FORUM OLYMPIAVN

K THI CHN HC SINH GII QUC GIA NM 2015

BOX HA HC

THI LUYN TP S 2
MN: Ha hc
PHN: Ha hc v c
Thi gian lm bi: 180 pht

Bi 1:
1. D c cng cu hnh electron lp ngoi cng l 6s1 nhng Cs (3,9 eV) li thp hn rt nhiu
so vi Au (9,2 eV). Hy gii thch s khc bit ny.
2. Vo nm 2000 ngi ta tng hp c mt phc axit / baz Lewis Me3NSO3. Hy v cu
trc ca phc cht ny, cho bit kiu lai ha ca N v S v th a ra d on cho gc CNS v
NSO (c gii thch).
3. S tn ti ca hp cht AgSO4 vn ang l mt ch rt c quan tm. Derzsi v cng s
a ra ba kh nng sau: Ag(II)SO4, Ag(I)2S2O8 v Ag(I)Ag(III)SO4. Hy xc nh momen t
ca tng kh nng (manheton Bohr) v cho bit c th phn bit c tng kh nng ch da
trn duy nht gi tr spin hay khng.
4. t chy mt nguyn t M trong khng kh 600oC thu c oxit MO2 cha 23,72% oxy v
khi lng. Bit khong cch gia hai nguyn t gn nhau nht trong mng c s lp
phng tm din ca kim loi l 269 pm. Hy xc nh khi lng ring ca kim loi ny.
Bi 2:
1. -caroten l tin cht ca vitamin A. Mch lin hp ca n gm 22 nguyn t cacbon vi
di trung bnh mi lin kt l 144pm. C th coi h thng lin hp ca phn t ny nh hp
th mt chiu vi di xp x 3,17 nm. Mi nguyn t cacbon ng gp mt electron .
a) Tnh s chnh lch nng lng gia HOMO v LUMO trong h thng lin hp.
b) Tnh di bc sng m phn t hp th electron c th dch chuyn gia hai trng thi
ny.

2. Xt phn ng: N2(k) + O2(k) 2NO(k) (1)

a) Tnh cc gi tr nhit ng hc Ho298, Go298 v So298 ca phn ng ny nu bit rng
entanpy v nng lng t do ca s to thnh NO ln lt l Hof,298 = 91,25 kJ/mol v l
Gof,298 = 87,58 kJ/mol v gii thch ti sao phn ng (1) khng th xy ra iu kin chun
(p = 1 bar, T = 298 K)
b) Vit phng trnh biu din s ph thuc nng lng t do vo nhit , cho rng H v S
khng ph thuc nhit
c) Xc nh nhit phn ng m lng NO l 0,1% (v th tch). Cho rng trong khng kh
c 78% N2 v 21% O2. Gi tr hng s kh R = 8,31 J/mol.K
d) NO hot ng ha hc rt mnh, n d phn ng vi nhiu cht nh oxy, halogen Cho rng
NO tc dng vi brom qua mt c ch hai bc nh sau:
NO + Br2

k1

NOBr2

k2
NOBr2 + NO
2NOBr

giai on chm

S dng c ch ny hy thit lp phng trnh ng hc cho s to thnh NOBr

Bi 3:
1. Trong mt h nc, tc phn hy phng x 222Rn (thi gian bn hy, t, 3,8 ngy) c
xc nh l 4,2 nguyn t.pht-1(100 L)1. Ton b lng 222Rn sinh ra t qu trnh phng x
ca 226Ra (t 1600 nm) ha tan c hot phng x 6,7 nguyn t.pht1 (100 L)1. Hot
phng x khng thay i theo thi gian. Bit rng mi nguyn t 226Ra phn r cho mt
nguyn t 222Rn, th nn s hao ht trong hot ca 222Rn m ch n vic 222Rn b mt
khi h nc do mt lng ng k 222Rn tht thot do mt qu trnh cha r.
a) Tnh nng 222Rn trong h theo n v nguyn t.(100L)1 v mol.L1.
b) Nu qu trnh cha r y tun theo quy lut ng hc bc nht th hy tnh hng s tc ca
qu trnh ny (pht-1).
c) Hy th on xem qu trnh cha bit ny l mt qu trnh vt l, ha hc hay sinh hc. Gii
thch l do.

2. Phn ng 2NO + O2 2NO2 c c ch c ngh nh sau:

Vi k1 k-1 >> k2.

1 [2 ]

a) Hy xc nh cc tr s a, b, c trong cng thc: 2

= [] [2 ] [2 ]

b) Mt biu thc tc khc cho phn ng trn c dng:

[2 ]

= 3 []2 [2 ]

Biu thc ny c th c n gin ha nu thi im ban u [NO] : [O2] = 2 : 1. Biu thc

tc n gin ha c dng

[2 ]

= 3 [2 ] . Hy thit lp mi quan h gia k3 v k-3 v

tm gi tr ca x.
c) Chng minh rng nng ca O2 thay i theo thi gian bng cch a ra mt biu thc c
th.
Bi 4:
1.

Mt pin volta c thit lp t hai na t bo in ha cha in cc hydro. Mt trong s

chng c nhng chm vo 100 cm3 dung dch 0,1 M HCl v in cc cn li nhng vo trong
100 cm3 dung dch CH3COOH 0,1 M. p sut hydro trong cc dung dch l 1 atm, nhit 20 oC,
F = 96485 C mol1, R = 8.314 J mol1 K1, Ka = 1.7510-5.
Hy tnh:

a) Th ca pin iu kin cho.

b) Th ca pin khi thm 60 cm3 dung dch NaOH 0,1 M NaOH vo mi dung dch u.
c) Th ca pin khi pha long mi dung dch u 10 ln.
d) Th tch dung dch NaOH 0,1M (cm3) cn thm vo dung dch CH3COOH ban u th ca
pin l E = 0,150 V?
2. Mt trang sch c cha 0,86 g Al2(SO4)3. Nhng quyn sch 500 trang vo 5,0L nc ha
tan ton b lng mui nhm trong sch. Ly 1,0 mL dung dch thu c cho vo bnh nh
mc v pha long n 1,0L. Xc nh nng tt c cc ion trong dung dch cui cng. Bit
pKa ca qu trnh phn ly nc th nht ca Al3+ l 4,95.

Bi 5:
Mt hp cht A rt c c mu vng c sinh ra khi trn hai axit c B v C. Sn phm ph
ca phn ng l kh E mu vng v nc. Mc d hai axit c bit n t rt lu, nhng mi n
nm 1831 th ngi ta mi quan st thy phn ng to thnh A. Mt cch khc thu c A l tin
hnh phn ng gia hai kh E v D, qu trnh ny khng sinh ra sn phm ph. Tuy nhin nhit
cao phn ng xy ra theo chiu nghch. Kh D c to thnh khi cho kim loi chuyn tip I phn
ng vi axit long C. Nu dng axit c th thay v D thu c mt kh M mu nu. Trong c hai
trng hp u thu c duy nht mt mui J mu xanh da tri. Kh M phn ng vi nc thu c
hai axit C v F. Axit F khi phn ng vi axit G thu c hp cht H, hp cht ny khi phn ng vi
axit B cho hai cht A v G. Hp cht H c th xem nh anhydrit ca hai axit ny. Khi cho B phn ng
vi KMnO4 thu c mt lng nh kh E. Kh ny c s dng tng hp cht K bng cch cho
phn ng vi mui NaCN. Nhit phn Hg(CN)2 thu c L l mt cht c tnh i xng. Khi cho axit
G phn ng vi bari clorua thu c kt ta trng. Kh D chuyn thnh kh M khi tip xc vi khng
kh.
Xc nh cc cht cha bit.

p n

im

Bi 1: (3,0 im)
1. Cs: [Xe]6s1 cn Au [Xe]4f145d106s1. Electron d v f ca Au chn km nn Z*
ca Au ln hn nhiu so vi Cs. iu ny dn n I1 ca Au ln hn rt

0.75

nhiu.
2. Cu trc phn t
0,75

Gc CNS s rt gn vi gc t din l tng (109,5o). Do cc lng cc S=O

0,5

y nhau nn gc OSO s tng ln v gc NSO s gim xung (khong 107 ). C S v

N u lai ha sp3.
3. Ag(I) l d10 , khng c e c thn nn momen t l 0
Ag(II) l d9, c 1e c thn, momen t 1,73B
Ag(III) l d8, c 2e c thn, momen t 2,83 B
Do momen t khc nhau nn vic kho st tnh cht t c th phn bit
c tng kh nng c th.
4. T % oxy tnh c khi lng phn t M l 102,9 g/mol (M l Rh, HS
khng cn xc nh chnh xc M l kim loi no).
Vi mng lp phng tm din th a 2 4r = 2 x 269,0.10-10 cm
Tnh c a = 3,804.10-8cm.
T tnh c khi lng ring ca kim loi l 12,76 g/cm3
Ph ch: Cu ny sai , yu cu tnh khi lng ring kim loi thay v oxit nn rt
xin li cc bn. Cu ny s khng tnh im trong thang im chnh thc.

0,25 x 4

Bi 2: (4,0 im)
1. Caroten c 22 electron . Vy HOMO l MO th 11 v LUMO l MO th 12.

0,25

Mc nng lng c tnh theo cng thc E = n2h2 / 8mL2, v bc sng

0,5 x 2 p

c tnh bng cng thc E = hc /

T tnh c E = 1,38.10-19J v = 1,44.10-6 m

2.
a) H 0r 2 H 0f, 298 182,5 kJ

G 0r 2 G 0f, 298 175,6 kJ

S0r, 298

1
(H 0r, 298 G 0r, 298 )
T

0,25

S0r, 298 24,62 J/K

Phn ng khng xy ra do G

0,5
0
r, 298

dng.

b) G 0r H 0r T S0r

0,5

G 0r 182500 24.62 T (J)

c) K

p 2 ( NO)
p(O2 ) p(N2 )

(10 3 ) 2
6.1 10 6
0.78 0.21

1,0

G 0r RTlnK
G0r 8.31 T ln(6.1106 ) 99.72 T

182500 24.62 T 99.72 T

T 1468 K
d) v

d NOBr
k 2 NO NOBr2
dt

v1
k NO Br2
1
v 1 k 1 NOBr2

0,25

v k2

v k2

v1
NO NOBr
v 1

0,25

k1
NO2 Br2 k'NO2 Br2
k 1

Bi 3: (4,0 im)
1.
a) Thi gian bn hy ca 222Rn = 0,693/3,8 ngy = 0,18 ngy-1 tc 1,3.104ph-1
Do tc phn r ca 222Rn l 4,2 nguyn t.ph-1.(100L)-1 ta c:

0,75

4,2 = kRnCRn CRn = 3,2.10-4 nguyn t.(100L)-1 = 5,5.10-22 mol.L-1

b) Do hot ca 222Rn khng thay i theo thi gian nn qu trnh sinh ra Rn
qua s phn r ca 226Ra phi cn bng vi qu trnh phn r phng x ca

0,75

chnh n v s mt mt do qu trnh cha bit. Da trn nh lut bo ton

khi lng ta rt ra c: 6,7 nguyn t.ph-1.(100mL)-1 = (kRn + kcha bit).CRn
Tnh c k = 0,79.10-4 ph-1
c) Do Rn l mt kh tr nn ch c th chu nh hng bi cc yu t vt l nh
nhit v p sut trong h. (Tht ra s mt Rn chnh do s khuch tn cc

0,5

phn t Rn trn b mt thot ra mi trng ngoi).

2.
a) Ta c:
1 d [ NO 2 ]

k 2 [ N 2O 2 ][ O 2 ]
2
dt
k
[ N 2O 2 ]
k
K 1
[ N 2O 2 ] 1 [ NO ] 2
2
k 1
k 1
[ NO ]
kk
v 1 2 [ NO ] 2 [ O 2 ] a 2 b 1 c 0
k 1

0,25 x 3
gi tr abc

b) Ta c:

[ NO ]
2 [ NO ] 2 [ O 2 ]
[ O2 ]
d [ O2 ]
k3' [ O 2 ]( 2 [ O 2 ]) 2 4 k3' [ O 2 ] 3
dt
x 3 k 4 k3'

0,5

c) Biu thc lin h gia nng oxy vo thi gian

[ O2 ]

[O ]

2 0

d [ O2 ]
4 k3' dt
[ O2 ] 3
0

1
1

4 k3' t
2
2 [ O2 ]
2 [ O 2 ] 02

( ( 2 ))

0,75

1
1

2 k3' t
2
[ O2 ]
[ O 2 ] 02

Bi 4: (5,0 im)
1.

RT H
EE
ln
F
pH 2

0,5

a) 0,10 M HCl [H+] = 0,10 M E1 = -0,058 V

0,10 M CH3COOH [H+] = (Ka.C)1/2 = 1,32.10-3 M E2 = -0,167 V

0,5

Epin = 0,109V
b) 0,025 M HCl [H+] = 0,025 M E1 = -0,093 V
0,5

Dung dch 2 gm 0,025 M CH3COOH v 0,0375 M CH3COONa

H K a

cacid
1,17.105 M
cbase

E2 = -0,286V

0,5

Epin = 0,193V
c) 0,010 M HCl [H+] = 0,010 M E1 = -0,116 V

0,5

0,10 M CH3COOH [H+] = (Ka.C)1/2 = 4,18.10-4 M E2 = -0,196 V

Epin = 0,080V
d) E2 = 0,0252ln[H+] = -0,150 0,058 = -0,208 V [H+] = 2,60.10-4 M
0,5

c
c
H K a acid 2, 60.104 acid 14,8
cbase
cbase

Ta c nacid + nbase = 0,010 mol nbase = 0,010 / 15,8 = 6,30.10-4 mol

Vy th tch NaOH cn l 6,30 cm3
2. Gi c l nng Al2(SO4)3
Al2(SO4)3 + 12H2O 2[Al(H2O)6]3+ + 3SO42-

[SO42-] = 3c

(1)

[Al(H2O6)]3+ [Al(H2O)5OH]2+ + H+

Al ( H 2O)5 (OH ) 2 H
Ka
Al ( H 2O)36

H2O H+ + OH-

KW = [H+][OH-]

(2)
(3)

2c = [Al(H2O)6]3+ + [Al(H2O)5OH]2+

(4)

3[Al(H2O)6]3+ + 2[Al(H2O)5OH]2+ + [H+] = 2[SO42-] + [OH-]

(5)

T (3) ta c [OH-] = KW / [H+]

(6)

T (4) ta c [Al(H2O)5OH]2+ = 2c - [Al(H2O)6]3+

(7)

Thay (1), (6), (7) vo (5) ta c.

3[Al(H2O)6]3+ + 2(2c - [Al(H2O)6]3+) + [H+] = 6c +
H 2c Al ( H 2O)36

Thay (4) vo (2): K a

KW
H

KW
0
H

(8)
1,0

(2c Al ( H 2O)36 H
Al ( H 2O)36

Ka[Al(H2O)63+] = 2c[H+] [Al(H2O)63+][H+]

Ka[Al(H2O)63+] + [H+] = 2c[H+]

2c H
3

Al H 2O 6

H K
a

(9)

0,5

2c H

K
W 0
Thay (9) vo (8): H 2c

H K a H

[H+]3 + Ka[H+]2 2c[H+]2 2cKa[H+] + 2c[H+]2 KW[H+] KWKa = 0

[H+]3 + Ka[H+]2 (2cKa + KW)[H+] KWKa = 0
[H+]3 + 1,123.10-5[H+]2 5,656.10-12[H+] 1,123.10-19 = 0
[H+] = 5,00.10-7 M , pH = 6,30
[OH-] = 2,00.10-8M
[SO42-] = 7,54.10-7M
[Al(H2O)63+] = 2,15.10-8M

0,5

[Al(H2O)5OH2+] = 9,84.10-7M
Bi 5: (4,0 im)
A: NOCl

B: HCl

C: HNO3

D: NO

E: Cl2

F: HNO2

G: H2SO4

H: NOHSO4

I: Cu

J: Cu(NO3)2

K: CNCl

L: (CN)2

M: NO2

ng 5
cht
ABCDE
c 1,0.
0,25 x 4
cho FGHI
v 0,5 x 4
cho JKLM

FORUM OLYMPIAVN

K THI CHN HC SINH GII QUC GIA NM 2015

BOX HA HC

THI LUYN TP S 2
MN: Ha hc
PHN: Ha hc hu c
Thi gian lm bi: 180 pht

Bi 1:
1. Hp cht A (C12H4Cl4O2) c tm i xng v ba mt phng i xng. A bn nhit, khng lm
mt mu dung dch brom v kali permanganat.
a) Lp lun xc nh cu trc A.
b) D on trng thi tn ti ca A nhit thng v tnh tan ca n.
c) T cu to, hy cho bit liu A c bn vi nh sng, kim v axit hay khng.
2. Phn ng sau c gio s Severus Snape thc hin thnh cng:

Da trn c s , ng ta buc Harry phi tin hnh mt phn ng tng t nh sau

Tuy nhin d th mi cch nhng Harry vn tht bi, v cu cu b pht cm tc.

a) Gii thch v sao Harry khng th thnh cng?
b) Khng th gii thch c l do tht bi ca mnh, Harry cu cu Hermione. Theo bn
Hermione s gii thch nh th no?
Bi 2:
1. ngh c ch cho cc phn ng sau y:

2. Nm 2005, Paul A. Clarke ng dng phn ng ngng t Maitland Japp tng hp hiu
sut cao Centrolobine. Phn ng Maitland Japp c ng dng tng hp cht trung gian
X nh sau:

a)

xut c ch phn ng to thnh X

b)

T X hy xut cch tng hp Centrolobine c cu trc nh sau:

Bi 3:
Thc hin chui chuyn ha sau:

1. Xc nh cu trc cc cht A C
2. T nhng hp cht hu c khng qu 2 carbon cng nhng cht v c v nhng cht xc
tc cn thit khc, hy xut cch tng hp tc nhn s dng trong qu trnh chuyn
ha t B sang C
Bi 4:
1. Hp cht A (cng thc nh hnh bn) khi un nng trong axit s
chuyn ha thnh B (C16H24O4). Oxy ha B bng CrO3 tip sau
x l sn phm thu c vi H+ trong metanol thu c C
(C18H26O5). Kh ha C bng LiAlH4 ri tip cho phn ng vi
PDC/DMF thu c tetraxiclic D (C15H20O3).
Hy xc nh cu trc cc cht cha bit.
2. Trong qu trnh dn kho phng th nghim th nhn vin phng th nghim v tnh tm thy
mt chai ha cht b mt nhn. Khi c m np kim tra th l mt th cht lng mu tm
m bc mi kh ngi. C quyt nh th nhn dng hp cht mu tm ny ch bng phn
ng thy phn.
u tin c tin hnh thy phn cht ny bng KOH, un nng mnh trong nhiu gi. Nhng
sau khi c cho nc vo tch ly lp hu c th ngc nhin cha, ch c nht mt pha
nc.
Tht vng, c thay i iu kin phn ng, chuyn sang s dng axit sunfuric c v cng
tin hnh un nng thy phn trong vi gi. Nhng pha sau mt ni bun l mt ni bun
ln hn, khi c tin hnh x l vi nc ly pha hu c th kt qu th nghim cng chng
khc g ln u tin c.
Khng cn cch no khc, c cu Bt ph h. V vi cu hi quen thuc Ti sao con khc th
Bt a ra cho c mt li khuyn hu ch: Hy thy phn trong iu kin m du. V ln
ny vi xc tc axit photphoric, mi lm pht un nng, sau thm base yu th c thu
c mt cht kt ta mu trng. Xc minh sau cho thy sn phm mu trng ny l mt
dn xut thm c cng thc phn t C7H8N2O.

a) Hy gii thch qu trnh th nghim v a ra nhng cu trc c th c ca cht lng mu tm.

b) Ti sao hp cht ny lu li c mu tm m?
Bi 5:
1. un D,L-alanin v -cloroacrylonitrin 1000oC trong anhydrit axetic d, ngi ta nhn thy
c s thot kh CO2 v sn phm duy nht thu c l 3-xiano-2,5-dimetylpyrole (A). xut
c ch cho s to thnh sn phm A.
2. X l mt andohexoz tn ti dng -pyranoz vi ch duy nht mt nhm th trc. Thoi
phn Wohl X thu c mt andopentoz m khi x l vi NaBH4 cho sn phm quang hot.
Lp lun xc nh cc cu trc c th c v ngh mt phng php xc nh chnh xc X.
3. Hy xut cch thc n gin nht nghch o cu hnh D, L ca mt -aminoaxit.

p n

im

Bi 1:
1. a) A l hp cht thm v khng lm mt mu dung dch brom v dung dch KMnO4. A c
khng no l 9. A thm, bn nhit nn da trn yu t i xng c th cho rng A gm

1,0

hai vng benzen ni vi nhau bng hai cu ete v tr ortho. Vy cng thc ca A l:

b) A c phn t khi ln, c nhiu lin kt phn cc nn n l cht rn. Da trn cu trc th
c th suy ra A km tan trong nc, tan tt trong dung mi hu c.

0,5

c) A tng i bn khi chiu sng bi h thm khng c lin kt no d b t khi chiu

sng. A c lin kt C sp2 Cl nn bn vng vi kim. A cng bn vi axit do cp e trn oxy

0,5

b lin hp vi h vng nn kh phn ng trong axit.

2. a) Nhn furan rt nhy vi mi trng c H+. Trong mi trng c H+ nhn furan b
polyme ha nhanh chng, dn ti khng thu c sn phm mong mun

0,5

b) thc hin phn ng trn thu c sn phm mong mun, cn thc hin nhng
iu kin sau:
- Chuyn nhm OH thnh mt nhm i ra tt

1,0

- To mt mi trng c anion Br- m khng c H+ thc hin phn ng m vng ba m

nhn furan khng b polymer ha
Hermione xut s dng cc acid Lewis mang anion Br- nh LiBr, MgBr2, khan v
kt qu thc nghim cho thy s dng MgBr2 thay cho HBr s gip thc hin phn ng

0,5

nh mong mun vi hiu sut kh (khong 30% 40%).

Bi 2:

1,0

1,0

2.a)

1,0

1,0

b)

Bc u tin nu th sinh s dng mi trng kim khng s dng km H2O2 s cho

phn ng retro-Michael
Kh nhm carbonyl khng s dng hon nguyn Wolf Kishner v mi trng kim s
u tin deproton OH ca nhn phenol thay v deproton trung gian hydrazine.
Bi 3:

0,75 x
3

0,75

0,5

0,5

Bi 4:

0,75 x
4

Cht rn mu trng sinh ra khi thy phn trong axit yu, tan km trong nc nhiu
kh nng l mt amit, tc cht u s l nitrin (thy phn nitrin trong axit v kim u
thu c axit c tan tt). Mt khc cht rn mu trng ch xut hin sau khi thm base

0,5

vo dung dch c axit ha trc cho thy cht rn mu trng s c nhm amin.
Nh vy hp cht cha bit c th c mt trong ba cu trc sau y

0,25

Hp cht c mu tm m do trong thi gian lu amin thm s b oxy ha thnh quinon.

0,25

Bi 5:
1. C ch

1,0

2. Da trn cu trc glucoz vn c cc nhm th nm e nn X buc phi l epimer

ca glucoz C2, C3 v C4. Tc X c th l mannoz, alloz hay galactoz.

1,0

Do thoi phn Wohl ri kh thu c anditol quang hot nn X ch c th l

mannoz hoc galactoz.
C th xc nh chnh xc X bng cch kh vi NaBH4, mannoz cho sn phm

1,0

quang hot cn galactoz th khng.

3. Qu trnh c biu din nh sau:
1,0