BO GIAO DUC VA AO TAO

E THI QUOC GIA CHON HOC SINH GIOI PHO THONG NAM HOC 1993 1994 HNG DAN CHAM E THI CHNH THC Mon thi : HOA HOC LP 12 BANG A Ngay thi : 02 - 03 - 1994

A. CAU HOI LY THUYET Cau I : 1. Neu phng phap hoa hoc co the dung e loai cac chat oc sau : a) SO2 , NO2 , HF trong kh thai cong nghiep b) Lng ln Clor trong phong th nghiem c) Pb2 + hoac Cu2 + trong nc thai cac nha may Viet ay u nhng phng trnh cac phan ng c su dung trong cac phng phap tren. 2. T 0,1 mol H 2 SO4 co the ieu che 1,12 lt; 2,24 lt; 3,36 lt SO2 c khong? Giai thch tai sao c hay khong c. Neu c, minh hoa bang nhng v du cu the cach giai thch tren. Viet ay u cac phng trnh phan ng. Trnh bay phng phap thu SO2 tinh khiet ieu che tren. Hng dan giai : Cau I : 1. a) Dung nc voi trong : Dan kh thai co kh oc qua nc voi trong, kh oc se b gi lai trong phan ng hoa hoc xay ra : Ca ( OH ) + SO2 = CaSO3 + H 2 O

Ca ( OH ) + 4NO2 = Ca ( NO3 ) + Ca ( NO2 ) + 2H 2 O Ca ( OH ) + 2HF = CaF2 + H2 O

2 2 2 2

b) Dung NH3 : dang kh hay long, phun vao khong kh co lan Cl2 . Co cac phan ng : 3Cl2 + 2NH3 = N 2 + 6HCl Do o Cl2 b loai khoi khong kh. c) Dung nc voi trong tac dung vi dung dch o e ket tua lng cation kim loai nang. Cu the :
Pb2+ + Ca ( OH ) = Pb ( OH ) + Ca2+
2 2 2 2

HCl + NH3 = NH 4 Cl

Cu2+ + Ca ( OH ) = Cu ( OH ) + Ca2+

2. 0,1 mol H 2 SO4 co the ieu che c 1,12 lt SO2 (ktc) ng vi 0,05 mol SO2 . Dung acid sunfuric ac tac dung vi kim loai Cu : 2H2 SO4 + Cu = CuSO4 + SO2 + 2H 2 O

0,1 mol 0,05 mol - 0,1 mol H 2 SO4 co the ieu che c 2.24 lt SO2 (ktc) ng vi 0,1 mol SO2 . Dung
acid sunfuric ac tac dung vi carbon : 2H 2 SO4 + C = CO2 + 2 SO2 + 2H2 O 0,1 mol 0,1 mol

- 0,1 mol H 2 SO4 co the ieu che c 3,36 lt SO2 (ktc) ng vi 0,15 mol SO2 . Dung acid sunfuric ac tac dung vi lu huynh : 2H 2 SO4 + S = 3SO2 + 2H 2 O

0,1 mol 0,15 mol Neu : a) San pham kh co SO2 lan hi nc, ta dan hon hp kh i qua acid sunfuric ac, hi
nc b gi lai, kh i ra la SO2 tinh khiet. b) San pham kh co SO2 lan hi ncva CO2 , ta dan hon hp kh i qua acid sunfuric ac, khi i ra la hon hp kh kho SO2 va CO2 . Sau o hoa long hon hp kh, roi chng cat phan oan. Hoac dung phng phap hoa hoc : Oxi hoa hon hp SO3 va CO2 . Dung H 2 SO4 hap thu SO3 oleum H 2 SO 4 , SO2 ( H 2 O ) H2 SO4 , c SO2 .
+S

Cau II : 1. Lam cac th nghiem sau : Th nghiem 1 : Cho vao dung dch H 2 SO4 loang ng trong 3 coc anh so 1, 2 va 3 moi coc mot mieng sat. Th nghiem 2 : Them vao coc 1 mot mieng nhom at tiep xuc vi mieng sat. Th nghiem 3 : Them vao coc 2 mot mieng ong at tiep xuc vi mieng sat. Th nghiem 4 : Them vao coc 3 mot mieng bac at tiep xuc vi mieng sat. Trnh bay va so sanh cac hien tng xay ra trong cac th nghiem tren. Viet phng trnh ve cac hien tng o. Giai thch s khac nhau ve cac hien tng xay ra trong cac th nghiem. 2. a) Hay viet s o va phng trnh ien phan xay ra khi ien phan dung dch CuSO4 vi hai ien cc bang Platin ( Pt ) . b) Sau khi ien phan c mot thi gian, ngat nguon ien ngoai va noi hai ien cc tren bang day dan, co hien tng g xay ra? Giai thch va minh hoa bang phng trnh hoa hoc. Hng dan giai : 1. Th nghiem 1 (TN1) : Ngam Fe trong dung dch H 2 SO4 loang (coc 1) co bot kh hidro thoat ra t la sat, v Fe a kh ion H + trong dung dch : Fe + H 2 SO4 = FeSO4 + H 2 TN2 : Kim loai Al tiep xuc vi Fe , H2 thoat nhanh va nhieu hn TN1. ay la hien tng an mon ien hoa. Al b an mon, bot kh thoat ra t la sat : cc am ( Al ) : nhom b an mon : Al - 3e = Al3+ ( Al b oxi hoa) cc dng ( Fe ) : ion hidro b kh : 2H + + 2e = H 2 TN3 : Cu tiep xuc vi la sat. So vi TN1, kh hidro thoat nhanh, nhieu hn t Cu , la Fe b oxi hoa nhanh (hien tng an mon ien hoa) :

Fe + 2H + = Fe2 + + H 2

cc am ( Fe ) : Fe b oxi hoa : Fe - 2e = Fe2+ cc dng ( Cu ) : ion hidro b kh : 2H + + 2e = H 2

TN4 : Ag tiep xuc vi Fe . Bot kh hidro thoat ra nhieu va nhanh nhat t Ag . Fe b oxi hoa rat nhanh (an mon ien hoa) : cc am ( Fe ) : Fe b oxi hoa nhanh : Fe - 2e = Fe2+ cc dng ( Ag ) : ion hidro b kh : 2H + + 2e = H 2 2. a) S o Catot (-) Cu2+ , H + ( HOH ) Cu2+ + 2e = Cu

CuSO 4 = Cu2+ + SO24 HOH H + + OH (+) Anot SO2- , OH - ( HOH ) 4

(1)
ien phan

H 2 O - 2e =

Phng trnh chung : CuSO4 + H 2 O Cu +

1 O + H 2 SO 4 2 2

1 O2 + 2H + 2

(2)

(3)

Neu catot het Cu2+ ma tiep tuc ien phan (phai co hieu ien the mi cao hn) th xay ra 1 tiep : H3 O+ + e = H 2 + H 2 O ( 4 ) 2 Con anot th van nh tren. Luc o ien phan H2 O trong s co mat cua H2 SO4 nen xay ra

1 ienphan nhanh hn : H 2 O H2 + O2 ( co H2 SO4 ) 2

( 5)

b) Neu dng s ien phan a) th ch mi xay ra phan ng ( 3 ) , luc o \noi 2 cc lai, ta co mot pin kieu nh pin Volta vi cc ( ) la Cu , cc ( + ) la Pt , dung dch H2 SO4 .

Pin nay se lam viec da vao phan ng hoa hoc : cc ( ) : Cu - 2e = Cu2+ 1 cc ( + ) : O2 + 2H + + 2e = H 2 O 2 1 pin Phng trnh chung : Cu + O2 + H 2 SO 4 CuSO4 + H 2 O ( 6 ) 2 Phan ng ( 6 ) se dng lai khi s chenh lech ien the hai cc khong con u ln, luc o pin ngng hoat ong. Cau III : 1. a) Neu y ngha ve cau tao cua cau hnh electron 1s2 2s2 2p 6 3s2 3p6 . b) Cau hnh nay co the gap loai chat nao? Minh hoa bang v du cu the. c) Neu tnh chat cua chat trong th du tren. 2. Da vao o am ien cac nguyen to trong bang sau : K hieu nguyen to o am ien

O
3,5

Na
0,9

Mg

Al

Si
1,8

S
2,5

Cl
3,0

1,2

1,5

2,1

a) Neu ban chat lien ket hoa hoc trong oxit cua moi nguyen to mc oxi hoa cao nhat. b) Phan loai cac oxit tren. Viet phng trnh phan ng neu ro tnh chat hoa hoc cua moi loai oxit.

3. Trnh bay co giai thch nhng yeu to quan trong nhat lam tang toc o giai oan oxi hoa SO2 thanh SO3 trong qua trnh san xuat H2 SO4 .
Hng dan giai : 1. K hieu (1) la cau hnh electron. Co the o la cau hnh electron cua : a) Nguyen t : luc o ta biet - ien tch hat nhan cua nguyen to la 18 v trong (1) co 18 electron. o la nguyen t cua nguyen to Ar . - Nguyen to nay chu ky 3 v trong (1) co 3 lp electron. - ay la nguyen to kh tr v so electron lp ngoai cung at ti bao hoa la 8. b) Ion dng (cation) : - Co the la ion co ien tch 1+ luc o nguyen t ban au co cau hnh electron la

+ ien tch hat nhan cua nguyen to la 19 v trong ( 2 ) co 19 electron. o la nguyen t cua nguyen to K . + Nguyen to nay chu ky 4 v trong ( 2 ) co 4 lp electron. + (1) la cau hnh electron cua K + . - Co the la ion co ien tch 2+ luc o nguyen t ban au co cau hnh electron la
1s2 2s2 2p6 3s2 3p6 4s2

1s2 2s2 2p6 3s2 3p 6 4s1

(2)

( 3)

+ ien tch hat nhan cua nguyen to la 20 v trong ( 3 ) co 20 electron. o la nguyen t cua nguyen to Ca . + Nguyen to nay chu ky 4 v trong ( 3 ) co 4 lp electron. + (1) la cau hnh electron cua Ca2 + . - Ve nguyen tac co the co cation ien tch t 3+ tr len. c) Ion am (anion) : - Co the la ion co ien tch 1- luc o nguyen t ban au co cau hnh electron la + ien tch hat nhan cua nguyen to la 17 v trong ( 4 ) co 17 electron. o la nguyen t cua nguyen to Cl . + Nguyen to nay chu ky 3 v trong ( 4 ) co 3 lp electron. + (1) la cau hnh electron cua Cl . - Co the la ion co ien tch 2- luc o nguyen t ban au co cau hnh electron la
1s2 2s2 2p6 3s2 3p 4
1s2 2s2 2p6 3s2 3p5

(4)

( 5)

+ ien tch hat nhan cua nguyen to la 16 v trong ( 5 ) co 16 electron. o la nguyen t cua nguyen to S . + Nguyen to nay chu ky 3 v trong ( 5 ) co 3 lp electron. + (1) la cau hnh electron cua S2 . Thc te ion nay kho ton tai. - Anion co ien tch t 3- tr i cang t gap. 2. T bang cua au bai a cho, ta lap cac bang sau : Cong thc oxit cao nhat

Na2 O

MgO

Al2 O3
2,0

SiO2
1,7

P2 O5
1,3

SO3
0,8

Cl2 O7
( 0,5 )

Hieu o am ien cua 2,6

2,3

O vi nguyen to X a) Ban chat lien ket hoa hoc : da vao hieu o am ien gia nguyen to O vi nguyen to X (tieu chuan la t 1,77 tr len, o la lien ket ion). Vay :
+ 2 - Co ca lien ket ion : Na2 O2 ; Mg2 + O2 ; Al3 + O3 . 2

(mc o lien ket ion giam theo th t day oxit tren). -Lien ket cong hoa tr phan cc (LKCHTPC) : Si O2 ; P2 O5 ; S O3 ; Cl2 O7 . (mc o LKCHTPC tang theo th t day oxit tren). b) Tnh chat hoa hoc cua moi oxit : - Na2 O la oxit baz : - MgO la oxit baz : - Al2 O3 la oxit lng tnh : + Oxit baz : + Oxit acid : - SiO2 la oxit acid rat yeu : - P2 O5 la oxit acid trung bnh : - SO3 la oxit acid manh : Al2 O3 + 6H3 O+ = 2Al3 + + 9H 2 O . Al2 O3 + 2OH = 2AlO2 + H 2 O . 2
2 SiO2 + 2OH ng chay = SiO3 + H 2 O . no
+ + + +

Na2 O + 2H3 O+ = 2Na+ + 3H 2 O . MgO + 2H3 O+ = Mg2 + + 3H 2 O .

P2 O5 + 6OH = 2PO3 + 3H 2 O . 4 SO3 + 2OH = SO2 + H 2 O . 4

- Cl2 O7 la oxit acid rat manh : Cl2 O7 + 2OH = 2ClO + H 2 O . 4 3. Mot cach gan ung co the gia thiet bieu th toc o cua phan ng ( ) theo 1 SO2 + O2 SO3 toa nhiet 2 v=
1 k.CSO .C 2 O2 2

- Tai mot nhiet o xac nh : s tang nong o dan en s tang toc o tao ra SO3 . Co the tang nong o tng chat hay ca hai cha. - Xuc tac lam tang toc o phan ng. Do o can dung xuc tac tot (xuc tac phu hop, xuc tac sach, co lng thch hp) - S tang nhiet o co li cho toc o phan ng nhng cung tang cng s phan huy SO3 do luc o can bang hoa hoc lai chuyen di sang trai. Do o phan ng nay ch nen tien hanh mot nhiet o thch hp va tac ong vao hai yeu to tren th co li cho toc o phan ng tao ra SO3 (tc la phan ng thuan).
Cau IV :

1. Khuay a gam mot chat trong b cm3 chat long co khoi lng rieng D1 e tao thanh mot dung dch co khoi lng rieng D2 . a) Thiet lap cong thc dung e tnh nong o phan tram theo khoi lng va nong o mol/l cua dung dch tren. b) Neu nhng ieu kien co the ap dung c cong thc thiet lap ra.

2. Co 6 dung dch ma dung moi la nc khong co nhan. Trong moi dung dch co mot trong cac chat sau : H2 SO4 , KOH , Pb ( NO3 ) , Be ( NO3 ) , Mg ( NO3 ) , NH4 NO3 .
2 2 2

Neu khong dung them chat nao khac, bang cach nao co the nhan ra chat trong moi dung dch? Neu nhng phng trnh hoa hoc xay ra. Hng dan giai : 100%.a 1000.n ; CM = 1.a) Bieu thc tnh : C% = a+b.D1 V Vi n=
a MA ; V
cm
3

a+b.D1 D2

M A la khoi lng 1mol chat .

b) Cong thc tong quat tnh nong o phan tram va non o mol/lt dan ra tren khong ap dung c trong cac trng hp sau : - Neu chat khuay vao chat long tan khong het (lng tan nho hn a gam), khoi lng dung dch se nho hn a + b.D1 - Neu chat khuay vao chat long tac dung vi chat long giai phong kh. Tuy a gam chat tan het, nhng khoi lng dung dch se khac a + b.D1 . Th du khuay CaC2 vao nc, giai phong kh axetilen, khoi lng dung dch giam. Hoac CaCO3 + dung dch HCl . - Neu chat khuay vao chat long tac dung vi no tao ra chat ket tua. Th du khuay a gam

CuSO4 va b cm3 chat long la dung dch NaOH , se tao ra chat ket tua la Cu ( OH )2 .
Tom lai, cac bieu thc tnh C% va CM neu tren ch ap dung c khi a gam chat tan het, khong giai phong kh, khong tao chat ket tua. Th du hoa tan ng trong nc, muoi trong nc, iode trong benzen B. BAI TOAN Hon hp A gom hai oxit sat. Dan t t kh hidro i qua m gam A ng trong ong s a nung en nhiet o thch hp. San pham tao nen la 2,07 gam nc va 8,48 gam hon hp B gom hai chat ran. Hoa tan B trong 200 ml H2 SO4 1M thu c mot dung dch D va 1971,2 ml H2 27,3 0C va 1atm. Cho D tac dung vi NaOH d se c ket tua E. Cho E tiep xuc vi khong kh e chuyen E hoan toan thanh chat ran F. Khoi lng cua E va F khac nhau 1,36 gam. 1. Tnh m. 2. Tm nong o cua hp chat va ion trong dung dch D (cho rang the tch dung dch D thay oi khong ang ke so vi the tch dung dch H2 SO4 a dung).

3. Thanh lap cong thc va tnh thanh phan phan tram theo khoi lng cua moi chat trong A. Hng dan giai : 1. Theo au bai co s o lien he : hhA + H 2 hhB + H 2 O 2,07 = 0,115 ( mol ) . 18 Ap dung nh luat bao toan khoi lng cho (1) ta co : m A = m B + m O trong H O = 8,48 + 16.0,115 Co so mol nc : n H
2O

t0

(1)

m A = m = 10,32 ( gam ) .

2. Trong B co Fe va mot oxit sat. Khi B tac dung vi H2 SO4 loang : (2) Fe + H 2 SO4 = FeSO 4 + H 2

Con oxit sat b hoa tan co the cung tao ra FeSO4 va ca Fe2 ( SO4 ) . Trong dung dch 3 D co the con H2 SO4 d. Khi tac dung D vi NaOH d :

2NaOH + H 2 SO4 = Na2 SO4 + H 2 FeSO4 + 2NaOH = FeSO4 + Na2 SO 4

3

(3)
(4)

Fe2 ( SO4 ) + 6NaOH = 2Fe ( OH )3 + 3Na2 SO4

4Fe ( OH )2 + O2 + 2H 2 O = 4Fe ( OH )3 Vat F la Fe ( OH )3 .

Vay E co Fe ( OH )2 va co the co ca Fe ( OH )3 . Khi tiep xuc vi khong kh th :

( 5)

- T ( 5 ) va so sanh hai cong thc hidoxit cua sat : khoi lng cua F khac so vi khoi lng cua E chnh la khoi lng cua nhom ( OH ) . Ta co : m 1,36 So mol nhom ( OH ) : n( OH ) = = = 0,08 ( mol ) . M ( OH ) 17 - Mat khac t ( 2 ) so mol cua hidro thoat ra la : 1971,2 1 PV 1000 = nH = = 0,08 ( mol ) 2 22, 4 RT ( 27,3 + 273) 273 So mol cua Fe co trong B : n Fe = n H = 0,08 ( mol ) .
2

So mol cua Fe ( OH )2 co trong E : n Fe ( OH ) = n( OH ) = 0,08 ( mol ) 2

(I)

- T ( I ) va ( II ) suy ra lng Fe ( OH )2 co trong E la do lng Fe trong B bien oi thanh . Vay phan oxit con lai trong B la Fe2 O3 . - Khoi lng cua Fe2 O3 trong B la : m Fe O = m B - m Fe = 8,48 - 56.0,08 = 4,0 gam . 2 3 So mol cua Fe2 O3 co trong B : n Fe
2 O3

- T ( 2 ) va ( 3 ) suy ra : n Fe ( OH ) = n FeSO = n Fe = 0,08 ( mol ) 2 4

( II )

- So mol cua H2 SO4 ban au : n H SO 2 4

m 4, 0 = = 0,025 ( mol ) . M 160 ( ) ban au = C M .V = 1.0,2 = 0,2 mol . =

- Ta co B + H2 SO4 : (2) Fe + H 2 SO4 = FeSO 4 + H 2 Fe2 O3 + 3H 2 SO4 = Fe2 ( SO 4 ) + 3H 2 O

3

( 2' )

- So mol Fe2 ( SO4 ) t ( 2' ) la : n Fe ( SO ) = n Fe O = 0,025 ( mol ) . 3 2 3 2 4 3 - So mol H2 SO4 tham gia phan ng ( 2 ) va ( 2' ) la :

- So mol FeSO4 t ( 2 ) la : n FeSO = n Fe = 0,08 ( mol ) . 4

nH

2 SO 4

phan ng

= n Fe + 3n Fe

2 O3

= 0,08 + 3.0,025 = 0,155 ( mol ) .

- Do o dung dch D co 3 chat tan : H2 SO4 d ; FeSO4 va Fe2 ( SO4 ) . 3 - Bo qua s thay oi the tch dung dch do phan ng tao ra ta co : Vdung dch D Vdung dch H SO = 0,2 ( lt ) .
2 4

- So mol H2 SO4 con lai : n H SO con lai = n H SO

2 4 2

ban au

- n H SO phan ng = 0,2 - 0,155 = 0,045 ( mol ) . 2 4

- Nong o CM cua cac chat trong dung dch D : n H SO 0,045 2 4 d H 2 SO4 d = = = 0,225M. V 0,2

FeSO4 =

n FeSO V

0,08 = 0,40M. 0,2 =

0,025 = 0,125M. V 0,2 - Nong o cua cac ion trong dung dch D : Fe2 ( SO 4 ) = 3

n Fe ( SO ) 2 4 3

H 2 SO4 + 2H2 O FeSO4 Fe2 ( SO4 )

2H3 O+ + SO2 4 2Fe3 + + 3SO2 4

Fe2 + + SO2 4

H3 O+ = 2. H 2 SO4 d = 2.0,225 = 0,45M. Fe2 + = FeSO = 0,40M. 4 Fe3 + = 2. Fe ( SO ) = 2.0,125 = 0,25M. 4 3 2 SO2 = H SO 4 2 4 ban au = 1M.

- ay khong xet s tao phc cua Fe2 + va Fe3 + vi H2 O - Khong xet s thuy phan cua cac muoi v dung dch co d H + . Can bang

Fe2 + + 2HOH Fe
3+

Fe ( OH )2 + 2H + Fe ( OH )3 + 3H +
t0

+ 3HOH

chuyen di sang trai.

3. Theo e bai hhA + H2 hhB + H 2 O .

Fe Mat khac theo ket qua cau 2. hhB = hhA ban au co Fe2 O3 . Fe2 O3 - Goi a la so mol ban au cua Fe2 O3 trong hhA.
b la so mol cua oxit Fe x O y con lai trong hhA. - ieu kien : x 2 ; y 3

( a)

0<a<

M Fe

m hhA
2 O3

10,32 = 0,6450 ( mol ) 160

0<b<
0<b<

M FeO
M Fe m hhA

m hhA

10,32 = 0,1433 ( mol ) 72

= 10,32 = 0,04448 ( mol ) 232
t0

( b)
( b)

3 O4

- Fe x O y b kh het, ta co : Fex Oy + yH 2 xFe + yH 2 O 1 y x Phan ng : b yb xb - Fe2 O3 phan ng khong het va con 0,025 mol (trong hhB) nen co :

Fe2 O3 + 3H 2 2Fe 1 3 2

t0

3H 2 O 3

Phan ng : ( a - 0,025 ) 2 ( a - 0,025 ) 3 ( a - 0,025 ) - Tong so mol Fe c tao tanh : n Fe = 2 ( a - 0,025) + xb = 0,08 ( mol ) . 0,13 - xb a= ( c) 2 - Tong so mol H2 O c tao tanh : n H O = 3 ( a - 0,025 ) + yb = 0,0115 ( mol ) . 2
0,19 - yb (d ) 3 0,13 - xb 0,19 - yb 0,01 = b= - Ket hp ( c ) va ( d ) ta co : 2 3 3x - 2y a= - T ( e ) ta thay v Fe x O y co the la : + FeO ( x = 1 ; y = 1) : t ( e ) suy ra b = 0,01 ( mol ) thoa man dieu kien ( b ) . + Fe3 O4 ( x = 3 ; y = 4 ) : t ( e ) suy ra b = 0,01 ( mol ) thoa man dieu kien ( b ) . - Vay trong hhA ban au co the la : + Trng hp 1 : FeO va Fe2 O3

(e)

m Fe O = m hhA - m FeO = 10,32 - 0,72 = 9,6 ( gam ) . 2 3

%FeO chiem =
%Fe
2 O3

n FeO = b = 0,01 ( mol ) m FeO = 0,01.72 = 0,72 ( gam ) .

m FeO m hhA
m Fe

=
2 O3

0, 72 .100% = 6,977% 10,32

= 9,6 .100% = 93,023% 10,32

chiem

m hhA

+ Trng hp 2 : Fe3 O4 va Fe2 O3

n Fe O = b = 0,01 ( mol ) m Fe O = 0,01.232 = 2,32 ( gam ) . 3 4 3 4

 m Fe O = m hhA - m Fe O = 10,32 - 2,32 = 8,0 ( gam ) . 2 3 3 4 m Fe O 2,32 3 4 %Fe O chiem = = .100% = 22,48% 3 4 m hhA 10,32
%Fe
2 O3 chiem

m Fe

m hhA

2 O3

8, 0 .100% = 77,52% 10,32