Tuyen Tap BT Hoa Vo Co

1
I. OLYMPIC HA HC VIT NAM:

K THI CHN HC SINH GII QUC GIA NM 2003 (BNG A)
1. Nhm clorua khi ho tan vo mt s dung mi hoc khi bay hi nhit khng qu
cao th tn ti dng dime (Al
2
Cl
6
). nhit cao (700
0
C) dime b phn li thnh monome (AlCl
3
). Vit
cng thc cu to Lewis ca phn t dime v monome; Cho bit kiu lai ho ca nguyn t nhm, kiu
lin kt trong mi phn t ; M t cu trc hnh hc ca cc phn t .
2. Phn t HF v phn t H
2
O c momen lng cc, phn t khi gn bng nhau (HF 1,91
Debye, H
2
O 1,84 Debye, M
HF
20,
2
H O
M 18); nhng nhit nng chy ca hidroflorua l
83
0
C thp hn nhiu so vi nhit nng chy ca nc l 0
0
C, hy gii thch v sao?
BI GII:
1.
* Vit cng thc cu to Lewis ca phn t dime v monome.
Nhm c 2 s phi tr c trng l 4 v 6. Ph hp vi quy tc bt t, cu to Lewis ca
phn t dime v monome:

Monome ; dime

* Kiu lai ho ca nguyn t nhm : Trong AlCl
3
l sp
2
v Al c 3 cp electron ho tr;
Trong Al
2
Cl
6
l sp
3
v Al c 4 cp electron ho tr .
Lin kt trong mi phn t:
AlCl
3
c 3 lin kt cng ho tr c cc gia nguyn t Al vi 3 nguyn t Cl.
Al
2
Cl
6
: Mi nguyn t Al to 3 lin kt cng ho tr vi 3 nguyn t Cl v 1 lin
kt cho nhn vi 1 nguyn t Cl (Al: nguyn t nhn; Cl nguyn t cho).
Trong 6 nguyn t Cl c 2 nguyn t Cl c 2 lin kt, 1 lin kt cng ho tr thng thng
v lin kt cho nhn.
* Cu trc hnh hc:
Phn t AlCl
3
: nguyn t Al lai ho kiu sp
2
(tam gic phng)
nn phn t c cu trc tam gic phng, u, nguyn t Al
tm cn 3 nguyn t Cl 3 nh ca tam gic.

Phn t Al
2
Cl
6
: cu trc 2 t din ghp vi nhau. Mi nguyn
t Al l tm ca mt t din, mi nguyn t Cl l nh ca t
din. C 2 nguyn t Cl l nh chung ca 2 t din.
- Al
O Cl

2.
* Phn t H-F Jt ; H-O-H

c th to lin kt hidro H
.
F c th to lin kt hidro H
O
M = 20
u = 1,91 Debye
M = 18
u = 1,84 Debye
O
O
O
O
O
O
Al
Cl
Cl Cl
120
0
120
0
120
0
Cl
Cl
Cl
Al
Cl
Cl
Cl
Al
Al
Cl
Cl
Cl
2
* Nhit nng chy ca cc cht rn vi cc mng li phn t (nt li l cc phn t)
ph thuc vo cc yu t:
- Khi lng phn t cng ln th nhit nng chy cng cao.
- Lc ht gia cc phn t cng mnh th nhit nng chy cng cao. Lc ht
gia cc phn t gm: lc lin kt hidro, lc lin kt Van der Waals (lc nh hng, lc
khuch tn).
*Nhn xt: HF v H
2
O c momen lng cc xp x nhau, phn t khi gn bng nhau v
u c lin kt hidro kh bn, ng l hai cht rn phi c nhit nng chy xp x
nhau, HF c nhit nng chy phi cao hn ca nc (v HF momen lng cc ln hn,
phn t khi ln hn, lin kt hidro bn hn).
Tuy nhin, thc t cho thy T
nc
(H
2
O) = 0
0
C > T
nc
(HF) = 83
0
C.
* Gii thch:
Mi phn t H-F ch to c 2 lin kt hidro vi 2 phn t HF khc hai bn
H-F
H-F
H-F. Trong HF rn cc phn t H-F lin kt vi nhau nh lin kt hidro to thnh chui mt
chiu, gia cc chui lin kt vi nhau bng lc Van der Waals yu. V vy khi un nng n nhit
khng cao lm th lc Van der Waals gia cc chui b ph v, ng thi mi phn lin kt hidro
cng b ph v nn xy ra hin tng nng chy.
Mi phn t H-O-H c th to c 4 lin kt hidro vi 4
phn t H
2
O khc nm 4 nh ca t din. Trong nc mi
phn t H
2
O lin kt vi 4 phn t H
2
O khc to thnh mng li
khng gian 3 chiu. Mun lm nng chy nc cn phi ph v mng
li khng gian 3 chiu vi s lng lin kt hidro nhiu hn so vi HF
rn do i hi nhit cao hn

K THI CHN HC SINH GII QUC GIA NM 2003
(BNG A)
Kim loi A phn ng vi phi kim B to hp cht C mu vng cam. Cho 0,1 mol hp
cht C phn ng vi CO
2
(d) to thnh hp cht D v 2,4 gam B. Ha tan hon ton D
vo nc, dung dch D phn ng ht 100 ml dung dch HCl 1 M gii phng 1,12 l kh
CO
2
(ktc). Hy xc nh A, B, C, D v vit cc phng trnh phn ng xy ra. Bit hp
cht C cha 45,07 % B theo khi lng; hp cht D khng b phn tch khi nng chy.
BI GII:
n
HCl
= 0,1 mol ; nCO
2
= 0,05 mol
Dung dch D phn ng ht 0,1 mol HCl gii phng kh CO
2

2
H
CO
n
n
+
=
0, 1
0, 05
=
2
1

suy ra hp cht D l mui cacbonat kim loi. Hp cht D khng b phn tch khi nng
chy, vy D l cacbonat kim loi kim. 2 H
+
+ CO
3
2-
= H
2
O + CO
2

C + CO
2
= D + B C l peroxit hay superoxit, B l oxi.
t cng thc ho hc ca C l A
x
O
y
.
Lng oxi trong 0,1 mol C (A
x
O
y
) l 16 x 0,05 + 2,4 = 3,2 (g); m
C
=
3, 2.100
45, 07
= 7,1 gam
Mc = 7,1 : 0,1 = 71 (g/mol). m
A
trong C = 7,1 - 3,2 = 3,9 (g).
x : y =
A
3, 9 3, 2
:
M 16
M
A
= 39 (g). Vy A l K ; B l O
2
; C l KO
2
; D l K
2
CO
3

3
Cc phng trnh phn ng: K + O
2
KO
2

4 KO
2
+ 2 CO
2
2 K
2
CO
3
+ 3O
2
|
K
2
CO
3
+ 2 HCl 2 KCl + H
2
O + CO
2
|
Vit phng trnh ho hc cho mi trng hp sau:
a) Cho kh amoniac (d) tc dng vi CuSO
4
.5H
2
O.
b) Trong mi trng baz, H
2
O
2
oxi ho Mn
2+
thnh MnO
2
.
Trong mi trng axit, H
2
O
2
kh MnO
4
-
thnh Mn
2+
.
BI GII:
a) C th vit CuSO
4
.5H
2
O dng [Cu(H
2
O)
4
] SO
4
.H
2
O. Do khi phn ng xy ra, NH
3
s th cc
phn t H
2
O cu ni:
[Cu(H
2
O)
4
] SO
4
.H
2
O + 4 NH
3
[Cu(NH
3
)
4
] SO
4
.H
2
O + 4 H
2
O
b) H
2
O
2
+ 2 e 2 OH
S kh
Mn
2+
+ 4 OH
2 e MnO
2
+ 2 H
2
O S oxi ho
Mn
2+
+ H
2
O
2
+ 2 OH
MnO
2
+ 2 H
2
O
c) 2 MnO
4
+ 8 H
3
O
+
+ 5 e Mn
2+
+ 12 H
2
O S kh
5 H
2
O
2
+ 2 H
2
O 2 e O
2
+ 2 H
3
O
+
S oxi ho
2MnO
4
-
+ 5 H
2
O
2
+ 6 H
3
O
+
2 Mn
2+
+ 5 O
2
+ 14 H
2
O

Nhng hai tm km, mi tm c khi lng 10 gam vo hai dung dch mui kim loi ho tr hai.
Sau mt thi gian xc nh, ly hai tm km ra khi dung dch, ra sch, lm kh ri cn li. Kt qa
cho thy mt tm c khi lng 9,5235 gam, tm kia c khi lng 17,091 gam.
Cho bit: Mt trong hai dung dch mui kim loi ho tr hai l mui st (II); lng km tham gia
phn ng hai dung dch l nh nhau.
1. Gii thch hin tng xy ra mi dung dch.
2. Cho bit kim loi no tham gia vo thnh phn dung dch mui th hai.
BI GII:
1. Khi nhng tm km vo dung dch mui Fe(II):
Zn + Fe
2+
Zn
2+
+ Fe (1)
V: M
Fe
< M
Zn
nn khi lng tm km gim i.
Khi nhng tm km vo dung dch mui th hai X
2+

Zn + X
2+
Zn
2+
+ X (2)
V: M
Zn
< M
X
nn khi lng tm km tng ln.
2. Gi x l s mol Zn phn ng, theo (1) ta c:
(10 65,38 x) + 55,85 x = 9,5235 x = 0,05 (mol)
V lng Zn tham gia phn ng 2 trng hp l nh nhau, theo (2) ta c:
(10 65,38 0,05) + M
X
0,05 = 17,091 M
X
= 207,2.
4
Vy X
2+
l Pb
2+
, X l Pb
Zn + Pb
2+
Zn
2+
+ Pb
Hon thnh cc phng trnh phn ng sau y:
1. NaCl + H
2
SO
4
c, nng
2. NaBr + H
2
SO
4
c, nng
3. NaClO + PbS
4. FeSO
4
+ H
2
SO
4
+ HNO
2

5. KMnO
4
+ H
2
SO
4
+ HNO
2

6. NaNO
2
+ H
2
SO
4
long
BI GII:
1. NaCl + H
2
SO
4
(c, nng) HCl + NaHSO
4

hoc 2 NaCl + H
2
SO
4
(c, nng) 2 HCl + Na
2
SO
4

2. 2 NaBr + 2 H
2
SO
4
(c, nng) 2 NaHSO
4
+ 2 HBr
2 HBr + H
2
SO
4
(c, nng) SO
2
+ 2 H
2
O + Br
2

2 NaBr + 3 H
2
SO
4
(c, nng) 2 NaHSO
4
+ SO
2
+ 2 H
2
O + Br
2

3. 4 NaClO + PbS 4 NaCl + PbSO
4

4. 2 FeSO
4
+ H
2
SO
4
+ 2 HNO
2
Fe
2
(SO
4
)
3
+ 2 NO

+ 2 H
2
O
5. 2 KMnO
4
+ 3 H
2
SO
4
+ 5 HNO
2
K
2
SO
4
+ 2 MnSO
4

+ 5 HNO
3
+ 3 H
2
O
6. 3 NaNO
2
+ H
2
SO
4
(long) Na
2
SO
4
+ NaNO
3
+ 2 NO

+ H
2
O

t chy kim loi magie trong khng kh. Cho sn phm thu c tc dng vi mt lng d
dung dch axit clohidric, un nng ri c dung dch n cn kh. Nung nng sn phm mi ny v lm
ngng t nhng cht bay hi sinh ra trong qa trnh nung.
Hy vit cc phng trnh phn ng xy ra trong th nghim trn v cho bit c nhng cht g
trong sn phm ngng t c.
BI GII:
Cc phn ng:
2 Mg + O
2
2 MgO
3 Mg + N
2
Mg
3
N
2
MgO + 2 HCl MgCl
2
+ H
2
O
Mg
3
N
2
+ 8 HCl 3 MgCl
2
+ 2 NH
4
Cl
MgCl
2
.6 H
2
O MgO + 2 HCl + 5 H
2
O
NH
4
Cl NH
3
+ HCl NH
4
Cl
Sn phm c ngng t: NH
4
Cl ; H
2
O ; HCl.
II. OLYMPIC HA HC QUC T:
t
o

t
o

5
OLYMPIC HA HC QUC T LN TH 28:
S polime ha lp th ca hydrocacbon cha no thng c coi l mt trong nhng phn ng
quan trng trong ha hc hu c cng nghip. Mui ca cc cation ln khng thng hng mang in tch
ln tn cng vo mt electron phn b dc theo cc lin kt t ca phn t olefin thng c
dng lm cht xc tc trong cc qa trnh ny. Anion cloroaluminat (AlCl
4
-
) thng c dng do c
n tch m c bt nh cao. Nhu cu pht trin cht xc tc mi thuc loi ny thc y cc nh
ha hc kho st tng tc trong h thng A B, trong A = Te (kt tinh) v B = TeCl
4
+ 4AlCl
3
. Hp
phn th hai B - c coi nh l mt cht tng t Te(IV) cloroaluminat Te[AlCl
4
]
4
, nhng li
khng th c lp c hp cht ny di dng hp cht ring bit. Ngwofi ta thy rng tng tc ca
cc hp phn A v B c th dn n s to thnh ba hp cht mi I, II v III trong cc h thng lc u
c cha theo th t 77,8; 87,5 v +1,7% theo s mol ca hp phn A. Ngi ta cng nhn thy trong
trng hp cc hp cht II v III khng c s to thnh sn phm ph km theo, nhng s hnh thnh
hp cht I c km theo s gii phng 1 mol TeCl
4
d bay hi ng vi 2 mol I.
C hai hp cht u c mu tm hng v c hai phn li thnh 3 ion m kho st tnh dn in
trong NaAlCl
4
cho thy: T php o nghim lnh tng NaAlCl
4
nng chy cho php tnh c khi
lng mol phn t ca I v II ln lt bng 112643g/mol v 86748g/mol. Ph hng ngoi IR ca c
hai hp cht ch quan st c c mt di c th c gn cho kiu rung ca lin kt tOo bi mt
nguyn t Te. Di ny nm tjai 133cm
-1
v v vy c nng lng thp n ni khng nghi ng g na
lin kt ny l mt loi Te-Te. S liu ph cng hng t ht nhn
27
Al NMR ca cc phc I v II cho
thy ch c mt loi nhm ph tr t din trong mi hp cht. Tuy nhin di ha hc quan st c
ca nhm vi cc hp cht I v II khc nhua, nh th cho thy cc nguyn t Al trong cc mi trng
khc nhau.
1. Hy xc nh t l nguyn t ti thiu ca Te:Al:Cl vi cc phc I, II v III.
2. Vit cng thc phn t ca cc hp cht I v II.
3. Vit cng thc cc anion v cation trong hp cht I v II.
4. Vit cng thc ha lp th ca cc cation v anion trong cu to ca I v II. Gi thit rng cc
cation trong I v II l nhng v d ca h thng thm v c.
5. I hay II c bn nhit cao hn. Bit rng AlCl
3
l mt cht cc k d bay hi.
6. Nu mt trong cc hp cht I v II c th chuyn thnh cht kia khi un nng th hy vit
phng trnh phn ng tng ng.
BI GII:
1. C th dng s lu v hm lng Te(kt tinh) xc nh cc t l Te:Al:Cl, nh vy:
77,8% Te (kt tinh) tng ng vi:
7Te (kt tinh) + 2TeCl
4
+ 8AlCl
3
v t l nguyn t b nht cho thnh phn m khng tch lng
d TeCl
4
l Te:Al:Cl = 9:8:32, trong hm lng Al v Cl l chn v c th chia ht cho 4. tng lc
hm lng Te vt qa bi s ca 4 l 1. Tr mt mol TeCl
4
t t l thu c ri chia cho 2 ta c
4Te+4Al+14Cl v t l l Te:Al:Cl = 2:2:7, t l ny c th c kim tra li bng cch so snh vi khi
lng phn t cho.
87,5% Te(kt tinh) ng vi:
7Te (kt tinh) + TeCl
4
+ 4AlCl
3
= 8Te + 4Al + 16Cl v t l l: Te:Al:Cl = 2:1:4
91,7% Te(kt tinh) ng vi:
11Te (kt tinh) + TeCl
4
+ 4AlCl
3
= 12Te + 4Al + 16Cl v t l l Te:Al:Cl = 3:1:4
2. Cng thc phn t c th c suy t cc khi lng phn t. C hai u ng vi gp i cng
thc n gin nht:
Vi cht I: Te
4
Al
4
Cl
14
.
Vi cht II: Te
4
Al
2
Cl
8
.
6
3. Thnh phn ca cc ion c trong cu to ca I v II c th c xc nh bng cch da trn c
im l c hai cht I v II u l nhng cht in ly to bi 3 ion v tt c nhng nguyn t telu
phi tng ng theo ph IR v ch c lin kt vi nhau, cng nh l cc nguyn t Al trong
c hai hp cht l tng t v c phi tr t din. t nht trong mt trng hp, c th l anion
AlCl
4
-
ph hp vi cht II nn v th c cng thc l [Te
4
]
2+
[AlCl
4
]
2
-
. Do mu tng t nn cc
cation trong c hai trng hp l tng t, cu to I phi cha cation [Te
4
]
2+
v anion [Al
2
Cl
7
]
-
,
iu ny ph hp vi cc s liu ph NMR, gn cho cc nguyn t Al trong cht I c hnh hc t
din khc so vi hnh hc t din ca cht II.
Hp cht I: Cation [Te
4
]
2+
Anion [Al
2
Cl
7
]
-

Hp cht II: Cation [Te
4
]
2+
Anion [AlCl
4
]
-

4. Hnh hc ca cc anion:
AlCl
4
-
c cu to t din n
Al
Cl
Cl
Cl
Cl

Al
2
Cl
7
-
gm hai t din c chung nh mt nguyn t clo
Al
Cl
Cl
Cl
Cl Al
Cl
Cl
Cl

Hnh hc ca cation: [Te
4
]
2+
c cu trc vung phng do c tnh thm.
Cu hnh vung phng l u i v cation c tnh thm, c ngha l ng phng v c bn lin
kt bng nhau cho cc cnh ca vng thm tng ng:
Te
Te
Te
Te
2+

5. bn nhit ca cht II phi cao hn cht I; c hai u l cc hp cht ion vi im nng chy
cao, nhng hp cht I c th chuyn thnh II bng phn ng tch AlCl
3
, l mt cht rn d tch
ra khi bay hi v c th tch ra mt cch tng i d dng nh un nng.
6. Te
4
[Al
2
Cl
7
]
2
= Te
4
[AlCl
4
]
2
+ AlCl
3
.
Gii hn d l mt trong nhng tham s c bn tng vic phn tch nh lng mt lng rt nh
(vt) ca cc nguyn t. Gii hn d c m t l khi lng nguyn t b nht c th c xc nh
bng mt phng php cho trc vi mt mc chnh xc cho trc. V d, xt hai phng php c
dng xc nh vi lng ca bitmut. Nm 1927, Bergh, nh ha hc ngi c, ngh rng bitmut
c th c kt ta di dng mui khng tan: 8-hydroxiqiunonlin tetraiodobitmutat
[C
9
H
6
(OH)NH][BiI
4
] c M = 862.7g/mol.
1) a) Vit cng thc cu to cation v anion ca mui ny.
b) Mc oxy ha ca nguyn t Bi trong hp cht ny l bao nhiu?
2) Xc nh khi lng nguyn t b nht ca bitmut (theo mg) c th c xc nh mt cch ng tin
cy bng phng php Bergh, nu khi lng b nht ca cht kt ta c th o c mt cch ng
tin cy l 50,0mg.
7
Mt phng php khc do R.Belcher v cng s t Birmingham pht trin xc nh hm
lng vt ca bitmut c gi l phng php a bi. Theo phng php ny, ngi ta tin hnh mt
chui cc phn ng ri tin hnh chun sn phm cui c m t chi tit di y.
Bc 1: Thm 50mg kali hexathioxianatocromat (III), K
3
[Cr(SCN)
6
] vo mt lng nh khong
2mL dung dch lnh c axit ho c cha mt lng vt Bi
3+
dn n kt ta nh lng ca bitmut.
3) Vit v cn bng phng trnh phn ng di dng ion thu gn.
Bc 2: Lc ly kt ta, ra bng nc lnh v x l vi 5mL dung dch natri hydrocacbonat
10%. Vic x l ny gip chuyn kt ta ban u thnh mt kt ta khc oxobitmut cacbonat
(BiO)
2
CO
3
vi s gii phng ion hexathioxianatocromat (III) vo dung dch.
4) Vit v cn bng phng trnh phn ng ny di dng ion thu gn.
Bc 3: Nc lc c axit ha nh v chuyn sang phu tch, sau thm 0,5mL dung dch iot
bo ho trong clorofom v lc mnh hn hp. Iot tin hnh phn ng oxi ha - kh vi ligand ca ion
phc v to thnh sn phm c c xianogen iodua [ICN] v ion sunfat.
Bc 4: Sau 5 pht, thm 4mL dung dch H
2
SO
4
2M vo hn hp. S axit ha ny dn n phn
ng oxy ha - kh vi s to thnh iot phn t.
Bc 5: Tch nh lng iot bng 4 phn clorofom. Lp dung dch nc c chuyn vo mt
bnh cha, thm vo 1mL nc brom v lc hn hp trong 5 pht. Brom ly d c th phn ng c
vi hydro xianua to thnh xianogen bromua BrCN v vi iot to thnh IO
3
-
.
Bc 6: loi lng d brom phn t, thm 3mL dung dch axit fomic 90% vo hn hp.
Bc 7: Thm lng d kali iodua (khong 1,5g) vo dung dch hi axit ny. Iot c th phn ng
vi BrCN theo cch tng t nh vi ICN to thnh iot phn t.
Bc 8: Chun dung dch thu c bng dung dch Na
2
S
2
O
3
0,00200M tiu chun. Nh vy
kt qa thu c s dng tnh hm lng bitmut trong mu em phn tch.
10) a) Vi mi mol bitmut c bao nhiu mol thiosunfat trong mu ban u?
b) Hm lng b nht ca bitmut c th xc nh c bng phng php Belcher l bao nhiu?
Gi thit rng s xc nh ny l ng tin cy nu dng khng di 1mL dung dch Na
2
S
2
O
3

0,00200M tiu chun.
11) Phng php phn tch a bi ny ca Belcher nhy hn phng php phn tch trng lng ca
Bergh bao nhiu ln?
BI GII:
1) a) Cng thc cu to ca cation v anion:
Cation:

N
H
OH

Anion:
8

Bi
I
I I
I

hay:
Bi
I
I
I
I

b) Mc oxy ha ca bitmut: +3
2) m = 12,1mg
3) Bi
3+
+ [Cr(SCN)
6
]
3+
= Bi[Cr(SCN)
6
]
4) 2Bi[Cr(SCN)
6
] + 6HCO
3
-

= (BiO)
2
CO
3
+ 2[Cr(SCN)
6
]
3-
+ 3H
2
O + 5CO
2
.
2Bi[Cr(SCN)
6
] + 5HCO
3
-

+ 5OH
-
= (BiO)
2
CO
3
+ 2[Cr(SCN)
6
]
3-
+ 3H
2
O v.v
(C th cn c nhng dng khc)
5) [Cr(SCN)
6
]
3-
+ 24I
2
+ 24H
2
O = Cr
3+
+ 6SO
4
2-
+ 6ICN + 42I
-
+ 48H
+

6) ICN + I
-
+ H
+
= I
2
+ HCN
7) a) 3Br
2
+ I
-
+ 3H
2
O = IO
3
-
+ 6Br
-
+ 6H
+
.
b) Br
2
+ HCN = BrCN + Br
-
+ H
+
.
8) Br
2
+ HCOOH = 2Br
-
+ CO
2
+ 2H
+
.
9) a) IO
3
-
+ 5I
-
+ 6H
+
= 3I
2
+ 3H
2
O
b) BrCN + 2I
-
+ H
+
= I
2
+ HCN + Br
-

10) a) Chun iot bng thiosunfat theo phn ng:
I
2
+ 2S
2
O
3
2-
= S
4
O
6
2-
+ 2I
-

Gi thit rng dung dch ban u cha 1mol Bi. Trong phn ng (5) mi mol Bi dn n s hnh
thnh 42 mol ion iodua ( thun tin, chia tt c cc h s ca phn ng cho 2), trong 6 mol ion I
-

c tiu th phn ng (6). Nh vy 36 mol iodua phn ng theo phng trnh 7a to 36mol IO
3
-

m vi phn ng 9a cho 108 mol I
2
nn cn 216 mol thiosunfat chun . Mt khc mt mol Bi
3+
to
ra 6 mol HCN theo cc phn ng (5) v (6). Brom oxy ha HCN trong phn ng 7b cho 6 mol BrCN,
m theo phn ng 9b to 6 mol iot nn cn thm 12 mol thiosunfat na. Nh vy, tng s mol thiosunfat
cn thit l 228mol.
b) ta c th tnh c kt qa l: 1,83.10
-3
mg = 1,83ug
11) 6600
Ligand (L) c th to phc c vi nhiu kim loi chuyn tip. L c tng hp do s un
nng hn hp gm bipiridin, axit axetic bng v hydro peoxit n 70-80
o
C trong 3 gi. Sn phm cui L
kt tinh di dng hnh kim nhuyn v c khi lng phn t bng 188. Mt phn ng tng t vi
piridin l:
9
N N
[O]
O

Phc ca L vi Fe v Cr c cng thc l FeL
m
(ClO
4
)
n
.3H
2
O (A) v CrL
x
Cl
y
(ClO
4
)
z
.H
2
O (B).
Thnh phn phn tch nguyn t v tnh cht l hc ca chng c cho trong bng 1 v 2. Quan h gia
mu v bc sng cho trong bng 3:
Bng 1: Thnh phn phn tch nguyn t:
Phc Phn tch nguyn t (% khi lng)
A Fe: 5,740; C: 37,030; H: 3,090; Cl: 10,940; N: 8,640
Cr: 8,440; C: 38,930; H: 2,920; Cl: 17,250; N: 9,080 B
Dng cc s liu sau:
S hiu nguyn t: Cr = 24; Fe = 26
Khi lng nguyn t: H = 1; C = 12; O = 16; Cl = 35,45; Cr = 52; Fe = 55,8
Bng 2: Tnh cht vt l:
Phc Momen t u (B.M) Mu
A 6,13 Vng
B Khng o Tm
Bng 3: Quan h gia bc sng v mu:
Bc sng (nm) v mu hp th Mu b sung (mu b)
400 (tm) Lc vng
450 (xanh) Vng
490 (lc xanh lam) Vng cam
500 (lc)
570 (lc vng) Tm
580 (vng) Xanh lam
600( Vng cam) Lc xanh lam
650 () Lc
1. Vit cng thc phn t ca L.
2. Nu L l mt ligand cng cua hai rng, vit cu tjao ca bipiridin dng. Vit cu to ca L
3. Ligand L c in tch tng cng l bao nhiu?
4. Vit cu to khi mt phn t L lin kt vi mt ion kim loi M
5. T cc s lu ghi trong bng 1 hy xc nh cng thc thc nghm ca A. Ga tr ca m v n trong
FeL
m
(ClO
4
)
n
.3H
2
O l bao nhiu?. Vit tn y ca A theo quy tn\c IUPAC. Khi A ho tan trong
nc th t l gia cation v anion l bao nhiu?
6. S oxy ha ca Fe trong A l bao nhiu? C bao nhiu electron d c mt trong ion Fe ca phc? Vit
cu hnh spin cao v spin thp c th tn ti c i vi phc ny. Cu hnh no, cao hay thp l
cu hnh ng? C chng c no l tt nht minh ho kt lun chn?
7. T bng 3, c lng bc sng (nm) ca A.
8. Phn tch chi tit B cho thy n c cha ion Cr
3+
. Hy tnh momen t ch vi spin ca hp cht ny.
9. Hp cht B l loi cht in phn 1:1. Hy xc nh cng thc thc nghim ca B v cc ga tr ca
x, y, z trong CrL
x
Cl
y
(ClO
4
)
z
.H
2
O.

10
BI GII:
1. Bit L c tng hp t bipiridin v trong phn ng bipiridin b oxy ha n gin thnh bipiridin
oxit.Khi lng phn t ca bipiridin l 156 (ca C
10
H
8
N
2
) trong khi khi lng phn t ca L l
188. Khc bit 32 do hai nguyn t oxy. V vy cng thc phn t ca L l C
10
H
8
N
2
O
2
.
2. Cu to ca bipiridin:
N N

Cu to c th c ca L:
N N
O O
N N
O O
N N
O O

3. in tch tng cng ca ligand L: khng.
4. Cu to:
N N
O O
M

5. Cng thc thc nghm ca A l: FeC
30
H
30
Cl
3
N
6
O
21

m = 3; n = 3
Cng thc ca phc: [FeL
3
](ClO
4
)
3
.3H
2
O
T l cation v anion l: 1:3
6. S oxy ha ca Fe: +3
S electron d trong ion Fe ca phc: 5
Cu hnh spin cao: (t
2g
)
3
(e
g
)
2

Cu hnh spin thp: (t
2g
)
5
(e
g
)
0

Cu hnh ng: spin cao do c momen t tnh c da vo s e c thn l 5,92B.M cn spin
thp l 1,73B.M. So snh vi ga tr momen t o c trong bng 2 ta rt ra c kt lun trn.
7. 450nm
8. 3,87B.M
9. CrC
20
H
18
N
4
Cl
3
O
9

x = 2
11
y = 2
z = 1
Phc vung phng cis-diaminodicloroplatin (II) l mt dc phm quan trng iu tr
ung th.
1. Vit cc ng phn cis v trans ca phc.
Mt s ion cng c cng thc nguyn Pt(NH
3
)
2
Cl
2
.
2. Vit tt c cng thc c th c ca ion trn nhng phi tha mn cc iu kin sau:
- C cng thc nguyn Pt(NH
3
)
2
Cl
2
.
- Anion v cation phi c vit r v tt c phi c cu trc vung phng.
- Anion v cation phi th hin c s tn ti ca mi phc platin (II) ring bit ca
mi hp cht.
3. Lp 5d ca platin c bao nhiu electron?
S tch mc nng lng trong gin nng lng obitan d ca phc vung phng lin
quan n phc bt din do lien kt kim loi ligand: Nu cc ligand nm trn trc z bin mt
m lin kt kim loi ligand vi cc ligand nm trn trc x v y tr nn mnh hn.
4. Trong s 5 obitan 5d ca platin, trong phc Pt vung phng th obitan no c mc nng
lng cao nht?
BI GII:
1. Cng thc cu to cc dng ng phn ca phn t cis-diaminodicloroplatin (II): (1
im)
Pt
Cl NH
3
Cl NH
3
cis
Pt
H
3
N Cl
Cl NH
3
trans

2. [Pt(NH
3
)
4
][PtCl
4
].
[Pt(NH
3
)
3
Cl][Pt(NH
3
)Cl
3
]
[Pt(NH
3
)
3
Cl]
2
[PtCl
4
]
[Pt(NH
3
)
4
][Pt(NH
3
)Cl
3
]
2

3. 8
4.
2 2
5
y x
d
. Trong phc t din 4 ligand u nm trn ng phn gic ca hai trc x v y.

Nu c y electron th mt electron s cao hn.
Phim en trng cha lp ph bc bromua trn nn l xenluloz axetat.
1. Vit phn ng quang ha xy ra khi chiu nh sng vo lp AgBr ph trn phim.
2. Trong qu trnh ny th lng AgBr khng c chiu sng s b ra bng cch cho to phc bi
dung dch natri thiosunfat. Vit phng trnh phn ng.
3. Ta c th thu hi bc t dung dch nc thi bng cch thm ion xianua vo, tip theo l km.
Vit cc phn ng xy ra.
BI GII:
1. Phn ng: - + Br Br r Ag r AgBr
h
2 / ) ( 2 ) ( 2
2
v

2. AgBr(r) + 2Na
2
S
2
O
3
Na
3
[Ag(S
2
O
3
)
2
] + NaBr
3. [Ag(S
2
O
3
)
2
]
3-
+ 2CN
-
[Ag(CN)
2
]
-
+ 2S
2
O
3
-

12
2[Ag(CN)
2
]
-
+ Zn [Zn(CN)
4
]
2-
+ 2Ag
+

Trong qa kh c mt s cng trnh v vic iu ch cc hp cht ca canxi ha tr 1. Mc d
bn cht ca cc hp cht y vn cha c bit nhng chng to ra c mt s quan tm rt ln
i vi cc nh ha tinh th.
C th chuyn CaCl
2
thnh CaCl bng: canxi, hydro, cacbon.
1. Vit cc phn ng xy ra.
Cho CaCl
2
phn ng vi Ca theo t l 1:1 ta ch nhn c mt cht mu xm khng ng nht.
Nhn di knh hin vi ta thy c mt phn mu bc v tinh th khng mu.
2. Tinh th khng mu v phn c nh kim l ca cht no?
Cho CaCl
2
phn ng vi hydro nguyn t ngi ta thu c sn phm mu trng cha 52,36%
Ca v 46,32% Cl v khi lng.
3. Xy dng cng thc thc nghim cho hp cht trn.
Khi CaCl
2
tc dng vi cacbon nguyn t ta thu c tinh th mu . T l s lng nguyn t
xc nh c bng php phn tch nguyn t l n(Ca):n(Cl) = 1,5:1. Thu phn cht ny thi thu c
sn phm nh thy phn Mg
2
C
3
.
4. a) Vit hai ng phn (mch khng vng) ca cht sinh ra khi thy phn.
b) Vit phng trnh phn ng xy ra (gi s khng sinh ra CaCl)
Khng phn ng no trong cc phn ng trn cho php ta xc nh c cu trc ca CaCl. C
th gi thit rng CaCl c mng tinh th tng t nh cu trc tinh th n gin.
Cho bit t l bn knh cation ca cc hp cht MX c cho bng:
S phi tr ca M Hnh dng ca cc
nhm X bao quanh
T l bn knh:
r
M
/r
X
Kiu cu trc Nng lng mng
li ca CaCl
L
H
o
3 Tam gic 0,155-0,225 BN -663,8 kJ.mol
-1
4 T din 0,225-0,414 ZnS -704,8 kJ.mol
-1
6 Bt din 0,414-0,732 NaCl -751,9 kJ.mol
-1

8 Lp phng 0,732-1,000 CsCl -758,4 kJ.mol
-1
5. a) CaCl c kiu cu trc tinh th no?. Bit r(Ca
2+
) ~ 120pm; r(Cl
-
) ~ 167pm
Mun bit CaCl c bn nhit ng hay khng ta khng ch s dng
L
H
o
m cn s dng H
s
.
b) Tnh H
s
ca CaCl vi cc s liu cho
xc nh CaCl c bn nhit ng hay khng ta phi tnh H
o
ca qa trnh
2CaCl Ca + CaCl
2
(b qua S).
6. S dng tnh ton cho bit phn ng trn c xy ra hay khng?
BI GII:
1. CaCl
2
+ Ca = 2CaCl.
2CaCl
2
+ H
2
= 2CaCl + 2HCl
4CaCl
2
+ C = 4CaCl + CCl
4
.
2. Tiu phn c nh kim mu bc: Ca
Tinh th khng mu: CaCl
2
.
3. n(Ca) : n(Cl): n(H) = 1 : 1 : 1
Cng thc thc nghim: CaClH
Lu rng phn ng gia CaCl
2
v hydro khng th no dn n CaCl m thay vo l hydrua
CaClH. Cu trc ca hp cht ny c xc nh php phn tch ph tia X nhng phng php ny
khng phi l mt phng php tt tm thy cc nguyn t nh nh hydro. Chnh v s bin mt ca
hydro trn ph tia X m trong mt thi gian di CaClH b tng lm l CaCl.
13
4. a) Cc cu trc ng phn:
C C C
H H
C CH
3
C H

b) Cng thc thc nghim: Ca
3
C
3
Cl
2
.
Lu rng: Nu t l s nguyn t n(Ca):n(Cl) = 1,5:1 (hay tt hn l 3:2 v c th vit li l
CaCl
2
.2Ca
2+
= Ca
3
Cl
4
4+
) v sn phm kh phi cha anion C
3
4-
nn phi cn hai cation Ca
2+
trung
ho in nn chnh v vy nn cng thc Ca
3
C
3
Cl
2
c chp nhn.
5. a) T l bn knh l r(Ca
2+
)/r(Cl
-
) = 0,719. Vy kiu tinh th s l kiu NaCl.
b) Tnh nhit sinh ca phn ng hnh thnh CaCl da vo chu trnh Born Haber:

Ca
+
(k)
+ Cl
-
(r)
CaCl
(r)

Ca
(k)
Cl
(k)

Ca
(r)
+ 0,5Cl
2(k)

Thay s vo ta tnh c: H
s
= -231,9kJ/mol
6. 2CaCl Ca + CaCl
2
c H
s
= -332,2kJ/mol.
Vy phn ng trn khng xy ra.
S tng hp v xc nh tnh cht ca vng kch thc nano l mt lnh vc ang rt pht trin.
Phng php Bruff Schiffrin tng hp vng kch thc nano (AuNP) da vo s bn nhit ng
v bn khng kh ca AuNP ta c th iu ch AuNP dng a phn tn c kch thc nm trong
khong t 1,5 v 5,2nm. Phng php ny c ni dung nh sau: Dung dch HAuCl
4
c trn ln vi
toluen trong dung mi tetra n octylamoni bromua. Dung dch thu c em trn ln vi
dodecanthiol v c un nng vi NaBH
4
. Nhng ht AuNP mu ti c sinh ra v nm pha hu
c. Sau 24 gi th dung mi toluen s c cho bay hi v khi rn thu c c ra vi hn hp dung
mi etanol v hexan tch thiol. Cc ht AuNP c th c phn lp v ho tan tr li trong dung mi
hu c thng thng m khng b phn hy hay t hp thun nghch (irrvesible aggregation).
1. Phng php ny cn s tip cn t trn xung hay t di ln?
a) Tip cn t trn xung lm cho ht nano c kch thc nh nht.
b) Tip cn t di ln c th bin cc phn t v nguyn t ring l thnh cu trc nano.
2. Trimetyl n octylamin bromua cn c th c s dng nh l mt cht chuyn pha. N c th
chuyn AuCl
4
-
t pha nc sang pha hu c. Tnh cht no gip cho n c th lm c iu
ny?
L
H
o

I
1

H
thng hoa

E
Cl
0,5H
phn ly
H
s
14
a) Mt pha ca phn t mang in dng, u cn li mang in m.
b) Mt pha c tnh a nc, mt pha c tnh k nc.
c) Mt pha mang tnh axit, mt pha mang tnh baz.
3. Vai tr ca NaBH
4
trong qa trnh iu ch ny l g?
a) Tc nhn kh ha.
b) Tc nhn oxy ha.
c) Tc nhn trung tnh.
d) Tc nhn to phc.
4. Nu ng knh trung bnh ca ht vng kch thc nano l 3nm th s nguyn t vng s l bao
nhiu trong mi phn nano? (bn knh nguyn t ca vng l 0,144nm). Ch ra bng tnh ton

a) 10
2

b) 10
3

c) 10
4

d) 10
5

5. Bng tnh ton hy ch ra phn trm s nguyn t vng trn b mt l bao nhiu v cho bit cu tr
li no ng.
a) 20 30%
b) 40 50%
c) 60 70%
d) 80 90%
BI GII:
1: b)
2: b)
3: a)
4: b)
3
3
3
3
3
3
10 1000
. .
3
4
. .
3
4
= =
|
|
.
|
\
|
= =
=
=
Au
AuNP
Au
AuNP
Au Au
AuNP AuNP
r
r
V
V
N
r V
r V
t
t

5: b)
4/3.t.r
AuNP
3
= 4/3.t.r
Au
3
.N
Au
.
Din tch b mt ca mt tiu phn nano cu vng: S = 4.t.r
AuNP
2

S = 4.t.r
Au
2
.N
Au
2/3

N
S
~ S
AuNP
/t.r
Au
2
= 4N
Au
2/3
.
P = N
S
/N
Au
= 4N
Au
1/3
.
N
Au
= 1000 P = 40%
III. BI TO CHUN B CHO OLYMPIC HA HC QUC T:
Mt c nghin cu sinh nhn mt l hng gm cc halognua kim loi kim nhng cc bnh u
mt nhn tr mt bnh cha kali bromua. Phng th nghim ni c lm vic khng h c bt k loi ph
k no v vy c dng ct trao i ion nhn bit cc mu halogenua kim loi kim mt nhn . Loi
nha c chn l loi nha polystiren mng li kiu axit mnh, cha cc nhm axit sunfonic (-SO
3
H)
15
nn ch cc proton c th trao i. C phn tch c su mu kim loi kim (v c KBr kim chng
phng php) theo cch sau:
C cn 5,00 0,01g mi mu, ri ho tan vi nc ct trong ng ong 100mL. Cho 40mL mi
dung dch qua ct; dung dch ra c thu vo ng ong c th tch 250mL, ra ct hai ln vi nc ct;
dung dch ra ny c thm nc c 250mL. Trc khi mu k tip c cho vo ct, c ti to
proton cho nha trong ct bng cch ra vi lng cn thit HCl 1M ri vi nc ct. C chun cc
mu 50mL ca mi dung dch ra, lm ba ln vi dung dch NaOH (nng l thuyt 3,26.10
-2
M) dng
cht ch th l phenolphtalein thu c cc kt qa sau:
Mu th nghim Th tch chun trung bnh
A 21,15 0,1mL
B 29,30 0,1mL
C 7,40 0,1mL
D 21,20 0,1mL
E 10,30 0,1mL
F 29,15 0,1mL
KBr 10,25 0,1mL
phn tch cc kt qa ny ta c th gi thit rng:
- Mi mu th t >99% tinh khit.
- Mi bnh u y cht, khng b nhim nc v khng kh
- Khng c trng hp hai bnh cha cng mt kim loi kim halogenua; l ha cht ch gm florua,
clorua, bromua v iodua, khng c hp cht ca atatin.
a) Hy cho bit l do v sao phi tin hnh cc th tc nu trn? Vit phng trnh phn ng ho hc
ca bt k phn ng no xy ra.
b) Mu th no c th chc chn c nhn bit t s phn tch ny? Mu th no c th gii hn kt
qa ch cn hai hoc ba kh nng?
c) Dng cc dng c c trong phng th nghim: knh thy tinh, giy qy, dung dch natri pesunfat
(Na
2
S
2
O
8
) trong mi trng axit v mt l cha dung dch h tinh bt c c th nhn bit c
c su mu th. Khng cn bit kt qa th nghim ca c vi cc ha cht nu trn, hy gii thch
lm th no vi cc vt liu trn l nhn bit c tt c cc mu th cha nhn bit c
cu b).
d) Tnh cht no ca kim loi kim halogenua ngn cn khng th nhn bit r rng mt s mu nhn
bit bng k thut trao i ion dng y? Liu mt hiu ng nh th c phi l tr ngi ng k
trong mt n lc tng t nhn bit mt s halogenua ca kim loi kim th MX
2
chng hn?
BI GII:
a) Hin nhin, cn xc nh khi lng mol phn t ca mi mu th M
r
(MX) bng cch trao i M
+

vi H
+
nh ct trao i ion v bng cch chun xc nh lng H
+
.
Cc phn ng gm:
M
+
+ [RSO
3
H] H
+
+ [RSO
3
-
M
+
]
H
+
+ OH
-
H
2
O
b) Phn tch kt qa:
S mol M
+
trong 5g = s mol OH
-
.(250/50).(100/40) = th tch chun .0,326.5.2,5
M
(r)
(MX) = khi lng mu th (5g)/s mol M
+
trong 5g
Thu c cc kt qa sau:

16
Mu th nghim M
r
(g/mol) D on cht MX c th l:
A 58,01 NaCl(58,44); KF(58,10)
B 41,88 LiCl(42,39); NaF(41,99)
C 165,81 KI(166,00); RbBr(165,37); CsCl(168,36)
D 57,88 NaCl(58,44); KF (58,10)
E 119,13 KBr(119,00); RbCl(120,92)
F 42,09 LiCl(42,39); NaF(41,99)
KBr 119,71 KBr(119,00); RbCl(120,92)
Cc kt qa trn cho thy, k thut th nghim hin nhin cha chnh xc c th xc nh r
rng tng mui. V d: nu mi mu u khc nhau, nu bit c mt mu chc chn l KBr th khi y
mu E chc chn phi l RbCl. Khi lng phn t ca RbCl ln hn KBr vy m mu E li c M
r
hi
nh hn da trn kt qa chun . Cn thy rng khi lng mol phn t qa gn nhau ca hai (c khi
ba halogenua) ca kim loi kim loi tr kh nng xc nh A, B, C, D, F.
c) Knh thy tinh: Cc mui liti ht m mnh, do li mt lng nh B v F trn cc knh thy
tinh k cn s cho php xc nh liti clorua: n s ht m v chy ra (nho) trong mt thi gian
ngn (tr khi khng kh trong phng th nghim qa kh).
Giy qy: Ion florua l mt ion lin hp ca axit yu HF nn dung dch mui florua c tnh kim. Do
giy qy s xc nh c dung dch long no ca B hoc F l NaF v dung dch long no ca
A hoc D l KF.
Pesunfat axit ha + h tinh bt: Pesunfat oxy ha I
-
thnh I
2
, to phc mu xanh thm vi h tinh
bt. Nh vy, nu C l KI s cho mu xanh thm ca phc vi tinh bt. Pesunfat cng oxy ha Cl
-

hoc Br
-
nhng khng c ch th c trng vi h tinh bt nn tc nhn ny khng gip phn bit
RbBr v CsCl (Tuy nhin, c th xc nh C vi cc phng php nu nn C l KI)
Khng c php th tm NaCl: bng phng php loi tr, cht no trong hai cht A v D khng
lm xanh qy tm l NaCl.
d) iu ngn cn vic xc nh r rng cc halogenua khc nhau ca cc kim loi kim MX bng s
trao i ion chnh l khi lng mol phn t gn trng nhau ca cc halogenua y. Nguyn nhn l
v cc hp cht ny c hai tiu phn u c ha tr I, ng thi cc kim loi kim c s hiu nguyn
t ch hn cc nguyn t halogen ng trc hai n v: do vy, bt i mt lp y ca kim loi
(chng hn K Na) v thm mt lp y vo halogen (nh F Cl) s cho hp cht c khi lng
phn t gn nh ging ht hp cht ban u.
Cc halogenua kim loi kim th ni chung khng c tr ngi ny, nu cng xt nh trn: bt i mt
lp y ca M (nh Ca Mg) v thm mt lp y vo halogen (nh F Cl) cho ra cc cht c
khi lng phn t hon ton khc nhau (78,08 v 95,21 g.mol
-1
theo th t cho CaF
2
v MgCl
2
).
S kho st cc phn ng to phc ca cc ion kim loi chuyn tip.
M
n+
+ mL
-
ML
m
(n-m)+

thng tr nn phc tp do s ccnh tranh ng thi ca cc qa trnh cn bng khc: v d nh
ligand L
-
thng l baz lin hp ca mt axit yu nn nng ca n trong dung dch ty thuc nhiu
vo pH. Trong trng hp ny, thng phi vit li hng s to phc ca cc kim loi chuyn tip
|
m
.
| |
| || |
n
n
m n
m
m
L M
ML
+
+
=
) (
|
bng cch thay [L
-
] bng o
L
C
T
(L), trong C
T
(L) l nng tng cng ca L tt c cc dng
trong dung dch (nh djang HL hay L
-
hoc ML
i
(n-i)+
) v o
L
l t l ca dng thch hp L
-
so vi L tng
17
cng. Phng php ny thng c dng, v d nh trong phn tch bng php o chun dng
EDTA, v EDTA (H
4
Y) l mt axit bn chc yu ch c kh nng cho phn ng to phc dng hon
ton mt proton Y
4-
. Khi y:
| | | | | | | |
4 3 2 1 3 2 1
2
2 1
3
1
4
4 3 2 1
4
a a a a a a a a a a
a a a a
Y
K K K K H K K K H K K H K H
K K K K
+ + + +
=
+ + + +
o
Vi K
a,i
l hng s ion ha th i ca EDTA (vi tr s ln lt bng 1,02.10
-2
;2,14.10
-3
; 6,92.10
-7

v 5,50.10
-11
).
a) Xc nh cc tr s ca o(Y
4-
) pH ln lt bng 2, 6, 10. Tnh nng d ca anion Y
4-
hon ton
mt proton trong 500mL dung dch c cha 3,252g EDTA tr s pH nu trn.
b) Hng s to phc K
Y
cho s to phc ca M
n+
vi Y
4-
, c ga tr 6,3.10
21
(Hg
2+
); 2,1.10
14
(Fe
2+
) v
5,0.10
10
(Ca
2+
). Ion kim loi no s tp phc vi EDTA c hu sut hn 99,9% trong dung dch c
cha 5,00.10
-3
M EDTA tng cng, c m vi pH l:
i) 2
ii) 6
iii) 10
c) Ion thu ngn (II) Hg
2+
c i lc mnh vi clorua:
Hg
2+
+ 4Cl
-
HgCl
4
2-

Vi hng s to phc l |
Cl
= 3,98.10
15
. Vi dung dch clorua 0,5M tng cng v 5,00.10
-3
M dung
dch EDTA tng cng, hy xc nh t l thu ngn tn ti di dng ion t do, di dng anion
tetraclorua v di dng phc EDTA ti pH bng:
i) 2
ii) 6
iii) 10
(Nn ga thit rng nng kim loi tng cng rt nh hn 0,05M)
e) Mt loi hn hng ch cha thu ngn, natri v canxi. Cho 5,218g mu ny tc dng vi mt tc
nhn oxy ha thch hp ri pha thnh 500mL. Ly 25mL dung dch ny; m ti pH = 2,6; em
chun vi dung dch 0,0122M dung dch MgY
2-
: tr s chun trung bnh l 44,19 mol.L
-1
. Khi
ly 10mL mu dung dch, m ti pH = 9,5 c tr s chun 57,43mol.L
-1
. Hy xc nh phn trm
khi lng ca thu ngn, canxi, natri trong hn hng.
BI GII:
a) Tnh c cc tr s sau:
pH o(Y
4-
) [Y
4-
](M)
2 3,712.10
-14
8,26.10
-16
6 2,249.10
-6
5,01.10
-8
10 0,3548 7,90.10
-3
Cc nng ca anion c xc nh nh C
T
(EDTA) = 0,02226M M
r
(C
10
H
16
N
2
O
8
) =
292,25g.mol
-1
b) Ta cn xc nh t l [MY
2-
]/[M
2+
], t l ny (nh xc nh hng s to phc) c tr s K
Y
[Y
4-
].
Ta c th xc nh [Y
4-
] t x bit cu a. Tnh c cc tr s sau:
pH [Y
4-
] [HgY
2-
]/[Hg
2+
] [FeY
2-
]/[Fe
2+
] [CaY
2-
]/[Ca
2+
]
2 1,856.10
-16
1,17.10
6
0,039 9,28.10
-6
6 1,1245.10
-8
7,08.10
13
2,36.10
6
562
10 1,774.10
-3
1,12.10
19
3,73.10
11
8,87.10
7
C th thy rng, ti pH = 2, ch Hg
2+
to phc vi lng ng k; ti pH = 6, c Hg
2+
v Fe
2+

u to phc, trong khi ti pH = 10, c ba ion kim loi u to phc vi hiu qa cao.
18
c) Do HCl l axit mnh, cn bng gia Hg
2+
v Cl
-
phi khng ph thuc pH; ta c th tnh c t
s [HgCl
4
2-
]/[Hg
2+
] bng 2,488.10
14
vi [Cl
-
] = 0,5M. Dng cc tr s [HgY
2-
]/[Hg
2+
] c c t
cu b) ta tnh c:
pH [HgY
2-
]/[Hg
2+
] %(Hg
2+
) %(HgY
2-
) %(HgCl
4
2-
)
2 1,17.10
6
4.10
-13
5.10
-7
>99,9
6 7,08.10
13
3.10
-13
22,2 78,8
10 1,12.10
19
9.10
-18
>99,9 2,2.10
-3

d) Cc kt qa thu c t cu b) ch ra rng, ti pH = 2, s to phc EDTA ca Ca
2+
l b qua
c: ta c th gi thit iu y vn ng ti pH = 2,6; v nh th EDTA ch phn ng vi Hg
2+

ti pH thp nh vy. Ti pH = 10, s to phc ca c Hg
2+
cng nh Ca
2+
l ng k, v ti pH =
9,5 s chun cho bit lng tng cng ca Hg
2+
v Ca
2+
. Ta phi gi thit rng EDTA khng
phn ng ng k vi Na
+
.Ti pH = 2,6, s mol Y
4-
= 5,391.10
-4
M
S mol ny bng s mol (Hg
2+
) trong 25mL; nn s mol Hg
2+
trong 500mL = 1,078.10
-4
mol. V
khi lng nguyn t ca Hg

l 200,59g.mol
-1
, cho php xc nh khi lng thu ngn trong
mu th l 2,163g.
Ti pH = 9,5; s mol Y
4-
= 5,391.10
-4
mol.
S mol ny bng tng s mol (Hg
2+
+ Ca
2+
) trong 10mL, nn tng s mol (Hg
2+
+ Ca
2+
) trong
50mL = 3,503.10
-2
mol, v v vy s mol Ca
2+
trong 500mL = 2,425.10
-2
mol tng ng vi
0,972g canxi trong mu th.
Suy ra khi lng natri trong mu th (gi s khng ln tp cht khc) l 2,083g. Nh vy hm
lng cc cht trong mu th l: Hg (41,45%); Na (39,32%), Ca (18,63%).
S bc x kh nh knh (Greenhouse gas) l mt mi quan tm hng u v mi trung. S gia
tng nng kh nh knh (CO
2
) trong kh quyn c ghi nhn vi thp nin qua.
a) Ta s c lng s phn b cc kh nh knh trong kh quyn tri t bng cch gi thit rng
nhng kh ny (CO
2
, hi H
2
O..) c khoanh vng trong tng c cao 10 11km (Cch m t
nh th khng chnh xc, nhng c mc ch minh ho mt s khi nim). nh hnng ca tng
kh - nh knh nh trn s ra sao i vi nhit kh quyn ti cao 5km?
b) nh hng ca tng kh nh knh ln nhit kh quyn ti 15km. Gii thch mt cch nh
tnh hiu ng ph ny ca tng nh knh (greenhouse layer).
c) S bin i nhit ti phn thp hn ca kh quyn s nh hng ra sao n cn bng ca CO
2

v ca H
2
O gia pha kh v pha ho tan trong nc? Liu s dch chuyn cn bng ca cc tiu
phn ny, t n, c nh hng g n nhit ca phn thp hn ca kh quyn?
d) Nay xt n tng cao hn tng nh knh l tng ozon. Ozon c to thnh cng nh b phn hy
u do cc qa trnh quang ha (photochemical). ngh mt c ch gii thch s to thnh v
phn hy ozon trong mt kh quyn cha oxy tinh khit.
e) Entanpy to thnh ca O v O
3
l H
o
f
(O) = 249kJ.mol
-1
v H
o
f
(O
3
) = 143kJ.mol
-1
. Xc nh
phtn vi di sng ln nht c kh nng quang phn oxy v ozon, theo th t.
f) Trong vng cc, s tan r ca ozon ti tng bnh lu quan st c trong ma xun. Ngi ta
ngh rng iu kin dn n s tan r tai ho ny (c bit di tn l thng ozon) ty mt s
yu t, trong c cn bng sau:
HCl
(k)
+ PSC = HCl*PSC (1)
ClONO
2(k)
+ PSC = ClONO
2
*PSC (2)
ClO
(k)
+ ClO
(k)
= ClOOCl (3)
PSC (vit tt ca Polar Stratospheric Cloud) ch my bnh lu ti cc vng cc to thnh t s
ngng t hi nc v cc cht bay hi khc ti tng rt cao ny. S to thnh PSC thng xy ra
19
ti tng bnh lu Nam Cc trong ma ng v u ma xun, nhng t hn ti cc Bc v nhit
khng qa thp. c bit rng s tan r ozon cng nghim trng khi cc cn bng trn di
theo chiu thun. Cn nh rng s to thnh lin kt thng l to nhit, vy nhit s nh
hng th no n cc cn bng trn?
g) S to thnh ozon trong tng bnh lu ti cc Bc l mt hin tng c ghi nhn gn y:
thot u, ngi ta hy vng cc Bc c min nhim vi s to thnh l thng ozon, nhng tht
ra khng phi vy. Cn c trn cc thng tin c trn y, ngh xem l gii no c th ng tin
cy c gii thch cho s pht trin l thng ozon ti cc Bc.
i) Mc CFC trong tng bnh lu ti Bc bn cu gn y tng ln bng mc CFC m
tng bnh lu ca Nam cc t trong thp nin trc.
ii) S trn xung lin tc ca cc kh nh knh vo phn thp hn ca kh quyn cng lm gim
lin tc nht tng bnh lu ti cc Bc.
iii) S gia tng nng hi nc trong tng bnh lu ti cc Bc lm cho s to thnh PSC d
dng hn trc y.
iv) S gia tng lng phng x hng ngoi n tng bnh lu ti cc Bc gy ra s gia tng
quang phn ca ozon ti cc Bc.
BI GII:
a) Cc kh nh knh lm nng h tng kh quyn, v mt s photon hng ngoi (IR) c ngun gc t
b mt tri t l ra thot khi kh quyn li b hp th v bn tr li; s bn tr li v b mt
tri t tng t nh khi bn i, lm cho h tng kh quyn nng ln.
b) Cc kh nh knh lm lnh thng tng kh quyn: v c t photon hng ngoi n c cao
ny t b mt, s hp th hng ngoi ny xy ra t cao 15km t hn l ra phi c. Hp th
hng ngoi t dn n nhit gim.
c) Cn bng xy ra l:
CO
2(aq)
CO
2(k)
V H
2
O
(l)
H
2
O
(h)
.
C hai cn bng ny u di theo chiu thun khi nhit tng: vy nng hi nc v CO
2
s
tng theo T. Do c hai u l kh nh knh, nn dn n hiu ng nh knh dng.
d) Trong kh quyn oxy tinh khit, s hnh thnh ozon bng qa trnh quang ha dn n s quang
phn oxy:
O
2
+ hv O + O (i)
Sau :
O + O
2
O
3
(ii)
S quang phn cng ph hy ozon:
O
3
+ hv O
2
+ O (iii)
(Mt qa trnh phn hy ozon khc c th l:
O
3
+ O O
2
+ O
2
(iv))
e) T entanpy to thnh cho sn (H
o
f
(O
2
) = 0kJ.mol
-1
), tnh c entanpy ca phn ng (i) v
(iii):
H
o
i
= 498kJ/mol = 8,27.10
-19
J/phn t
H
o
iii
= 106kJ/mol = 1,76.10
-19
J/phn t
Vi E = hv = hc/ ta c:
1
= 2,40.10
-7
m = 240nm
2
= 1,129.10
-6
m = 1129nm
20
y l cc photon c di sng di nht c nng lng quang phn O
2
v O
3
theo th t
(thc t, s quang phn c hiu qa ozon cn di sng ngn hn ga tr ngh, v nhng l
do khng xt n trong phm vi cu hi ny).
f) C ba cn bng ny khi xt theo chiu thun u c s to thm mt lin kt, nn nhit cao,
cn bng s di qua tri v di qua phi khi nhit h thp.
g) Ba gi thuyt c th b bc b nh sau:
i. Khi nim rng mc CFC Bc bn cu t hn Nam Bn cu l iu khng tng: mc
cng nghip ha mnh nht, v phng thch CFC nhiu nht l Bc bn cu (Thc vy,
nng CFC h tng kh quyn l tng t nhau trn ton a cu: chng c trn rt
u)
iii. Trong khi s gia tng hi nc lm tng kh nng to PSC, khng c chng c g v s
chuyn dch hi nc n tng Bnh cc Bc (c chng ch l chuyn n h tng kh
quyn).
iv. nh hng ca s gia tng nng cc kh nh knh (v chng vn ang gia tng!) l lm
gim lng hng ngoi n c tng bnh lu. Ngoi ra d cc photon gn - hng - ngoi c
nng lng cao hn mnh lin kt O
2
O, chng thc s khng quang phn ozon.
Gi thuyt ii) l cu tr li c ngha nht cc kh nh knh s lm nng h tng kh quyn v
lm lnh thng tng kh quyn (Tuy nhin, iu khng c ngha l c ch ny l nguyn
nhn ng thin nhin lun phc tp hn ta mong i).
Tng hp mt hp cht ca crom. S phn tch nguyn t cho thy rng thnh phn c Cr
(27,1%); C (25,2%), H(4,25%) theo khi lng, cn li l oxy.
a) Tm cng thc thc nghim ca hp cht ny.
b) Nu cng thc thc nghim gm mt phn t nc, ligand kia l g? Mc oxy ha ca Cr l bao
nhiu?
c) Kho st t tnh cho thy hp cht ny l nghch t, phi gii thch t tnh ca hp cht ny nh
th no? V th cu to ph hp ca cht ny.
BI GII:
a) Cng thc thc nghim CrC
4
H
8
O
5
.
b) T cng thc thc nghim CrC
4
H
8
O
5
, hp cht l [Cr(CH
3
COO)
2
(H
2
O)]. Nh vy, ligand l cc
nhm axetat. Do nhm (CH
3
COO
-
) c in tch 1 nn mc oxy ha ca Cr l +2.
c) Ion Cr
2+
l h d
4
, ngha l h c 4e thuc obitan d. S phn b 4 electron phi thuc loi spin
nng lng cao do ligand yu. Ch yu t ny cho thy [Cr(CH
3
COO)
2
(H
2
O)] c tnh thun
t. Tuy nhin t cc kt qa thc nghim, hp cht ny li c tnh nghch t l do hp cht
ny dng nh hp c cu to nh sau:
21
Cr Cr
O O
C
CH
3
O O
C
CH
3
O
O
C
H
3
C
O
O
C
CH
3
OH
2
H
2
O

Trong cu to ny, hai nguyn t Cr to lin kt bn, bao gm mt sigma, hai pi v mt delta,
vi bc lin kt tng cng l 4. S hnh thnh lin kt bn i hi tt c cc electron thuc obitan
d u phi cp i. V vy da theo tnh cht t, hp cht dng nh hp l nghch t.
Clorat v peclorat c s dng trong s ch to dim qut, pho v cht n. Bc th nht
trong vic sn xut kali clorat l s in phn dung dch nc ca kali clorua.
a) Vit cc phng trnh phn ng xy ra ti hai in cc. Cl
2
c to thnh anot v OH
-
c
to thnh catot
b) Clo to thnh phn ng vi ion hydroxit to thnh clorat. Vit phng trnh phn ng.
c) Hy tnh khi lng kali clorua v in lng (theo Ah, ampe gi) cn thu c 100g KClO
3
.
BI GII:
a) Catot: 2H
2
O
(l)
+ 2e = 2OH
-
(aq)
+ H
2(k)

Anot: 2Cl
-
(aq)
= Cl
2(aq)
+ 2e
b) Phn ng: 3Cl
2(k)
+ 6OH
-
(aq)
= ClO
3
-
(aq)
+ 5Cl
-
(aq)
+ 3H
2
O
(l)

c) m
KCl
= 60,83g
Q = 131Ah
Mi trng d nhim ch lun l mt iu ng lo ngi. Trong c th con ngi, mc c hi
ca ch c th c gim bt vi liu php chelat bng cch s dng cc ligand c tim nng hnh
thnh cc phc Pb
2+
bn c th c thn bi tit. Ligand EDTA
4-
c dng cho mc ch ny nh s
hnh thnh phc [Pb(EDTA)]
2-
rt bn vng (hng s bn vng, K(Pb) = 10
18
M
-1
). Ligand c cung
cp bng cch tim truyn dung dch Na
2
[Ca(EDTA)], mui natri ca phc canxi tng i km bn
(K(Ca) = 10
10,7
M
-1
). S trao i ca canxi vi ch ch yu din ra trong mch mu.
a) Mc ch c trong mu ca mt bnh nhn l 83ug/dL. Hy tnh nng mol ca ch trong
mu bnh nhn ny.
b) Trong mt th nghim lm mu, ngi ta iu ch mt dung dch cha Ca(NO
3
)
2
.4H
2
O v
Na
2
[Ca(EDTA)] c nng mi cht theo th t bng 2,5mM v 1,0mM. Thm Pb(NO
3
)
2
rn
vo t c nng ch tng ng vi nng ch trong mu bnh nhn nu trn. Hy tnh
tr s gn ng ca t l [Pb(EDTA)]
2-
/Pb
2+
trong dung dch thu c ti cn bng. Khng xt
tnh cht axit baz ca cc tiu phn c lin quan v s thay i th tch dung dch coi nh
khng ng k.
22
c) S bi tit ca phc [Pb(EDTA)]
2-
qua thn hin nhin l mt qa trnh bc nht theo nng
[Pb(EDTA)]
2-
trong mu. Sau 2 gi, nng ca phc [Pb(EDTA)]
2-
trong mu ca hu ht cc
bnh nhn thng gim 60%. Hy tnh chu k bn hy sinh hc ca phc [Pb(EDTA)]
2-

BI GII:
a) [Pb
2+
] = 83/(207,2.0,10) = 4,00uM
b) Xt phn ng: [Ca(EDTA)]
2-
(aq)
+ Pb
2+
(aq)
[Pb(EDTA)]
2-
(aq)
+ Ca
2+
(aq)

Vi hng s cn bng K = K(Pb)/K(Ca) = 10
7,3
. Do kh nng to phc mnh v ion Ca
2+
c d
so vi tng lng ligand EDTA
4-
, hin nhin tt c ligand s ni kt trong phc ch hoc phc
canxi. V [Pb(EDTA)
2-
] << [Ca(EDTA)
2-
] nn nng thc ca cc ion Ca
2+
v [Ca(EDTA)]
2-

s phi rt gn vi nng hnh thc v biu thc tnh K cho:
| || |
| || |
| |
| |
| |
| |
6
2
2
2
2
2 2
2 2
10 . 0 , 8
) ( ) (
) (
) (
= =
=
+
+
+
Ca
EDTA Ca
K
Pb
EDTA Pb
Pb EDTA Ca
Ca EDTA Pb
K

c) Nng ca phc [Pb(EDTA)]
2-
l 40% lng ban u sau 2 gi. Nh vy 0,4 = e
-2k
cho kt qu
l k = 0,458gi
-1
. Nh vy ta c th tnh c t
1/2
= 1,5 gi.
Ureaza l mt enzym c cha niken lm xc tc cho phn ng thu phn ure (H
2
NCONH
2
) thnh
ion amoni v ion cacbamat (H
2
NCOO
-
). Ion cacbamat b thu phn tip sau trong mt qa trnh t
xy ra khng xc tc bi ureaza.
a) Vit phng trnh phn ng thu phn ion cacbamat.
b) Mi n v cu trc cp ba ca protein ureaza c cha hai ion niken(II). Nhng ion kim loi ny
phi tr vi cc nguyn t cho tng ng nhnh ca cc aminoaxit trong cu trc cp mt ca
protein. Hy vit cng thc cu to cc nhnh ca aspartat, histidin v khoanh trn nhng
nguyn t ng vai tr cho ca mi nhnh.
c) Hai tm niken (II) ca ureaza cng c ni li bng cc nhm cacboxylat cu ni v mt phn
t nc cu ni. Nhm cacboxylat cu ni thuc nhnh ca lysin c chuyn thnh mt dn
xut cacbamat. Hy vit cng thc cu to dn xut cacbamat ca nhnh lysin.
d) Vit cu hnh electron ca ion niken (II).
e) bit c mt s hnh hc phi tr ca niken (II). Trong hp cht phi tr bt din, cc obitan
d c phn b gia hai mc nng lng. Hy cho bit obitan no trong s 5 obitan d chim cc
mc nng lng theo th t cao hn hoc thp hn trong hnh hc bt din. Gii thch nh
lng kt qa tm c bng cch so snh s phn b trong khng gian ca cc obitan d.
f) Mt s phc ca niken (II) li c hnh hc vung phng, l c cu ch yu trong cc phc ca
ion kim loi paladi (II) v platin (II). Hy v hai ng phn ca [Ni(SCH
2
CH
2
NH
2
)
2
] vung
phng v ghi r ng phn no l cis hoc trans.
g) V tt c ng phn hnh hc ca [Pt(NH
3
)(pyridin)ClBr] vung phng.
BI GII:
a) H
2
NCOO
-
(aq)
+ H
2
O
(l)
= NH
3(aq)
+ HCO
3
-
(aq)

b) Cu to ca cc nhnh:
23
H
2
C C
O
O
HC
N
CH
H
N
H
2
C
aspartat
histidin

c) Cu to ca dn xut cacbamat:
H
2
C
C
H
2
H
2
C
C
H
2
H
N
C
O
-
O

d) 1s
2
2s
2
2p
6
3s
2
3p
6
3d
8
4s
2
.
e) Mc nng lng cao hn d(z
2
) v d(x
2
y
2
). Mc nng lng thp hn d
xy
, d
xz
v d
yz
.
Trong mt trng ligand bt din, cc trc vung x, y, z (gc ti tm kim loi) c hng sao
cho mi nguyn t trong 6 nguyn t lin kt thuc ligand phi nm trn cc trc ny. Nh vy
cc electron ca cc nguyn t trong ligand hnh thnh cch sp xp cc in tch m quanh
nguyn t kim loi. Cch sp xp ny c nh hng khc nhau trn cc obitan d khc nhau. Cc
obitan d
xy
, d
xz
v d
yz
u c mt electron tp trung ch yu trong vng gia in tch cc
ligand. Trong khi , cc obitan d(z
2
) v d(x
2
y
2
) c mt electron tp trung trong vng gn
in tch ca cc ligand hn so vi cc obitan d
xy
, d
xz
v d
yz
. Tng tc y electron lm tng
nng lng ca cc obitan d(z
2
) v d(x
2
y
2
) so vi nng lng ca cc obitan d
xy
, d
xz
v d
yz
.
f) Cng thc ca phc:
Ni
H
2
N
C
H
2
CH
2
S
S
H
2
C
H
2
C
N
H
2
cis
Ni
S
C
H
2
CH
2
H
2
S
N
S
H
2
C
H
2
C
N
H
2
trans

g) Cng thc cu to ca phc:
Pt
H
2
N Cl
Br N
Pt
H
2
N N
Br Cl
Pt
NH
2
Br
Cl
N

Mt vi tnh cht ca mt hp cht v c cha bit A c lit k di y:
24
- A l mt cht rn mu trng hi vng, d chy ra v thng hoa khi un nng. A c khi lng phn
t l 266.
- A phn ng mnh lit vi nc cho dung dch B.
- Khi mt dung dch hn hp gm NH
4
OH v NH
4
Cl c thm vo dung dch B th nhn c kt
ta keo mu trng.
- Mt mu dung dch B phn ng vi dung dch hn hp nitric axit v bc nitrat cho kt ta vn cc
mu trng C. Kt ta trng ny nhanh chng tan i khi thm vo dung dch NH
4
OH mc d khi ta
cho d NH
4
OH th li xut hin kt ta trng D.
- Kt ta D c lc v ho tan trong NaOH thu c dung dch trong sut E.
- Khi cho kh CO
2
li qua dung dch E th li sinh ra kt ta D.
- Cht A ho tan khng in ly trong ete khng ln nc. Khi dung dch ny phn ng vi LiH th s
to thnh sn phm F. Nu dng d LiH th F s chuyn thnh G.
a) Xc nh cht A.
b) Xc nh cc cht t B n G v vit tt c cc phng trnh phn ng xy ra.
BI GII:
a) Trong bc th ba ca php phn tch ta thu c kt ta trng keo, iu ny chng t rng dung
dch B c cha Al
3+
v dung dch B cng to kt ta trng vi AgNO
3
, kt ta ny tan i khi ta
thm NH
4
OH vo chng t rng dung dch B c cha Cl
-
. Vy cht A s l Al
2
Cl
6
(M
A
= 266).
b) Cc phn ng xy ra:
Al
2
Cl
6
+ 12H
2
O = 2[Al(H
2
O)
6
]
3+
+ 6Cl
-

6AgNO
3
+ 6Cl
-
= 6AgCl + 6NO
3
-

AgCl + 2NH
4
OH = [Ag(NH
3
)
2
]
+
Cl
-
+ H
2
O
Al
3+
+ 3NH
4
OH = Al(OH)
3
+ 3NH
4
+

Al(OH)
3
+ NaOH = Na
+
[Al(OH)
4
-
]
[Al(OH)
4
]
-
+ CO
2
= Al(OH)
3
+ HCO
3
-

Al
2
Cl
6
+ LiH = (AlH
3
)
n
+ LiH
d
= LiAlH
4

a) Nit c rt nhiu oxit. Mt trong s nhng oxit quan trng ca nit l NO
2
, mt kh mu nu
rt hot ng ha hc.
(i) V cng thc Lewis ca NO
2
v hy xc nh hnh dng ca n da trn thuyt
VSEPR.
(ii) S dng thuyt VSEPR hy xc nh hnh dng ca hai ion NO
2
-
v NO
2
+
. So snh
hnh dng ca hai ion trn vi NO
2
.
b) Xem xt hai hp cht khc ca nit l trimetylamin (Me
3
N) v trisiliylamin (H
3
Si)
3
N. Gc lin
kt o c ca hai hp cht ny ln lt l 108
o
v 120
o
. Hy gii thch s khc nhau ny.
c) By gi ta tip tc xt nit v bo triflorua. Nng lng lin kt ca BF
3
l 646kJ/mol v trong
NF
3
l 280kJ/mol. Gii thch s khc nhau ny.
d) Nhit si ca NF
3
l 129
o
C trong khi vi NH
3
l 33
o
C. Amoniac phn ng nh l mt
baz Lewis trong khi NF
3
th khng. Ga tr momen lng cc ca mi cht tng ng l 0,24D
v 1,48D mc d flo c m in ln hn nit. Gii thch ti sao:
(i) C s khc bit qa ln ca nhit si.
(ii) Momen lng cc ca NF
3
qa nh.
e) Phn ng ca dung dch natri nitrat vi hn hng natri cng nh phn ng gia etyl nitrit vi
hydroxylamin di s c mt ca natri etylat u cho cng mt sn phm. Sn phm ny l mui
ca mt axit yu khng bn ca nit. Xc nh axit ny v vit cng thc cu to ca n. Axit
25
ny d dng ng phn ha to thnh mt hp cht c s dng lm nhin liu cho ng
c phn lc. Vit cng thc cu to ca cht ny.
BI GII:
a) (i) S electron xung quanh nguyn t nit: 7
Vy NO
2
c cng thc cu to:
N O O

Nhng theo thuyt VSEPR th do phn t c mt electron c thn nn do sc y ca electron
ny vi hai cp electron lin kt nn phn t NO
2
khng th c cu to thng nh trn m phi
c cu to gc (132
o
). Nh vy cu to ca NO
2
s l:
N
O
O
132
o

(ii) Xt NO
2
+
: S electron xung quanh nguyn t N = 5 + 2 + 2 1 = 8 (Mi nguyn t oxy xung
quanh gp 2e)
Cu trc Lewis s l:
::N::O O

Nh vy s khng c sc y ca cc eletron khng tham gia lin kt trn nguyn t nit. Hai
lin kt sigma s c phn b ph hp nht l 180
o
lm gim ti a sc cng v gc cn cc
lin kt pi th khng lm nh hng n hnh dng ca phn t. Vy NO
2
+
s c cu to:
N O O

Xt NO
2
-
: S electron xung quanh nguyn t N: 5 + 2 + 1 = 8
Cc cu trc Lewis ca NO
2
-
:
N O O
N
O
O
115
o

i vi NO
2
-
th do cn mt cp electron cha lin kt c sc y mnh hn mt electron nn
gc lin kt s gim xung so vi phn t NO
2
.
b) Vi trng hp trimetylamin th dng hnh hc l thp tam gic bi v trn nguyn t nit c mt
cp electron cha lin kt lm gc lin kt gim xung t 109,4
o
cn 108
o
:
N
H
3
C CH
3
H
3
C
N
SiH
3
H
3
Si SiH
3

Tuy nhin i vi (SiH
3
)
3
N th do c s tham gia ca obitan d vo lin kt, n s xen ph cng
vi obitan p ca nguyn t N to cho lin kt N-Si c tnh cht gn nh ca mt lin kt i nn
cp electron t do trn nguyn t nit s tr nn nh x v khng nh hng n dng hnh hc
ca phn t. Kt qa l phn t s c dng tam gic phng vi gc lin kt l 120
o
.
26

N Si
obitan d trong
obitan p day

c) C NF
3
v BF
3
u l nhng hp cht mang tnh cng ha tr. NF
3
th dng thp tam gic tuy
nhin BF
3
th dng tam gic phng do trong lin kt B F c mt phn lin kt i (bi v c
su xen ph gia obitan p ca bo v flo). Nh vy nng lng lin kt N-F phi ln hn B-F
N
F
F
F
B
F
F
F

d) (i) Nhit si ca cc cht khc nhau tu thuc vo lin kt hydro. NH
3
c to thnh lin kt
hydro cn NF
3
th khng.
Kh nng ht electron v ca F rt cao nn lm gim tnh baz ca N trong NF
3
, chnh v vy
NF
3
khng phn ng nh mt baz.
(ii) m in ca NF
3
lun b hn NH
3
do:
N
H
H
H
N
F
F
F

Chnh v tng cc momen lng cc ngc hng nh vy cho nn momen lng cc ca NF
3

lun b hn NH
3
.
e) 2NaNO
3
+ 8Na(Hg) + 4H
2
O = Na
2
N
2
O
2
+ 8H
2
O + 8Hg
NH
2
OH + EtNO
2
+ 2NaOEt = Na
2
N
2
O
2
+ 3EtOH
Na
2
N
2
O
2
l mui ca axit hyponitr c cu trc nh sau:
N N
HO OH
N N
HO
OH

ng phn ca n l H
2
N NO
2
(Nitramit) c cng thc cu to:
N N
O
O H
H

27
Mt s ln cc qa trnh to thnh cc mui v cc tinh th c th c hiu ra bng cch xc
nh nng lng vi cc m hnh ion n gin trong ion c bn knh n gin v in tch ca ion
phi l mt s nguyn. M hnh ny c s dng m t s phn ly ca cc hp cht ion trong pha
kh. Thng cc qa trnh phn ly u dn trc tip n cc nguyn t trung ho nhng nng lng phn
ly c th c tnh bng cch ta gi s c mt qa trnh m trong cc hp cht ion b phn ly ra cc
ion t do v tip theo l s trung ho in tch. chnh l chu trnh Born Haber.
Nng lng lin kt, i lc electron v nng lng ion ha ca cc phn t hai nguyn t sau
c cho sn di y:
Nng lng lin kt ca KCl = -464kJ.mol
-1
Nng lng lin kt ca NaCl = -423kJ.mol
-1

Nng lng lin kt ca MgCl = -406kJ.mol
-1

Nng lng lin kt ca CaCl = -429kJ.mol
-1

i lc electron ca Cl = -360kJ.mol
-1

Nng lng ion ha ca Na = +496kJ.mol
-1

Nng lng ion ha th nht ca Ca = +592kJ.mol
-1

Nng lng ion ha th hai ca Ca = +1184kJ.mol
-1

a) Thit lp chu trnh Born Haber cho s phn ly ca NaCl thnh cc nguyn t v tnh nng
lng phn ly ca NaCl. Gi thit rng lin kt l 100% ion.
b) Thit lp mt chu trnh Born Haber cho s phn ly ca CaCl
2
thnh ba nguyn t v tnh nng
lng phn ly ca CaCl
2
, gi s rng di lin kt trong phn t ba nguyn t th ngn hn 9%
so vi cc phn t hai nguyn t.
BI GII:
a) Chu trnh Born Haber cho s phn ly thnh cc nguyn t ca NaCl:
NaCl Na
+
+ Cl
-

Na
+
+ Cl
-
Na + Cl
Nng lng mt i bc 1 l 464kJ.mol
-1
.
Nng lng thu vo bc 2 l (nng lng ion ha ca Na + i lc electron ca Cl)=-
136kJ.mol
-1

Vy nng lng phn ly l 328kJ.mol
-1
.
b) Chu trnh Born Haber cho s phn ly ca CaCl
2
.
CaCl
2
Ca
2+
+ 2Cl
-

Ca
2+
+ 2Cl
-
Ca + 2Cl
Nng lng lin kt ca Ca
2+
Cl
-
= -429.2/0,91 = -943kJ.mol
-1
.
(Ga tr o c i vi CaCl l 429 nhng in tch ca Ca l +2 v di lin kt gim mt
lng l 0,91 ln)
Nng lng mt bc u = -(nng lng lin kt ca CaCl
2
) = 2.942 nng lng cp ha
ca Cl-Cl
Nng lng cp ha ca Cl-Cl = (429/2).(1/0,91) = 236kJ.mol
-1
.
Vy nng lng mt i bc 1 s bng = +1650kJ.mol
-1
.
Nng lng thu vo bc 2 s bng -(2 i lc electron Cl + tng nng lng ion ha ca Ca) =
-1020kJ.mol
-1
.
Vy nng lng phn ly s l: 630kJ.mol
-1

28
Cc ion kim loi mang in tch 2+ trong dy u tin ca kim loi chuyn tip vi cc cu hnh
d
1
, d
2
, , d
9
to ra ch yu l phc bt din c cng thc chung l ML
6
(L: phi t mt rng). Kho st
tnh cht t ca cc phc ny ta c th chia ra lm hai loi. Mt loi c s electron khng tham gia lin
kt bng vi s electron trong M
2+
(k)
th phc ny c gi l phc spin cao v mt loi c s
electrong khng tham gia lin kt nh hoc bng 0 th gi l phc spin thp. Nu s chnh lch gia
hai mc nng lng t
2g
v e
g
l v nng lng cp ha l P. Hy d on cu hnh electron c bn ca
cc phc trn. Bit rng nguyn l Aufbau v nguyn l loi tr Pauli u c tun theo.
BI GII:
d
1
: t
g
1
e
g
o

d
2
: t
g
2
e
g
o

d
3
: t
g
3
e
g
o

d
4
: t
g
4
e
g
o
(>P) hay t
g
3
e
g
1
(<P)
d
5
: t
g
5
e
g
o
(>P) hay t
g
3
e
g
2
(<P)
d
6
: t
g
6
e
g
o
(>P) hay t
g
4
e
g
2
(<P)
d
7
: t
g
6
e
g
1
(>P) hay t
g
5
e
g
2
(<P)
d
8
: t
g
6
e
g
2

d
9
: t
g
6
e
g
3

Canxi xianamit (CaCN
2
) l mt loi phn bn a nng v c tc dng tt. N c th c sn
xut rt d dng t cc loi ha cht thng thng nh CaCO
3
. Qa trnh nhit phn ca CaCO
3
cho ra
mt cht rn mu trng X
A
v mt kh khng mu X
B
khng duy tr s chy. Mt cht rn mu xm X
C

v kh X
D
c hnh thnh bi phn ng kh X
A
vi cacbon. X
C
v X
D
cn c th b oxy ha to
thnh cc sn phm c mc oxy ha cao hn. Phn ng ca X
C
vi nit cui cng cng dn ti vic to
thnh CaCN
2
.
1. Vit tt c cc phng trnh phn ng xy ra.
2. Khi thu phn CaCN
2
th thu c cht g? Vit phng trnh phn ng
3. Trong ha hc cht rn th ion CN
2
2-
c th c ng phn. Axit ca c hai anion u c bit
(ch tn ti trong pha kh). Vit cng thc cu to ca c hai axit v cho bit cn bng chuyn ha
gia hai axit trn dch chuyn v pha no?
BI GII:
1) CaCO
3

AT
CaO + CO
2

CaO + 3C CaC
2
+ CO
CaC
2
+ N
2
CaCN
2
+ C
Qa trnh trn c gi l qa trnh Frank Caro. Qa trnh ny rt quan trng trong k thut.
2) CaCN
2
+ 3H
2
O CaCO
3
+ 2NH
3

3) Cng th ca hai ng phn l:
HN = C = NH
N C NH
2

Hp cht u tin l axit ca anion cacbondiimit v hp cht th hai l xianamit.
Cn bng s chuyn dch v pha to thnh hp cht c tnh i xng cao hn.
Cc nguyn t kim loi chuyn tip c phn b rt rng ri trong v tri t. Rt nhiu trong
s c rt nhiu ng dng trong i sng hng ngy, chng ta d dng bt gp chng mi lc mi ni
nh: ng nc bng st, dy ng v cc chi tit t ng bng crom
29
Crom l mt kim loi mu trng bc, c tn bt ngun t ting Hy Lp chroma c ngha l mu
sc do hp cht ca crom c rt nhiu mu khc nhau. Mu sng ca hp cht crom(VI) dn n nhng
ng dng ca n lm cht mu trong mu v v knh mu.
1. Trong dung dch axit, th ion cromat c mu vng s chuyn thnh ion dicromat c mu cam. Vit
phng trnh phn ng.
2. S oxy ha ca crom trong hai hp cht trn l bao nhiu?
3. y c phi l phn ng kh khng? Hy gii thch.
4. ng lc lm dch chuyn cn bng ca phn ng trn l g?
5. Vit cng thc khng gian ca CrO
4
2-
v Cr
2
O
7
2-
.
BI GII:
1. 2CrO
4
2-
(aq)
+ 2H
+
(aq)
Cr
2
O
7
2-
(aq)
+ H
2
O
2. +6
3. Khng phi, bi v s oxy ha ca nguyn t kim loi khng thay i.
4. Nng ion H
+
(hay pH ca dung dch)
5. Cc cng thc:
Cr
O
O
O
O
2-
Cr
O
O
O
O
Cr
O
O
O
2-

IV. OLYMPIC HA HC CC NC TRN TH GII:
OLYMPIC HA HC O 1999:
Nguyn t X (c nhiu dng th hnh) c mt anion cha oxy ng vai tr quan trng trong
nhum nc. m in ca n nh hn oxy. N ch to hp cht phn t vi halogen. Ngoi hai oxit
n phn t cn c nhng oxit cao phn t. X codn coa vai tr rt quan trng trong sinh ha. Cc obitan
p ca n ch c mt electron.
1. l nguyn t no?. Vit cu hnh ca n.
X c th to c vi hydro nhiu hp cht cng ha tr c cng thc chung l X
a
H
b
; dy hp
cht ny tng t nh dy ng ng ca ankan.
2. Vit cng thc cu to 4 cht u ca dy.
Mt trong s 4 hp cht trn c ba ng phn lp th (tng t axit tactric)
3. Xc nh hp cht ny.
Nguyn t X to c nhng axit c cha oxy (oxoaxit) c cng thc chung l H
3
XO
n
vi n = 2,
3 v 4.
4. Vit cng thc cu to ca 3 axit ny. nh du (du sao hoc mi tn) cc nguyn t H v ghi s
oxy ha ca X trong cc hp cht ny.
Mt hp cht d vng ca X, vi cu trc phng do J. Liebig v F.Wohler tng hp t nm 1834,
c to thnh t NH
4
Cl vi mt cht pentacloro ca X; sn phm ph ca phn ng ny l mt kh d
tan trong nc v phn ng nh mt axit mnh
5) a) Vit phng trnh phn ng.
b) Vit cng thc cu to ca hp cht (NXCl
2
)
3
.
Hp cht v c va nu trn c tnh cht khc thng khi b un nng: n si 256
o
C khi b
un nng nhanh. Nu un nng chm n bt u nng chy 250
o
C; lm ngui nhanh cht lng ny th
ta c mt cht tng t cao su.
6) Gii thch tnh cht c bit ny.
30
BI GII:
1) Photpho. Cu hnh [Ne]3s
2
3p
3

2) Cng thc cu to ca 4 cht u tin:
P
H
H
H
P P
H
H
H
H
P
P
P
H
H
H
H
H
P
P
P
P H
H
H
H
H
H
1 2 3 4

3) 4
4) Cng thc cu to ca cc cht:
P
OH
H
H
O
+1
P
OH
H
OH
O
+3
P
OH
OH
OH
O
+5

5) a) 3NH
4
Cl + 3PCl
5
= (NPCl
2
)
3
+ 12HCl
b) Cng thc cu to:

P
N
P
N
P
N Cl
Cl
Cl
Cl
Cl Cl

6) un nng nhanh cht nng chy khng b gy vng
un nng chm vng b b gy to thnh cc phn t polyme c h lin hp pi:
N
P
N
Cl Cl
P
N
P
Cl Cl

A. Thuyt Pauling
Thm dung dch kali hydroxit vo dung dch nc ca Co
2+
, mt kt ta mu xanh c hnh thnh.
Trong dung dch KOH c th s hnh thnh phc spin cao c s phi tr 6.
a) Vit phng trnh ion ca cc phn ng
b) Cho bit tn ca phc
c) Vit s lai ha cho phc v cho bit kiu lai ha

B. Thuyt trng phi t

31
Ion phc bis(terpyridyl)coban(II) tn ti mt phn trng thi spin cao, mt phn trng thi
spin thp ph thuc vo cc ion lin kt trc tip vi nguyn t trung tm ClO
4
-
/Cl
-
/NCS
-
/Br
-
.
a) Cho bit ba dng hnh hc c th c ca phc
b) Da vo thuyt trng phi t hy v gin obitan cho cc trng hp phc spin cao v thp
c) Tnh momen t (M.B) ca cc phc trn
Xt cc phc sau: [Co(CN)
6
]
3-
, [Co(CO
3
)
2
(NH
3
)
2
]
-
, [Co(CO
3
)
3
]
3-
and [Co(NO
2
)
6
]
3-
. Mu ca cc ion
phc ny s l: xanh, vng, cam v da tri (khng nht thit l phi cng djng vi cc phc trn)
d) Hy cho bit tn ca tng phc v xc nh mu ca chng:
BI GII:
A. Thuyt Pauling
a) Co
2+
+ 2 OH
-
Co(OH)
2
|
Co
2+
+ 6 OH
-
[Co(OH)
6
]
4-

b) hexahydroxocobaltat(II)
c)

3d 4s 4p 4d
Kiu lai ha: d
2
sp
3

B. Thuyt trng phi t:
a) Bt din
b) Ta c:

e
g
e
g

t
2g
t
2g
Spin cao Spin thp
c) Phc spin thp:
B B mag
73 . 1 3 u = u = u
spin cao:
B B mag
87 . 3 15 u = u = u
d) Ta c bng:

Cng thc Tn gi Mu sc
[Co(CN)
6
]
3-
Hexaxianocobantat(III) Vng
[Co(NO
2
)
6
]
3-
Hexa-N-nitritocobantat(III) Cam
[Co(CO
3
)
3
]
3-
Tricacbonatocobantat(III) Xanh
[Co(CO
3
)
2
(NH
3
)
2
]
-
Dicacbonatodiamincobantat(III) Xanh da tri
Kim loi A c tm thy trong t nhin di dng hp cht, ch yu l khong vt orthosilicat
vi cng thc chung l M
x
(SiO
4
)
y
, ngoi ra n cng cn c tm thy di dng oxit. Oxit cua n c
nhiu dng th hnh v n thng c kt tinh dng n ta bin dng vi s phi tr7. nhit trn
1100
o
C cu trc tinh th ca n s c chuyn sang dng t phng. Trn 2000
o
C cu trc ca oxit s
l lp phng bin dng. Kiu mng li ca dng sau cng ging nh mng kiu florit trong ion
kim loi c cu trc lp phng tm din vi hng s mng a
o
= 5,07pm. Anion O
2-
chim cc hc t
din. Cu trc trn c th c bn ha nhit phng bng cch s dng CaO. Khi lng ring ca
oxit kim loi tinh khit (cu trc lp phng) l 6,27g/cm
3

32
1. V cu trc mng c s ca oxit.
2. Cng thc hp thc ca oxit.
3. Cho bit s oxy ha ca kim loi trong oxit
4. Trong orthosilicat th kim loi cng c s oxy ha nh trong oxit. Hy cho bit cng thc phn t
ca orthosilicat.
5. Xc nh A
6. Vit cu hnh electron ca A.
7. Cho bit s phi tr ca cation v anion trong oxit.
8. Tnh i lc electron ca oxy trong qa trnh: O
(k)
+ 2e O
2-

Cho bit:
H
o
S
(A) = 609kJ/mol, I
n
(A/A
n+
) = 7482kJ/mol, H
o
phn ly
(O
2
2O) = 498kJ/mol
U (oxit) = -10945kJ/mol, H
o
sinh
(oxit) = -11000kJ/mol
C hai bc iu ch kim loi ny. Bc 1: cacbon v clo s phn ng vi silicat nhit
cao v s sinh ra clorua ca A (s oxy ha ca A trong clorua khng i) cng vi oxit cacbon v silic
tetraclorua. Bc 2: clorua ca A s phn ng vi Mg sinh ra kim loi. Thu phn clorua s thu c
oxit trn.
9. Vit cc phng trnh phn ng xy ra.
10. Vit phng trnh phn ng thy phn clorua ca A
A c th to c cc phc cht bn vng vi cc halogen vi s phi tr 6, 7, 8 c bit.
Chng ta s kho st phc [ACl
2
F
4
]
m+/-
vi s oxy ha ca A khng i so vi oxit.
11. Cho bit cng thc ca phc v tn ca n.
12. C bao nhiu cht ng phn ca ion phc (ng phn cu to v ng phn lp th). V cng thc
cu to ca cc cht i nh.
BI GII:
1. Mng tinh th oxit: M
n+
; O
2

2. Cng thc ca oxit: MO
2

3. S oxy ho ca kim loi: +4.
4. Cng thc ca orthosilicat: MSiO
4

5. Ta c:
d = m(nguyn t)/V( mng) =
3
0
.
2 . 4
a N
M M
A
O M
+

33

mol g M
a N d
M
O
A
M
/ 22 , 91 2
4
. .
3
0
= =
Vy kim loi l zirconi (Zr)
6. Cu hnh electron ca Zirconi [Kr]4d
2
5s
2
.
7. S phi tr ca cation: 8
S phi tr ca anion: 4
8. Xy dng chu trnh Born Haber tnh v thu c kt qa l A = 628kJ/mol
9. Cc phng trnh phn ng xy ra l:
ZrSiO
4
+ 4C + 4Cl
2
ZrCl
4
+ SiCl
4
+ 4CO
ZrCl
4
+ 2Mg Zr + 2MgCl
2

10. Phng trnh phn ng thu phn: ZrCl
4
+ 2H
2
O ZrO
2
+ 4HCl
11. in tch ca ion phc: +2
Tn ca ion phc: diclotetraflozirconat:
12. S ng phn: 6
Mt cp ng phn i quang:

Polysunfuapolynitrua (polythioazyl) l hp cht c mu ng, n c tnh dn in rt tt v tr
thnh vng dn di 0,33K. Hp cht ny c iu ch bng cch:
Bc 1: iu ch disunfuadiclorua bng cch cho kh clo kh tc dng vi lu hunh nng chy
240
o
C.
Bc 2: Disunfuadiclorua phn ng vi clo v amoniac trong CCl
4
20 25
o
C thu c
tetrasunfuatetranitrua (S
4
N
4
).
1. Vit cc phng trnh phn ng xy ra
2. Tetrasunfuatetranitrua c cu trc dng vng. Vit cng thc cu to ca n.
Tetrasunfuatetranitrua dng tinh th c mu cam, trn 130
o
C d phn hy n khi va p v gii
phng nguyn t. Trong sn phm c hnh thnh l hunh nitrua SN, n c th ng vai tr nh
mt phi t trong phc [RuCl
4
(H
2
O)NS]
-
.
3. V gin MO ca SN
4. Tnh bi lin kt v momen t ca SN
5. Cho bit tn ca phc nu tn ca phi t SN l thionitrosyl
Nu tetrasunfuatetranitrua c bc bo v v em nung nng n 300
o
C trong chn khng th ta
thu c disunfuadinitrua. Hp cht ny tn ti lu di nhit thp v b polyme ha chm nhit
phng to ra polythioazyl (SN)
x
.
6. S
2
N
2
c tnh thm. V hai cng thc cng hng ca cht ny.
7. V gin Frost Musulin cho h thm v xc nh bc lin kt pi.

Cl
Zr
Cl
F
F
F
F
Zr
Cl
Cl
F
F
F
F
34
BI GII:
1. Cc phn ng xy ra:
2S + Cl
2
= S
2
Cl
2

S
2
Cl
2
+ 4NH
3
+ 4Cl
2
= S
4
N
4
+ 12HCl
2. Cu to ca S
4
N
4
:

3. Gin MO ca SN:

4. bi lin kt N = 2,5
Momen t:
B
3u
5. Tn ca phc: aquatetracloruathionitrosylrutenat (III)
6. Hai cng thc cng hng ca SN:

N
N
N
N
S
S
S
S
o
s
b
o
s
*
t
z
b
t
y
b
o
x
b
t
y
*
t
z
*
o
x
*
S
N
SN
2s
2s
2p
2p
N
S
N
S
N
S
N
S
35
7. Gin Frost Musulin ca S
2
N
2
:

bi lin kt pi = 0,25
Nguyn t Me, c tn ca n thn sc p do s phong ph mu sc ca cc hp cht ca n
nm nhm cc nguyn t d.
Trong k thun th s iu ch Me bt u t mt trong s cc oxit A ca n. Qung tng ng
cha oxit b oxy ha trong mt qa trnh nung chy sau cho phn ng vi mui ca kim loi kim
v cui cng kim loi Me c phn lp bng cch ngm chit
Oxit ca A cha 43,98% oxy v khi lng. Trong hp cht ny nguyn t Me cho s oxy ha
l. Me c iu ch bng cch cho oxit A phn ng vi Canxi kim loi 950
o
C.
1. Hy s dng tnh ton xc nh nguyn t ny l nguyn t no?
2. Vit cu hnh lp v ngoi cng ca nguyn t trng thi c bn.
3. Vit cng thc v cho bit tn ca A.
4. Vit phn ng gia A vi canxi
Trong qa trnh trn th nguyn t c ho tan vo trong NaCl nng chy ng vai tr nh cht
in phn (phn lng cha ion Me
3+
). S dng mt hiu in th l 60V, kim loi tinh khit b kt ta
in cc lm bng tantan. Trc khi in phn khi lng in cc ny l 500g. Sau khi in phn 16
gi th qa trnh in phn xy ra vi cng dng in l 50,0A.
5. Kim loi no catot v anot trong qa trnh in phn.
6. Tnh khi lng kim loi kt ta. Nu hiu sut ca qa trnh in phn l 90%
7. Tnh tinh khit (%) trong kim loi th s dng in phn
Nguyn t Me c kiu mng tinh th lp phng tm khi. Khi nghin cu cu trc bng
phng php ph tia X vi bc sng = 71,1pm th b nhiu x khi tip xc vi mt phng tinh th
(111). Gc nhiu x o c c gii tr l 11,7
o

8. Tnh hng s mng a
o

9. Tnh bn knh nguyn t ca nguyn t Me.
10.Tnh t khi ca nguyn t Me
un nng oxit lng tnh A vi dung dch NaOH c th ta thu c mui B (ng hnh vi
mui ortho photphat) v kt tinh dng decahydrat.
Thm axit mnh vo dung dch mui B bo ha, th anion s b proton ha cho ra dng axit
lin hp. Nu tip tc thm proton khc th s dn n kt qa l s c s tch ra hai phn t nc. nu
tip tc thm proton th mt cation C c mu vng s c hnh thnh.
11. Vit cng thc cu to ca mui B.
12 Cho bit cng thc ca cation C?
Cation C c th b kh dn tng bc. Nu ln lt mt i mt e th mt cation D mu xanh da
tri c hnh thnh, sau s l cation E v cui cng l cation F. Trong hai bc u tin th c s
tch ra nguyn t oxy. Cc ga tr th kh chun ca cc bc c cp trn, k c th kh ca s
kh to thnh Me c cho di (trong mi trng axit):
E(C/D) = 1.00 V
36
E(D/E) = 0.359 V
E(E/F) = -0.256 V
E (F/Me) = -1.186 V
13. Vit cng thc cu to ca cc cation D, E v F .
14. Vit na phn ng ca cp oxy ha kh C/D.
15. V gin Frost ca cc tiu phn ca Me c cp trn.
16. Tiu phn no bn vng nht?
17. Di iu kin ca phn ng d ly th tiu phn no s phn ng?
Nguyn t Me to ra cc hp cht phc c cc s phi tr v s oxy ha khc nhau.
V d:
1) [Me(bipyr)
3
]
+

2) [Me(CO)
6
]
-

3) [MeO(O
2
)
2
ox]
3-

4) [MeOCl
2
(N(CH
3
)
3
)
2
]
18. V gin MO cho phi t peroxo c hai rng.
19. Xc nh bc lin kt v tnh cht.t ca anion ny
20. Cho bit tn h thng ca cc phc s 2 v 3.
21. Xc nh s oxy ha ca nguyn t trung tm ca mi phc v ng thi da vo thuyt VSEPR
xc nh dng hnh hc ca phc v t xc nh xem c phc no bt i xng.
BI GII:
1. oxit A: 56.02% Me, 43.98% O
Vi cng thc Me
2
O
b
ta c:
2
.
98 . 43
16 02 . 56
) (
b
Me M

=
b = 1, Me
2
O M(Me) = 10.19 g/mol (loi)
b = 3, Me
2
O
3
M(Me) = 30.57 g/mol (loi)
b = 5, Me
2
O
5
M(Me) = 50.95 g/mol: vanadi
2. Electron ha tr ca lp ngoi cng: 3d
3
4s
2

3. Cng thc phn t A: V
2
O
5
: vanadi(V)-oxide
4. Phng trnh phn ng: V
2
O
5
+ 5Ca 2V + 5CaO
5. catot: tantalum anot: vanadi khng tinh khit
6. Khi lng kim loi gii phng:

7. tinh khit: 91,2%
8. Hng s mng:

9. Bn knh nguyn t r = 3d/4 = 131pm
10. Khi lng ring:

g 456
96485 3
9 . 0 95 . 50 57600 50
F z
M t I
m =
n
=
pm 303 m 10 303
3
10 175 3
a
m 10 175
7 . 11 sin 2
10 1 . 71
sin 2
3
3
a
d
12
12
0
12
12
0
= =

=
=
=
O
= =
3
3 10
23
3
0
gcm 08 . 6
) 10 303 (
10 022 . 6
95 . 50
2
a
) V ( m 2

= p
37
11. Cng thc ca B: Na
3
VO
4
.10H
2
O
12. Cng thc ca C: VO
2
+

13. D: VO
2+
; E: V
3+
; F: V
2+

14. Na phn ng: VO2
+
+2H
+
+ e
-
VO
2+
+ H2O
15. Gin Frost:

16. Tiu phn bn vng nht: V
3+
.
17. Khng.
18. Gin MO:

19. Bc lin kt: 1.
T tnh: nghch t
20. Tn h thng ca 2: hexacacbonylvanadat(-I)
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1 2 3 4 5 6
z
E

OZ
V
V
2+

V
3+

VO
2
+
VO
2+

2
b

2*
2x
b

2x*
2y 2z
2y 2z
38
Tn h thng ca 3: oxalatooxodiperoxovanadat(V).
21. Kt qa thu c cho bng:
Phc S oxy ha Dng hnh hc Tnh bt i
xng
[Me(bipyr)
3
]
+
+I Bt din c
[Me(CO)
6
]
-
-I Bt din Khng
[MeO(O
2
)
2
ox]
3-
+V
Lng thp ng
gic c
[MeOCl
2
(NMe
3
)
2
] +IV
Lng thp tam
gic C
OLYMPIC HA HC BUNGARI 1999:
Theo l thuyt cng thc ca khong pyrit l FeS
2
. Trong thc t, mt phn ion disunfua (S
2
2-
) b
thay th bi ion sunfua (S
2-
) v cng thc tng ca pyrit c th c biu din l FeS
2-x
. Nh vy ta c
th coi pyrit nh l mt hn hp ca FeS
2
v FeS. Khi x l mt mu khong vi brom trong KOH d
th xy ra cc phn ng sau:
FeS
2
+ Br
2
+ KOH Fe(OH)
3
+ KBr + K
2
SO
4
+ H
2
O
FeS + Br
2
+ KOH Fe(OH)
3
+ KBr + K
2
SO
4
+ H
2
O
Sau khi lc th cht khng tan c tch khi dung dch v:
- Fe(OH)
3
trong phn rn c kt ta li v nung nng chuyn thnh Fe
2
O
3
c khi lng l
0,2g
- Cho d dung dch BaCl
2
vo pha lng c 1,1087g kt ta BaSO
4
.
a) Xc nh cng thc tng ca pyrit
b) Xc nh s oxy ha ca cc nguyn t tham gia vo qa trnh xc nh cht kh v cht oxy ha.
c) Vit cc phng trnh ca hai phn ng trn, nu r cn bng electron.
d) Tnh lng brom (theo gam) cn thit oxy ha mu khong.
BI GII:
a) n(S) = 1,1087/233,4 = 4,75.10
-3
mol; n(Fe) = 0,2.2/160 = 2,5.10
-3
mol
n(Fe) : n(S) = 1 : 1,9 cng thc l FeS
1,9

b) Fe
2+
; S
1-
; Br
0

Fe
3+
; S
6+
; Br
1-

Fe
2+
; S
2-
; Br
0

Fe
3+
; S
6+
; Br
1-

Fe
2+
; S
1-
; S
2-
: cht kh; Br
0
: cht oxy ha
c) Fe
2+
- e = Fe
3+
Fe
2+
- e = Fe
3+

S
2
2-
- 14e = 2S
6+
15 2 S
2-
- 8e = S
6+
9 2
Br
2
+ 2e = Br
-
2 15 Br
2
+ 2e = Br
-
2 9
2FeS
2
+ 15Br
2
+ 38KOH 2Fe(OH)
3
+ 30KBr + 4K
2
SO
4
+ 16H
2
O
2FeS + 9Br
2
+ 22KOH 2Fe(OH)
3
+ 18KBr + 2K
2
SO
4
+ 8H
2
O
d) 2 x = 1,9 x = 0,1: 90% mol FeS v 10% mol FeS
2

m
1
(Br
2
) = 2,7g
m
2
(Br
2
) = 0,18g
39
m(Br
2
) = m
1
+ m
2
= 2,88g
Ion nitrit l c t cho nhiu vi sinh vt v vy n thng c dng lm tc nhn bo qun
trong cng nghip thc phm. Nhng c nhng vi khun Nibacter c th oxy ha tng hp ATP. Khi
oxy ha xy ra cc phn ng sau:
NO
2
-
+ H
2
O NO
3
-
+ 2H
+
+ 2e 81,06kJ
O
2
+ 4H
+
+ 4e 2H
2
O + 316,52kJ
a) Tnh lng ATP to thnh theo l thuyt nu khi chuyn 1mol ATP thnh ADP (v photphat v
c) pht ra nng lng l 30,6kJ.
b) Gii thch con ng m hydro v electron c chuyn t c cht ti oxy nhng c th
eucariot ho kh.
c) Gi tn qa trnh sinh tng hp to thnh nhng chui vi nng lng. Lng cc i ATP thu
c l bao nhiu?
d) S oxy ha sinh hc trong t bo eucariot v lin hp vi sinh tng hp ATP c thc hin
u?
e) ATP l loi hp cht ha hc no?. Vit cng th cu to ca ATP.
BI GII:
a) Phn ng tng hp khi oxy ha nitrit thnh nitrat l:
2NO
2
-
+ O
2
= 2NO
3
-
+ Q
Q = 158,26 - 81,06 = 77,2 kJ/mol
Lng cc i ATP l: 77,2/30,6 = 2,52mol
b) Do mt dy nhng cht mang trung gian trong chui h hp.
c) Oxy ha photphoryl ha: Lng cc i ATP l 3 mol.
d) Trong tinh th (mitochondria)
e) Nucleotit to lp t nit, riboza v P: aenin riboza P P P:
Trong cng nghip, sn xut ng c tin hnh qua nhiu giai on, trong s c giai on
gi l ng. N l hn hp ca CuS v FeS. Cho mt mu 4,1865g ng tc dng vi HNO
3

c, cc qa trnh l:
CuS + HNO
3
= Cu(NO
3
)
2
+ H
2
SO
4
+ NO + H
2
O
FeS + HNO
3
= Fe(NO
3
)
3
+ H
2
SO
4
+ NO + H
2
O
Khi thm mt lng d dung dch BaCl
2
, s to thnh 10,5030 gam kt ta.
1. Cn bng cc phng trnh phn ng trn, nu r s trao i electron v cn bng electron.
2. Phn trm mol ca CuS trong ng l bao nhiu?.
3. Tnh phn trm ca khi lng ng trong mu.
BI GII:
1. 3CuS + 14HNO
3
= 3Cu(NO
3
)
2
+ 3H
2
SO
4
+ 8NO + 4H
2
O
S
2-
+ 8e = S
6+
3
N
5+
+ 3e = N
2+
8
FeS + 6HNO
3
= Fe(NO
3
)
3
+ H
2
SO
4
+ 3NO + 2H
2
O
Fe
2+
- e = Fe
3+

9e 1
S
2-
+ 8e = S
6+

N
5+
+ 3e = N
2+
3
BaCl
2
+ H
2
SO
4
= BaSO
4
| + 2HCl
2. n(CuS) + n(FeS) = n(BaSO
4
) = 0,045mol (1)
40
m(CuS) + m(FeS) = 4,1865g (2)
T (1) v (2) ta thu c kt qa: n(CuS) = 0,03 mol
%CuS = 66,67%
3. %Cu = 45,54%
OLYMPIC HA HC UCRAINA 1999:
Hai cht A v B cha anion phc bt din c cng thnh phn nguyn t nhng chng khc nhau
v momen t (u = [n(n +2)]
1/2
trong n l s electron khng cp i): u
A
= 0, u
B
= 1,72D. Khi cho
20mL dung dch 0,1M ca A tc dng vi 1,3240g Pb(NO
3
)
2
th to thnh 1,2520g kt ta trng v trong
dung dch ch cn li mui kali. Khi cho 1,2700g FeCl
3
vo mt lng d dung dch ca A th to thnh
1,6200g kt ta trng C (51,85% khi lng l st). Khi ra ngoi khng kh C tr thnh xanh l v
chuyn thnh D. Dung dch ca B tc dng vi FeCl
2
to thnh ngay mt kt ta xanh l E c thnh
phn ging ht D.
a) Cc cht A, B, C, D, E l nhng cht g?. Tnh ga tr ca n i vi cht B.
b) Vit cc phng trnh phn ng.
c) S khc nhau gia D v E l g ?
BI GII:
a) n(Pb(NO
3
)
2
) : n(A) = 1,3240/331:0,1 .0,02 = 2:1 Anion trong A l X
4-

2Pb
2+
+ X
4-
= Pb
2
X|
4.10
-3
2.10
-3
2.10
-3

M(Pb
2
X) = 1,252/2.10
-3
= 626 M(X
4-
) = 212
2Fe
2+
+ X
4-
= Fe
2
X|
0,01 0,005
n(FeCl
2
) = 0,01; M(FeX
2
) = 324
n(Fe) = 324.0,5185/56 = 3; C l Fe
2
[FeY
6
]
1,72 = [n(n+2)]
1/2
n ~ 1; u = 0; Fe
3+
. Vy Y l CN; A l K
4
[Fe(CN)
6
]; B: K
3
[Fe(CN)
6
];
C: Fe
2
[Fe(CN)
6
]; D v E: KFe[Fe(CN)
6
]
b) K
4
[Fe(CN)
6
] + 2Pb(NO
3
)
2
= Pb
2
[Fe(CN)
6
]| + 4KNO
3

K
4
[Fe(CN)
6
] + 2FeCl
2
= Fe
2
[Fe(CN)
6
]| + 4KCl
2Fe
2
[Fe(CN)
6
] + 2K
4
[Fe(CN)
6
] + O
2
+ H
2
O = 4KFe[Fe(CN)
6
] + 4KOH
K
3
[Fe(CN)
6
] + FeCl
2
= KFe[Fe(CN)
6
]| + 2KCl
c) KFe
2+
[Fe
3+
(CN)
6
] v KFe
3+
[Fe
3+
(CN)
6
] ch l cng mt hp cht.
83,3g mt hn hp hai nitrat A(NO
3
)
2
v B(NO
3
)
2
(A l kim loi kim th, B l kim loi d) c
nung ti khi to thnh nhng oxit, th tch hn hp kh thu c gm NO
2
v O
2
l 26,88L (0
o
C v
1atm). Sau khi cho hn hp kh ny qua dung dch NaOH d th th tch ca hn hp kh gim 6 ln.
a) A v B l nhng kim loi no?.
b) Tnh thnh phn ca hn hp nitrat.
c) Vit cc phng trnh phn ng.
d) Nu nung nhit cao hn na th c th thu c nhng mui g?.
BI GII:
a) n(NO
2
+ O
2
) = 1,2mol
n(O
2
) = 0,2mol
n(NO
2
) = 1mol
%NO
2
= 83,3% v %O
2
= 16,7% n(NO
2
) : n(O
2
) = 5 : 1
2Me(NO
3
)
2
= 2MeO + 4NO
2
+ O
2
; n(NO
2
) : n(O
2
) = 4 : 1
O
2
oxy ha BO thnh B
2
O
X

41
2A(NO
3
)
2
= 2AO + 4NO
2
+ O
2

a a 2a 0,5a
2B(NO
3
)
2
= 2BO + 4NO
2
+ O
2

b b 2b 0,5b
2BO + (x 2)/2O
2
= B
2
O
X
; n(O
2
) = 0,05mol
b b(x 2)/4
b(x 2)/4 = 0,05
b = 0,2/(x 2)
Me(NO
3
)
2
NO
2

M(trung bnh) = 167g/mol
Vy M(trung bnh) ca c hai kim loi = 43g/mol
Vy A l Canxi (Ca) (M
A
= 40g/mol)
M(trung bnh) = 40a + b.M
B
/0,5
2a + 2b = 1
a = (1 2b)/2 = 0,5 0,2/(x 2) = (0,5x 1,2)/(x 2)
43 = (40(0,5x 1,2) + 0,2M
B
))/((x 2) .0,5))
x = 4; M
B
= 55g/mol
Vy B l Mn.
b) %Ca(NO
3
)
2
= 80%; %Mn(NO
3
)
2
= 20%
c) Cc phn ng xy ra:
2Ca(NO
3
)
2
= 2CaO + 4NO
2
+ O
2

2Mn(NO
3
)
2
= 2MnO + 4NO
2
+ O
2

2NO
2
+ 2NaOH = NaNO
2
+ NaNO
3
+ H
2
O
d) xCaO + MnO
2
= Ca
x
O
x-1
MnO
3
: manganat kim (1 s x s 4)
Cho 6,84g oxiclorua A(tinh th ) tc dng vi nc nng to thnh tinh th ngm nc B.
Nung B thu c 4,64g C c mu vng. 300
o
C, C phn ng vi CCl
4
cho 7,94g D mu tm. un nng
D trong HI kh thu c bt E l mt cht nghch t, v nh hnh mu nu.
a) Xc nh cc cht A, B, C, D, E bit rng ch c 1/3 s nguyn t iot trong E l to kt ta vi
Ag
+
.
b) Vit cc phng trnh phn ng.
c) Vit cng thc cu to ca A v D. Nguyn t trung tm, c cc lin kt cng di vi clo l
trng thi lai ha no?.
d) Th ngh cu to ca E trng thi rn v gii thch v sao ch c 4 ch khng phi tm
nguyn t iot tham gia phn ng trao i?.
BI GII:
a) 2MO
x
Cl
n-2x
M
2
O
n

68,4/(A + 35,5n 55x) = 4,64/(2A 16n) A = 50n 116x
M
2
O
n
2MCl
2

4,64.2/(2A +16n) = 7,94/(A + 35,5n) A = 30,67n
50n 116x = 30,67n n = 6x v A = 184g/mol
Vy A l WOCl
4
; B l WO
3
.H
2
O; C: WO
3
; D l WCl
6
; E l [W
6
I
8
]I
4

b) WOCl
4
+ 3H
2
O = WO
3
.H
2
O| + 4HCl
WO
3
.H
2
O = WO
3
+ H
2
O|
2WO
3
+ 3CCl
4
= 2WCl
6
+ 3CO
2

6WCl
6
+ 36HI = [W
6
I
8
]I
4
+ 36HCl + 12I
2

42
[W
6
I
8
]I
4
+ 4AgX = 4AgI + [W
6
I
8
]X
4
.
c) Ion trung tm W cc trng thi lai ha sau:
dsp
3
(WOCl
4
); d
2
sp
3
(WCl
6
)
OLYMPIC HA HC C 1999:
Nhng hp cht ha hc no c th c tng hp ch t khng kh (c xem l hn hp ca
oxi v nit) v nc?. Bn hy vit cc phng trnh phn ng c cn bng. C th k n qa
trnh nhiu bc, ngha l cc sn phm c th tng hp c t khng kh cng c th tip tc phn
ng vi nhau. Nng lng, cc dng c bt k v cc cht xc tc thng dng c xem nh cho sn
nhng khng phi l cc cht khc (nh ng, halogen)
BI GII:
Nc c th c phn tch thnh hydro v oxy nh in phn:
1. Nit v oxy tc dng vi nhau to thnh nit dioxit:
N
2
+ 2O
2
= 2NO
2

2. Nit dioxit cn bng vi Nit tetraoxit:
2NO
2
= N
2
O
4

3. Tng hp amoniac:
N
2
+ 3H
2
= 2NH
3

4. Oxy ha amoniac thnh nit monoxit:
4NH
3
+ 5O
2
= 4NO + 6H
2
O
5. Tng hp dinit trioxit bng cch lm bo ho NO
2
lng (hay N
2
O
4
) vi NO:
NO + NO
2(l)
= N
2
O
3
.
6. Axit nitric:
2N
2
O
4
+ O
2
+ H
2
O = 4HNO
3

7. Amoni nitrat:
HNO
3
+ NH
3
= NH
4
NO
3

8. iu ch dinit monooxit bn cch un nng amoni nitrat:
NH
4
NO
3
= N
2
O + H
2
O
9. Kh oxy ca axit nitric to thnh hydroxilamin:
HNO
3
+ 6H
+
+ 6e = NH
2
OH

+ 2H
2
O
10. Dn hn hp ng lng mol ca NO v NO
2
vo dung dch amoniac to thnh amoni
nitrit:
NO + NO
2
+ 2NH
4
+
+ 2OH
-
= 2NH
4
NO
2
+ H
2
O
420,0g mt hn hp gm (NH
4
)
2
CO
3
.H
2
O, FeCO
3
v NaCl c un nng. Cht kh hnh thnh
c lm kh v sau chim mt th tch l 124,0dm
3
( nhit 22
o
C v p sut 1021hPa).
Cng khi lng ca hn hp c x l bng mt lng d axit clohydric long. Mt phn
trm ca dung dch hnh thnh c chun bng dung dch kali dicromat 0,1M. Sau khi chun
xong tn ht 27,2cm
3
.
Bn hy tnh khi lng ca tng mui trong hn hp.
BI GII:
St cacbonat phn ly da vo phng trnh: FeCO
3
= FeO + CO
2

Amoni cacbonat hydrat phn ly theo phng trnh: (NH
4
)
2
CO
3
.H
2
O = 2NH
3
+ CO
2
+ H
2
O
Mui n khng phn ly.
Da vo nh lut kh ta c th tnh c ton b lng cc cht kh hnh thnh NH
3
v CO
2
.
Php chun cho ta lng Fe
2+
v nh vy l c lng cacbon dioxit hnh thnh t st cacbonat. Ly
tng lng cc cht kh hnh thnh tr i lng cht ny ta s c lng cc cht kh hnh thnh t
43
amoni cacbonat hydrat (bao gm 2/3 l NH
3
v 1/3 l CO
2
). 1/3 lng cht cn li ny l lng cht
amoni cacbonat hydrat. Bng cch nhn vi cc khi lng. Bng cch nhn vi cc khi lng mol
tng ng ta c khi lng ca cc cht cn tm.
Tng lng cc cht kh c hnh thnh c tnh theo pV = nRT
n = 5,16mol
Chun : 6Fe
2+
+ Cr
2
O
7
2-
+ 14H
+
(nc)
= 6Fe
3+
+ 2Cr
3+
+ 7H
2
O
Lng cht dicromat trong mt mu th: 2,72.10
-3
mol
Lng cht st trong mt mu th: 6.2,72.10
-3
= 1,632.10
-2
mol
Tng lng cht st: 1,632mol
Tng khi lng st cacbonat: 1,632.115,86 = 189,1g
Lng cht kh hnh thnh t amoni cacboant hydrat = 3,53mol
Lng cht amoni cacbonat hydrat = 3,53: 3 = 1,18 mol
Tng khi lng amoni cacbonat hydrat = 134,2g
Tng khi lng mui n = 96,7g
Ch c sn xut t loi qung hay gp nht trong thin nhin ca n: galen. Thnh phn chnh
ca galen l ch (II) sunfua nhng trong qung vn cn nhiu thnh phn kim loi khc trong c ch
nguyn t. iu ny rt cn thit xc nh tinh khit ca mu qung, n c tnh bi t l ca
lng ch c mt dng nguyn t so vi tng lng ch c mt trong qung.
Vic sn xut ch t qung galen c bt u t vic nung chy galen trong mt lng gii hn
khng kh to ra ch (II) oxit v gii phng ra l hunh dioxit.
a) Vit phng trnh phn ng.
b) Ti sao vic phn ng xy ra vi mt lng gii hn khng kh li quan trng?
c) Vi ch nguyn t th trong iu kin chuyn g s xy ra?. Hy vit tt cc phn ng lin
quan.
d) Hy vit phng trnh biu din s ph thuc lng ch c mt trong galen (dng PbS) so vi
lng SO
2
thot ra (o 298K v 101,3kPa)
Ch (II) oxit hnh thnh trong iu kin trn li tip tc c kh bng galen nhit cao
sinh ra ch lng v li tip tc gii phng lu hunh dioxit.
e) Vit phng trnh phn ng xy ra.
f) Ch r cht oxy ha.
Mt mu gm 10,45g qung giu galen c phn tch xc nh hm lng ch. 2/3 mu c
nung chy vi mt lng gii hn khng kh sinh ra PbO v gii phng 66,2mL SO
2
(o 298K v
101,3kPa).
g) Tnh s mol ch sunfua c trong mu galen ban u.
h) Tnh tinh khit ca galen.
i) Tnh khi lng ch oxit sinh ra.
Lng ch oxit ny c nung chy vi 1/3 lng galen cn li. Ch lng sinh ra c lm lnh
v em cn c 0,8663g
j) Tnh % ch nguyn t trong mu.
100,0mL dung dch ch nitrat c pha ch chnh xc bng s mol ch c trong mu galen c
cp trn. Sau ta thm dung dch NaOH 0,200M. Sau khi thm vo th ch hydroxit c kt ta
v khi thm lng d NaOH th kt ta b ha tan tr li. Sau khi kt ta b ho tan hon ton ta thy tn
ht 83,3mL dung dch NaOH.
k) Bng nhng d kin cho. Hy s dng xc nh cng thc cu to ca phc ch.

44
BI GII:
a) 2PbS
(r)
+ 3SO
2(k)
= 2PbO
(r)
+ 2SO
2(k)

b) trnh b oxy ha xa hn.
c) 2PbO
(r)
+ O
2(k)
= 2PbO
2(r)

d) n(PbS) = 0,0409.V(SO
2
)
e) 2PbO
(r)
+ PbS
(r)
= 3Pb
(r)
+ SO
2(k)

f) Pb
2+
l tc nhn oxy ha.
g) 4,06.10
-3
mol
h) 92,9% (93%)
i) 0,605g
j) 2,9%
k) [Pb(OH)
4
]
2-
(n(Pb
2+
) : n(OH
-
) = 1 : 4)
S kh ton phn l mt phn rt quan trng trong ha v c, cc tiu phn hu c nh etanol v
andehit tng ng ca n l etanal c th tham gia vo phn ng kh. Axit ha dung dch c cha ion
dicromat c th oxy ha c hai cht trn thnh axit etanoic trong khi anion dicromat chuyn v dng
Cr
3+
. Dung dch bc nitrat trong amoniac ch c th oxy ho etanal to ra axit etanoic v trong qa
trnh ny ion Ag
+
b kh ha v Ag.
Mt nh ha hc tr chun b 500,0mL dung dch hn hp gm etanol v etanal (cha bit c th
lng ca mi cht). xc nh hm lng ca tng cht trong hn hp th anh ta truc tin phi tiu
chun ha dung dch K
2
Cr
2
O
7
0,05M sau axit ho bng cch chun n vi dung dch st (II)
sunfat. Dung dch st (II) sunfat ny c chun b bng cch ho tan 7,43g FeSO
4
.7H
2
O vo lng
chnh xc 100,0mL nc. 25,0mL dung dch ny phn ng ht vi 23,12mL dung dch dicromat v
22,45mL dung dch dicromat ny sau khi c tiu chun ha th phn ng ht vi 50,0mL hn hp
etanol v etanal.
Cui cng, mt lng d dung dch bc nitrat trong amoniac c thm vo 50,0mL dung dch
hn hp etanol/etanal khc v nh ha hc ny nhn thy rng kt ta bc kim loi thu c l 0,234g.
Ngi ny nhn thy rng by gi c d kin xc nh c hm lng etanol v etanal trong
dung dch hn hp.
a) Vit na phn ng ca cc qa trnh:
i. S kh Cr
2
O
7
2-
.
ii. S oxy ha etanol.
iii. S oxy ha etanal.
iv. S kh Ag
+

v. S oxy ha Fe
2+
.
b) S dng cc d kin phn trn hy cn bng cc phn ng sau:
i. Cr
2
O
7
2-
vi etanol.
ii. Cr
2
O
7
2-
vi etanal.
iii. Cr
2
O
7
2-
vi Fe
2+

iv. Ag
+
vi etanal.
c) Ti sao ta buc phi axit ha dung dch dicromat?
d) Tnh nng ca dung dch K
2
Cr
2
O
7
s dng trong php phn tch trn.
e) Tnh s mol bc nitrat cn tm oxy ha etanal trong dung dch hn hp v t tnh s mol
ca etanal trong 50,0mL dung dch hn hp ny.
f) S dng cu e hy tnh nng ca ion dicromat cn thit oxy ha etanol trong 50,0mL dung
dch hn hp.
45
g) Tnh hm lng ca etanol v etanal trong 500,0mL dung dch ban u.
BI GII:
a) i. Cr
2
O
7
2-
+ 14H
+
+ 6e = 2Cr
3+
+ 7H
2
O
ii. CH
3
CH
2
OH + H
2
O = CH
3
COOH + 4e + 4H
+
.
iii. CH
3
CHO + H
2
O = CH
3
COOH + 2e + 2H
+

iv. Ag
+
+ e = Ag
v. Fe
2+
= Fe
3+
+ e
b) i. 2Cr
2
O
7
2-
+ 3CH
3
CH
2
OH + 16H
+
= 4Cr
3+
+ 3CH
3
COOH + 11H
2
O
ii. Cr
2
O
7
2-
+ 3CH
3
CHO + 8H
+
= 2Cr
3+
+ 3CH
3
COOH + 4H
2
O
iii. Cr
2
O
7
2-
+ 6Fe
2+
+ 14H
+
= 2Cr
3+
+ 6Fe
3+
+ 7H
2
O
iv. CH
3
CHO + 2Ag
+
+ H
2
O = CH
3
COOH + 2Ag
(r)
+ 2H
+

c) Cn bng ca cc phn ng c s tham gia ca proton chuyn dch v pha tri. Chnh v vy,
vic tng thm nng proton lm chuyn dch cn bng v pha phi.
d) 0,0482M
e) 0,00108mol
f) 0,000720mol
g) n
etanol
= n
etanal
= 0,0108mol
Oxit c th c phn loi thnh oxit axit, oxit baz hay oxit lng tnh. Cc oxit ion u l oxit
baz, n phn ng vi nc cho ra dung dch baz. V d nh Li
2
O:
Li
2
O
(r)
+ H
2
O
(l)
= 2Li
+
(aq)
+ 2OH
-
(aq)

iu ny c gii thch l anion O
2-
(aq)
c tnh oxy ha rt mnh v n d dng phn ng vi
nc sinh ra ion OH
-

O
2-
(aq)

+ H
2
O
(l)
= 2OH
-
(aq)

Oxit ca cc phi kim l cc oxit axit: V d: CO
2
.
CO
2(aq)
+ H
2
O
(l)
= H
2
CO
3(aq)

Oxit cha cc nguyn t c trng thi chuyn tip m in u l nhng oxit lng tnh. N c
y tnh cht ca oxit axit v oxit baz. V d: Al
2
O
3
.
Al
2
O
3(r)
+ 6H
+
(aq)
= 2Al
3+
(aq)
+ 3H
2
O
(l)
.
Al
2
O
3(r)
+ 2OH
-
(aq)
+ 3H
2
O
(l)
= 2[Al(OH)
4
]
-
(aq)

a) Vit cc phn ng ca bari oxit v indi oxit vi nc (y l cc oxit baz).
b) L hunh dioxit v trioxit u l nhng oxit axit. Vit cc phng trnh phn ng ca cc oxit
ny vi nc.
c) Trong cu b th axit no s c tnh axit mnh hn. Hy nu ra quy lut.
d) Hy sp xp cc oxyaxit ca clo theo chiu tng dn tnh axit.
e) Trong hai oxit ca thic l SnO v SnO
2
th oxit no c tnh baz mnh hn. Gii thch.
f) Beri oxit v asen(III)oxit u l nhng oxit lng tnh. Hy vit cc cn bng axit v baz cho
mi cht.
Cc peroxit(O
2
2-
), supeoxit(O
2
-
) v nitrua (N
3-
) ion (ca kim loi) th hin tnh baz rt mnh khi
chng phn ng vi nc v trong mi trng hp chng u sinh ra dung dch kim. Hydro peoxit l
sn phm sinh ra khi cho peoxit v supeoxit phn ng vi nc, sn phm ph l oxy.
g) Vit cc phn ng xy ra khi cho bari peoxit v kali supeoxit phn ng vi nc.
h) Khi cc nitrin phn ng vi nc th ngoi dung dch kim ra cn thu c cht no?
i) Tng t nh vy vi trng hp ca photphin.
j) Trong hai sn phm hai cu h v i th sn phm no c tnh baz mnh hn. Gii thch.

46
BI GII:
a) BaO
(r)
+ H
2
O
(l)
= Ba
2+
(aq)
+ 2OH
-
(aq)

In
2
O
3
+ 3H
2
O
(l)
= 2In
3+
+ 6OH
-
(aq)
(hay In(OH)
3(r)
)
b) SO
2(aq)
+ H
2
O
(l)
= H
2
SO
3(aq)

SO
3(aq)
+ H
2
O
(l)
= H
2
SO
4(aq)

c) SO
3
c tnh axit mnh hn, nh vy H
2
SO
4
c tnh axit mnh hn.
i vi mt dy cc axit th axit mnh hn s l axit c nhiu nguyn t oxy gn vi nguyn t
trung tm hn. Zumdahl gi thit rng iu ny xy ra do nguyn t oxy c tnh m in cao th c
kh nng rt electron ra khi nguyn t trung tm v c lin kt O H. Kt qa l lin kt O H tr nn
phn cc hn v yu i. Chnh iu lm tng tnh axit ca cc axit c cha nhiu nguyn t oxy lin
kt vi nguyn t trung tm.
Cng c th gii thch nh sau: S c s oxy ha +6 trong SO
3
v H
2
SO
4
cn trong SO
2
v H
2
SO3

th lu hunh c s oxy ha +4. trng thi oxy ha +6 th lu hung c kh nng ht electron t cc
nguyn t O ln cn. Nh vy lin kt O H s b yu i v tnh axit s tng ln.
d) HClO < HClO
2
< HClO
3
< HClO
4
.
e) SnO c tnh baz mnh hn. Do trng thi oxy ha +2 th Sn t c kh nng ht e cc nguyn
t O ln cn hn l khi trng thi c s oxy ha +4.
f) BeO
(r)
+ 2H
+
(aq)
= Be
2+
(aq)

+ H
2
O
(l)

BeO + 2OH
-
(aq)
+ H
2
O
(l)
= [Be(OH)
4
]
2-
(aq)

As
2
O
3(r)
+ 6H
+
(aq)
= 2As
3+
(aq)
+ 3H
2
O
(l)
.
Al
2
O
3(r)
+ 6OH
-
(aq)
= 2AsO
3
3-
(aq)
+ 3H
2
O
(l)

g) BaO
2(r)
+ 2H
2
O = Ba
2+
(aq)
+ 2OH
-
(aq)
+ H
2
O
2(aq)
+ O
2(k)

2KO
2(r)
+ 2H
2
O
(l)
= 2K
+
(aq)
+ 2OH
-
(aq)
+ H
2
O
2(aq)
+ O
2(k)

h) Mg
3
N
2(r)
+ 6H
2
O
(l)
= 3Mg
2+
(aq)
+ 6OH
-
(aq)
+ 2NH
3(aq)

i) Na
3
P
(r)
+ 3H
2
O
(l)
= 3Na
+
(aq)
+ OH
-
(aq)
+ PH
3(k)

j) NH
3
l baz mnh hn, N c m in ln hn P nn nguyn t N trong NH
3
s kt hp vi
proton d dng hn nguyn t P trong PH
3
.

Tuyen Tap BT Hoa Vo Co

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Tuyen Tap BT Hoa Vo Co

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I. OLYMPIC HA HC VIT NAM:

. Trong phc t din 4 ligand u nm trn ng phn gic ca hai trc x v y.

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