TRNG I HC VINH

KHOA HO HC
P N THI OLYMPIC HA HC SINH VIN-2015
========
Cu 1 (5 im)
1.1. a) p dng phng trnh kh l tng:
pV
101300 205
nCH4
6
8.38 103 mol
RT 10 8.314 298.15
1 8.38 103 16
nH 2O
4.81102 mol.
18
2
n = 4.8110 / 8.38 103 5.75 --> CH45.75H2O
H 1 1
R T T
1 2

b) Thay T1 = 298 , T2 = 268 , p1 = 1 atm vo phng trnh p2 p1e

xc nh c p2
= 0,45 atm hay 45kPa.
1.2.
+ I1(O) < I1(N): do cu hnh electron ca N na bo ha phn mc ngoi cng (2p3) nn bn hn
ca O (phn mc ngoi cng 2p4- hn cu hnh na bo ha 1 electron).
N: 2p3
O: 2p4
+ Gin MO ca cc phn t N2 v O2: khc nhau cc electron c nng lng cao nht in
vo cu hnh MO (v c gin nng lng MO ca N2 v O2):
lk 2
* 2
lk 4
lk 2
* 0
*
lk
N2
s )
s )
x y )
z )
x y ) khng c e trn MO . MO nng lng thp hn
AO ca N
lk 2
* 2
lk 2
lk 4
* 2
O2
c 2 e trn MO* nng lng cao hn AO trong
s )
s )
z )
x y )
x y )
O.
Do c electron trn MO * nn I1(O2) < I1(N2) v I1(O2) < I1(O),
Do e cao nht trong N2 in vo MOlk nng lng thp hn AO N nn I1(N2) > I1(N).
1.3. a) Khi tng p sut lc u mu s m hn sau nht i, nhng vn m hn so vi lc
cha tng
Khi gim p sut lc u mu s nht hn sau m ln, nhng vn nht hn so vi lc cha
gim.
b)
N2O4
2NO2
Tng s mol
Cn bng
a(1 - )
2a
a(1 + ) = 0,0024.
Vi a = 0,002 = 0,2 = 20%.
Kp = P.4. 2/(1 - 2) = 0,17.
Nu = 0,3 P = 0,43 atm.
Cu 2 (4 im)
2.1. Vi dung dch: NaHCO3 tnh c pH = 8,34
NaHSO3 tnh c pH = 4,50
NaHC2O4 tnh c pH = 2,80
- Dng metyl da cam nhn ra dung dch NaHC2O4 qua du hiu ha hng
- Dng phnolphtalein nhn ra dung dch NaHCO3 qua du hiu ha hng
- Dung dch NaHSO3 lm metyl ha vng.
2.2. Dung dch CH3COOH c pH = 3,5 nn [H+] = 10-3,5
Nng ban u:
Nng sau p.:

CH3COOH CH3COO- + H+
C
C-10-3,5 10-3,5 10-3,5
K

(10 3,5 ) 2
C 10

3,5

10 4,76

Ka = 10-4,76

C = 6,07.10-3M

- Dung dch Ba(OH)2 c pH = 11,5 [H+] = 10-11,5 [OH-] = 10-2,5 = 3,16.10-3M.

Sau khi pha trn dung dch, ta c:

CH COOH
3

6,07.10 3.10
3,035.10 3 ;
20

C
OH

3,16.10 3.10
1,58.10 3
20

CH3COOH
+ OH- CH3COO- + H2O
-3
Nng ban u:
3,035.10
1,58.10-3
Nng phn ng:
1,58.10-3
1,58.10-3
1,58.10-3
Nng sau phn ng:
1,455.1
1,58.10-3
Ta c dung dch m: CH3COOH 1,455.10-3M + CH3COO- 1,58.10-3M
CH3COOH
CH3COO- +
H+
Ka = 10-4,76
Nng ban u:
1,455.10-3
1,58.10-3
-3
Nng sau p.:
1,455.10 x
1,58.10-3 + x
x

Ka

x.(1,58.10 3 x)
10 4,76
1,455.10 3 x

x = 1,565.10-5 = [H+] pH = 4,8

2.3.

2.(Vtb.C )
2.(Vtb.C ).10 5
mol / lCaCO
mg / lCaCO
3
3
V
V

cng (C) = 162 mg CaCO3/ lit

Cu 3 (5 im):
3.1. C th xy ra 1 trong hai trng hp sau:
Th nghim
Hin tng
Ly vo ng nghim 1 t
Bt S tan to
bt S, cho thm vi git
thnh dung dch
etanol thm t, thm t
khng mu
t khong 2-3ml dung dch
NaOH 2N, un nng nh
n khi cht rn tan ht
1

Gii thch
S phn ng vi dung dch NaOH theo phng
trnh ha hc sau:
3S + 6NaOH 2Na2S + Na2SO3 + 3H2O

Ly vi git dung dch

sang mt ng nghim khc,
nh t t tng git dung
dch HCl long

C kh mi xc
thot ra

Do xy ra cc phn ng sau:
Na2S + 2HCl 2NaCl + H2S
Na2SO3 + 2HCl 2NaCl + H2O + SO2

Ly vo ng nghim 1 t
bt S, cho thm vi git
etanol thm t, thm t
t khong 2-3ml dung dch
NaOH 2N, un nng nh
n khi cht rn tan ht

Bt S tan to
thnh dung dch
mu vng

Do xy ra cc phn ng sau:
3S + 6NaOH 2Na2S + Na2SO3 + 3H2O
S d tip tc phn ng:
(n-1)S + Na2S Na2Sn (n2) (vng)
S + Na2SO3 Na2S2O3

Ly vi git dung dch

sang mt ng nghim khc,
nh t t tng git dung
dch HCl long

C kh mi xc
thot ra, xut
hin vn c
mu vng, dung
dch t mu vng
chuyn thnh
khng mu

Do xy ra cc phn ng sau:
Na2Sn + 2HCl 2NaCl + H2S + (n-1)S
Na2S2O3 + 2HCl 2NaCl + H2O + SO2+ S
C th cn c cc phn ng sau:
Na2S + 2HCl 2NaCl + H2S
Na2SO3 + 2HCl 2NaCl + H2O + SO2

3.2.

a/ Phng trnh phn ng:

MnO2 + 4HCl(c) MnCl2 + Cl2 + 2H2O
thu c kh clo kh, sch cn phi s dng cc cht trong bnh 1 v 2 c tc dng lm sch
v kh kh clo.
- Kh clo iu ch theo s trn thng c ln kh HCl, lm sch ta cn s dng 1
cht hp th kh HCl bnh 1, thng dng H2O (v HCl d tan trong nc, cn kh clo rt t tan
trong nc).
- Kh clo sau khi dn i qua bnh 1 s cha hi nc, lm kh ta cn phi s dng 1
cht ht nc bnh 2, thng dng dung dch H2SO4 c.
b/ Trong th nghim trn vai tr ca MnO2 l cht oxi ha mnh v dng rn, do c th thay
MnO2 bng cc cht rn c tnh oxi ha mnh tng t nh: KMnO4, K2Cr2O7, PbO2tuy nhin
trong phng th nghim thng s dng MnO2 l ha cht ph bin v r tin hn.
c/ Trong th nghim ny khng th s dng dung dch HCl long, v trong dung dch HCl long
(ch yu cha H+ v Cl-) c tnh kh yu hn dung dch HCl c (c cha HCl), nn phn ng
khng xy ra.
d/ Cc lu v an ton trong th nghim:
- Th nghim s dng dung dch HCl c d bay hn, l kh c
- Sn phm kh Cl2 to thnh l kh c
Do khi tin hnh cn ch :
- Tin hnh th nghim trong t ht
- Cn thn khi ly dung dch HCl c
- S dng lng ha cht va , trnh trng hp kh Cl2 to thnh tht thot ra ngoi
gy c (nu lng kh to thnh nhiu khng s dng ht cn hp th vo dung dch kim)
3.3. Gi tr pH ca nc bin i dng c xu hng gim dn theo s liu sau:
Thi k
Trc cch mng cng nghip (th k 18)
Nhng nm 1990 Nm 2005
Gi tr pH
8,179
8,104
8,069
a) Gii thch nc bin c pH>7, trong khi mu nc ct trong khng kh c pH nh
hn 7.
+ Nc bin cn bng vi h khong cht canxi cacbonat (v c magie cacbonat), nn c
cn bng:
CO2 + MCO3 + H2O = M(HCO3)2
V cha nhiu HCO3- nn pH > 7.
Nc ct ch c ha tan CO2 t kh quyn m khng cha MCO3, nn cha CO2 ha tan
c phn ly axit:
CO2 + H2O = H+ + HCO3- pH<7.
b) nh gi mc gim pH v mc tng nng [H+] ca nc bin theo s liu trn
+ pH:
Thi k
Trc cch mng cng nghip (th k 18)
Nhng nm 1990
Nm 2005
Gi tr pH

], %

8,179

8,104

8,069

0,075 (trong gn 300 nm)

0,035 (trong 15 nm)

Tng 18,85% (trong gn 300 nm)

Tng 8,39% (trong 15 nm)

+ S gim pH nc bin th hin nh hng ca s tng hm lng CO2 trong kh quyn

cn bng vi nc i dng, v CO2 t do trong nc to ra cn bng phn ly H+:
CO2 + H2O = H+ + HCO3- Tc gim pH nh vy c xu hng tng dn nhanh. Do n s nh hng n cc
cn bng ha hc v cc h sinh thi bin lin quan n CO2 v h cacbonat.

+ Thi cn thit t hiu bit trn: s gia tng hm lng CO2 trong kh quyn rt nhanh
chng, tc ng rt mnh m n mi trng ton cu thng qua cc hiu ng mi trng khi
quyn, nc bin (c th lit k mt s hiu ng mi trng). Cn tng cng ph bin v thc
hin cc bin php, gii php mang tnh cn bn v ton cu gim thiu lng pht thi CO2,
quy m cng nghip cng nh i sng hng ngy, mi quc gia cng nh ton th gii (c th
lit k mt s gii php c th).
Cu 4 (4 im)
4.1. Phn ng iu ch ietyl phtalat (DEP):
O
+ 9/2O2

V2O5, to

C
O

+ 2CO2 + 2H2O

C
O

C
O

+ 2C2H5OH

O
C OC2H5

H2SO4 c

+ H2O

to

O
- Phn ng iu ch i-2-etylhexylphtalat (DEHP):

OC2H5

4.2. Lp lun xc nh c CTCT v tn gi ca cc cht A, B v C l:

CH2CH3

CH3

CH3

CH3

H3C

CH3

CH3

1,3,5-trimetylbenzen (A)

1,2,3-trimetylbenzen (B)

CH3
1-etyl-4-metylbenzen (C)

4.3. a) T chuyn ha ca eugenol thnh metyleugenol v axit eugenoxiaxetic suy ra cng thc
cu to ca eugenol:
HO

CH2CH=CH2

H3CO
-T chuyn ha (3) ta c cng thc cu to ca isoeugenol v vanilin l:

HO

CH=CH-CH3

HO

CHO

H3CO
isoeugenol
vanilin
b) nh gi gn ng v nhanh chng hm lng eugenol trong mt loi tinh du hng nhu,
ta da trn nguyn tc eugenol tc dng vi dung dch kim to thnh eugenat tan trong nc,
phn cn li l hn hp nhiu cht phc tp m a phn l hidrocacbon khng tc dng vi dung
dch kim, khng tan trong nc v nh hn nc nn ni ln trn. T ta tin hnh phn ng
trong bnh cassia (hay bnh nh mc c chia vch). Sau khi thc hin phn ng xong, cho thm
th tch dung dch kim a phn tinh du khng tham gia phn ng ln phn c bnh c chia vch.
c lng tinh du khng tham gia phn ng phn c bnh.
Hm lng phn trm eugenol trong tinh du c tnh theo cng thc:
X%= (a-b).100/a
a: lng tinh du em nh lng (ml)
b: lng tinh du c c phn c bnh (ml)
Cu 5 (2 im)
Principle of COD determination

H3CO

In environmental chemistry, the chemical

oxygen demand (COD) test is commonly used to
indirectly measure the amount of organic
compounds in water for evaluation of water
pollution.

Trong ha hc mi trng, th
nghim xc nh nhu cu oxy ha hc
(COD) thng dng o gin tip hm
lng cht hu c trong nc nhm nh
gi s nhim nc.

The organic matter present in environmental water

sample gets oxidized completely by potassium
dichromate (K2Cr2O7) in the presence of sulfuric
acid (H2SO4), siver sulfate (Ag2SO4) and mercury
sulfate (HgSO4) to produce CO2 and H2O. The
sample is refluxed with a known amount of
potassium dichromate (K2Cr2O7) in the sulfuric
acid medium and the excess potassium dichromate
is determined by titration against ferrous amonium
sulfate, using ferroin as an indicator. The
dichromate consumed by the sample is equivalent
to the amount of oxygen required to oxidize the
organic matter of the sample

Cc cht hu c trong mi trng nc b

oxy ha hon ton bi kali icromat c mt
axit sulfuric, bc sulfat v thy ngn sulfat,
to thnh CO2 v nc. Mu c un
nng hi lu vi lng kali icromat
bit trc trong axit sulfuric v lng d
icromat c xc nh bng php chun
vi st (II) amoni sulfat, dng feroin
lm ch th. Lng icromat tiu tn bi
chun mu tng ng lng oxy cn
thit oxy ha cht hu c trong mu.