$6 GIAO DYC VA DAO TAO KY THI CHON DOL TUYEN DY THI HQC SINH GIO!
PHOC QUOC GIA LOP 12 THPT NAM HQC 2018-2019
Mon: Hoa hoe
C 13 wang
Cau 1 (2,5 diém):
La) Vé gidn dé nang Iwgng obitan phan tte (MO) cho phan ti O2. Tir d6 cho biét céu hinh
electron ctia cac tiéu phan: O2; O:; 0} va O2
b) Gan cac gid tri d6 dai lién két sau cho cae lién két trong mdi tiéu phan : 1,49 A ; 1,26 A;
121A va LIZA.
c) Sap xép nang Ivong ion héa cia cae tiéu phan sau day theo ther tu tir thap dén cao: O,
>, 0, ; O;. Giai thich,
2. a) Viét phuong trinh biéu dién cac bién déi hat nhan: °*Mo tac dung voi notron va hat
nhan vira duge tao thanh lai tiép tue phan ra B tao ra Tc
b) Mét mau natri photphat NasPO. nang 54,5 mg cé chira dong vi phéng xa ?P (co khoi
Iugng 32,0 dvC). Néu 15,6% s6 nguyén tir photpho trong hgp chat la *?P (con lai 1a photpho
6 trong ty nhién) thi co bao nhiéu hat nhan “P phan ra trong mot gidy doi voi mau nay?
Cho biét: thoi gian ban hiry ciia P 1a 14,3 ngay; P tu nhién cé khéi long nguyén tir trung
binh 1a 30,97 dvC,
Huéng din giai
¥[Néiqung
a | Gian dd MO cua O2 -
kin, Bit |
al 0.25 |
ti. Tap, Ba ieee
I] 9 “| Cau hinh electron:
Or: (6, 9°(6%,
(ap) ay) iy)?
ORY (a, ,)'
3.) (3) (6y,)° (Ms, )" (Ey)!
63,)° (63, y,)°(,)"
Bac lién két (BLK): O2: BLK = 2 > doo = 1,26A
0; BLK = 3/2 > doo =1,49 A
0} : BLK = 5/2 = doo =1,21 A
OF : BLK = 3 > doo =1,12 A
0,25
) Thir ty nang long ion héa: 0, O cé nang long ion héa cao nhat
0,25
0,25
2b
2a
%Mo + °n > Mo; Mo Te + B.
Trong mau NasPOs nay co chira 15,6% Nas“POs (M = 165 dvC) va (100-
15,6)% NasPOs (M = 163,97 dvC) gdm cae déng vi P tu nhién
=> khéi lung phan tir trung binh cia mau photpho dang xét
15,6%, 165+ 84,4%.163,97 = 164,13 dvC
54,5.10°
164,13
= tong sd mol P trong mau 1a: = 3,321.10 (mol)
=> 6 nguyén tir ?P 1a : 3,321.10, 0,156.6,022. 10° = 3.12.10! (nguyén tir)
In2
——-+— =5,61.107(s"')
14,3.24.60.60
Hang sé phan ra cla 2P : k=
=> s6 hat nhan *P phan ra trong mét gidy la : 5,61.107.3,12.10" =
1,75.10!(phan ra.s")
0,25
0,25
0,25
Trang 2/13 Cau 2 (3,5 diém:
1. Niken(11) oxit ¢6 edu tric mang tinh thé giéng mang tinh thé ciia natri clorua. Cae ion O°
tao thanh mang lap phuong tim mat, cdc héc bat dign co cdc ion Ni?*. Khoi lugng riéng cua
niken(II) oxit 18 6,67 g/cm}. Néu cho niken(II) oxit tic dung v6i liti oxit va oxi thi duge ede
tinh thé tring ¢6 thanh phan LigNi.sO:
FLO + (1-x)NiO + 402 — LiNirxO
Cau tric mang tinh thé cia Li,Ni.4O gidng céu trac mang tinh thé cia NiO, nhung mét so
ion Ni?* duge thé bang cac ion liti va mét s6 ion Ni?’ bj oxi héa dé bao dam tinh trung hoa
dign ciia phan tir. Khéi hrgng riéng cia tinh thé LisNii.xO 1a 6,21 gem’.
a) Vé mét 6 mang co sé ciia niken(II) oxit.
b) Tinh x (chap nhan thé tich cia 6 mang co so kh6ng thay ddi khi chuyen tir NiO thanh
LixNitxO).
¢) Tinh phan tram sé ion Ni?" da chuyén thanh ion Ni** va viét cong thire thyc nghiém
don gian nhat cua hop chat LisNi1xO bang cach dung Ni(II), Ni(III) va cae chi s6 nguyén.
2. A la mudi ciia kim loai X. Két qua phan tich mudi A bing phuong phap phan tich nguyén
16 duge tom tat trong bang sau:
Nguyén t a c Ss Nee
% khéi lugng | 0,00 0,00 14,38 | 0,00 3,62
Két qua theo doi su thay doi khdi Iugng theo nhiét 6 khi nung nong mudi A cho thay, truée
khi bi nhiét phan hay hoan toan, khdi hrong mudi A bi giam 30%.
é thyc hign duge cae phan img trong dung dich nude theo so dé sau:
H
. 1 + badng
aan
wnt, Bg
oy
c
<— a°=
Pini 40™
Tinh x: |
0,25
0,25
le
Thay x vao céng thite LisNii-sO, ta c6 Lip. |NinoO hay cong thite 1a LiNisOio. |
Vi phan tir trung hoa dién nén trong LiNivOio c6 8 ion Ni? va I ion Ni>
Vay cir 9 ion Ni* thi cé I ion chuyén thanh Ni”.
Phan trim sé ion Ni?’ da chuyén thanh ion Ni** la ; 100% = 11,1%
Céng thite thye nghiém don gidn nhat: LiNi(IN)(Ni(I))sO10._
0,25
0,25
2a
a) Ta c6: %X = (100% - (3,62 + 57,38 + 14,38)% = 24,62%
62 $738, 14,38
Ru Po Ms 7908 16 32,07
Phan tir A chi chira 1 nguyén ttr X = A c¢ dang: X(HsOsS)q (voi n_ nguyén)
62 5
gin=1=> My =—2—=54,95 => Xin
Vin=1=> My= 2
= 3,59:3,59:0,448 =8:8:1
: 24,62 hae aaa
6in= My =——-—— = 109,9 => khong 6 kim loai thoa man
Véin=2 => My, 0,448/2 2
V6in=3 => My= a“ =164,9 = X = Ho, tuy nhién kim loai nay khong
), 4
c6 cdc phan img nhu so dé => loai.
Vay cong thite thye nghiém cia A li MnHsOxS
0,25
0,25
2b
Tir so do chuyén héa ta thay: A + BaCls —> I+ J mau trang = A chira
Trang 4/13 go sunfat (SO} ) => 66 thé viet A dudi dang: MnHxOsSOx, 0,25
| Mat khac truée khi A bj phan hiy c6 su giam 30% khdi lugng = A phai
chira H20 va sy gidm khdi lugng nay ing voi 4 phan tir H2O da tach ra tir
mot phan tir A’
4.(2.1,008+1,16).100%
%H,O = —— ~ = 30%
54,95 +8. 1,008 + 8.16 +1.32,07 ° 0,25
Vay A li Mn$Ox.4H20; Mangan (11) sunphat ngém 4 phan tir nude.
2e | Cac chat va ion tir B dén |: Oo
B: [Mn(NH3)c]* C: Mn(OH)2 D: Mn0(OH)2
E: MnS F: MnCOs G: Mno, 0,25
H: [Mn(CN)o}* I: MnCle
Cac PTHH:
MnSOs+6NHs = —> [Mn(NH)sJ? + S02
MnSOy+2NaOQH =——»+Mn(OH)2 + Na2SOx ed
Mn(OH): + 1/202 —»MnO(OH)2
MnSOy + H202 + 20H" ——»MnO(OH)2 + SO} + H20 0,25
MnSOs + (NHi)2S_ ——>MnS_ + (NHs)2SO«
Mn$Os + (NH4)2CO3 —+MnCO3 + (NH,)2SOs
2MnSO, + SPbO2 + 4H’ —»2MnO, + 5Pb? +280; + 2H:
MnSOs + 6CN° —»[Mn(CN)oJ* + $02 0,25
MnSOs + BaClz »MnCh + BaSOw
Cau 3 (2,5 diém):
1. a) Tinh nhiét d6 16n nhat cia ngon Ira khi dot chay CH trong khéng khi & 4p suat 1
atm. Cho biét: - Khong khi chira 20% O2; 80% No (vé thé tich).
- Lugng khéng khi duge lay sao cho long O2 vita du dé phan img,
- Nhiét d6 ban dau 1a 298 K.
(Ch)ujorw) =33,58 J/ K.mol ; (Ch )oo,gy = 37.1 I / Kmol (C3), = 29,13 J/K.mol
(Ati, a,),y. g, =—7481 KI/ mol :(AHS, sy)... ,, = 7393.51 KI/ mol ;
ean) > }co,00
(Hip), ogg) = 241682 KI / mol
008)
b) Chuyén khéng thuan nghich 1,0 mol khi li tuéng don nguyén ti tir trang thai I (0,6 lit, 298
K dén trang thai 11 (1,2 lit 6 $00 K). Tinh bién thién entropi cua qua trinh
Trang S/13 2. 6 25°C. xét pin e6 so dd: Pb/PbSOw// CHsCOOH (0,01 M) /H2 (P
46 dign cue trai gdm mot day Pb nhung vio dung dich
Cho biét: B: =-0,126V; ~0,359V
a) Tinh thé cia dign cue bén trai so dé pin.
bao hda PbSOs.
= 1,0 atm),Pt. Trong
. it (6 dié bén
b) Stre dign dong ciia pin bing 0,0414 V. Tinh pH ciia dung dich axit (6 dign cue
Phai so d6 pin) va hing sé axit ca CHxCOOH.
Hung din giai
Y__ | Ngidung
(4H3.),=2(AHE se), H(AMB se), (AHS
a [CH +20%) —> COm + 2hOw ©)
5
= (AHS, ), = 2.(-241,82) + (-393,51) —(-74,81) = 802,34 kJ/mol 0.28
Ta cé so dd: |
Ban diu Két thie |
CHa: a mol a |
0, |
| 0.25
|
Trung gian
O24): a mol
H;0q: 2a mol |
Noy: 8a mol |
[T) =298K
P= 1 atm |
Ap dung dinh luat Hess => AH) + AH = 0 aos
= a(AHa), F(a, #ACHoy, +8CD,} (Tans = 298) = 0
|
~(4H3,),
= Ty, = 2984 ss
= (Chco,iny + ACH In,on + (CPs,
802,34.10
= 298 ~ = 2676,64 K 0,25
= Tas se 33,58 +8.29,13
1b | Khi li trong don nguyén tir => Cy = 3/21
AS= Rin V2 nC, tn 028
Trang 6/13 ——— aa a SE! —
AS=1,08,314.In-2241,0.2.8,314.In 22
| 0,6 2
[2a | pe + 26 ge Pb (1) AG? =-2FE*, 0,25
| PbSOs + 2e <= Pb+ SO; (2) AG} = -2FE 50,94
| PSO; <=> Pb? + SO} (3) AG} =-RTInTy..,
|
| (3) =(2)- (1) = AG? = AGS - AG?
Suy ra:
2.96500 *
= (—0, 359 — (—0,126) |=1,31.10
Tra, =00( BE Chia Bien | 80( Sara -.389-(-0126) o2s
Traso, = [Pb** ISO; ]=[Pb* = [SOF } = 131.10"
=> [Pb*]=[SO? ]=1,145.10% M
0,059 s 0, ee =o
E, sy $y BPO] = -0,126+ Ia 145 10")~=-0,242V | 9 96
|
2b | E=E,—Er= Ep=E + Er=0,0414 — 0,242 =- 0,2006 V
2H’ + 2e > Ha
0,059, [H'}
» “ee 0,059pH
| => -0,059pH = -0,2006 = pH = 3,4. 0,25
| pH = 3,4 = bé qua cn bang phan li cua H20.
CH:COOH <= CH;COO’ +H Ka
BD 0,01
Phanli x x x
u 0,01 -x x x
10 -
= K, =EIICH.COO | yt 5e5.10° ner
[CH,COOH] —0,01-x 0,01-10 ‘
_ |
Cau 4 (2,5 diém):
Phan img khir phite ciia Fe(II1) ({FeL}* ) thanh phire ciia Fe(II) ({FeLs)") bang axit ascobic
(H2Asc) duge m6 ta boi PTHH: 2[FeLs}** + HzAse > 2[FeLs}* + Ase +2H" —(*)
Co ché ciia phan img duce dé nghi nhu sau:
HoAse = = HY + HAsc™ (1) va (-1)
Urea + HAsc’ > [FeLoJ?" + HAsct Q)
HAsc* <=> H' + Asc* (3) va (-3)
Trang 7/13 [Feo] + Asc’ > [FeLoP" + Ase (4)
(1) va (1) la céc phan tng nhanh so voi céc phan tng khac.
a) Tim biéu thite tinh hing sé can bing Ki (cita cae phan tng
b) Chi ra céc tiéu phan trung gian phan img trong co ché trén va cl
nguyén li ndng d6 dimg cho nhimg tiéu phan nao ? Tai sao?
©) Téc dé phan ting (*) duce dinh nghia la te 46 tao thinh san ph
thite dinh nghia téc 46 ciia phan img, Tim biéu thire cla toc do phan tng tr co ©
biét phan img c6 bac déng hoc hay khéng ?
d) Trong mét sé thi nghiém nguoi ta thay tée dé phan img co dang:
v=k(FeL,,}” [HAsc]. Hay cho biét cdc digu kién thi nghiém dé thu duge bieu thie toc dd
(1) va (1) theo kr va ke
hho biét 6 thé 4p dung
am Asc. Viét biéu
hé va cho
nhu trén. Cho biét biéu thite cia k va don vi ctia k (trong hé SI) trong truong hop nay
Huéng din giai
¥ | Noidung Diem
a | Tacé: v, =k{H,Asc]; v,, =k [H'][HAsc’]
Phan img dat cn bang khi v, =v , = k,[H,Asc]=k ,[H’][Asc ]
_[HJIAse
[H,Asc] — k,
b | Cac tigu phan trung gian phan img: HAsc, HAsc* va Asc™
0,25
=>K
- Co thé 4p dung nguyén li néng d6 dimg cho cac tiéu phan HAsc* va Asc”
vi ching la cde géc tu do, 1a cae tiéu phan co hoat tinh cao nén néng d6 cia
| chung rat nhé so véi cae chat phan img va sin phim va gin nhu khong déi
trong qua trinh phan img,
- Khéng ap dung duge nguyén li néng dé dimg cho HAsc” vi (1) va (-1) 1a
cae giai doan nhanh nén no nam can bang voi H2Asc va do do c6 néng dé |
tuong déi lén.
© |. Theo dinh nghia: v = ie
- Tir co ché: v= AS) 4 fret [Asc’] (*) | 0.25
Ap dung nguyén li ndng dé dimg: |
d[HAsc’]
dt
d[Asc"]
dt
[Fel] [HAsc ]-k,[HAse"]+k ,[H" ][Asc""]=0 Oo |
|
= k,[HAsc’]~k_[H’ J[Asc” ]-k,[FeL, }"[Asc” ]= 0 Q |
|
|
Tit (1) va (2) => k,[FeL,,]"[HAsc ]k,[FeL,]”[Ase™ ]=0 (**)
Mat khéc: (1) va (-1) la céc giai doan nhanh nén
Trang 8/13 0,25
0,25
| phan ang, DE e6 durge didu dé thye nghiém c6 thé tién hanh trong digu kign
| du luong lin H’ tie la trong méi trudng axit dic hoge trong dung dich dém.
Cach thre hign trong diéu kign dur Iugng 1én H" sé kim héim phan img do lam
| chuyén dich can bang (1) va (-1)) theo chiéu nghich, Cach thuc hign trong
dung dich dém c6 nhiéu uu diém hon.
Goi [H’} 1a néng dé H’ trong dung dich dém, khi dé:
[FeL,]"[H, Asc]
kik,
= pe —Kiks
| kOfH
Phan img co bac 2 => don vi cia k trong hé SI: m* mols"
0,25
| 0,25
0,25
Cau 5 (3,0 diém)
Hap thy hoan toan 0,010 mol khi H2S vio nude cat, thu duge 100,0 mL dung dich A.
cho tir tir CH;COONa vao dung dich thu duoc
a) Tinh néng d@ can bang ctia cac ion trong dung dich A.
b) Trén 10,0 mL dung dich A voi 10,0 mL dung dich FeClz 0,02 M, thu duge 20,0 mL
dung dich B. Co két tia xuat hién tir dung dich B hay khong?
¢) Tinh gia tri pH cua dung dich B dé ©6 thé téch duge ion Fe? hoan ton ra khoi dung
dich dudi dang két tua, biét ring ion Fe?’ duge coi la tach hoan ton ra Khoi dung dich khi
nong dé con lai cua sat(II) trong dung dich la 10° M
d) Dé diéu chinh pH ctia dung dich B den khi két tia hoan toan ion Fe?’ (ndng d6 con
Jai cua sat(II) trong dung dich la 10° M) ta co the ding dung dich dém axetat. Tién hanh
nhu sau, dau tién cho CHsCOOH die vao 20,0 mL dung dich B dén ndng dé 0,10 M; sau dé
khi
1 tha hon toan Fe®* thi hét mr
(gam), Tinh gid tri ca m. Coi thé tich dung dich khong doi sau khi cho thém dém axetat
Cho biét: — pKs(FeS) = 17,2; pKai(H28) = 7,025 pKua( H28) = 12,90;
pK.(CH3COOH) = 4,75; */{FeOH") = 105??; M(CHsCOONa) = 82
Huéng dan giai
Bg
|
|
|
[ Noi dung
| Nong do ciia HS trong dung dich A: C = 0,10M
Do Kai(HoS) >> Kao(H2S) va C.Kui(H2S) >> Kw, do vay ¢6 thé bo qua can
bing phan li ndc 2 cia H2S va can bang phan li cua H20. Can bing chinh
quyét dinh pH trong dung dich la:
al
Diem
=a
Trang 9/13 FF
(0,1 -x) x x
10)
| > [H+] = [HS]=x= 10%, [S*]= 102M 0,25
Sau khi tron:
| C(Fe2*) = 0,01 M; C(H2S) = 0,05 M. 0,25
| Nhan xét: Do Kai(H2S) >> Kio( HS); C.Kai(H2S) = C. *{FeOH ) >> Kw, do
| vay c6 thé bo qua can bang phan li nac 2 cla H2S va can bang phan li cua
| H20. Cac can bang chinh quyét dinh pH trong dung dich la:
H2S = HO + HS Ka = 107?
Fe +HO2 HO + FeOH+ += 10°?
{H'] = [HS] + (FeOH’]
> [H] = CARS). Ka/((H'] + Kai) + Ce"). *B (IH) ~ *2) 0,25
| Thay Kai = 107%, * = 10% vao phuong trinh tren > [H”] = 1.26.10“ M
| [Fe] = CaFe pH LH] = +f) = 9,905.10 M
> [S*] = CMDS). Kos Kea) (HP * [H [Kus ~ Kar Kez) = 3,78.10°" Mz
— [Fe?’].[S*] = 9,905. 10°. 3,78. 10°! = 101642 > Ks(FeS) 0,28
| > Co két tia FeS xuat hién, 0,25
| Tai thoi diém két tia hoan toan Fe® thi [Fe] + [FeOH ] = 10° M
[Fe? J+ 2) =10°M [Fe] = 10% 0,25
Mat khac
[S*] =(0,05-0,01). ——_Kake
h? +K,.h+K, Ky 0,25
[Fe?-].[S*] = K, = 10172,
1077? 5h a
> h= 10% — pH = 5,09. 0,25
Phan img tao két tua: 7
Fe + HS = 2H + FeS
Trude pu 0,01 0,05
Sau pu - 0,04 0,02 | 0,25
Goi C la ndng do CHyCOONa thém vao dung dich dé dén pH = 5,09,
[H*] = 0,02 + [HS-] - ({CH,COOH] - 0.10) | 0,25
=10° = 0,02 + 0,040" - [ice one - 0,10)
10) a | Sie 10 +10 J |
=> C=0,278M. | 0,25
| 0,25
=} m(CHsCOONa) = 0,456 gam. civ 6 (3,5 diém):
a) Cho biét co ché cia phan tg sau:
+ 9082
b) Hoan thanh so dé phan img sau:
1) (BUOOH, TW(O-/Pr),
Son det tactrat
2) NaBH;CN,
7 BF;.0Et,
2
1) Os, PhaP>
eC 3H yr)
2 9
Et0,P_cozet
3) PhgP/H0
1) Bscl
K (CoptagNOg) |
2) LHMDS
BF,.OE1,, CH,C!
G (CyoHaoO2)
he,
aac 1) Tsc/pyr
(Cos) SO
(2) NaBH, oa
OH OTs
BO 1260s
J (CroHieNO2)
Bul, PhCH
1) LIA,
L(CasHayNOs)
2)(Pt
3) Na, NH
hS)2, BusP
(BsCI: PhSO2Cl; LHMDS: [(CH3)3Si]2NLi hay TMS2NLi ).
Huéng din
i [Nai dung == Dien
oA Soe
| s
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