh XNe 2+ nht l Li v Na do nng lng ion
ha th 2 c bit ln (v s tch electron t lp v bo ha).

Cu 2 (3,0 im)
(5/4 im) Xc nh th tch mu ca bnh nhn bng phng php o phng x
2.1. (1/4 im)
a)
67 + e 67
31Ga 30Zn

b) Ht nhn mi to thnh do s phn r thng mt trng thi kch thch no c mc nng lng
cao hn trng thi c bn. Khi tr v trng thi c bn n cho bc x . (thng th bc x xy ra
mun hn vo khong 10-16 s).
2.2. (1/4 im)
a) A = .N N = A/ = 1,09.108. 78,24.3600/ ln2 = 4,43.1013 nguyn t
67
4, 43.1013.67
Khi lng ca Ga trong dc cht: m = 23 g = 4,930.10-9 g
6, 02.10
b) Khi lng ca dc cht c tng hp:
10, 25.103.296, 7
m(GaC6H5O6.3H20) = g = 4,362.10-2 g
69, 72
Hot phng x ca 1g dc cht (hot phng x ring):
As = 1,09.108 Bq/43,62.10-3 g = 2,50.109 Bq/g
2.3. (3/4 im)
a) Hot phng x ban u ca 1mL dung dch: Ao = 1,09.108 Bq/100mL = 1,09.106 Bq/mL
Hot phng x ca liu 1mL dung dch khi tim:
A = Ao.e-t = Ao.e-ln2.t/t1/2 =1,09.106Bq/mL.e-ln2.8/3,26.24 = 1,015. 106 Bq/mL
b) Hot phng x cn li sau 1 gi (1mL): A =1,015. 106 Bq.e-ln2.1/3,26.24 =1,006.106Bq
1,006.106Bq /V = 105.6 Bq/mL (V l th tch mu)
V = 1,006.106Bq/210,2 Bq/mL = 4,786.103 mL

Trang 2/9
(7/4 im) Nhin liu urani
2.4. (3/4 im)
a) Ch phng x mi lm thay i s khi v mi thot bin lm s khi thay i 4 n v khi
lng nguyn t (u). Mt chui n phng x ni tip nhau s lm s khi thay i 4n (u). Nh vy c
th c 4 h phng x vi cc s khi 4n; 4n + 1; 4n + 2; 4n + 3.
238
U thuc h urani c s khi A = 4n + 2.
235
U thuc h actini c s khi A = 4n + 3.
206
b) Pb c s khi A = 4n + 2 thuc h urani, l hu du ca 238U
207
Pb c s khi A = 4n + 2 thuc h actini, l hu du ca 235U
234
U thuc h urani. T 238U cn c 1 phn r v 2 phn r to ra 234U.
(Ch : hc sinh c th lp lun rng (theo nh lut chuyn dch phng x) thot bin lm s khi
thay i 4 n v khi lng nguyn t (u), nn cc ng v thuc cng mt h phi c s khi khc
nhau mt s nguyn ln ca 4. Ri t rt ra cc kt lun nh trn.
c) 226Ra c s khi tha mn cng thc A = 4n + 2, n l hu du ca 238U.
Tng quan gia cc chu k bn r v thi gian tn ti ca tri t khong 10 10 nm cho php t
c cn bng th k.
A(238U) = A(226Ra) (A l hot phng x)
238U.N238U = 226Ra.N226Ra ( l hng s tc phn r, N l s nguyn t)
(ln2/4,47.109.365.24.3600).(9,9274 g/238).6,02.1023. =.(ln2/1600.365.24.3600). N226Ra
1600 9,9274
N226Ra = . .6, 02.1023 = 8,99.1015 nguyn t
4, 47.109 238
m(226Ra) = (8,988.1015/6,02.1023).226 = 3,37.10-6 g
2.5. (4/4 im)
a) T l ng v 235U trong urani t nhin = 0,72%. Gi x l s tn urani t nhin cn dng, ta c
phng trnh:
0,72x/100 = 22,04.4/100 + (x-22,04).0,2/100 x = 161,06 tn.
b) T kt qu ca phn 2.4.c) c th thy rng khi lng 226Ra trong qung rt nh. Lng 226Ra cn
li trong nc lc cng phi rt nh n mc khng kt ta c khi c mt ion SO 42- (thy luyn bng
axit sunfuric m tch s tan ca sunfat kim th kh nh). Tuy nhin vi nng rt nh nh vy hot
phng x ca Ra vn cn rt nguy him vi mi trng.
tch Ra ra khi nc lc sau khi kt ta urani, c th a vo nc lc ny dung dch BaCl 2. Kt
ta BaSO4 s ko theo RaSO4 vo pha rn (cng kt).
Ch thch: Nu th sinh a ra phng n trao i ion tch Ra cng cho im.

Cu 3 (3,0 im).
3.1 (3/4 im).
k AB Z AB .e E AB / RT (1)
E AC / RT
k AC Z AC .e (2)
Chia v (1) cho (2) ri ly logarit 2 v nhn c:
k Z E E AB
ln AB ln AB AC
k AC Z AC RT
Bi ZAB v ZAC l hng s, EAC - EAB > 0 Khi T th kAB/kAC.
Nh vy, tng chn lc B th cn tng nhit .

3.2 (6/4 im).

a) S mol c trong bnh N2O5:
n(N2O5) = pV/RT = 0,10.atm.V (L) /0,082L.atm.mol-1.K-1.298 K = 4,1.10-3.V mol.
n( N 2O5 ) p ( N 2O5 ) 0,1
[N2O5] = = = (mol / L) = 4,1.10-3 mol/L
V RT 0, 082.298
v = 3,46.10-5 s-1. 4,1.10-3.mol/L = 1,42.10-7 mol.L-1.s-1
b)
N2O5 2NO2 + (1/2)O2
Trang 3/9
Po 0 0
Po -x 2x x/2
Ptng = Po -x + 2x + x/2 = Po +(3/2)x = (7/4)Po x = Po/2 v Po - x = Po/2.
cng nhit , khi th tch bnh phn ng khng thay i, s gim p sut ring phn t l vi s
gim s mol. Trong phn ng bc 1, thi gian cn thit nng cht phn ng gim i mt na
bng:
t1/2 = ln2/k = 0,693/3,46.10-5 s-1 = 2.104 s
Trong phn ng bc 1, khi nng gim i mt na (so vi ban u) th tc phn ng cng gim i
mt na
d [N 2 O5 ] d[N 2 O5 ]
v(t = t1/2) = = (1/2)v(ban u) = - (1/2)v(ban u) = -7,1.10-8 mol.L-1.s-1
dt dt
c) Thi gian phn ng bn phn ca phn ng bc 1 khng ph thuc vo nng u. khi lng
N2O5 cn li 12,5% (1/8 nng u) cn thi gian 3 ln thi gian phn ng bn phn:
t = 3.2.104 s = 6.104 s
d [N 2 O5 ]
d) V tc phn hy N2O5, biu th bi khng i nn cc gi tr trn vn khng i.
dt
Hc sinh c th suy lun cch khc, nu ng vn c im.
* So snh
p*2NO2 p*1/2
O2 p*4NO2 p*O2
K(1)= * ; K(2)= *2 ; K(1) = K(2)1/2.
p N 2 O5 p N2O5
(p* l p sut ring phn trng thi cn bng)
GO(1) = -RTlnK(1) = -(1/2)RTlnK(2); GO(2) = -RTlnK(2) GO(1) = (1/2)GO(2)

3.3 (3/4 im).

Phn ng c th xy ra theo c ch hai giai on:
k1
2NO k
1
N2O2 (a) (nhanh)
N2O2 + O2 k2 2NO2 (b) (chm)
Cng (a) vi (b) s thu c phn ng tng cng (3).
Giai on (b)chm, quyt nh tc chung ca phn ng, nn:
v = k2[N2O2][ O2] (*)
Do giai on (b) chm v (a) nhanh nn c th coi cn bng (a) c thit lp, khi c:
[N2O2]/[NO]2 = k1/k-1 [N2O2] = (k1/k-1)[NO]2 (2*)
Thay (2*) vo (*) thu c:
v = (k1/k-1)k2[NO]2[ O2] = k[NO]2[ O2] vi k = (k1/k-1)k2.
Nh vy t c ch gi nh c th rt ra c nh lut tc thc nghim. C ch l c kh nng.
Ch : Th sinh c th a ra c ch khc. Nu chng minh cht ch rng c ch ph hp vi
thc nghim th cho im.

Cu 4 (3,0 im).
4.1 (1/4 im).
[H + ] [H + ][CO32- ] K
K 2+ -
2+ - 2-
a2 = 632
[Pb ][HCO3 ] [Pb ][HCO 3 ][CO3 ] T
4.2 (11/4 im).
a) i vi phn ng (1)
G(1) = (-92.6 394.2 228.5 + 626.0 + 33.0) kJ/mol = -56,3 kJ/mol
K(1) = e- G(1)/RT = e56300/8,314.298 = 7,4.109.
i vi phn ng(2)
G(2)=(-184.8 -228.5 + 318.0 + 33.0) kJ/mol = - 62,3 kJ/mol
- G(2)/RT 62300/8,314.298 10
K(2) = e =e = 8,3.10

Trang 4/9
b) i vi phn ng (1)
2.6 104 4 10
3
G(1)= -RTlnK(1)+ RT.ln
pH 2 S
iu kin (1) u th theo chiu thun:
2.6 104 4 10
3
G(1) =-RTlnK(1) + RT.ln <0 (a)
pH 2 S
2.6 104 4 10 3
pH2S > = 1,4.10-16 bar (b)
7, 4.109
bo v c mu trng PbCO3 th nng H2S c php trong khng kh ti a l:
34.(1,4.10-16.1000 L)/(0,082 L.bar.mol-1.K-1.298K) = 1,9.10-13 g/m3
i vi phn ng (2)
4 103
G(2) = - RTlnK(2) + RT.ln
pH 2 S
iu kin (2) u th theo chiu thun:
4 103
G(2) = - RTlnK(2) + RT.ln <0 (c)
pH 2 S
4 103 -14
pH2S > 10 = 4,8.10 bar
8,3.10
bo v c mu trng ZnO th nng H2S c php trong khng kh ti a l:
34.(4,8.10-14.1000 L)/(0,082 L.bar.mol-1.K-1.298K) = 6,7.10-11 g/m3
c) ZnO u th hn v:
- Phn ng (1) T din bin nhng nng H2S nh hn;
- Sn phm ca (1) l PbS c mu en cn sn phm ca (2) l ZnS vn cn l mu trng.
d) PbS + 4H2O2 PbSO4 + H2O (3)
e) PbS + 2 O2 PbSO4 (4)
G = -811.5 kJ/mol + 92.6 kJ/mol = - 718.9 kJ/mol
1
G = - 718.9 kJ/mol + RT.ln = - 711,1 kJ/mol
0.207 2
Phn ng (4) c th t din ra trong khng kh nhit 298 K. Oxi ca khng kh c th ti to mu
trng bng cch oxi ha PbS PbSO4.
g) Vi p(H2S) = 5.1.10-9 bar th
2.6 104 4 10
3
G(1) = -56,3 kJ/mol + RTln -43 kJ/mol.
5,1.109
Trong khng kh xy ra ng thi 2 qu trnh: to ra v lm mt PbS.
k1
PbCO3 (r) + H2S (k) PbS + ...
O2
PbSO4
k2
Xt v phng din nhit ng hc th s oxi ha PbS bi oxi khng kh thun li hn rt nhiu. S
i mu ca PbCO3 c th l do phn ng oxi ha PbS bi oxi khng kh b cn tr ng hc.

Cu 5 (2,5 im)
5.1 (2/4 im, mi cht im)
BX3 - hp cht thiu electron nn c tnh cht c trng l nhn thm i electron (axit Lewis). bo
ha electron, BH3 v BCl3 c hai cch khc nhau:
- BCl3 nhn thm e bng cch to thm lin kt pi (khng nh ch) vi ba nguyn t Cl bn cnh.
Phn t c cu trc tam gic phng.

Trang 5/9
- H khng th to lin kt pi nn, BH3 nhn thm e bng cch to lin kt ba tm 2 electron B-H-B to
thnh ime B2H6. Phn t c cu trc ime gm hai t din BH 4 ni vi nhau qua hai nguyn t H cu
ni (H/s phi v hnh minh ha)

5.2. (2/4 im)

(1/4) t cng thc n gin nht ca A, B l XCln v XClm ta c
M X m.35, 45
1,516 M X 68, 70.(m 1,516n)
M X n.35, 45
thay cc gi tr nguyn m, n s c
m 2 3 4 4 5 5 5 6 6 6
n 1 1 1 2 1 2 3 1 2 3
MX 33.25 101.95 170.65 66.50 239.35 135.20 31.05 308.05 203.90 99.75
X (loi) (loi) (loi) (loi) (loi) (loi) P (loi) (loi) (loi)

p s ph hp m =5, n = 3, Mx = 31,05 tng ng vi X l P

(1/4 im)
Cl Cl
Cl
A l PCl3 B l PCl5 P Cl
P
Cl Cl
Cl Cl

5.3. (9/8 im)

Ch da vo cu trc phn t ca A v B, hc sinh c th d on A s phn ng vi BCl3 v trn P
cn i e cha tham gia lin kt cn B th s khng phn ng, ngc vi d kin u bi cho.
- Cng thc d on sn phm (nu c) ca A v BCl3 l
Cl Cl
Cl
P B
Cl
Cl Cl

- D on hnh thnh lin kt cu Cl l khng logic, v kh nng cho cp e ca P tt hn nhiu cho

vi Cl cng ha tr trong P-Cl (khng so vi anion Cl -). Mt khc nu BCl3 khng c xu hng to
lin kt cu nh B2H6 hay Al2Cl6.
-Bn cht l khi to thnh lin kt P-B, cu trc tam gic phng ca BCl 3 chuyn thnh chp tam
gic, h khng nh ch ca BCl 3 b ph v. Lin kt Cl3P:BCl3 khng b p nng lng cn
ph v h khng nh ch ca BCl3 do vy A khng phn ng vi BCl3
(6/8 im) Cu trc hnh hc ca C:

- T l lun trn, C khng th l hp cht cng ha tr kiu Cl4PCl BCl3

- C khng tan trong CCl4 => l hp cht ion
- BCl3 ch c mt cch duy nht to ion: BCl3 + Cl
[BCl4]
- PX5 c kh nng mt X- to nn [PX4]+ (v cng c kh nng nhn 1 Cl- to nn [PX6]-)

(PX5 c th to thnh anion bt din PX6- khi lin kt P-X bn v X c kch thc b (X = F, Cl) v cation t din PX 4+
khi X c kch thc ln (X = Cl, Br, I.). Thc t, th rn, PCl 5 tn ti dng [PCl4]+[PCl6]- lm bn mng li tinh
th dn n n c nhit thng hoa cao hn rt nhiu so vi nhit nng chy ca PCl 3 - Hc sinh khng cn gii
thch iu ny)

Trang 6/9
 - Nu hoc sinh d on c to thnh cation PCl32+ th khng hp l v n l axit Lewis mnh hn
BCl3 rt nhiu nn n s ly Cl- ca BCl4- Cl Cl

- Kt hp li ta c th d on cht D l [PCl4]+[BCl4]- P Cl B Cl
Cl Cl Cl Cl
(2/8 im) Cu trc hnh hc suy lun t thuyt VSEPR nh hnh bn

(1/8 im) [PCl4]+[BCl4]- + 7H2O H3PO4 + H3BO3 + 8HCl

5.4. (3/8 im) mi phn ng 1/8 im

a. BCl3 + (CH3CH2)3N (CH3CH2)3N:BCl3 (BCl3 th hin tnh axit Lewis)
b. Hc sinh c th vit mt trong hai phn ng sau
2BCl3 + 6NaH (d) B2H6 + 6 NaCl (thay th X bng H, hay gc ankyl)
BCl3 + 4NaH (d) Na[BH4] + 6 NaCl
o
1000 C
c. BCl3 + NH3 BN + 3HCl

Cu 6. ( 3,0 im)
6.1. (2/4 im) Cng thc YBa2Cu3O7
6.2. ( 2/4 im) 1/2 Y2O3 + 2BaCO3 + 3CuO + 1/4 O2 YBa2Cu3O7 + 2CO2
Ch : - Sn phm l CO khng c im v CO s kh A
- H/s c th vit di dng hn hp oxit, hoc cn bng vi h s nguyn, hoc vit
phn ng qua nhiu giai on..

6.3. (4/4 im) S oxi ha trung bnh ca Cu = +7/3 trong c hai loi ion Cu khc nhau, +2 v +3.
C 1 nguyn t Cu nh mng c s c s phi tr 4, vung phng (s oxi ha n)
C 2 nguyn t Cu (hon ton ging nhau) trn cnh mng c s c s phi tr 5, chp y vung
(s oxi ha m)
S oxi ha trung bnh (n + 2m)/3 = 7/3. n =3, m=2 l ph hp.
Vy c mt Cu+3 nm nh (cu hnh d8 ph hp vi cu trc vung phng)
C hai Cu+2 nm trn cc cnh mng c s.
Ch : Hc sinh khng ch ra c c im khc nhau gia hai loi Cu, m ch da vo v tr ca n,
khng c im.
6.4. (4/4 im) : vit PTP c 2/4 im, tnh ton c 2/4 im.
t cng thc YBa2Cu3Ox, MA = 554,2 + 16x
s oxi ha trung bnh ca Cu = n = (x-3,5).2/3 = (2x-7)/3
Phn ng oxi ha KI: Cu+n + (n1)e + I CuI

(n-1)I (n1)e (n1)/2 I2
+n
Cu + nI CuI + (n1)/2 I2
n 1 0,3315 2 x 10 0,3315
S mol I2 = . .3 thay gi tr ca n => S mol I2 = .
2 554, 2 16 x 2 554, 2 16 x
Phn ng chun : I2 + 2S2O32 2I + S4O62,
0,3315.(2 x 10)
S mol ca S2O32 = 2 x nI2 = = 0,018 . 0,1 = 0,0018 mol
554, 2 16 x
1,913 x = 13,009 => x = 6,8 => cng thc thc nghim: YBa2Cu3O6,8

Trang 7/9
Cu 7. (10/4 im)
7.1. (3/4 im)
0 0
t nng ca SO2 v Na2SO3 trc khi trn l C1 = CSO ; C2 = CSO2
2 3

sau khi trn: CSO = 0,5C1; CSO2 = 0,5C2.

2 3
pK a1 pK a2
Khi chun dung dch A n pH = 4,4 = 4,485 = pHHSO-3 thnh phn ca
2
h thu c l HSO-3 , ngha l trong hn hp A phi c SO 2. Nh vy sau khi trn dung dch SO 2 vi
dung dch Na2SO3, SO2 cn d:
2-
SO2 + H2O + SO3 2 HSO-3
0,5C1 0,5C2
0,5(C1 C2) 0 C2

Thnh phn ca dung dch A: SO 2 0,5(C1 C2) M; HSO-3 C2 M, mi trng axit Khi chun
dung dch A n pH = 4,4 dung dch s chuyn t mu sang mu vng. Thm tip phenolphtalein
vo hn hp chun v chun n pH = 9,0 dung dch s chuyn t mu vng sang mu hng.
Chun n pH = 4,4 h thu c gm HSO-3 v SO2 (b qua SO32) trong HSO-3 chim
[HSO-3] K a1 101,76
0,998 99,8% 100%=> chun ht nc 1
[HSO-3] [SO2] [H+] K a1 104,4 101,76

SO2 + OH HSO-3
20,00 . 0,5.(C1 C2) = 12,50 . 0,20 (1)

Chun n pH = 9,0, h gm HSO3- v SO32- (b qua SO2):

[SO32- ] K a2 107,21
0,984 = 98,4% 100%
[HSO-3] [SO32- ] [H+] K a2 109,0 107,21
thnh phn ca h gm 100% SO32- , chun ht nc 2
HSO-3 + OH SO32- + H2O
20,00 . {0,5(C1 C2) + C2} = 27,50 . 0,20 (2).
T (1) v (2) C2 = 0,15 M; C1 = 0,40 M

7.2. ( 1/4 im) Khi cha chun , pHA chnh l pH ca h m:

SO2 + H2O HSO-3 + H+ Ka1 = 10-1,76
0,125 x 0,15 + x x
x.(0,15 x)
101,76
0,125 x
x = [H+] = 0,012 pHA = 1,92

7.3. (1/4 im) Theo bi chun dung dch A vi 2 ch th ring r, nn trn ng cong chun
s c 2 bc nhy chun .

Trang 8/9
 0,016 1000
7.4. (3/4 im) Gi tan ca BaSO3 trong nc l s s = . = 7,36.10-4 (M)
217,33 100
2-
BaSO3 Ba2+ + SO3 Ks = ? (1)
s s
SO32- + H2O HSO-3 + OH- Kb1 = 10-6,79 (2)

HSO-3 SO2 + OH Kb2 = 10-12,24 (3)

V Kb2 << Kb1 nn c th b qua (3). Xt qu trnh (2):
SO32- + H2O HSO-3 + OH Kb1 = 10-6,79
C 7,36.10-4
[ ] 7,36.10-4 x x x x = 1,08.10-5
- -
Vy [OH ] = [HSO3 ] >> Kb2. B qua (3) l hp l.
2-
[Ba2+] = s = 7,36.10-4 (M); [ SO3 ] = 7,36.10-4 - 1,08.10-5 = 7,25.10-4 (M)
Ks = [Ba2+].[ SO32- ] = 5,33.10-7

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