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Hai lin kt c hnh thnh bng cch ghp chung cc electron c thn v mt lin kt cho
nhn.
MO: (KK): s2 s2* x2 = y2 z2
2) I1(C) < I1(O) v in tch hiu dng vi electron ha tr tng t C n O.
I1(CO) > I1(O): v nng lng ca electron z ca CO thp hn nng lng ca electron ha tr
oxy.
3)
OLYMPIC HA HC SINH VIN TON QUC 2005 (Bng A):
L thuyt lng t d on c s tn ti ca obitan ng ng vi s lng t ph l = 4 (g l k
hiu ca s lng t ph n = 4).
1) Hy cho bit s electron ti a m phn lp ng c th c
2) D on sau phn mc nng lng no th n phn mc ng.
3) Nguyn t c electron u tin phn mc ng ny thuc nguyn t c s th t Z bng bao
nhiu?
BI GII:
1) Phn mc nng lng ng ng vi ga tr l = 4 s c 2l + 1 obitan nguyn t, ngha l c 2.4+1= 9
obitan nguyn t. Mi obitan nguyn t c ti a 2e. Vy phn mc nng lng ng c ti a 18e.
2) Phn mc nng lng ng xut hin trong cu hnh electron nguyn t l 5g bi v khi s lng t
chnh n = 5 th lp electron ny c ti a l 5 phn mc nng lng ng vi l = 0 (s); l =1 (p); l =
2 (d); l = 3 (f) v l = 4 (g). Theo quy tc Klechkowski th phn mc 5g c tng s n + l = 9. Phn
mc ny phi nm st sau phn mc 8s.
3) (Rn)7s25f146d107p68s25g1.
Z = 121.
OLYMPIC HA HC SINH VIN TON QUC 2005 (Bng A)
1) Hy cho bit cu hnh hnh hc ca phn t v ion di y, ng thi sp xp cc gc lin kt
trong chng theo chiu gim dn. Gii thch.
a) NO2; NO2+; NO2-.
b) NH3; NF3.
2) So snh momen lng cc gia hai phn t NH3 v NF3. Gii thch.
3) Thc nghm xc nh c mome lng cc ca phn t H2O l 1,85D, gc lin kt HOH l
104,5o, di lin kt O H l 0,0957 nm. Tnh ion ca lin kt O H trong phn t oxy (b
qua momen to ra do cc cp electron ha tr khng tham gia lin kt ca oxy)
Cho bit s th t Z ca cc nguyn t: 7(N); 8(O); 9(F); 16(S)
1D = 3,33.10-30 C.m
in tch ca electron l -1,6.10-19C; 1nm = 10-9m.
BI GII:
1) gii thch cu ny ta c th dng thuyt VSEPR hoc thuyt lai ha (hoc kt hp c hai).
a)
N
O
N
O
sp
sp2
(1) v (3): hnh gp khc.
(2) : thng
Gc lin kt gim theo th t sau: (2) (1) (3) do (2) khng c lc y electron ha tr ca N
khng tham gia lin kt, (1) c mt electron ha tr ca N khng lin kt dy lm gc ONO hp li i
cht. (3) gc lin kt gim nhiu hn do c 2 electron khng lin kt ca N y.
b)
sp
N
H
sp3
Gc lin kt gim theo chiu HNH - FNF v m in ca F ln hn ca H l in tch lch
v pha F nhiu hn lc y km hn.
(NH3) > (NF3)
Gii thch:
sp3
N
H
F
F
sp3
X
X
X
sp
F
F
F
Cl
S
Si
Cl
sp
Cl
sp2
Si
B
F
sp3
O
F
sp2
F
F
sp3
4 cht u tin c cu to bt i xng nn c momen lng cc ln hn 0.
THI CHN HC SINH GII QUC GIA VIT NAM NM 2002 (Bng A):
1. Liu php phng x c ng dng rng ri cha ung th. C s ca liu php l s bin i
ht nhn.
59
27Co
0n
60
X?
X? 28Ni + ... ;
(1)
h = 1,25 MeV
(2)
(a) Hy hon thnh phng trnh ca s bin i ht nhn trn v nu r nh lut no c p dng
hon th nh phng trnh.
(b) Hy cho bit im khc nhau gia phn ng ht nhn vi phn ng oxi ho-kh (ly th d t
phn ng (2) v phn ng Co + Cl2 CoCl2).
2. C cu hnh electron 1s22s22p63s23p63d54s1
(1)
Z2
(n: s lng t chnh, Z: s n v in tch ht nhn).
n2
(a) Tnh nng lng 1e trong trng lc mt ht nhn ca mi h N6+, C5+, O7+.
(b) Qui lut lin h gia En vi Z tnh c trn phn nh mi lin h no gia ht nhn vi
electron trong cc h ?
(c) Tr s nng lng tnh c c quan h vi nng lng ion ho ca mi h trn hay khng ?
Tnh nng lng ion ho ca mi h.
4. p dng thuyt lai ho gii thch kt qu ca thc nghim xc nh c BeH2, CO2 u l phn t
thng.
BI GII:
1. (a) nh lut bo ton vt cht ni chung, nh lut bo ton s khi v bo ton in tch ni ring,
c p dng:
in tch : 27 + 0 = 27; S khi : 59 + 1 = 60 X l 27Co60.
59
60
27Co + 0n1 27Co .
S khi : 60 = 60; in tch : 27 = 28 + x x = 1. Vy c 1e0.
60
60
27Co 28Ni + -1e; hv = 1,25MeV.
(b) im khc nhau
Phn ng ht nhn : xy ra ti ht nhn, tc l s bin i ht nhn thnh nguyn t mi. V d
(b) trn.
Phn ng ho hc (oxi ho - kh) : xy ra v electron nn ch bin i dng n cht, hp
cht. V d : Co + Cl2 Co2+ + 2Cl CoCl2.
Cht dng trong phn ng ht nhn c th l n cht hay hp cht, thng dng hp cht. Cht
dng trong phn ng oxi ho - kh, ph thuc vo cu hi m phi ch r n cht hay hp cht.
Nng lng km theo phn ng ht nhn ln hn hn so vi nng lng km theo phn ng ho
hc thng thng.
2. (a) Dng lng t biu din cu hnh :
(b) (1) l cu hnh e ca nguyn t v cu hnh d bn bo ho nn thuc kim loi chuyn tip (theo
HTTH cc nguyn t). Thuc kim loi chuyn tip th ion khng th l anion; nu l cation, s e = 24
th Z c th l 25, 26, 27 ... Khng c cu hnh cation no ng vi cc s liu ny. Vy Z ch c th
l 24.
(Nguyn t Ga c cu hnh [ar] 3d104s24p1, ion Ga2+ c cu hnh [ar] 3d104s1 bn nn khng th cn
c vo lp ngoi cng 4s1 suy ra nguyn t).
(c) Z = 24 nguyn t Cr, Kim loi (chuyn tip). Dng n cht c tnh kh.
Cr + 2HCl CrCl2 + H2
3. (a) Theo u bi, n phi bng 1 nn ta tnh E1. Do cng thc l E1 = 13,6 Z2 (ev) (2)
Th t theo tr s Z:
lai ho sp
2 obitan lai ho sp cng trn trc Z, mi obitan xen ph vi 1 obitan 1s ca H to ra lin kt .
Vy BeH2 HBeH (2 obitan p thun khit ca Be khng tham gia lin kt).
CO2, cu hnh electron : C 1s22s22p2; O 1s22s22p4. Vy C l nguyn t trung tm lai ha sp
lai ho sp
1. Nhm clorua khi ho tan vo mt s dung mi hoc khi bay hi nhit khng qu
cao th tn ti dng dime (Al2Cl6). nhit cao (7000C) dime b phn li thnh monome
(AlCl3). 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 H2O c momen lng cc, phn t khi gn bng nhau (HF 1,91
Debye, H2O 1,84 Debye, MHF 20, M H O 18); nhng nhit nng chy ca hidroflorua l
830C thp hn nhiu so vi nhit nng chy ca nc l 00C, hy gii thch v sao?
2
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
Cl
Al
Cl
Cl
Cl
Cl
;
Al
Al
dime
Cl
Cl
Cl
Cl
Cl
1200
Cl
1200
Al
0
120
Cl
O
O
O
O
2.
* Phn t
H-F
M = 20
Jt ;
= 1,91 Debye
H-O-H
M = 18
= 1,84 Debye
c th to lin kt hidro HO
c th to lin kt hidro HF
* 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 H2O 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 Tnc (H2O) = 00C > Tnc(HF) = 830C.
* 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-FH-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 H2O khc nm 4 nh ca t din. Trong nc mi
phn t H2O lin kt vi 4 phn t H2O 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.
THI CHN HC SINH GII QUC GIA VIT NAM NM 2004 (Bng A):
1. Trong s cc phn t v ion: CH2Br2, F - , CH2O, Ca2+, H3As, (C2 H5 )2O , phn t v ion no
c th to lin kt hidro vi phn t nc? Hy gii thch v vit s m t s hnh thnh lin
kt .
2. a) U238 t phn r lin tc thnh mt ng v bn ca ch. Tng cng c 8 ht c phng ra
trong qa trnh . Hy gii thch v vit phng trnh phn ng chung ca qu trnh ny.
b) Uran c cu hnh electron [Rn]5f36d17s2. Nguyn t ny c bao nhiu electron c thn? C
th c mc oxi ho cao nht l bao nhiu?
3. Trong nguyn t hoc ion dng tng ng c t 2 electron tr ln, electron chuyn ng
trong trng lc c to ra t ht nhn nguyn t v cc electron khc. Do mi trng thi
ca mt cu hnh electron c mt tr s nng lng. Vi nguyn t Bo (s n v in tch ht
nhn Z = 5) trng thi c bn c s liu nh sau:
Cu hnh electron
Cu hnh electron
-340,000
-600,848
-637,874
- 660,025
- 669,800
1s
1s2
1s22s1
1s 2s
1s22s22p1
Trong : eV l n v nng lng; du - biu th nng lng tnh c khi electron cn chu
lc ht ht nhn.
a) Hy trnh by chi tit v kt qa tnh cc tr s nng lng ion ho c th c ca nguyn t Bo
theo eV khi dng d kin cho trong bng trn.
b) Hy nu ni dung v gii thch qui lut lin h gia cc nng lng ion ho .
4. Nng lng lin kt ca N-N bng 163 kJ.mol1, ca NN bng 945 kJ.mol1. T 4 nguyn
t N c th to ra 1 phn t N4 t din u hoc 2 phn t N2 thng thng. Trng hp no
thun li hn? Hy gii thch.
BI GII:
H
O
H
H
C
H
O ... H
C2H 5
O. . .H
C2H 5
82Pb
206
+ 8 He + 6.
Vy nguyn t
92U
238
l +6 v U[Rn]5f36d17s2 6 e
U [Rn]+6 .
Vi ht
1s1
1s2
1s22s1
B4+
B3+
B2+
Nng lng
(theo eV)
- 340,000
- 600,848
- 637,874
Cu hnh
electron
1s22s2
1s22s22p1
Vi ht
Nng lng
(theo eV)
B+
B
- 660,025
- 669,800
C nh ngha: Nng lng ion ho (ca mt nguyn t) l nng lng t nht cn tch 1 e
khi nguyn t trng thi c bn m khng truyn thm ng nng cho e .
I
Vy gia nng lng ca 1 e trng thi c bn v nng lng ion ho I tng ng c lin h:
= -
(1).
Vy vi s ion ho M (k 1)+ - e
M k+ ; Ik
(2),
Ta c lin h:
Ik = - = - [EM(k -1)+ - EMk+ ]
(3)
Trong : k ch s e b mt (do s ion ho) ca vi ht c xt, c tr s t 1 n n; do k+
ch s n v in tch dng ca ion M k+ ;
Ik l nng lng ion ho th k ca nguyn t M c biu th theo (2).
Xt c th vi nguyn t Bo: v Z = 5 nn nguyn t c 5 e; vy k = 1 n 5. p dng phng
trnh (2) v (3), dng s d kin bng trn cho Bo, ta c:
*
Bo e
B+ ;
I1
( vy k = 1);
I1 = - [ EB EB+] = (669,800 + 660,025 ). Vy I1 = 9,775 eV .
B2+ ;
I2
( vy k = 2);
*
B+ e
I2 = - [ EB+ EB2+] = (660,025 + 637,874). Vy I2 = 22,151 eV .
*
B2+ e
B3+
;
I3
( vy k = 3);
I3= - [EB2+ EB3+] = (637,874 + 600,848). Vy I3 = 37,026 eV .
*
B3+ e
B4+
;
I4
( vy k = 4);
I4= - [EB3+ EB4+] = (600,848 + 340,000). Vy I4 = 260,848 eV .
*
B4+ e
B5+
;
I4
( vy k = 5);
I5= - [EB4+ EB5+] = (340,000 + 0,000). Vy I5 = 340,000 eV .
I1
Tng r
Li+
Na+
K+
Be2+
Mg2+
Gim r
Be2+ v Li+ ng electron vi nhau nhng Be2+ c in tch ht nhn nhiu hn nn phi c bn
knh nh hn.
Vy Be2+ c bn knh nh nht
2. i vi tinh th lp phng tm din (mt), mi mng c s c s n v cu trc l
1
1
x8 + x6 = 4 . Vy khi lng ring ca tinh th l:
8
2
4(55,8 + 16)
= 5,91(g / cm 3 )
d=
23
7 3
0,432.10
.6,022.10
THI CHN HC SINH GII QUC GIA VIT NAM NM 2005 (Bng A):
Cc vi ht c cu hnh electron phn lp ngoi cng: 3s1, 3s2, 3p3, 3p6 l nguyn t hay
ion? Ti sao?
BI GII:
Cu hnh electron ca cc lp trong ca cc vi ht l 1s22s22p6, ng vi cu hnh ca [Ne].
1. Cu hnh [Ne] 3s1 ch c th ng vi nguyn t Na (Z = 11), khng th ng vi ion.
Na l kim loi in hnh, c tnh kh rt mnh. Th d: Na t bc chy trong H2O nhit thng.
2 Na + 2 H2O 2 NaOH + H2
2.
Cu hnh [Ne] 3s2 ng vi nguyn t Mg (Z = 12), khng th ng vi ion. Mg l kim loai hot
ng. Mg chy rt mnh trong oxi v c trong CO2.
2 Mg + O2
2 MgO
3.
Cu hnh [Ne] 3s23p3 ng vi nguyn t P (Z = 15), khng th ng vi ion. P l phi kim hot
ng. P chy mnh trong oxi.
4 P + 5 O2
2 P2O5
4. Cu hnh [Ne] 3s23p6:
a) Trng hp vi ht c Z = 18. y l Ar, mt kh tr.
Rn
RaD
3,83 ngay
27,1 nam
RaA
3,05ph
5 ngay
RaB
26,8ph
138 ngay
RaE
Po
Pb
RaC
19,7ph
RaC'
1,63.10-4s
1. Vit nm phn r phng x u tin, dng cch biu din cho thy s hiu nguyn t, s khi ca tt
c cc ht nhn c lin quan.
c lng ban u cho thy cc chu k bn hy ca tt c cc sn phm phn r ca radi, tr
RaD v Po, c th c coi nh khng ng k so vi thi gian o t. Dng c lng ny tin hnh
cc tnh ton sau:
2. a) C bao nhiu nguyn t He c hnh thnh t mi nguyn t radi phn r sau 83 ngy?
b) C tng cng bao nhiu nguyn t heli c to thnh trong th nghim?
3. Hy tnh tr s gn ng ca s Avogadro t s liu trn. Bit ti 0oC v 1atm th V = 22,4L.
tnh c s Avogadro chnh xc hn, chu k bn hy ca Radon (t1/2(Rn) = 3,83 ngy)
khng th b qua, v chu k ny l ng k so vi thi gian tin hnh th nghim t; ngha l khng phi
mi nguyn t radon b phn r vo cui th nghim.
4. Chn tng quan gia tc phn r k ca bt k ht nhn no cho so vi chu k bn hu t1/2 ca
n.
a) k = 1/T1/2.
b) k = ln2/T1/2.
c) k = ln2.T1/2.
d) k = /T1/2.
k1
k2
Rn
RaA
5. a) Dng s ng hc n gin: Ra
(trong k1 v k2 l hng s tc ca cc phn ng tng ng). Vit biu thc quan h gia s
nguyn t radon vo lc cui th nghim NRn v s nguyn t radi NRa.
- NRn = k1.NRa/k2.
- NRn = k2.NRa/k1.
- NRn = k1.NRa/2k2.
- NRn = k1.NRa/3k2.
b) Tnh NRn dng tc phn r radi cho trn (x = 3,42.1010 ht mi gam radi trong mt giy).
6. C bao nhiu nguyn t heli c th c to thnh t cc nguyn t radon cn li lc cui th
nghim NRn, nu tt c cc nguyn t ny phn r thnh RaD?
- 4NRn.
- 2NRn.
- 5NRn.
- NRn.
- 3NRn.
7. Dng li gii ca cc cu hi trn, hy tnh mt gi tr gn ng tt hn ca
a) S nguyn t Heli to thnh.
b) S Avogadro.
BI GII:
1)
222
222
4
88 Ra 86 Rn + 2 He
222
86
218
Rn 84
Po + 42 He
218
84
214
Po 82
Pb + 42 He
214
82
214
Pb 83
Bi + e
214
83
214
Bi 84
Po + e
210
Po 82
Pb + e
2) a) 4
214
84
3.
4.
5.
= 9,58.10 y
1
,
91
228
S ht He thu c:
NHe = 9,58.1020.20.5 = 9,58.1022 ht
VHe = 3,56.103cm3 = 3,56L.
5) A = .N
0,693 0,693.N
t1 / 2 =
=
= 5,75 nm.
A
OLYMPIC HA HC QUC T 2001:
S ph thuc gia di sng v quang ph vch ca nguyn t hydro c bit n ln u
tin bi mt lot cc cng trnh ca mt gio vin ngi Thy S l ng Johan Jakob Balmer. Balmer
a ra cng thc thc nghim:
1
1
1
= RH 2 2
n
2
m e .e 4
Vi RH =
= 109768cm 1
8. o3 .h 3 .c
RH l hng s Rydberg, me l khi lng electron. Niels Bohr chng minh c cng thc
trn bng l thuyt nm 1913. Cng thc ny ng vi h nguyn t, ion ch c 1e.
1.1. Tnh bc sng di nht bng (1 = 10-10m) trong dy Balmer ca ion He+, b qua s chuyn
ng ca ht nhn.
1.2. Mt cng thc tng t nh cng thc ca Balmer c p dng cho cc vch ph khc sinh ra
khi i t mc nng lng cao hn xung mc nng lng thp nht. Vit cng thc v hy s
dng n tnh nng lng trng thi c bn ca nguyn t hydro (eV)
Nguyn t hydro muon1 cng tng t nh nguyn t hydro nhng cc electron b thay th
bng muon. Khi lng ca muon gp 207 ln khi lng electron trong khi in tch ca n cng
ging nh in tch ca electron. Muon c thi gian tn ti rt ngn nhng bi ton ny chng ta
khng xt n s km bn ca n.
1.3. Xc nh mc nng lng th nht v bn knh Bohr th nht ca nguyn t hydro muon. B
qua s chuyn ng ca cc ht nhn. Bit bn knh ca qy o th nht ca nguyn t hydro l
o
h2
a o = o 2 = 0,53 A
me e
Bc tranh ton cnh v l thuyt qy o ca Bohr c thay th bng l thuyt lng t
vi khi nim v obitan. Obitan 1s (r) trng thi c bn ca nguyn t hydro c cho di y:
1
1s =
e r / a0
3
a 0
r l khong cch t electron ti ht nhn, ao l bn knh Bohr.
1.4.
1.5.
1.6.
1.7.
1.8.
n
2
1
1 1
2.
= R H 2 2 ; n = 2,3,4...
n
1
E = -hcRH = -13,6eV.
3 Mc nng lng thp nht = -207.13,6 = -2,82keV.
o
101
1 / 2 =14 , 6 ph
1 / 2 =14 , 3 ph
43 Tc t
44 Ru
Mo t
101
4. Mt mu tinh khit ch cha Mo cha 5000 nguyn t 101Mo. Hi c bao nhiu nguyn t
101
Mo; 101Tc; 101Ru s xut hin sau 14,6 pht.
BI GII:
1. N = N o e 0,693t / t1/ 2
No N
= e 0, 693t / t1/ 2 1
N
(No N): S nguyn t 232Th phn r = s nguyn t 208Pb hnh thnh.
Thay s vo ta tnh c: t = 2,01.109 nm.
2. t x = (206Pb/238U). Ta c:
x = e 0,693t / t1/ 2 1
Thay t = 2,01.109 nm v t1/2 = 4,47.109 nm ta thu c kt qa x = 0,366
101
42
233
233
233
n , )
232
3. 90
Th (
90 Th
91 Pa 92 U
4 S nguyn t ca 101Mo (N1) trong mu sau mt chu k bn hy l: N1 = 2500
S nguyn t 101Tc c cho bi h thc:
N
N 2 = 1 o e 1t e 2t
2 1
Vi No = 5000 l s nguyn t 101Mo ban u
0,693
1 =
14,6
0,693
2 =
14,3
V ti thi im t = 14,6ph ta tnh c N2 = 1710
S nguyn t 101Ru ti 14,6ph l N3 = No N1 N2 = 790 nguyn t.
OLYMPIC HA HC QUC T 2005:
1. V cng thc Lewis ca mi phn t sau:
a) N2.
b) NH3.
c) O3.
d) SO3.
2 V cng thc Lewis ca cacbon monoxit v xc nh in tch hnh thc, trng thi oxy ha ca
cacbon v oxy trong cacbon monoxit.
Thioure S, S dioxit c khung cu to nh sau:
H
O
S
O
3 Vit cng thc Lewis cho Thioure S, S dioxit vi in tch hnh thc ca tt c cc nguyn t
bng khng.
4 Da vo thuyt sc y cp electron (VSEPR). Hy xc nh dng hnh hc ca nguyn t lu
hunh, cacbon v nit da vo cu trc Lewis ra cu 3.
4a. Dng hnh hc ca nguyn t lu hunh l dng no trong 3 dng sau:
a) Thp tam gic.
b) Tam gic phng.
c) Ch T
4b. Dng hnh hc ca nguyn t cacbon l dng no trong 3 dng sau:
a) Thp tam gic.
b) Tam gic phng.
c) Ch T.
c. Dng hnh hc ca nguyn t Nit l dng no trong 3 dng sau:
a) Thp tam gic.
b) Tam gic phng.
c) Ch T.
Cu trc phn t trng thi rn thng c xc nh bi phng php ph tia X. Da vo
phng php ny th cu trc ca Thioure S, S dioxit s nh sau:
H
65o
b)
c) O
O
O
O
O
O
O
O
O
2:
hay
C
O
C
O
-1
+1
in tch hnh thc: C ; O
O
O
d)
O
O
O
O
O
4:
S (b): tam gic phng
C (b): tam gic phng
N (a): thp tam gic
5:
N
S
O
C
N
C
N
+
N
III.
BI TP CHUN B CHO CC K THI OLYMPIC HA HC QUC T:
OLYMPIC HA HC QUC T 1998:
Cc kh him tng c ngh l hon ton tr v hon ton khng c kh nng to lin kt ha
hc. Ngy nay nhn thc trn thay i, hu ht cc sch gio khoa ha hc m t mt s hp cht
c cha krypton v xenon c lp c.
a) Dng thuyt lin kt ha tr (VB), d on hnh hc phn t c th c ca XeF2 v XeF4.
b) S oxy ha ca Xe trong mi hp cht trn l bao nhiu? Ta d on chng phn ng nh mt cht
oxy ha hay cht kh?
c) Heli c bit nh l mt nguyn t tr nht trong mi nguyn t; d vy tnh "tr" ca heli cng ch
gii hn trong phn ng ca n vi cc nguyn t v phn t trung ho khc. Cc hp cht ca heli, vi
cc lin kt ha hc hnh thc ca heli v cc nguyn t khc, c th tn ti khi xt ton b tiu phn c
mang in tch (thng l in tch dng). V d, nguyn t Heli c th to c cc hp cht quan st
c (khng nht thit tn ti lu) vi H+, vi He+ v vi He2+. Dng thuyt MO xc nh bc lin
kt cho mi trng hp.
d) Cc cation 2+ (di-cation) hai nguyn t bn vng c cng thc XHe2+ thng ch c th c khi nng
lng ion ha IE(X+) < IE(He): ngha l, khi nng lng cn thit ion ha tip X+ nh hn nng
lng cn thit ion ha He. Khng cn da vo bng tr s cc mc nng lng ion ha k tip ca
nguyn t, hy xc nh nguyn t 'Z' no trong khong t H n Ar ph hp nht vi tiu chun ny.
e) Nguyn t no ngay st vi nguyn t Z nh trn (ngha l nguyn t st tri, st phi, st trn, st
di nguyn t Z trong bng tun hon) l thch hp nht cng to c mt di-cation bn vng vi
He? Nguyn t no ngay st nguyn t Z l kh c th to c di-cation nh trn?
BI GII:
a)
Xe F
F
Xe F
XeF2 c 5 i electron trn Xe, vy cu to s da trn cu hnh electron lng thp tam
gic. Trong 3 kh nng sau:
F
F
Xe
F
F
Xe
Xe
Xe
Xe
1s
1s
He
*
1s
1s
He+
He
*
1s
1s
He
He
2+
T cc gin ny, c th thy rng c HeH+ v He22+ u c bc lin kt l , trong khi He2+ c
bc lin kt l 0,5.
d) Cc nguyn t nhm II c nng lng ion ha th hai kh thp (V Be+ Be2+ hoc Mg Mg2+ to
ra mt lp ngoi cng bo ho, c cu hnh kh him 1s2 hay 1s22s22p6). Mg2+ c hiu ng mn che tt
hn Be2+ nn IE(Mg+) < IE(Be+). Do Mg ph hp nht vi 'Z'.
e) Trong cc nguyn t k cn Mg: Ca c nng lng ion ha th hai thp nht trong s cc nguyn t
(Be, Na, Al, Ca). V nhng l do tng t nu trn. Nn Ca thch hp nht to dication bn vi He.
Na+ c lp v ngoi cng bo ho, nn rt kh xy ra qa trnh Na+ Na2+. V vy kh nng na
to dication vi He l t nht
OLYMPIC HA HC QUC T 1998:
Heli l nguyn t duy nht trong bng tun hon tm thy c trong mt vt th ngoi tri t
(ho quang mt tri) trc khi c lp c trong phng th nghim. Ta bit c nhiu tnh cht l hc
v ha hc ca heli; nhng trong gn 30 nm, t nm 1868, ph mt tri l ngun duy nht cung cp
thng tin v nguyn t him ny.
a) Vi kin thc hin nay v l thuyt lng t, ph ny cha nhiu d kin hu ch phn tch. Chng
hn nh ph thy c bao gm mt dy cc vch hp th ti di sng 4338, 4540, 4858, 5410 v
6558 (1 = 10-10m). Khong cch gia cc vch ch ra rng s hp th tu thuc trng thi kch thch
ca nguyn t hoc ion "kiu hydro" (nh nhng tiu phn c cu hnh electron tng t H). Tiu phn
ny l He, He+ hay He2+?
b) Ta thy rng mc nng lng chung cho cc trung gian lin quan n vch hp th ny u trng
thi nng lng thp ni = 4. Cc vch hp th tng ng trng thi nf cao hn c c im g? Tnh
hng s kiu Rydberg (ngha l hng s tng ng RH trong quang ph hydro nguyn t) ca tiu
phn hp th (Hei+) th hin trong cc trung gian trn?
c) Nng lng ion ha (Ionization energy, vit tt l IE) ca cc tiu phn thng c o theo
electronvon (eV). T nh IE(Hei+)?
d) T ph nguyn t, c bit rng IE(He+)/IE(He) = 2,180. Tng ca hai nng lng ion ha ny l
nng lng xut hin, AE(He2+), ca s to thnh He2+ t He. Tr s AE(He2+) l lng t b nht ca
nng lng phi cung cp cho He tch c hai electron ca nguyn t. Tnh tn s v di sng ca
photon c nng lng thp nht c kh nng nh hng n s ion ha kp ca heli. nh sng mt tri
ti b mt tri t c th l ngun cung cp cc photon ni trn c hiu qa khng?
Cc hng s cn thit:
c = 2,997925.10-8 ms-1
h = 6,62618.10-34Js
1eV = 96,486kJ.mol-1 = 2,4180.1014Hz
BI GII:
a) Nguyn t heli c 2e; tiu phn "kiu hydro" ch c 1e. Do tiu phn cp phi l He+
b) Ph hydro tun theo biu thc:
1
1
E = R H 2 2
n
i nf
Trong trng hp ny, cc vch ca He+ s tun theo:
1
1
E = R He 2 2
4
n f
hc 1
1
R He + =
4 2 n 2f
Nay th cc ph vo biu thc tng quan trn. Gi s rng di sng di nht quan st c l
6558 (l chuyn tip c nng lng thp nht) tng ng vi nf = 5; ta c:
Nf
"R(He+)"
6,558.10-7
5
1,35.10-17J
5,410.10-7
6
1,06.10-17J
-7
4,858.10
7
0,97.10-7J
4,540.10-7
8
0,93.10-17J
-7
4,338.10
9
0,91.10-17J
Nu ng, mi chuyn tip phi cho cng ga tr R(He+). R rng l khng ng nn phi chn li:
Nu ta chn nf = 6 cho chuyn tip 6558, ta c:
"R(He+)"
Nf
6,558.10-7
5
8,72.10-18J
-7
5,410.10
6
8,72.10-18J
4,858.10-7
7
8,72.10-18J
4,540.10-7
8
8,72.10-18J
-7
4,338.10
9
8,72.10-18J
Ga tr thu c ca R(He+) khng i, vy kt qa ny l ng.
c) IE(He+) bng R(He+). i thnh electronvon, cn nhn cho 6,02205.1023 mol-1 v chia cho
96486J.mol-1.eV-1: tnh c IE(He+) = 54,44eV
d) IE(He+)/IE(He) = 2,180; nn IE(He) = 24,97eV
Vy AE(He2+) = 79,41eV = 1,272.10-17J
C th tnh tn s, = E/h = 1,920.1016 s-1, v di sng = c/v = 15,61nm, ca photon cso nng
lng thp nht c kh nng ion ha kp (2 ln). di sng ny rt ngn hn di sng ca ph thy
c (kh kin) (300nm < < 700nm): mt tri khng phi l "th en" nng to nhiu phtn nh
vy v hu ht s b kh quyn hp th trc khi n c tri t.
OLYMPIC HA HC QUC T 1998:
Mt mu diclopropadien c phn tch bng khi ph k. Khi ph cho thy mt mi rt r t
l khi:in tch (m/z) l 75, mt mi khc ti m/z = 77. iu kin vn hnh nht nh ch quan st
thy hai mi trn trong khi ph. iu kin khc, cng mt mu th cho mt s mi khc, bao gm
m/z = 82 (khng c 83) v m/z =28 (nhng khng c 27). Khng ty thuc vo iu kin vn hnh, mi
ti m/z = 77 lun c cng bng 60% cng ca mi ti m/z = 75.
D
C
Cl
C
D
67
Ga + 01 e 30
Zn(+ )
68
Ge + 01 e 31
Ga(+ )
d) i) Dc phm phng x lc u cha 1,47.10-4 mol Ga, ngha l (1,47.10-4.5,0.10-7) = 7,35.10-11
mol 67Ga hay 4,43.1013 nguyn t ca ng v ny.
Vi s phn r phng x, tc phn ng c bc 1
v = It = knt(67Ga)
k = ln2/t1/2 = 2,461.10-6s-1 v Io = 1,09.108Bq (trong 100mL t = 0)
Vi liu 1mL ti t = 8 gi
It = I o e t / t1/ 2 .Vlu/Vtng cng = 9,84.105Bq.
ii) phng x ca liu 1mL cn li sau 1 gi na s bng
It = 9,72.105Bq
So snh phng x ny vi phng x lc u ca 1mL mu mu thu c h s pha
long = 9,72.105/105,6 = 9201
Th tch mu ca bnh nhn nh vy bng 9,20L.
OLYMPIC HA HC QUC T 1999:
a) Chui phn r thin nhin 238U92 206Pb82 bao gm mt s phn r anpha v beta trong mt lot cc
bc k tip.
i) Hai bc u tin bao gm 234Th90 (t1/2 = 24,10 ngy) v 234Pa91 (t1/2 = 6,66 gi). Hy vit cc
phn ng ht nhn ca hai bc u tin trong s phn r ca 238U v tnh tng ng nng theo
MeV ca cc sn phm phn r.
Cc khi lng nguyn t bng: 238U = 238,05079u; 234Th = 234,04360u; 234Pa = 234,04332u v
4
He = 4,00260u.
1u = 931,5MeV v mn = 1,00867u; 1MeV = 1,602.10-13J.
ii) Phn r k tip ca 238U dn n 226Ra88 (t1/2 = 1620 nm) m sau bc x cc ht anpha to
thnh 222Rn (t1/2 = 3,83 ngy). Nu mt th tch mol ca radon trong iu kin ny l 25,0L th
th tch ca radon cn bng bn vi 1,00kg radi l bao nhiu?
iii) Hot ca mt mu phng x ca mt phn t trong chui 238U gim 10 ln sau 12,80 ngy.
Hy tm hng s phn r v chu k bn hy ca n.
b) Trong s phn hch nh nguyn cm ng ntron ca 235U92, cui cng thng thu c hai sn phm
bn l 98Mo42 v 136Xe54. Gi s rng cc ht ny c to ra t qa trnh phn hch nguyn thy,
hy tm:
i) Ht c bn no c phng thch.
ii) Nng lng phng thch mi phn hch theo MeV v theo Jun.
iii) Nng lng phng thch t mi gam 235U theo n v kWh.
68
32
mt mu khong vt c th coi l khng i theo thi gian. thi im (t = 0) khi khong vt kt tinh,
nhng ng v ny c th ln trong khong vt di dng tp cht. Hm lng ban u ca cc ng v
(no(238U), no(206Pb) v n(204Pb) ln trong cc mu khong khc nhau c th cng khc nhau. Tuy nhin t
l ban u ca cc ng v ca cng mt nguyn t, v d nh t l no(206Pb)/(204Pb) s nh nhau i vi
mi mu khong vt kt tinh trong cng mt khi to ).
a) Vit h thc lin lc cho thy nt(206Pb) l mt hm theo nt(238U) v no(206Pb), k v t, vi t l thi gian
mu khong bt u kt tinh v k l hng s phn r phng x ca 238U.
Cc mu khong vt khc nhau c cha nhng hm lng ban u khc nhau ca cc ng v tp
238
cht U v 206Pb. V vy tui ca mt mu khong vt cho trc khng th suy ra c t s o ca
nt(238U) v nt(206Pb) m thi. Tuy nhin n(204Pb) t l vi hm lng ban u ca ch trong mt mu
khong vt cho trc, v v th cng t l vi no(206Pb).
Cc cp tr s tng quan ca nt(238U), nt(206Pb) v n(204Pb) vi nhng mu khong vt khc
nhau pht xut t cng mt th c th c xc nh nh khi ph. Mi cp y s biu din tng
im ring bit trn mt th vi trc honh nt(238U)/n(204Pb) v trc tung nt(206Pb)/n(204Pb). Ni vi
nhau, cc im trn s to thnh mt ng thng v tui ca c th tnh c t dc.
Gn y, ngi ta thu c cc cp t l ng v sau ca cc khong vt c trong mt loi
Isua:
nt(206Pb)/n(204Pb)
nt(238U)/n(204Pb)
1,106
12,098
1,883
12,733
2,632
13,305
2,859
13,567
2,896
13,588
3,390
13,815
b) Hy tnh tui ca loi Isua
c) im ct trc y ca th c ngha g?
BI GII:
a) Phn tng trong 206Pb phi bng phn gim t 238U, nh vy:
nt(206Pb) - no(206Pb) = no(238U) - nt(238U)
Do nt(238U) = no(238U)e-kt. thay vo phng trnh trn ta c:
nt(206Pb) = nt(238U)(ekt - 1) + no(206Pb)
b) T phng trnh trn:
n t 206 Pb n t 238U
n o ( 206 Pb)
kt
=
+
(
e
1
)
n( 204 Pb) n 204 Pb
n( 204 Pb)
n 206 Pb
n 238U
Do t 204
l mt hm tuyn tnh ca t 204
. T cc s liu, bng hi quy tuyn tnh cho php
n Pb
n Pb
ln 2
tnh dc bng ,769 = ekt - 1, vi k =
= 1,551.10 9 . Suy ra t = 3,7Ga
9
4,468.10
(
(
)
)
)
)
)
)
14,200
14,000
y = 0.7822x + 11259
2
R = 0.9909
13,800
13,600
13,400
13,200
13,000
12,800
12,600
12,400
12,200
12,000
0
c) im ct trc y biu th t s
1,000
(
n(
no
3,000
4,000
206
204
2,000
Pb
. 2 = E
vi h =
2
2m dx
ii.
T iu kin bin dn n: (0) = 0; (L) = 0
nx
tho mn iu kin ny.
Ch c biu thc = sin
L
h2 d 2
h 2 2 2
h 2 2 2 h 2 2
nx
nx
=
En =
iii.
.
sin
n =
n sin
2m dx 2
L
L
2mL2
2mL2
8mL2
x
1N ( x) = N sin
iv.
L
+
L
Ly tch phn: 1 = 1N ( x) dx = N 2
2
Vi N l mt s thc bt k th ta c: N =
2
L
2
x
sin
L
L
-10
L = 5 . 1,4.10 = 7.10-10m
Ba mc nng lng u ca h s l:
h2
= 1,22.10 19 J
E1 =
2
8mL
E 2 = 4 E1 = 4,88.10 19 J
1N ( x) =
b)
E 3 = 9 E1 = 10,98.10 19 J
Vy mc nng lng cc tiu ca h l: E3 E2 = 6,10.10-19J.
c)
iu kin lm cho () n tr l:
() = ( + 2)
() = ei = () = ei( + 2)
ei2 = 1
= m vi m = 0; 1; 2; 3
Ta c th thy rng hnh chiu momen gc khng th l mt s thc nhng c th nhn cc ga
tr l m vi m c th nhn cc ga tr t -m n +m (k c s 0)
r 2 ao
1s = 2 e
ao
2p
r
=
cos e 2 ao
ao
r2
3d 2 = 2 3 cos 2 1 e 3ao
z
ao
Hy xc nh hnh dng ca cc obitan trn.
c) Vic gii phng trnh Schrodinger cho h nguyn t 1electron ph hp tt vi l thuyt c in
ca Bohr v s lng t ha nng lng.
13,6Z 2
En =
n2
cho tin s dng th cc ga tr s ca cc hng s xut hin trong cng thc trn c chuyn
ht v n v eV.
iu th v l khi ta s dng cng thc trn cho phn t heli trung ha. Trong nguyn t heli lc
ht nhn tc dng ln electron b gim bt do electron khc chn mt. iu ny c ngha l in
tch ca ht nhn tc dng ln electron khng phi l Z = 2 na m s nh hn gi l in tch
hiu dng (Zeff). Nng lng ion ha ca nguyn t heli trng thi c bn l 24,46eV. Tnh
Zeff.
BI GII:
a)
i.
N
1s
= Ne
r
ao
1 = 1Nz dv = a o3 N 2
N = (a o3 )
(N l mt s thc bt k)
1
2
( )
1
3 2
o
r
ao
= a
e
ii. Xc sut tm thy electron gia khong r v r + dr
N
1s
( )
3 1
o
2r
ao
e dr
= 4r . a
Xc sut l cc i khi r = rmax. Ly o hm bc nht biu thc trn ta c:
2
2r
d 2 ao
r e
dr
=0
r = rmax
rmax = a o
Vy electron 1s d tm thy nht trong khu vc r = ao.
b) 2s = 0 ti r = 2ao
Vy hnh dng ca obitan 2s l mt khi cu c bn knh 2ao.
Hnh dng ca obitan 3dz2 trn mt phng xy
1
3d 2 = 0 khi 3cos2 1 = 0 = cos 1
z
3
Hnh dng l mt hnh nn vi mt phn trm trc xy cn mt phn di.
Lu : Tt c cc hm sng u bin mt khi r . Ti r = 0 th cc hm khc u khng tn
ti (tr 1s).
c)
Mi electron lp n = 1 ca nguyn t heli c nng lng Z2eff = 13,6eV
Mc nng lng thp nht ca heli Z2eff = 27,2eV
trng thi c bn ion He+ c nng lng = -4.13,6 = -54,4eV
Nng lng ion ho = (-54,4 + Z2eff. 27,2) = 24,46 Zeff = 1,70
OLYMPIC HA HC QUC T 2001:
a) Ta c cc phn ng phn hch 235U bng ntron nhit:
235
38
140
92 U + n 94 Sr + ... Xe + ...
U + n 141
56 Ba + ... + 3n
Hy b sung nhng phn cn thiu.
b) Xem nh cc phn ng phn r trn c bc 1. Cc tiu phn khng bn s t phn r cho Zr
v Ce. Vit cc phn ng ht nhn xy ra v tnh nng lng sinh ra (MeV). Cho bit cc s liu
sau:
m(235U) = 235,0493u
m(94Zr) = 93,9063u
m(140Ce) = 139,9054u
mn = 1,00866u
1u = 931,5Mev/c2.
c) Trong l phn ng ht nhn c s dng 1kg kim loi uran thin nhin. Khi tng nng lng sinh
ra t 1 Megawatt ngy (MWd) th n c ly ra khi h thng phn ng. Hy tnh %235U vo
thi im ny. Bit rng trong uran thin nhin th lng uran nguyn cht ch chim 0,72%. Gi
s rng tt c nng lng sinh ra u do 235U.
BI GII:
a) Cc phn ng xy ra:
235
38
140
92 U + n 94 Sr + 54 Xe + 2n...
235
92
92
U + n 141
56 Ba + 36 Kr + 3n
b) Phn ng xy ra:
235
94
140
92 U + n 40 Zr + 58 Ce + 2 n + 6e
Nng lng gii phng Q = [m(235U) m(94Zr) m(140Ce) m(n)]c2 = 213,3eV
c) 1MWd = 8,64.1010J
235
92
8,64.1010
S nguyn t U phn r =
= 2,53.10 21
13
213,3.1,602.10
Nh vy khi lng uran = 0,99g
Vy m(235U) cn li = 7,2 0,99 = 6,21g
%235U = 0,621%
OLYMPIC HA HC QUC T 2001:
ng v phng x 210Bi l sn phm ca qa trnh phn r 210Pb ri n tip tc phn r sinh
210
ra Po. 210Po cng s tip tc phng x cui cng thu c ng v bn 206Pb.
210
210
210
206
Bi
Pb
Po
Pb
T1/2=138,4d
T1/2 = 22,3y
T1/2 = 5,01d
235
d
N 2 e 2t = 1 N 1o e (2 1 )t
dt
1
2 1
2 1
N 1o e 1t e 2t
N 1o e (2 1 )t + C
1 N 1o
2 1
Ti thi im t =T ta c:
dN 2
=0
dt t =T
Gii phng trnh ny ta thu c: T = 24,9 ngy
T y ta tnh c s nguyn t N2 = 2,04.1012 v khi lng 210Po = 7,11.10-10g
c) tc phn r ca 210Po ti t = T l 1,18.105Dps
tc phn r ca 210Bi = tc phn r ca 210Po = 1,18.105Dps
OLYMPIC HA HC QUC T 2003:
1) C bao nhiu nh hp th i vi mt phn t CO, mt phn t H2O, mt phn t benzen, ahy my
phn t C60 trong ph hng ngoi.
a) 1
b) 2
c) 3
d) 4
e) xp x 30
f) 54
g) 120
h) 174
i) 720
j) Khng th xc nh c nu cha c thm thng tin.
2) Hai phn t gm hai nguyn t cha bit cho mt pic n ca hp th dao ng trong vng hng
ngai ca ph cng hng t electron (EMR). Phn t XY hp th tn s cao hn phn t WZ.
Khng nh no sau y l ng?
a) XY v WZ l cc ht nhn khc nhau.
b) Lin kt gia X v Y mnh hn lin kt gia W v Z.
c) MXY ln hn MWZ.
d) Tn s dao ng c trng ca XY cao hn WZ.
BI GII:
1) S dao ng c trng l 3N 6 cho phn t khng thng v 3N 5 cho phn t thng. Chnh v vy
ta s c cc kt qa sau:
CO : 1; H2O : 3; C6H6 : 30; C60 : 174
2) Nhng phn t c tn s dao ng trong ph hng ngoi u l nhng phn t c tn ti lng cc
hay l nhng ht nhn bn trong cc phn t l d hch.
i vi nhng phn t hai nguyn t c dao ng i xng th tn s c trng c cho bi
1 k
(vi k l hng s lc v l khi lng rt gn ca phn t). Nu khng
phng trnh: =
2
cho bit cc yu t khc th ta khng th ni trc iu g v hng s lc cng nh khi lng rt
gn ca phn t ( mnh ca lin kt th khng ph thuc vo k nhng li lin quan mt thit n
nng lng phn ly lin kt). Tn s c trng th bng vi tn s hp th ca cc photon bi v
nng lng dao ng c cho bi h thc: Edd = (v + 0,5)h v nng lng cng hng l
E=E=1 E = 0.
OLYMPIC HA HC QUC T 2003:
14
C l ng v phng x c chu k bn hy t = 5700 nm. N tn ti trong t nhin do n lin
tc c sinh ra trong kh quyn nh l mt sn phm ca phn ng ht nhn gia nguyn t nit v
ntron sinh ra bi tia v tr.
Chng ta gi s rng tc ca qa trnh hnh thnh l hng s trong hng ngn nm v bng vi
tc phn r. Chnh v vy lng 14C trong kh quyn lun lun khng i. Kt qa l 14C trong kh
quyn lun i cng vi cc ng v bn 12C v 13C trong kh quyn v tham gia vi vai tr nh nhau
trong cc phn ng ha hc ca cacbon. N sinh ra CO2 vi oxy v i vo cc qa trnh sng qua cc
phn ng quang ha di t l 14C/12C lun c gi khng i trong cc phn t hu c.
Vn ny c s dng xc nh tui ca cc ngun gc sinh hc (v d: tc, vi). Chng
c phn lp bng vi con ng sau ci cht ca vt th hu c (v d: trong cc lng m). T l
14 12
C/ C trong cc mu trn khng phi lun l mt hng s nht nh m lun gim i theo thi gian v
14
C lin tc b phn r.
Lng 14C c trong cc vt th sng (tnh trn tng s nguyn t C) c phn r l 0,277Bq/g
(1Bq = 1Dps (phn r / giy)).
a) Tnh tui ca mt mu cht c t l 14C/12C = 0,25
b) Chuyn g xy ra vi nguyn t 14C khi n b phn r?
c) Nu 14C nm trong cc phn t hu c (nh DNA, protein v,v) trong c th sng m b phn
r th s xy ra hin tng g?
d) Tnh phng x ca mt ngi 75kg. Gi s rng s phng x trong c th con ngi ch do
14
C thc hin v lng C trong c th l 18,5%.
BI GII:
a) Gi No l t l 14C/12C trong vt th sng v N cng l t l trn sau khi vt cht mt khong thi
gian t.
Ta c:
N = Noe-t vi l hng s phng x ( = ln2/t1/2).
iu ny dn n h thc:
N
ln
No
t
N
t=
= 1 / 2 ln
= 11400 nm.
ln 2 N o
ln 2
OLYMPIC HA HC QUC T 2003:
Uran (Z = 92) l mt nguyn t phng x tn ti trong t nhin. N l mt hn hp ca hai ng
238
v U (99,3%, T = 4,47.109 nm) v 235U(0,7%, T = 7,04.108 nm). C hai ng v ny u phng x
v u c to ra cc phn ng tng hp ht nhn. S phn r ca chng sinh ra cc lng khc nhau
ca cc ht v , qua nhiu qa trnh phn r khc nhau th s dn n vic hnh thnh cc ng v bn
206
Pb82 v 207Pb82 mt cch tng ng. Cc qa trnh ny c gi l hai chui phng x. S phng x
- khng chu nh hng ca cc qa trnh phn r khc nhau khng chu nh hng ca s chuyn
ha.
235
Mc d cc my ph c phn gii thp nhng cc mnh ion c th pht sinh ra nhiu mnh
lin tip c khi lng danh ngha khc nhau. iu ny ch c th xy ra i vi cc ion c cng cng
thc ha hc nhng cc ng v to thnh ion mnh th khc nhau. V d: ion CH3+ gm c cc mnh
ion c khi lng danh ngha t 15 (mnh 12C1H3+) n 19 (mnh 13C2H3+).
Cng ca cc mnh ng v ph thuc vo thnh phn ca cc nguyn t cu thnh cc
mnh ng v trong thin nhin. i vi cacbon th nhiu nht l 98,90% 12C v 1,10% 13C. Vi H
th 1H chim 99,985% v 2H chim 0,015%. Kt q al pic c cng cao nht l 12C1H3+ (M = 15),
pic c cng cao th hai l hai pic 13C1H3+ v 12C1H2H+, cn pic c M = 19 (13C2H3+) th c cng
gn nh bng 0 do lng 13C v 2H c rt t trong thin nhin.
Di y s cho bit cch tnh cng cc pic ng v ca ion mnh CH2Cl mt cch chnh
xc. Bit Cl gm hai ng v (75,77% 35Cl v 24,23% 37Cl).
+ Mnh M = 49: 12C1H235Cl: 0,989.(0,99985)2.0,7577 = 0,7431
+ Mnh M = 50: 13C1H235Cl: 0,011.(0,99985)2.0,7577 = 0,00833
12 2 1 35
C H H Cl: 0,989.0,00015.0,99985.0,7577 = 0,00011
12 1 2 35
C H H Cl: 0,989.0,99985.0,00015.0,7577 = 0,00011
= 0,0085
+ Mnh M = 51: 13C2H1H35Cl = 1,25.10-6
13 1 2 35
C H H Cl = 1,25.10-6.
12 1
C H237Cl = 0,240
= 0,240
+ Mnh M = 52: 13C2H235Cl = 1,9.10-10.
13 1
C H237Cl = 0,00266
12 1 2 37
C H H Cl = 3,59.10-5.
12 2 1 37
C H H Cl = 3,59.10-5
= 0,0027
+ Mnh M = 53: 13C2H1H37Cl = 4,0.10-7.
13 2 1 37
C H H Cl = 4,0.10-7.
12 2
C H237Cl = 5,4.10-9.
-7
= 8,1.10
+ Mnh M = 54: 13C2H237Cl = 6.10-11.
Cng ca mi pic (t M n M +5) t l vi s ph bin ca mi ng v hp phn trong ion
mnh v s tnh ton xc sut dn n tng kh nng xut hin cc hp phn ca cc pic c cng khi
lng phn t. Pic c cng cao nht c gi l pic c s v cng ca cc pic lin quan c
xc nh bi % ca n so vi pic c s.
T th d trn ta c:
M = 49
= 100%
M = 50
(0,0085/0,7491).100
= 1,14%
M = 51
(0,240/0,7491).100
= 31,98%
M = 52
(0,0027/0,7491).100
= 0,36%
M = 53
= 1.10-4%
M = 54
= 8.10-9%
28
1) Silic t nhin l hn hp ca 3 ng v bn Si, 29Si v 30Si. Trong khi clo t nhin l hn hp
ca hai ng v l 35Cl v 37Cl. C bao nhiu pic ng v ca ion SiCl2+.
2) Tt c cc ion mnh sau: (a): N2+; (b): CO+; (c): CH2N+; (d): C2H4+ u c khi lng danh ngha l
M = 28 v khng th phn bit c chng bng cc my ph phn gii thp. Tuy nhin so snh
fH(TiO2) = -944,7kJ.mol-1
fH(CO) = -110,5kJ.mol-1
fH (TiC + 1,5O2 TiO2 + CO) = -870,7kJ.mol-1.
Nm 1919, Born v Haber c lp tm ra ng dng ca nguyn l th nht nhit ng hc vo
s hnh thnh cht rn t cc nguyn t thnh phn. Bng cch ny ta c th c c nhng thng tin
chnh xc v nng lng mng li ca tinh th cht rn.
KCl ng hnh vi TiC v n kt tinh theo kiu mng ca NaCl.
3) S dng cc gi tr cho sn xy dng chu trnh Born Haber ca s hnh thnh KCl t cc
nguyn t v tnh nng lng mng li ca KCl.
Hthng hoa = 89kJ.mol-1
Entanpi ca KCl: K(r) K(k)
Hphn li = 244kJ.mol-1
Entanpi phn ly ca clo: Cl2(k) 2Cl
H = -355kJ.mol-1.
i lc electron ca clo: Cl(k) + e Cl-(k)
+
Hion ha = 425kJ.mol-1.
Nng lng ion ha ca kali: K(k) K + e
Entanpi ca s hnh thnh KCl: K(r) + 0,5Cl2 KCl(r) fH = -438kJ.mol-1.
BI GII:
1) r(Ti4+) /r(C4-) = 0,527 kiu mng tinh th ca NaCl.
fH = -870,7kJ.mol-1
(1)
2) TiC + 1,5O2 TiO2 + CO
-1
fH = -110,5kJ.mol
(2)
C + 0,5O2 CO
Ly (1) 3(2) ta c: TiO2 + 3C TiC + 2CO
Nh vy ta tnh c fH = 539,2kJ.mol-1.
3 Chu trnh Born Haber ca s hnh thnh KCl:
UL
KCl(r)
K+(k) + Cl-(k)
Bit:
Hion ha
H
K+(k)
Cl(k)
fH
0,5Hphn li
Hphn li
K(r)
0,5Cl2(k)
Ta tnh c UL = -719kJ.mol-1.
CH3
H3C
CH3
H3C
C
H
CH
CH
(CH2)11
(CH2)11
CH3
CH3
b) 543,5nm
c) 100nm
d) 200nm
e) Xp x 1m
BI GII:
1) Phn t pht quang trong vng kh kin do s khng nh c ca cc electron trn h lin kt , nh
vy cu tr li ng l (4).
2) Mt vng vi ng knh 4mm bao quanh mt b mt c din tch S = r2 = 1,26.10-5m2
S nguyn t phm nhum trong khu vc ny l: 10/(10-6)2.1,26.10-5 = 126.106
N c chuyn n b mt bi s bc hi ca 10L dung dch, nh vy nng ca n phi l:
(1,26.108/10-5)/(6,022.1023) = 2,1.10-11mol.L-1.
3) Vi E = hc/ th nng lng ca mi photon l: E = 3,66.10-19J
Nh vy nng lng kch thch cn thit l: 1,1.10-8J.s-1 = 11nW.
4) Trung bnh c c 10 phn t/L, nh vy 1 phn t s chim mt din tch S = 10-13m2.
Din tch ton khu vc chiu x = (50.10-9)2 = 7,85.10-15m2 nhn c 3.1010 photon/s v khu vc
chim gi bi mt phn t s nhn c: 3.1010.10-13/(7,85.10-15) = 3,82.1011 photon/s
Ch c 2,3.105 photon c hp th mi giy nn khu vc m hp th photon s l:
= 6.10-20m2 hay l 62.
5) Mt phn t dilC12 hp th 2,3.105 photon/s th nh vy s photon pht quang s l 161.103
photon/s.
Da vo hu sut d th kt qa s l: N = 0,2.0,55.161.103 = 17710 photon d c/s.
Trong khong 10ms th s photon d c s l 177 photon.
6) Mi im trn khu vc c chiu x ca mu c tip xc vi cng mt s lng photon/s (chiu
sng ng b). Mt phn t m c nh v trung tm ca im th s nhn c nhiu photon
hn l n bt k mt im no khc ca im chiu x. Do khu vc chiu x c qut nhanh nn
phn t s tr nn c mu, thi gian c mu cng nhiu khi n bn trong khu vc chiu sng. y
chnh l l do ti sao cc im pht quang ca mt phn t lun c mt kch thc nh nhau v bng
vi khu vc chiu sng. Nh vy p n ng l cu c.
OLYMPIC HA HC QUC T 2005:
Electron trong phc ca st vi hemoglobin c th c xc nh nh trong mt h m
electron di chuyn t do nh trong hp th hai chiu. Da vo m hnh ny th nng lng ca electron
s c tnh bi cng thc:
2) 4e
3) Nghch t.
4) Bc sng di nht xy ra s kch thch l E = (25 20)Eo.
Vi Eo = (6,63.10-34)/(8.9,11.10-31.(1.10-9)2) = 6,02.10-20J
Nh vy E = (25 20)Eo = 3,01.10-19J
= 606nm
OLYMPIC HA HC QUC T 2005:
Hu ht cc nguyn t trong bng h thng tun hon u c nhiu hn 1 ng v. Khi lng
nguyn t ca mt nguyn t c tnh ton da trn mi quan h v thnh phn ca cc ng v. V d:
Khi lng nguyn t ca clo xp x 35,5 bi v hm lng ca 35Cl gn gp 3 ln so vi 37Cl. Trong
ph khi lng, thay cho khi lng phn t trung bnh th ta nhn c pic khi lng ca cc ng v
(35Cl: 75,77%; 37Cl: 24,23%; 12C: 98,9%; 13C: 1,1%; 79Br: 50,7%; 81Br: 49,3%). Cc ng v rt c
ngha trong vic phn tch nh lng bng phng php ph khi lng.
1) c thi gian duy tr th t l ca cc ion M v M + 2 c s dng trong vic phn tch nh lng
2,3,7,8 tetraclo dioxin (2,3,7,8 - TCDD) bng phng php sc k - khi ph l t l tiu chun. Tnh t
l l thuyt ny.
Chiu cao ca cc mnh ng v (cng ) c th c pht hin bng cch s dng cng thc
sau: (a + b)n vi a l hm lng tng i ca ng v nh, b l hm lng tng i ca ng v nng
v n l s nguyn t clo c mt.
2) Ion phn t thng c chn trong php phn tch nh lng. Cng ca ion phn t cn c
sa li nu tn hu b gy nhiu bi cc hp cht khc. Trong php phn tch cc nguyn t khng phi
halogen vi khi lng phn t l 136 th ion phn t c chn trong php phn tch nh lng. Hy
ngh mt biu thc ton hc hu chnh c tn hiu ca ion phn t nu cht phn tch c cng
thi gian duy tr nh n - butylbromua.
BI GII:
1) 0,77
2) Tn hiu hiu chnh = (m/z 136tn hiu) - 1,03(m/z 138 tn hiu)
OLYMPIC HA HC QUC T 2005:
Mt s i lng vt l c th o c, nu c th cho kt qa s th c th dn n sai s. Sai s
tiu chun c nh ngha bi biu thc:
< G 2 > < G >2
Vi G l ga tr ring ca hng s vt l o c; <G> l tr trung bnh ca G; <G2> l ga tr
trung bnh ca G2. Ga tr tng bnh ca <G> v <G2> c th nhn c bng cch o lp li nhiu ln
khi thc hin cng mt php o xc nh i lng G. nh ngha ny c th p dng c cho c l
thuyt c in v l thuyt lng t. hai v d lin quan n vic xc nh lch tiu chun , mt l
da vo tinh cht ca phn t kh v hai l s dng hp th mt chiu s c a ra di y:
=
F ( v) = 4v 2
exp
2RT
2 RT
Vi v l tc ca phn t, M l khi lng ca phn t. T l nhit tuyt i v R l hng s kh.
Tnh tc trung bnh <v> v lch tiu chun V hay s phn b tc ca phn t O2 300K (O2 =
32g/mol, R = 8,31J.K-1.mol-1).
2) Gi s mt ht chuyn ng theo phng x c chun ha di dng hm sng:
= [(1 / 2 ) exp( x 2 / 2)]1 / 2 ; x
Tnh chuyn dch trung bnh <x> v lch tiu chun x sau khi x i c mt qung ng kh
di.
3) Trong c hc lng t, momen ca ht trong hp th mt chiu cso th c xc nh nh sau:
ih d
p=
vi h l hng s Planck. Tnh momen trung bnh <p> v lch tiu chun p vi tiu phn
2 dx
c hm sng c m t cu 2.
4) Tnh bt nh v v tr v momen ca ht xp vi cc d kin cho trn.
Mt s biu thc tch phn:
1/ 2
1 3 5 (2n 1)
2 n +1
0 x exp(ax )dx =
2 n +1
a
!
n
2 n +1
2
0 x exp(ax )dx = 2a n+1 vi n = 0,1,2,3
BI GII:
1) Tc trung bnh:
3/ 2
Mv 2 3
8RT
M
v dv =
< v >= vF (v)dv = 4
= 4,45.10 2 ms 1
exp
2
2
RT
RT
M
2n
Mv 2 4
3RT
M
v dv =
< v 2 >= vF (v)dv = 4
exp
= 2,33.10 5 ms 1
M
2RT 0
2 RT
0
2
-1
V = 1,87.10 ms
2) To trung bnh:
+
+
x2
1
dx = 0
< x >= * xdx =
x
exp
2
2
2
2
x = 1
< p >= * i
dx = 0
dx =
2
x
4
2
lch chun p:
+
h2 2
h2
< p 2 >= * i
dx
=
2
2
16 2
4 x
p = h/4
4) xp = h/4
IV.
OLYMPIC HA HC CC QUC GIA TRN TH GIi:
OLYMPIC HA HC ITALY 1999:
Trong cc cht sau, cht no khng to lin kt hydro vi nc:
a) NH3
b) HF
c) CH3OH
d) CH3 CH3
BI GII: cu d
OLYMPIC HA HC ITALY 1999:
Lin kt to thnh gia hai nguyn t c cu hnh electron ha tr l 2s22p5 s thuc loi lin kt:
a) Ion
b) Cng ha tr
c) Kim loi
d) Cng ha tr khng phn cc.
BI GII: cu d
OLYMPIC HA HC ITALY 1999:
Rutherford ch ra rng mu nguyn t ca Thomson l sai kh bn cc ht vo l vng mng
th:
a) Rt nhiu ht i qua l vng.
b) a s ht b lch i
c) Mt s ht b lch i hoc bt tr li.
d) Mt s ht b chuyn ha thnh nguyn t heli
BI GII: cu c
OLYMPIC HA HC C 1999 (Vng 4):
1) Ht nhn 80Ge c tnh cht phng x v phn r cng vi s gii phng ra cc tia . Ht nhn no s
hnh thnh trong qa trnh ny?
2) 148Gd l cht phng x , ht nhn no s c to thnh?
3) Ch c 4 ng v bn: 204, 206, 207 v 208. Mt trong s l sn phm cui cng ca mt dy
phn r bt u t 235U. Hy gii thch l ng v no ca ch?
4) Trong qa trnh cu 3 th c bao nhiu phn r ?
5) Bi trong t nhin ch gm c ht nhn 209Bi. Ngi ta bn ph n bng cc ht . Qa tnh ny gii
phng hai ntron. Hi ht nhn no hnh thnh?
Nm 1988, tm khn lim Turin ni ting c nghin cu bng phng php phng x cacbon.
Trong khi cng phng x ca mt gam cacbon ly t cc c quan sng l 735 phn r trong mt gi
th 1g cacbon ly t tm khn lim cho thy hot tnh l 677 phn r trong mt gi. Thi gian bn hy
ca 14C l 5570 nm.
6) Tnh tui ca tm khn .
BI GII:
1) 80As
2) 144Sm
3) 207Pb v 235 207 = 28 (7 phn r )
4) 4 phn r
5) 211At.
6) Khong nm 1327
OLYMPIC HA HC C 2002:
Cu hnh electron trng thi c bn ca Al3+ l:
a) 1s22s22p63s23p1.
b) 1s22s22p63s23p6.
c) 1s22s22p6.
d) 1s22s22p63s2.
e) 1s22s22p43s2.
BI GII: cu c
OLYMPIC HA HC C 2002:
232
Th90 chuyn ha thnh 208Pb82 sau mt lot phn r anpha v beta. Hi c bao nhiu phn r
anpha v beta?
Anpha Beta
A.
3
2
B.
4
8
C.
5
2
D.
6
4
E.
8
8
BI GII: cu b
OLYMPIC HA HC C 2002:
Phn t no c cc nguyn t nm trong cng mt mt phng?
1. NH3.
2 XeF4.
3. SF4.
4. ICl4a. 1,2 v 3
b. 2 v 3
c. 3 v 4
d. 2 v 4
e. Tt c u ng.
BI GII: cu d
OLYMPIC HA HC C 2003:
Da vo thuyt lin kt ha tr hy cho bit s lai ho ca nguyn t trung tm trong phn t
XeF2.
a) sp3
b) sp
c) dsp3
d) d2sp3
e) sp2.
BI GII: cu c
OLYMPIC HA HC C 2003:
Tnh bc sng ca nh sng cn thit c th phn ly nguyn t brom. Bit EBr-Br = 193kJ/mol
a) 6,19.10-7m
b) 1,03.10-30m
c) 1,98.10-28m
d) 1,93.10-12m
e) 1,25.10-8m
BI GII: cu a
OLYMPIC HA HC C 2003:
Nhng phn t no sau y c cc:
1) NH3
2) AsF3
3) CHCl3
4) BeF2
5) SnCl4
a) 1, 2 v 3
b) 1 v 3
c) 2, 3 v 4
d) 2, 4 v 5
e) Tt c
BI GII: cu a
OLYMPIC HA HC C 2004:
Nguyn t no c bn knh ln nht?
a) As
b) Br
c) P
d) S
e) Se
BI GII: cu a
OLYMPIC HA HC C 2004:
Trong nhng nm u tin ca th k 19 th John Dalton lit k mt lot cc khi lng
nguyn t. Mt trong s l vic xy dng nguyn t lng ca amoniac. Bng cch gi thit khi
lng ca hydro l 1 th ng c th tnh c cng thc ca amoniac. Nhng ng ng nhn rng
cng thc phn t ca amoniac l NH. Vy khi lng nguyn t ca amoniac m ng xc nh l
bao nhiu?
a) 2
b) 5
c) 14
d) 16
e) 42
BI GII: cu b
OLYMPIC HA HC C 2004:
Trong cc cht sau th cht no c nhit si nh nht:
a) NH3
b) H2O
c) C3H8
d) (CH3)2O
e) CH4.
BI GII: cu e