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S GIO DC V O TO

S GIO DC V O TO

THNH PH NNGHNG DN CHM K THI HC SINH GII THNH PH

MN: HA HC LP 11

Thi gian: 150 pht (khng k thi gian giao )

Cu I M(3 im)

1. Hy so snh v gii thch s khc nhau v phn cc phn t, nhit si v mnh tnh baz gia NH3 v NF3.

2. N2O4 phn li 20,0% thnh NO2 27oC v 1,00 atm. Hy xc nh (a) gi tr Kp; (b) phn li ca N2O4 ti 27oC v 0,10 atm; (c) phn li ca 69g N2O4 trong bnh 20 L 27oC.

3. Tnh pH ca dung dch thu c khi thi ht 224 mL kh CO2 vo 200 mL dung dch NaOH 0,05M, bit axit cacbonic c , .

P NIM

1. Cu to:

NH3 phn cc hn NF3 do trong NH3 lng cc lin kt v lng cc electron t do cng chiu, cn trong NF3 lng cc lin kt v lng cc electron t do ngc chiu.

Nhit si ca NH3 cao hn do NH3 to c lin kt H lin phn t.

NH3 l mt baz cn NF3 th khng, do trong NF3 cc nguyn t F ht electron lm gim mt electron trn nguyn t N.

2. Xt phn ng phn li:

N2O4 (2NO2

n

0

n(

2n(n-n(

2n(Phn mol:

,

(a)

(b)

(c)

(

3.

V s mol CO2 v NaOH bng nhau nn h ch cha NaHCO3. C th tnh pH ca h lng tnh ny bng cng thc:

0,75

(0,253)

1,50

(0,503)

0,75

(0,25+0,5)

Cu II (3 im)

1. Vit phng trnh phn ng xy ra khi cho NH4Cl tc dng vi CuO v vi ZnO. Cho bit ng dng thc t ca NH4Cl tng ng vi cc phn ng ny.

2. Ha tan 10,00 g hn hp gm Cu2S v CuS bng 200,0 mL dung dch MnO4- 0,7500 M trong mi trng axit. Sau khi un si ui ht kh SO2 sinh ra, lng MnO4- cn d trong dung dch phn ng va ht vi 175,0 mL dung dch Fe2+ 1,000 M.

(a) Vit cc phng trnh phn ng xy ra (dng phng trnh ion thu gn).

(b) Tnh phn trm khi lng CuS trong hn hp ban u.

P NIM

1. Trong thc t, NH4Cl c dng nh sch b mt kim loi trc khi hn:

4CuO + 2NH4Cl ( N2 + 3Cu + CuCl2 + 4H2O

ZnO + 2NH4Cl ( ZnCl2 + 2NH3 + H2O

2. (a)Phng trnh phn ng:

5Cu2S + 8MnO4- + 44H+ ( 10Cu2+ + 5SO2 + 8Mn2+ + 22H2O

(1)

5CuS + 6MnO4- + 28H+ ( 5Cu2+ + 5SO2 + 6Mn2+ + 14H2O

(2)

5Fe2+ + MnO4- + 8H+ ( 5Fe3+ + Mn2+ + 4H2O

(3)

(b)Xc nh %

(1) (

(

t s mol Cu2S v CuS ln lt l x v y, ta c:

(

1,50

(0,503)

0,75

(0,253)

0,75

Cu III (4 im)

1. Ch dng cht ch th phenolphtalein, hy phn bit cc dung dch NaHSO4, Na2CO3, AlCl3, Fe(NO3)3, NaCl, Ca(NO3)2. Cc phn ng minh ha vit di dng ion thu gn.

2. Ha tan ht 2,2 g hn hp kim loi A gm st v nhm trong 150 mL dung dch HNO3 2M thu c dung dch B v 448 mL (ktc) kh C gm N2O v N2 c t khi so vi khng kh bng 1,2414. Thm 13,6 g NaOH nguyn cht vo dung dch B thu c kt ta D, lc kt ta D thu c dung dch nc lc E.

(a) Tnh phn trm khi lng mi kim loi trong hn hp A ban u.

(b) Nung kt ta D n khi lng khng i th thu c bao nhiu gam cht rn khan?

(c) Tnh th tch dung dch HCl 0,5M cn thm vo dung dch E thu c 2,34 g kt ta.

P NIM

1. Trch mu th cho mi ln th nghim:

Cho phenolphtalein vo mi mu th. Mu th c mu hng l dung dch Na2CO3, cc mu th cn li khng mu.

CO32- + H2O ( HCO3- + OH- Dng Na2CO3 lm thuc th cho vo cc mu th cn li.

Mu th c si bt kh khng mu l NaHSO4CO32- + 2H+ ( H2O + CO2

Mu th to kt ta trng keo v si bt kh khng mu l AlCl32Al3+ + 3CO32- + 3H2O ( 2Al(OH)3+ 3CO2

Mu th to kt ta nu v si bt kh khng mu l Fe(NO3)32Fe3+ + 3CO32- + 3H2O ( 2Fe(OH)3+ 3CO2

Mu th to kt ta trng l Ca(NO3)2Ca2+ + CO32- ( CaCO3

Mu th khng to hin tng l NaCl.2. (a) t s mol N2O v N2 ln lt bng a v b, ta c:

t s mol Fe v Al ln lt bng x v yCht kh

Cht oxi ha

Fe - 3e ( Fe3+

10H+ + 2NO3- + 8e ( N2O + 5H2O

3x x

0,10 0,08

Al - 3e ( Al3+

12H+ + 2NO3- + 10e ( N2 + 6H2O

3y y

0,12

0,10

V nn axit d, phn ng khng to Fe2+.

Ta c:

Vy v

(b)Thm NaOH vo dung dch B [H+ (0,15.2-0,22 = 0,08 mol), Fe3+ (x = 0,02 mol), Al3+ (y = 0,04 mol) v NO3-]

H+ + OH- ( H2O

(1)

Fe3+ + 3OH- ( Fe(OH)3

(2)

Al3+ + 3OH- ( Al(OH)3

(3)

Al(OH)3 + OH- ( AlO2- + 2H2O(4)

( sau (1), (2), (3), (4) vn cn d OH-, kt ta D l Fe(OH)3 (0,02mol)

2Fe(OH)3 ( Fe2O3 + 3H2O, ( mrn =

(c)Thm HCl vo dung dch E [Na+, OH- (0,04 mol), AlO2- (0,04 mol) v NO3-]

OH- + H+ ( H2O

(5)

AlO2- + H+ + H2O ( Al(OH)3(6)

Al(OH)3 + 3H+ ( Al3+ + 3H2O(7)

Trng hp 1: Xy ra (5), (6) v AlO2- d

, (

Trng hp 2: Xy ra (5), (6), (7)

(

1,50

(0,256)

1,00

0,50

1,00

(0,502)

Cu IV (3 im)

1. Tnh hiu ng nhit phn ng hidro ha etilen to etan, bit nhit chy ca C2H6 v C2H4 ln lt bng -368,4 kcal/mol v -337,2 kcal/mol [sn phm chy l CO2 (k) v H2O (l)], nhit hnh thnh H2O (l) l -68,32 kcal/mol.

2. (a) Vit cng thc cu to v gi tn anken t cacbon nht ng thi c ng phn hnh hc v ng phn quang hc. (b) Vit cc ng phn hnh hc v quang hc ng vi cu to (s dng cng thc Fisher) v xc nh cu hnh mi ng phn (Z/E v R/S). (b) Vit cu to cc sn phm chnh hnh thnh khi cho anken trn tc dng vi dung dch nc brom c lng nh mui natri clorua.

P NIM

1. (1)C2H6 (k) + 7/2O2 (k) ( 2CO2 (k) + 3H2O (l)

(2)C2H4 (k) + 3O2 (k) ( 2CO2 (k) + 2H2O (l)

(3)H2 (k) + 1/2O2 (k) ( H2O (l)

Ly (2) - (1) + (3) ta c:

C2H4 (k) + H2 (k) ( C2H6 (k)

2. (a) Cu to:

(b)Cu hnh:

(c)Cu to cc sn phm:

1,00

0,25

1,00

(0,254)

0,75

(0,253)

Cu V (3 im)1. Hidrocacbon A c khi lng phn t bng 80. Ozon phn A ch to andehit fomic v andehit oxalic.

(a) Xc nh cu to v gi tn A.

(b) Dng c ch gii thch cc sn phm hnh thnh khi cng Br2 vo A theo t l mol 1:1, gi tn cc sn phm ny.

2. Hp cht A c cng thc phn t C9H8. A lm mt mu Br2 trong CCl4; hidro ha A trong iu kin m du to ra C9H10, cn trong iu kin nhit v p sut cao th to ra C9H16; oxi ha mnh lit A sinh ra axit phtalic [1,2-C6H4(COOH)2]. Lp lun xc nh cu to ca A.

P NIM

1. (a) Cng thc tng qut cho A l CxHyTa c , cng thc phn t C6H8

T sn phm ozon phn ta thu c cu to ca A:

(b)C ch v sn phm:

2. A (C9H8) c bt bo ha

A lm mt mu Br2 v cng m du 1 phn t H2 cho thy A c 1 lin kt i.

A cng ti a 4 phn t H2 v khi oxi ha to axit phtalic cho thy A c vng benzen v ngoi ra cn mt vng 5 cnh na.

Cng thc ca A:

0,50

0,50

(0,252)1,50

(0,503)0,50

Cu VI (4 im)

Chia 3,584 L (ktc) hn hp gm mt ankan (A), mt anken (B) v mt ankin (C) thnh 2 phn bng nhau. Phn 1 cho qua dung dch AgNO3 d trong NH3 thy th tch hn hp gim 12,5% v thu c 1,47g kt ta. Phn 2 cho qua dung dch brom d thy khi lng bnh brom tng 2,22g v c 13,6g brom tham gia phn ng. t chy hon ton kh ra khi bnh brom ri hp th sn phm chy vo dung dch Ba(OH)2 d th thu c 2,955g kt ta.

1. Xc nh cng thc cu to A, B v C.2. T A vit dy chuyn ha (ghi r iu kin phn ng) iu ch 1,1-dibrompropan v 2,2-dibrompropan.

3. Vit phng trnh phn ng xy ra khi cho C tc dng vi dung dch KMnO4 trong (i) mi trng trung tnh nhit phng v (ii) mi trng axit (H2SO4) c un nng.P NIM

1. Trong mt phn, ta c: . Dung dch AgNO3/NH3 ch hp th ankin, t cng thc ankin l RCCH (gi s khng phi l C2H2).

RCCH + AgNO3 + NH3 ( RCCAg + NH4NO3(1)

( (R + 132)0,01 = 1,47

( R = 15 (CH3-), cng thc ca ankin l CH3CCH

Dung dch brom hp th anken (CnH2n) v ankin

CnH2n + Br2 ( CnH2nBr2

(2)

C3H4 + 2Br2 ( C3H4Br4

(3)

,

T

( n = 2, cng thc ca anken l CH2=CH2.

Kh ra khi bnh brom l ankan (CmH2m+2),

CmH2m+2 + ( nCO2 + (n+1)H2O(4)

CO2 + Ba(OH)2 ( BaCO3 + H2O

(5)

T (4): , cng thc ankan l CH3CH2CH3.

2. iu ch:

3. Phn ng ca C:

5CH3CCH + 8KMnO4 + 12H2SO4 ( 5CH3COOH + 5CO2

+ 8MnSO4 + 4K2SO4 + 12H2O0,75

0,75

0,50

1,00

(0,502)1,00

(0,502)

S GIO DC V O TO

THNH PH NNGHNG DN CHM K THI HC SINH GII THNH PH

MN: HA HC LP 11


Cu VII (4 im)

1. Nu hin tng xy ra v vit phng trnh phn ng minh ha trong cc trng hp sau:

(a) Ha tan t t cho n d dung dch NaOH vo dung dch AlCl3, sau thm HCl vo dung dch thu c n d.

(b) Thm dung dch K2CO3 vo dung dch Fe(NO3)32. A l dung dch Na2CO3 0,1M; B l dung dch hn hp Na2CO3 0,1M v KHCO3 0,1M v C l dung dch KHCO3 0,1M.

(a) Tnh th tch kh CO2 (ktc) thot ra khi cho t t tng git n ht 50 mL dung dch HCl 0,1M vo 100 mL dung dch A v khi cho ht 100 mL dung dch B vo 200 mL dung dch HCl 0,1M.

(b) Xc nh s mol cc cht c trong dung dch thu c khi thm 100 mL dung dch Ba(OH)2 0,1M vo 150 mL dung dch C.

(c) Tnh pH ca cc dung dch A v C, bit axit cacbonic c pK1 = 6,35 v pK2 = 10,33.

(d) ngh phng php nhn bit cc anion c trong dung dch B.P NIM

1. (a) Thm dung dch NaOH vo dung dch AlCl3 thy xut hin kt ta trng keo, sau tan li:

Al3+ + 3OH- ( Al(OH)3

Al(OH)3 + OH- ( Al(OH)4-

Thm HCl vo dung dch thu c li thy xut hin kt ta trng keo, sau tan li:

Al(OH)4- + H+ ( Al(OH)3 + H2O

Al(OH)3 + 3H+ ( Al3+ + 3H2O0,50

(b)Thm dung dch K2CO3 vo dung dch Fe(NO3)3 thy xut hin kt ta nu v si bt kh khng mu: 2Fe3+ + 3CO32- + 3H2O ( 2Fe(OH)3 + 3CO20,25

2. (a) Cho t t tng git n ht 50 mL dung dch HCl 0,1M vo 100 mL dung dch Na2CO3 0,1M

CO32- + H+ ( HCO3-

0,01

0,005

0,005

0,005

0,005

0

Do CO32- d nn khng c giai on to CO2,

0,50

Cho ht 100 mL dung dch Na2CO3 0,1M v KHCO3 0,1M vo 200 mL dung dch HCl 0,1M:

CO32- + 2H+ ( H2O + CO2

(1)

HCO3- + H+ ( H2O + CO2

(2)

V nn H+ phn ng ht.

Gi s (1) xy ra trc th ta c

Gi s (2) xy ra trc th t (1) v (2) ta c

Thc t (1) v (2) ng thi xy ra nn:

1,00

(b)Thm 100 mL dung dch Ba(OH)2 0,1M vo 150 mL dung dch KHCO3 0,1M

HCO3- +OH- (CO32- + H2O

0,015

0,02

0,015

0,015

0

0,005

0,015

Ba2+ +CO32- ( BaCO3

0,01

0,015

0,01

0,01

0

0,005

Dung dch cn 0,005 mol KOH v 0,005 mol K2CO30,50

(c)Dung dch A c cc cn bng:

CO32- + H2O HCO3- + OH-

Kb1 = 10-3,67

HCO3- + H2O H2O + CO2 + OH-Kb2 = 10-7,65

H2O H+ + OH-

KN = 10-14

V Kb1 >> Kb2 >> KN nn cn bng (1) l ch yu:

pH = 14 - (pKb1 + pC) = 14 - (3,67 + 1) = 11,67

Dung dch C l dung dch lng tnh nn:

pH = (pK1 + pK2) =(6,35 + 10,33) = 8,340,75

(d)Trch mu th, thm BaCl2 d vo mu th thy xut hin kt ta trng (tan trong axit), nh vy mu th c CO32-.

Ba2+ + CO32- ( BaCO3Lc tch kt ta, thm HCl vo dung dch nc lc thy si bt kh khng mu (lm c nc vi trong), vy dung dch c HCO3-

HCO3- + H+ ( H2O + CO2. 0,50

Cu VIII (4 im)

1. (a) Amoniac c tnh oxi ha hay tnh kh? Vit phng trnh phn ng minh ha. (b) Trong dung mi amoniac lng, cc hp cht KNH2, NH4Cl, Al(NH2)3 c tnh axit, baz hay lng tnh ? Vit cc phng trnh phn ng minh ha.2. Ha tan 4,8 gam kim loi M bng dung dch HNO3 c nng d, hay ha tan 2,4 gam mui sunfua kim loi ny cng trong dung dch HNO3 c nng, th u cng sinh ra kh NO2 duy nht c th tch bng nhau trong cng iu kin.

(a) Vit cc phng trnh phn ng di dng phng trnh ion.

(b) Xc nh kim loi M, cng thc phn t mui sunfua.

(c) Hp th kh sinh ra c hai phn ng trn vo 300 mL dung dch NaOH 1M, ri thm vo mt t phenolphtalein. Hi dung dch thu c c mu g? Ti sao?

P NIM

1. (a) NH3 va c tnh oxi ha, va c tnh kh :

Tnh oxi ha: K + NH3 (l) ( KNH2 + 1/2H2Tnh kh:2NH3 + 3CuO ( 3Cu + N2 + 3H2O 0,75

(b) KNH2 l mt baz, NH4Cl l axit v Al(NH2)3 c tnh lng tnh.

Phn ng trung ha: KNH2 + NH4Cl ( KCl + 2NH3Phn ng ca cht lng tnh vi axit: Al(NH2)3 + 3NH4Cl ( AlCl3 + 6NH3

Phn ng ca cht lng tnh vi baz: Al(NH2)3 + KNH2 ( K[Al(NH2)4]

075

2. (a) Phng trnh phn ng:

M + 2mH+ + mNO3- ( Mm+ + mNO2 + mH2O

(1)

M2Sn + 4(m+n)H+ + (2m+6n)NO3- ( 2Mm+ + nSO42- + (2m+6n)NO2

+ 2(m+n)H2O

(2)1,00

(b) V s mol NO2 hai trng hp l bng nhau nn ta c:

( , nghim thch hp l n = 1, m = 2 v M = 64.

Vy M l Cu v cng thc mui l Cu2S.0,75

(c)

Cu + 4HNO3 ( Cu(NO3)2 + 2NO2 + 2H2O

(

( xy ra va phn ng:

2NO2 + 2NaOH ( NaNO3 + NaNO2 + H2O

Dung dch thu c c mu hng do NO2- to mi trng baz:

NO2- + H2O HNO2 + OH-0,75

Cu IX (4 im)1. (a) Tnh t l cc sn phm monoclo ha (ti nhit phng) v monobrom ha (ti 127oC) isobutan. Bit t l kh nng phn ng tng i ca nguyn t H trn cacbon bc nht, bc hai v bc ba trong phn ng clo ha l 1,0 : 3,8 : 5,0 v trong phn ng brom ha l 1 : 82 : 1600. (b) Da vo kt qu tnh c cu (a), cho nhn xt v cc yu t nh hng n hm lng cc sn phm ca phn ng halogen ha ankan.2. Dng c ch phn ng gii thch ti sao khi x l 2,7-imetylocta-2,6-dien vi axit photphoric th thu c 1,1-imetyl-2-isopropenylxiclopentan.

3. Hiro ha mt hirocacbon A (C8H12) hot ng quang hc thu c hirocacbon B (C8H18) khng hot ng quang hc. A khng tc dng vi Ag(NH3)2+ v khi tc dng vi H2 trong s c mt ca Pd/PbCO3 to hp cht khng hot ng quang hc C (C8H14).

1. Lp lun xc nh cu to (c lu cu hnh) v gi tn A, B, C.

2. Oxi ha mnh lit A bng dung dch KMnO4 trong H2SO4.Vit phng trnh ho hc. P NIM

1. (a) T l sn phm:

0,50

0,50

(b)Hm lng sn phm halogen ha ph thuc ba yu t:

Kh nng tham gia phn ng th ca ankan: Phn ng halogen ha u tin th hidro trn nguyn t cacbon bc cao hn.

Kh nng phn ng ca halogen: Brom tham gia phn ng yu hn so vi clo, nhng c kh nng chn lc v tr th cao hn so vi clo.

S nguyn t hidro trn cacbon cng bc: Khi s hidro trn cc nguyn t cacbon cng nhiu th hm lng sn phm cng ln.

0,75

2. C ch:

0,75

3. (a) A c bt bo ha , B c v C c .

V A cng 3 phn t hidro to ra B nn A c cc lin kt bi hoc vng ba cnh.

A cng 1 phn t H2 to ra C v A khng tc dng vi Ag(NH3)2+ nn A c mt lin kt ba dng -C(C-R.

A cng phi cha mt lin kt i dng cis- (Z) v tr i xng vi lin kt ba, v khi A cng 1 phn t H2 (xc tc Pd lm cho phn ng chy theo kiu cis-) to C khng hot ng quang hc.0,50

Cu to ca A, B, C l:

0,75

(b) Phng trnh phn ng:

5CH3CH=CHCH(CH3)C(C-CH3 + 14KMnO4 + 21H2SO4 (

( 10CH3COOH + 5CH3CH(COOH)2 + 14MnSO4 + 7K2SO4 + 16H2O0,25

Cu X (4 im)

1. Limonen (C10H16) l tecpen c trong v qu cam, chanh v bi. Oxi ha limonen bng kalipemanganat to cht A.

(a) Dng d kin trn v qui tc isopren xc nh cu trc ca limonen.

(b) Vit cng thc cc sn phm chnh hnh thnh khi hidrat ha limonen. 2. iu ch nitrobenzen trong phng th nghim v tnh hiu sut phn ng, ngi ta tin hnh cc bc sau:

Cho 19,5 ml axit nitric vo mt bnh cu y trn c 200 mL lm lnh bnh v lc, sau thm t t 15 mL H2SO4 m c, ng thi lc v lm lnh n nhit phng. Lp ng sinh hn hi lu (nc hay khng kh), cho tip 13,5 mL benzen qua ng sinh hn vi tc chm v gi nhit khng qu 500C, ng thi lc lin tc (a).

Sau khi cho ht benzen, tip tc un nng bnh phn ng trn bp cch thu trong 30-45 pht v tip tc lc. Sau lm lnh hn hp phn ng v qua phu chit. Tch ly lp nitrobenzen trn. Ra nitrobenzen bng nc ri bng dung dch Na2CO3 (b). Tch ly nitrobenzen cho vo bnh lm kh c cha cht lm kh A th rn (c). Chng ct ly nitrobenzen bng bnh Vuy-c trn bp cch thu thu ly nitrobenzen sch. Cn lng nitrobenzen thy c 15 gam (d).

(a) Vit phng trnh ho hc chnh v cc phng trnh th hin c ch ca phn ng. Cho bit v sao cn phi lc bnh lin tc v gi nhit phn ng 500C? Nu khng dng H2SO4 m c, phn ng c xy ra khng?

(b) V sao cn phi ra nitrobenzen bng nc, sau bng dung dch Na2CO3?

(c) A c th l cht no?

(d) Tnh hiu sut phn ng nu khi lng ring ca benzen 0,8g/mL.

P NIM

a. (a) Cu to:

0,75

(b) Cc sn phm chnh khi hidrat ha:

0,75

4. (a) Phn ng:

C6H6 + HONO2 C6H5NO2 + H2O

(1)

C ch phn ng:

0,75

Hn hp phn ng h d th nn cn phi lc u hay khuy mnh lin tc to thnh nh tng, bo m s tip xc tt gia cc tc nhn. Phi gi 500C v nu nhit cao hn s tng lng sn phm initrobenzen. Nu khng dng H2SO4, phn ng vn xy ra do vn c s hnh thnh NO2+ theo phng trnh sau:

HO-NO2 + HNO3 H2O+-NO2 + NO3-

H2O+-NO2 + HNO3 H3O+ + NO3- + NO2+ (1)

Tuy nhin khi khng c H2SO4 phn ng xy ra chm v hiu sut to NO2+ sinh ra trong (1) rt thp. Khi c mt H2SO4 m c, cn bng chuyn di v pha thun nn phn ng xy ra nhanh hn. 0,75

(c) Cn phi ra bng nc loi axit, sau ra bng dung dch Na2CO3 loi ht axit d v d kim tra kt qu do phn ng gia axit v Na2CO3 sinh kh. 0,25

(b)A l cht ht nc dng rn, nn A c th l CaCl2, ... khan 0,25

(d) Hiu sut phn ng:

(

0,50

A l hidrocacbon khng lm mt mu dung dch brom. t chy hon ton 0,02 mol A v hp thu sn phm chy vo dung dch cha 0,15 mol Ca(OH)2 thu c kt ta v khi lng bnh tng ln 11,32 gam. Cho dung dch Ba(OH)2 d vo dung dch thu c kt ta li tng ln, tng khi lng kt tu hai ln l 24,85 gam. A khng vi dung dch KMnO4/H2SO4 nng, cn khi monoclo ha trong iu kin chiu sng th ch to mt sn phm duy nht.

1. Xc nh cng thc cu to v gi tn A.

2. Ngi ta c th iu ch A t phn ng gia benzen v anken tng ng trong axit sunfuric. Dng c ch phn ng gii thch phn ng ny.

3. Mononitro ha A bng cch cho phn ng vi axit nitric (c mt axit sunfuric c) th sn phm chnh thu c l g? Ti sao?

P NIM

1. Dung dch Ca(OH)2 hp th ht sn phm chy ca A cha CO2 v H2O

CO2 + Ca(OH)2 ( CaCO3 + H2O

(1)

2CO2 + Ca(OH)2 ( Ca(HCO3)2

(2)

Ca(HCO3)2 + Ba(OH)2 ( CaCO3 + BaCO3 + 2H2O(3)0,50

t s mol CO2 tham gia cc phn ng (1) v (2) ln lt l x v y, ta c:

,

T

0,50

t cng thc tng qut ca A l CxHy:

CxHy + (x+y/4)O2 ( xCO2 + y/2H2O

Ta c

Cng thc phn t ca A l C10H14

0,50

V A khng lm mt mu dung dch brom (cu trc thm), khng tc dng vi dung dch KMnO4/H2SO4 (ch c mt nhm th) v monoclo ha (nh sng) ch to mt sn phm duy nht (nhm th c cu trc i xng cao) nn cu to ca A l:

1,00

2. C ch:

(CH3)2C=CH2 + H2SO4 ( (CH3)2C+-CH3 + HSO4-

1,00

3. Nhm ankyl ni chung nh hng th vo cc v tr ortho- v para-. Tuy nhin, do nhm t-butyl c kch thc ln gy n ng khng gian nn sn phm chnh l sn phm para-:

0,50

S GIO DC V O TO

THNH PH NNGHNG DN CHM THI HC SINH GII THNH PH

MN: HA HC LP 11


CHNH THC

ny c hai (2) trang

Cu XI (4 im)

1. Tnh pH ca dung dch thu c khi trn ln 50,0 mL dung dch NH4Cl 0,200 M vi 75,0 mL dung dch NaOH 0,100 M. Bit Kb (NH3) = 1,8.10-5.

2. Phn l mui sunfat kp ca mt cation ha tr mt (nh K+ hay NH4+) v mt cation ha tr ba (nh Al3+, Fe3+ hay Cr3+). Phn st amoni c cng thc (NH4)aFe(SO4)b.nH2O. Ha tan 1,00 gam mu phn st vo 100 cm3 H2O, ri chia dung dch thu c thnh hai phn bng nhau. Thm dung dch NaOH d vo phn mt v un si dung dch. Lng NH3 thot ra phn ng va vi 10,37 cm3 dung dch HCl 0,100 M. Dng km kim loi kh ht Fe3+ phn hai thnh Fe2+. oxi ha ion Fe2+ thnh ion Fe3+ tr li, cn 20,74 cm3 dung dch KMnO4 0,0100 M trong mi trng axit.(a) Vit cc phng trnh phn ng dng ion thu gn v xc nh cc gi tr a, b, n.

(b) Ti sao cc phn khi tan trong nc u to mi trng axit ? P NIM

1. ;

NH4Cl + NaOH ( NaCl + NH3 + H2O

0,08 0,06

0,06 0,06 0,06

0,02 0 0,06

Xt cn bng :

NH3 + H2O NH4+ + OH-0,06 0,02

x x x

0,06x 0,02+x x

, gn ng

(

0,50

1,00

2. (a) t s mol ca phn st (NH4)aFe(SO4)b.nH2O trong mi phn l x mol.

Phng trnh phn ng phn mt :

NH4+ + OH- ( NH3 + H2O

ax0 axFe3+ + 3OH- ( Fe(OH)3NH3 + H+ ( NH4+ax ax

Phng trnh phn ng phn hai :

Zn + 2Fe3+ ( Zn2+ + 2Fe2+

x

0 x

5Fe2+ + MnO4- + 8H+ ( 5Fe3+ + Mn2+ + 4H2O

x x/510,25

Ta c :

(a = 1

Cng thc ca phn c vit li l NH4+Fe3+(SO42-)b.nH2O

(b = 2

T M = 18 + 56 + 96.2 + 18n =

(n = 12

Cng thc ca phn st amoni l NH4Fe(SO4)2.12H2O

(b) Phn tan trong nc to mi trng axit v cc ion NH4+, Al3+, Fe3+ v Cr3+ u nhng ion axit (cc ion K+ c tnh trung tnh, cn SO42- c tnh baz rt yu).

NH4+ + H2O NH3 + H3O+M3+ + H2O M(OH)2+ + H+

Cu XII (4 im)

1. Vit phng trnh phn ng xy ra khi ln lt cho cc n cht As v Bi tc dng vi dung dch HNO3 (gi thit sn phm kh ch l kh NO).

2. So snh (c gii thch) tnh tan trong nc, tnh baz v tnh kh ca hai hp cht vi hidro l amoniac (NH3) v photphin (PH3).

3. Mt giai on quan trng trong qu trnh tng hp axit nitric l oxi ha NH3 trong khng kh, c mt Pt xc tc.

(a) Xc nh nhit phn ng ca phn ng ny, bit nhit hnh thnh cc cht NH3 (k), NO (k) v H2O (k) ln lt bng 46 kJ/mol; + 90 kJ/mol v - 242 kJ/mol.

(b) Trong cng nghip, ngi ta s dng nhit v p sut th no qu trnh ny l ti u ? Ti sao ?

P NIM

1. Phng trnh phn ng :

3As + 5HNO3 + 2H2O ( 3H3AsO4 + 5NO

Bi + 4HNO3 ( Bi(NO3)3 + NO + 2H2O

1,00

2. Tnh tan :

NH3 tan tt hn PH3 trong nc, do phn t phn cc hn v c kh nng to lin kt hidro vi nc.

Tnh baz :

NH3 c tnh baz mnh hn PH3, do lin kt N-H phn cc mnh hn lin kt P-H, lm cho nguyn t N trong phn t NH3 giu electron hn, d dng nhn proton hn (mt nguyn nhn na gii thch cho iu ny l ion NH4+ bn hn PH4+).

Tnh kh :

PH3 c tnh kh mnh hn nhiu so vi NH3, do nguyn t P l mt phi kim c m in nh v phn t PH3 km bn hn NH3.

3. (a)4NH3 (k) + 5O2 (k) ( 4NO (k) + 6H2O (k)

(b)V phn ng l ta nhit, nn tng hiu sut cn gim nhit . Tuy nhin nu h nhit qu thp s lm gim tc phn ng, nn thc t phn ng ny c tin hnh 850-900oC v c xc tc Pt. V phn ng thun l chiu lm tng s phn t kh, nn tng hiu sut phn ng cn gim p sut. Tuy nhin, iu kin p sut gy tng gi thnh cng ngh sn xut, nn ta ch dng p sut thng (1 atm).

Cu XIII (4 im)

1. Dng hnh v, m t th nghim c tin hnh trong phng th nghim xc nh s c mt ca cc nguyn t C v H c trong glucoz.2. Hon thnh cc phn ng di y. Xc nh sn phm chnh ca mi phn ng v dng c ch gii thch s hnh thnh sn phm chnh .(a) CH3-CH=CH2 (propilen) + HCl ((b) CH3-CH2-CH(OH)-CH3 (ancol s-butylic)

(c) C6H5CH3 + HNO3

3. Dng s xen ph obitan nguyn t m t cc phn t CH3-CH=C=CH-CH3 (phn t A) v CH3-CH=C=C=CH-CH3 (phn t B). Cho bit A, B c ng phn hnh hc hay khng ? Ti sao ?P NIM

1. Th nghim xc nh s c mt ca cc nguyn t C v H c trong glucoz :

1,5

2. Phn ng v c ch phn ng:

(a) Phn ng :

C ch (cng AE) :

Sn phm chnh hnh thnh theo hng to cacbocation trung gian bn vng hn. D thy rng cacbocation (X) bn hn (Y) (do in tch c gii ta nhiu hn, vi 6H), nn sn phm chnh l isopropyl clorua.

0,50

(b) Phn ng :

C ch (tch E1) :

Sn phm chnh c hnh thnh theo hng to sn phm bn hn. y, (X) bn hn (Y) do c s nguyn t H tham gia lin hp, lm bn ha lin kt nhiu hn.

0,50

(c) Phn ng :

C ch (th SE2Ar) : HONO2 + H2SO4 ( HSO4- + H2O + +NO2

Phn ng dnh hng th vo v tr meta-, do mt electron v tr ny trong phn t toluen giu hn cc v tr ortho-, para-. ng thi phn ng th vo v tr ny to s gii ta in tch tt nht phc .0,50

3. M hnh phn t :

Trong trung hp ny, cc nhm th khng ng phng, nn phn t khng xut hin hin tng ng phn hnh hc.

Trong trng hp ny, cc nhm th ng phng, nn phn t xut hin hin tng ng phn hnh hc.1,00

Cu XIV (4 im)

1. Thi 672 mL (ktc) hn hp kh A gm mt ankan, mt anken v mt ankin (u c s nguyn t cacbon trong phn t bng nhau) qua dung dch AgNO3/NH3, th thy c 3,4 AgNO3 tham gia phn ng. Cng lng hn hp kh A trn lm mt mu va ht 200 mL dung dch Br2 0,15 M.

(a) Xc nh thnh phn nh tnh v nh lng cc cht trong A

(b) ngh phng php tch ring tng cht ra khi hn hp A.

2. Oxi ha m gam hp cht hu c A bng CuO ri cho sn phm sinh ra gm CO2 v hi H2O ln lt i qua bnh 1 ng Mg(ClO4)2 v bnh 2 ng 2 lt Ca(OH)2 0,0 2 M th thu c 2 gam kt ta. Khi lng bnh 1 tng 1,08 gam v khi lng CuO gim 3,2 gam, MA < 100. Oxi ha mnh lit A, thu c hai hp cht hu c l CH3COOH v CH3COCOOH.

(a) Xc nh cng thc cu to v gi tn A.

(b) Vit cc dng ng phn hnh hc tng ng ca A.

(c) Khi cho A tc dng vi Br2 theo t l mol 1:1, th to c nhng sn phm no ? Gii thch.

P NIM

1. (a) Nu ankin c dng RC(CH :

RC(CH + AgNO3 + NH3 ( RC(CAg + NH4NO3( v

iu ny tri gi thit, v s mol Br2 ch bng

Vy ankin phi l C2H2 v nh vy ankan l C2H6, anken l C2H4.

T phn ng :

C2H2 + 2AgNO3 + 2NH3 ( C2Ag2 + 2NH4NO3( n(C2H2) = 1/2n(AgNO3) = 0,01 mol

T cc phn ng :

C2H2 + 2Br2 ( C2H2Br4C2H4 + Br2 ( C2H4Br2

( n(C2H4) = 0,01 mol

( n(C2H6) = 0,01 mol0,50

(b)Thi hn hp qua binh cha dung dch AgNO3/NH3 d. Lc tch kt ta, ha tan kt ta trong dung dch HCl d thu c kh C2H2.C2H2 + 2AgNO3 + 2NH3 ( C2Ag2 + 2NH4NO3

C2Ag2 + 2HCl ( C2H2 + 2AgCl

Kh ra khi bnh cha dung dch AgNO3/NH3, thi tip qua dung dch nc brom d. Chit ly sn phm v un nng vi bt Zn (trong CH3COOH) thu c C2H4 :

C2H4 + Br2 ( C2H4Br2

C2H4Br2 + Zn ( C2H4 + ZnBr2Kh ra khi bnh cha dung dch brom l kh C2H61,00

2. (a) n(H2O) = 0,06 mol ( n(H) = 0,12 mol

T cc phn ng :



vi v ( n(CO2) bng 0,02 mol hoc 0,07 mol.

n(O) tham gia phn ng bng

Vy s mol O trong A bng :

n(O) = 0,02mol + 0,06 mol 0,2 mol < 0 (loi)

n(O) = 0,07mol + 0,06 mol 0,2 mol = 0 mol

( A l hidrocacbon c cng thc n gin C7H12V MA < 100, nn cng thc phn t ca A chnh l C7H12 ()

Cu to ca A ph hp vi gi thit l:

1,00

0,50

(b) Cc dng ng phn hnh hc :

0,50

(c) Tc dng vi brom theo t l mol 1:1 th to c cc sn phm :

0,50

Cu XV ( 4 im)

1. Trnh by phng php phn bit mi cp cht di y (mi trng hp ch dng mt thuc th n gin, c vit phn ng minh ha) :

(a) m-bromtoluen v benzylbromua

(b) phenylaxetilen v styren

2. T benzen v cc cht v c, xc tc cn thit khc c , vit cc phng trnh phn ng ha hc iu ch :

(a) meta-clonitrobenzen

(b) ortho-clonitrobenzen

(c) axit meta-brombenzoic

(d) axit ortho-brombenzoic

3. Hidrocacbon X c phn t khi bng 128, khng lm nht mu dung dch Br2. X tc dng vi H2 (xc tc Ni, t) to cc sn phm Y v Z. Oxi ha mnh lit Y to sn phm l axit o-phtalic, o-C6H4(COOH)2.

(a) Xc nh cu to v gi tn X, Y, Z.

(b) Vit phn ng to ra sn phm chnh, khi cho X ln lt tc dng vi dung dch HNO3 c (H2SO4 c xc tc) v Br2 (xc tc bt st). Bit mi phn ng, t l mol cc cht tham gia phn ng l 1:1.

P NIM

1. Phn bit cc cht :

(a) Dng AgNO3, benzyl bromua cho kt ta vng :

C6H5CH2Br + AgNO3 + H2O ( C6H5CH2OH + AgBr + HNO3(b) Dng dung dch AgNO3/NH3, phenylaxetilen cho kt ta vng xm :

C6H5C(CH + AgNO3 + NH3 ( C6H5C(CAg + NH4NO3

1,00

2. iu ch :

0,25

0,50

0,25

0,50

3. (a) X (CxHy), c 12x + y = 128 (y 2x + 2) c hai nghim thch hp l C10H8 v C9H20. Tuy nhin, v X tc dng c vi hidro, nn cng thc ng l C10H8 ().

V X khng lm nht mu nc brom nn cu to thch hp ca X l naphtalen v ph hp vi gi thit th Y l tetralin v Z l decalin :

1,00

(b) Phn ng :

0,50

S GIO DC V O TO

THNH PH NNGHNG DN CHM THI HC SINH GII THNH PHMN: HA HC LP 11


CHNH THC

ny c hai (2) trang

Cu XVI (4 im)

3. Tnh pH ca dung dch thu c khi trn ln 50,0 mL dung dch NH4Cl 0,200 M vi 75,0 mL dung dch NaOH 0,100 M. Bit Kb (NH3) = 1,8.10-5.

4. Phn l mui sunfat kp ca mt cation ha tr mt (nh K+ hay NH4+) v mt cation ha tr ba (nh Al3+, Fe3+ hay Cr3+). Phn st amoni c cng thc (NH4)aFe(SO4)b.nH2O. Ha tan 1,00 gam mu phn st vo 100 cm3 H2O, ri chia dung dch thu c thnh hai phn bng nhau. Thm dung dch NaOH d vo phn mt v un si dung dch. Lng NH3 thot ra phn ng va vi 10,37 cm3 dung dch HCl 0,100 M. Dng km kim loi kh ht Fe3+ phn hai thnh Fe2+. oxi ha ion Fe2+ thnh ion Fe3+ tr li, cn 20,74 cm3 dung dch KMnO4 0,0100 M trong mi trng axit.(a) Vit cc phng trnh phn ng dng ion thu gn v xc nh cc gi tr a, b, n.

(b) Ti sao cc phn khi tan trong nc u to mi trng axit ? P NIM

1. ;

NH4Cl + NaOH ( NaCl + NH3 + H2O

0,08 0,06

0,06 0,06 0,06

0,02 0 0,06

Xt cn bng :

NH3 + H2O NH4+ + OH-0,06 0,02

x x x

0,06x 0,02+x x

, gn ng

(

0,50

1,00

2. (a) t s mol ca phn st (NH4)aFe(SO4)b.nH2O trong mi phn l x mol.

Phng trnh phn ng phn mt :

NH4+ + OH- ( NH3 + H2O

ax1 axFe3+ + 3OH- ( Fe(OH)3NH3 + H+ ( NH4+ax ax

Phng trnh phn ng phn hai :

Zn + 2Fe3+ ( Zn2+ + 2Fe2+

x

0 x

5Fe2+ + MnO4- + 8H+ ( 5Fe3+ + Mn2+ + 4H2O

x x/510,25

Ta c :

(a = 1

Cng thc ca phn c vit li l NH4+Fe3+(SO42-)b.nH2O

(b = 2

T M = 18 + 56 + 96.2 + 18n =

(n = 12

Cng thc ca phn st amoni l NH4Fe(SO4)2.12H2O

(b) Phn tan trong nc to mi trng axit v cc ion NH4+, Al3+, Fe3+ v Cr3+ u nhng ion axit (cc ion K+ c tnh trung tnh, cn SO42- c tnh baz rt yu).

NH4+ + H2O NH3 + H3O+M3+ + H2O M(OH)2+ + H+

Cu XVII (4 im)

4. Vit phng trnh phn ng xy ra khi ln lt cho cc n cht As v Bi tc dng vi dung dch HNO3 (gi thit sn phm kh ch l kh NO).

5. So snh (c gii thch) tnh tan trong nc, tnh baz v tnh kh ca hai hp cht vi hidro l amoniac (NH3) v photphin (PH3).

6. Mt giai on quan trng trong qu trnh tng hp axit nitric l oxi ha NH3 trong khng kh, c mt Pt xc tc.

(a) Xc nh nhit phn ng ca phn ng ny, bit nhit hnh thnh cc cht NH3 (k), NO (k) v H2O (k) ln lt bng 46 kJ/mol; + 90 kJ/mol v - 242 kJ/mol.

(b) Trong cng nghip, ngi ta s dng nhit v p sut th no qu trnh ny l ti u ? Ti sao ?

P NIM


3As + 5HNO3 + 2H2O ( 3H3AsO4 + 5NO

Bi + 4HNO3 ( Bi(NO3)3 + NO + 2H2O

1,00

2. Tnh tan :

NH3 tan tt hn PH3 trong nc, do phn t phn cc hn v c kh nng to lin kt hidro vi nc.

Tnh baz :

NH3 c tnh baz mnh hn PH3, do lin kt N-H phn cc mnh hn lin kt P-H, lm cho nguyn t N trong phn t NH3 giu electron hn, d dng nhn proton hn (mt nguyn nhn na gii thch cho iu ny l ion NH4+ bn hn PH4+).

Tnh kh :

PH3 c tnh kh mnh hn nhiu so vi NH3, do nguyn t P l mt phi kim c m in nh v phn t PH3 km bn hn NH3.

3. (a)4NH3 (k) + 5O2 (k) ( 4NO (k) + 6H2O (k)

(b)V phn ng l ta nhit, nn tng hiu sut cn gim nhit . Tuy nhin nu h nhit qu thp s lm gim tc phn ng, nn thc t phn ng ny c tin hnh 850-900oC v c xc tc Pt. V phn ng thun l chiu lm tng s phn t kh, nn tng hiu sut phn ng cn gim p sut. Tuy nhin, iu kin p sut gy tng gi thnh cng ngh sn xut, nn ta ch dng p sut thng (1 atm).

Cu XVIII (4 im)

4. Dng hnh v, m t th nghim c tin hnh trong phng th nghim xc nh s c mt ca cc nguyn t C v H c trong glucoz.5. Hon thnh cc phn ng di y. Xc nh sn phm chnh ca mi phn ng v dng c ch gii thch s hnh thnh sn phm chnh .(a) CH3-CH=CH2 (propilen) + HCl ((b) CH3-CH2-CH(OH)-CH3 (ancol s-butylic)

(c) C6H5CH3 + HNO3

6. Dng s xen ph obitan nguyn t m t cc phn t CH3-CH=C=CH-CH3 (phn t A) v CH3-CH=C=C=CH-CH3 (phn t B). Cho bit A, B c ng phn hnh hc hay khng ? Ti sao ?P NIM

4. Th nghim xc nh s c mt ca cc nguyn t C v H c trong glucoz :

1,5

5. Phn ng v c ch phn ng:

(a) Phn ng :

C ch (cng AE) :

Sn phm chnh hnh thnh theo hng to cacbocation trung gian bn vng hn. D thy rng cacbocation (X) bn hn (Y) (do in tch c gii ta nhiu hn, vi 6H), nn sn phm chnh l isopropyl clorua.

0,50

(b) Phn ng :

C ch (tch E1) :

Sn phm chnh c hnh thnh theo hng to sn phm bn hn. y, (X) bn hn (Y) do c s nguyn t H tham gia lin hp, lm bn ha lin kt nhiu hn.

0,50

(c) Phn ng :

C ch (th SE2Ar) : HONO2 + H2SO4 ( HSO4- + H2O + +NO2

Phn ng dnh hng th vo v tr meta-, do mt electron v tr ny trong phn t toluen giu hn cc v tr ortho-, para-. ng thi phn ng th vo v tr ny to s gii ta in tch tt nht phc .0,50

6. M hnh phn t :

Trong trung hp ny, cc nhm th khng ng phng, nn phn t khng xut hin hin tng ng phn hnh hc.

Trong trng hp ny, cc nhm th ng phng, nn phn t xut hin hin tng ng phn hnh hc.1,00

Cu XIX (4 im)

3. Thi 672 mL (ktc) hn hp kh A gm mt ankan, mt anken v mt ankin (u c s nguyn t cacbon trong phn t bng nhau) qua dung dch AgNO3/NH3, th thy c 3,4 AgNO3 tham gia phn ng. Cng lng hn hp kh A trn lm mt mu va ht 200 mL dung dch Br2 0,15 M.

(c) Xc nh thnh phn nh tnh v nh lng cc cht trong A

(d) ngh phng php tch ring tng cht ra khi hn hp A.

4. Oxi ha m gam hp cht hu c A bng CuO ri cho sn phm sinh ra gm CO2 v hi H2O ln lt i qua bnh 1 ng Mg(ClO4)2 v bnh 2 ng 2 lt Ca(OH)2 0,0 2 M th thu c 2 gam kt ta. Khi lng bnh 1 tng 1,08 gam v khi lng CuO gim 3,2 gam, MA < 100. Oxi ha mnh lit A, thu c hai hp cht hu c l CH3COOH v CH3COCOOH.

(a) Xc nh cng thc cu to v gi tn A.

(b) Vit cc dng ng phn hnh hc tng ng ca A.

(c) Khi cho A tc dng vi Br2 theo t l mol 1:1, th to c nhng sn phm no ? Gii thch.

P NIM

1. (a) Nu ankin c dng RC(CH :

RC(CH + AgNO3 + NH3 ( RC(CAg + NH4NO3( v

iu ny tri gi thit, v s mol Br2 ch bng

Vy ankin phi l C2H2 v nh vy ankan l C2H6, anken l C2H4.

T phn ng :

C2H2 + 2AgNO3 + 2NH3 ( C2Ag2 + 2NH4NO3( n(C2H2) = 1/2n(AgNO3) = 0,01 mol

T cc phn ng :

C2H2 + 2Br2 ( C2H2Br4C2H4 + Br2 ( C2H4Br2

( n(C2H4) = 0,01 mol

( n(C2H6) = 0,01 mol0,50

(b)Thi hn hp qua binh cha dung dch AgNO3/NH3 d. Lc tch kt ta, ha tan kt ta trong dung dch HCl d thu c kh C2H2.C2H2 + 2AgNO3 + 2NH3 ( C2Ag2 + 2NH4NO3

C2Ag2 + 2HCl ( C2H2 + 2AgCl

Kh ra khi bnh cha dung dch AgNO3/NH3, thi tip qua dung dch nc brom d. Chit ly sn phm v un nng vi bt Zn (trong CH3COOH) thu c C2H4 :

C2H4 + Br2 ( C2H4Br2

C2H4Br2 + Zn ( C2H4 + ZnBr2Kh ra khi bnh cha dung dch brom l kh C2H61,00

2. (a) n(H2O) = 0,06 mol ( n(H) = 0,12 mol

T cc phn ng :



vi v ( n(CO2) bng 0,02 mol hoc 0,07 mol.

n(O) tham gia phn ng bng

Vy s mol O trong A bng :

n(O) = 0,02mol + 0,06 mol 0,2 mol < 0 (loi)

n(O) = 0,07mol + 0,06 mol 0,2 mol = 0 mol

( A l hidrocacbon c cng thc n gin C7H12V MA < 100, nn cng thc phn t ca A chnh l C7H12 ()

Cu to ca A ph hp vi gi thit l:

1,00

0,50

(b) Cc dng ng phn hnh hc :

0,50

(c) Tc dng vi brom theo t l mol 1:1 th to c cc sn phm :

0,50

Cu XX ( 4 im)

4. Trnh by phng php phn bit mi cp cht di y (mi trng hp ch dng mt thuc th n gin, c vit phn ng minh ha) :

(a) m-bromtoluen v benzylbromua

(b) phenylaxetilen v styren

5. T benzen v cc cht v c, xc tc cn thit khc c , vit cc phng trnh phn ng ha hc iu ch :

(a) meta-clonitrobenzen

(b) ortho-clonitrobenzen

(c) axit meta-brombenzoic

(d) axit ortho-brombenzoic

6. Hidrocacbon X c phn t khi bng 128, khng lm nht mu dung dch Br2. X tc dng vi H2 (xc tc Ni, t) to cc sn phm Y v Z. Oxi ha mnh lit Y to sn phm l axit o-phtalic, o-C6H4(COOH)2.

(a) Xc nh cu to v gi tn X, Y, Z.

(b) Vit phn ng to ra sn phm chnh, khi cho X ln lt tc dng vi dung dch HNO3 c (H2SO4 c xc tc) v Br2 (xc tc bt st). Bit mi phn ng, t l mol cc cht tham gia phn ng l 1:1.

P NIM

1. Phn bit cc cht :

(a) Dng AgNO3, benzyl bromua cho kt ta vng :

C6H5CH2Br + AgNO3 + H2O ( C6H5CH2OH + AgBr + HNO3(b) Dng dung dch AgNO3/NH3, phenylaxetilen cho kt ta vng xm :

C6H5C(CH + AgNO3 + NH3 ( C6H5C(CAg + NH4NO3

1,00

2. iu ch :

0,25

0,50

0,25

0,50

3. (a) X (CxHy), c 12x + y = 128 (y 2x + 2) c hai nghim thch hp l C10H8 v C9H20. Tuy nhin, v X tc dng c vi hidro, nn cng thc ng l C10H8 ().

V X khng lm nht mu nc brom nn cu to thch hp ca X l naphtalen v ph hp vi gi thit th Y l tetralin v Z l decalin :

1,00

(b) Phn ng :

0,50

S GIO DC V O TO

THNH PH NNGHNG DN CHM THI HC SINH GII THNH PH

MN: HA HC LP 11


Cu XXI (4 im)

1. Xt hp cht vi hidro ca cc nguyn t nhm VA. Gc lin kt HXH (X l k hiu nguyn t nhm VA) v nhit si c cho trong bng di y.

c imNH3PH3AsH3SbH3

Gc HXH107o93o92o91o

Nhit si (oC)-33,0-87,7-62,0-18,0

So snh v gii thch s khc bit gi tr gc lin kt v nhit si ca cc cht ny.

2. Khi cho NH3 vo dung dch AgNO3 th thy c vn c mu trng tan li ngay trong NH3 d, nhng khi thm AsH3 vo dung dch AgNO3 th li thy xut hin kt ta Ag v dung dch thu c c cha axit asen. Vit phng trnh phn ng v gii thch ti sao c s khc bit ny.

3. Xt phn ng tng hp amoniac : N2 (k) + 3H2 (k) 2NH3 (k)

450oC hng s cn bng ca phn ng ny l KP = 1,5.10-5. Tnh hiu sut phn ng tng hp NH3 nu ban u trn N2 v H2 theo t l 1:3 v th tch v p sut h bng 500 atm.

P NIM

1. T N n Sb bn knh nguyn t tng dn, c trng lai ha sp3 ca nguyn t X trong phn t XH3 gim dn, nn gc lin kt tr v gn vi gc gia hai obitan p thun khit. (Cng c th gii thch l t Sb n N m in ca nguyn t trung tm tng dn, bn knh nguyn t gim dn, lm khong cch gia cc cp electron lin kt gim, lc y gia chng tng, nn gc lin kt tng).0,50

NH3 to c lin kt H lin phn t, cn PH3 th khng, do vy t NH3 n PH3 nhit si gim. T PH3 n SbH3 nhit si tng do phn t khi tng.

1,00

(0,502)


AgNO3 + NH3 + H2O ( AgOH + NH4NO3AgOH + 2NH3 ( Ag(NH3)2OH

NH3 c tnh baz mnh hn AsH3, nhng ngc li AsH3 c tnh kh mnh hn NH3.1,50

(0,503)

3. Gi x v h ln lt l s mol ban u ca N2 v hiu sut phn ng.

N2 (k) + 3H2 (k) 2NH3 (k)

nox

3x

0

nhx

3hx

2hx

x(1-h)

3x(1-h)

2hx( (n = x(4-2h)

EMBED Equation.3

vi

, vy hiu sut phn ng bng 46,7%1,00

(0,502)

Cu XXII (4 im)

1. Trn ln 7 mL dung dch NH3 1M v 3 mL dung dch HCl 1M thu c dung dch A. Thm 0,001 mol NaOH vo dung dch A thu c dung dch B.

(a) Xc nh pH ca cc dung dch A v B, bit .

(b) So vi dung dch A, gi tr pH ca dung dch B c s thay i ln hay nh ? Nguyn nhn ca s bin i ln hay nh l g ?

2. Tnh th tch dung dch Ba(OH)2 0,01M cn thm vo 100 mL dung dch Al2(SO4)3 0,1M thu c 4,275 gam kt ta.

P NIM

1. (a) Xt phn ng ca dung dch NH3 v dung dch HCl :

NH3 + H+ ( NH4+Co 0,7M 0,3M

C 0,3M

0,3M[C] 0,4M 0 0,3M

Vy dung dch A gm cc cu t chnh l NH3 0,4M, NH4+ 0,3M v Cl-.0,50

NH3 + H2O NH4+ + OH- Kb

Co0,4M

0,3M

CxM

xM

xM

[C](0,4-x)M

(0,3+x)MxM

0,50

Khi thm 0,001 mol NaOH vo dung dch A c phn ng :

NH4+ + OH- ( NH3+H2O

Co 0,3M 0,1M

0,4M

C 0,1M

0,1M

0,1M

[C] 0,2M 0 0,5M

Vy dung dch B gm cc cu t chnh l NH3 0,5M, NH4+ 0,2M v Cl-.0,50

NH3 + H2O NH4+ + OH- Kb

Co0,5M

0,2M

CxM

xM

xM

[C](0,5-x)M

(0,2+x)MxM

0,50

(b) S khc bit gi tr pH ca dung dch B so vi dung dch A l khng ln, do trong dch A tn ti mt cn bng axit baz, cn bng ny c kh nng lm gim (chng li) tc ng thay i nng axit (H+) hoc baz (OH-).0,50

2. Theo gi thit v . Gi x l s mol Ba(OH)2 cn thm vo, nh vy v .

Ba2+ + SO42- (BaSO4

(1)

nox (mol)

0,03 (mol)

Al3+ + 3OH- (Al(OH)3(2)

no0,02 (mol)2x (mol)

Al(OH)3 + OH- (Al(OH)4-(3)

0,50

Xt trng hp ch xy ra phn ng (1) v (2). Trong trng hp ny Al3+ tham gia phn ng va hoc d : , v nh vy Ba2+ phn ng ht phn ng (1).

Ta c : m(kt ta) =

Vy th tch dung dch Ba(OH)2 s dng l

0,50

Nu xy ra cc phn ng (1), (2) v (3) th

(loi).0,50

Cu XXIII (4 im)

1. Chn cht ph hp, vit phng trnh (ghi r iu kin phn ng) thc hin bin i sau :

2. Dung dch A gm 0,4 mol HCl v 0,05 mol Cu(NO3)2. Cho m gam bt Fe vo dung dch khuy u cho n khi phn ng kt thc thu c cht rn X gm hai kim loi, c khi lng 0,8m gam. Tnh m. Gi thit sn phm kh HNO3 duy nht ch c NO.

P NIM

1. Cc phng trnh phn ng :

(1) N2 + 3H2 2NH3(2) 4NH3 + 5O2 4NO + 6H2O

(3) 2NO + O2 ( 2NO2

(4) 4NO2 + O2 + 2H2O ( 4HNO3

(5) 5Mg + 12 HNO3 ( 5Mg(NO3)2 + N2 + 6H2O

(6) N2 + O2 2NO(7) 2NO2 + 2KOH ( KNO2 + KNO3 + H2O

(8) 5KNO2 + 2KMnO4 + 3H2SO4 ( 5KNO3 + K2SO4 + 2MnSO4 + 3H2O 2,00(0,258)

2. Trong dung dch A :

Dung dch A c 0,4 mol H+, 0,05 mol Cu2+, 0,4 mol Cl-, 0,1 mol NO3-

Khi cho Fe vo dung dch A xy ra cc phn ng :

(1) Fe +4H+ + NO3- ( Fe3+ +NO +2H2O

0,4 0,1

0,1 0,4 0,1

0,1

0 0 0,1

(2) Fe + 2Fe3+ (3Fe2+0,050,1

(3) Fe + Cu2+ (Fe2+ + Cu

0,16 0,05 0,05 1,00

S mol Fe tham gia cc phn ng t (1) n (3) l 0,1+ 0,05 + 0,05 = 0,2 (mol)

Hn hp 2 kim loi sau phn ng gm Fe d Cu, (m - 56(0,2) + 0,05 (64 = 0,8 m

( m = 40 (gam) 1,00

Cu XXIV (4 im)

1. Di y l cc gi tr nhit nng chy v nhit si ca n-pentan v neopentan. Gii thch s khc bit nhit nng chy v nhit si gia cc cht ny.

n-PentanNeopentan

Nhit si (oC)369,5

Nhit nng chy (oC)-130-17

2. X, Y, Z ln lt l ankan, ankadien lin hp v ankin, iu kin thng tn ti th kh. t chy 2,45 L hn hp ba cht ny cn 14,7 L kh O2, thu c CO2 v H2O c s mol bng nhau. Cc th tch kh u o 25oC v 1 atm.

(a) Xc nh cng thc phn t ca X, Y v Z.

(b) Y cng Br2 theo t l mol 1:1 to ba sn phm ng phn. Dng c ch phn ng gii thch s hnh thnh cc sn phm ny.

3. Hon thnh cc phng trnh phn ng :

P NIM

1. Nhit si ca neopentan thp hn n-pentan v khi phn t c cng nhiu nhnh, tnh i xng cu ca phn t cng tng, din tch b mt phn t cng gim, lm cho bn tng tc lin phn t gim v nhit si tr nn thp hn. 0,50

Tri li, tnh i xng cu li lm cho mng tinh th cht rn tr nn c kht hn v bn vng hn, nn nhit nng chy cao hn.

0,25

2. (a) Gi cng thc trung bnh ca X, Y, Z l (do s mol CO2 v H2O bng nhau).

, ta c :

V X, Y, Z iu kin thng u tn ti th kh (trong phn t, s nguyn t C ( 4), nn cng thc phn t ca X l C4H10 v Y, Z l C4H6. 0,75(0,253)

(b) C ch phn ng :

0,75(0,50+0,25)

3. Cc phng trnh phn ng :

CH3CH2Br + Mg CH3CH2MgBr

EMBED ChemDraw.Document.5.0

1,75

(0,257)

Cu XXV ( 4 im)

1. Cht X c cng thc phn t C7H6O3. X c kh nng tc dng vi dung dch NaHCO3 to cht Y c cng thc C7H5O3Na. Cho X tc dng vi anhirit axetic to cht Z (C9H8O4) cng tc dng c vi NaHCO3, nhng khi cho X tc dng vi metanol (c H2SO4 c xc tc) th to cht T (C8H8O3) khng tc dng vi NaHCO3 m ch tc dng c vi Na2CO3.

(a) Xc nh cu to cc cht X, Y, Z, T v vit cc phng trnh phn ng xy ra. Bit cht X c kh nng to lin kt H ni phn t.

(b) Cho bit ng dng ca cc cht Y, Z v T

2. t chy hon ton 10,08 L hn hp kh gm hai ankanal A v B thu c 16,8 L kh CO2. Nu ly cng lng hn hp ny tc dng hon ton vi lng d dung dch AgNO3 trong NH3 th thu c 108 gam Ag kim loi.

(a) Xc nh A v B, bit cc kh u o 136,5oC v 1 atm.

(b) Tin hnh phn ng canizaro gia A v B. Cho bit sn phm to thnh v gii thch.

P NIM

1. (a) Cu to cc cht :

1,00

(0,254)

Phng trnh phn ng :

HOC6H4COOH + NaHCO3 ( HOC6H4COONa + H2O + CO2HOC6H4COOH + CH3OH HOC6H4COOCH3 + H2O

HOC6H4COOH + (CH3CO)2O CH3COOC6H4COOH + CH3COOH0,75

(0,253)

(b) Y vi hm lng rt nh c s dng lm cht bo qun thc phm v pha ch nc xc ming (c tc dng dit khun); Z c s dng ch to dc phm aspirin v T l thnh phn chnh ca du gi xanh.0,75

(0,253)

2. (a) Xc nh A v B.

;

v

A l HCHO0,50

Gi cng thc ca B l RCHO (hay CnH2nO) v s mol ca A, B ln lt l a, b.

HCHO 4Ag

RCHO 2Ag

Ta c :

Vy B l CH3CH2CHO0,50

(b) Phn ng canizaro :

HCHO + CH3CH2CHO + OH- ( HCOO- + CH3CH2CH2OH

Hp cht d tham gia phn ng cng AN hn (nguyn t cacbon trong nhm cacbonyl dng in hn) v c nhiu H lin kt vi nhm cacbonyl hn, c xu hng chuyn thnh ion cacboxilat. 0,50

(0,252)

1

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