I. OLYMPIC HA HC VIT NAM: K THI CHN HC SINH GII QUC GIA NM 2003 (BNG A) 1.

Nhm clorua khi ho tan vo mt s dung mi hoc khi bay hi nhit khng qu cao th tn ti dng dime (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 2 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? 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
; dime

Cl Al Al Cl

Cl Cl

Cl

* Kiu lai ho ca nguyn t nhm : Trong AlCl3 l sp2 v Al c 3 cp electron ho tr; Trong Al2Cl6 l sp3 v Al c 4 cp electron ho tr . Lin kt trong mi phn t: AlCl3 c 3 lin kt cng ho tr c cc gia nguyn t Al vi 3 nguyn t Cl. Al2Cl6: Mi nguyn t Al to 3 lin kt cng ho tr vi 3 nguyn t Cl v 1 lin kt cho nhn vi 1 nguyn t Cl (Al: nguyn t nhn; Cl nguyn t cho). Trong 6 nguyn t Cl c 2 nguyn t Cl c 2 lin kt, 1 lin kt cng ho tr thng thng v lin kt cho nhn. Cl * Cu trc hnh hc: 1200 1200 Phn t AlCl3: nguyn t Al lai ho kiu sp2 (tam gic phng) Al nn phn t c cu trc tam gic phng, u, nguyn t Al tm cn 3 nguyn t Cl 3 nh ca tam gic. Cl Cl
1200

Phn t Al2Cl6: cu trc 2 t din ghp vi nhau. Mi nguyn t Al l tm ca mt t din, mi nguyn t Cl l nh ca t din. C 2 nguyn t Cl l nh chung ca 2 t din. Al O Cl 2. * Phn t

O O O O O O

H-F

M = 20 Jt ; = 1,91 Debye

H-O-H

M = 18 = 1,84 Debye

c th to lin kt hidro HF

c th to lin kt hidro HO

* 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-FH-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 K THI CHN HC SINH GII QUC GIA NM 2003 (BNG A)

Kim loi A phn ng vi phi kim B to hp cht C mu vng cam. Cho 0,1 mol hp cht C phn ng vi CO2 (d) to thnh hp cht D v 2,4 gam B. Ha tan hon ton D vo nc, dung dch D phn ng ht 100 ml dung dch HCl 1 M gii phng 1,12 l kh CO2 (ktc). Hy xc nh A, B, C, D v vit cc phng trnh phn ng xy ra. Bit hp cht C cha 45,07 % B theo khi lng; hp cht D khng b phn tch khi nng chy. BI GII:
nHCl = 0,1 mol ; nCO2 = 0,05 mol
+

nH 0, 1 2 = = 0, 05 1 n CO2 suy ra hp cht D l mui cacbonat kim loi. Hp cht D khng b phn tch khi nng chy, vy D l cacbonat kim loi kim. 2 H+ + CO32- = H2O + CO2 C + CO2 = D + B C l peroxit hay superoxit, B l oxi. t cng thc ho hc ca C l AxOy . 3, 2.100 Lng oxi trong 0,1 mol C (AxOy ) l 16 x 0,05 + 2,4 = 3,2 (g); mC = = 7,1 gam 45, 07 Mc = 7,1 : 0,1 = 71 (g/mol). mA trong C = 7,1 - 3,2 = 3,9 (g). 3, 9 3, 2 : x:y= MA = 39 (g). Vy A l K ; B l O2 ; C l KO2 ; D l K2CO3 M A 16
Dung dch D phn ng ht 0,1 mol HCl gii phng kh CO2

K + O2 KO2 4 KO2 + 2 CO2 2 K2CO3 + 3O2 K2CO3 + 2 HCl 2 KCl + H2O + CO2 K THI CHN HC SINH GII QUC GIA NM 2004 (BNG A) Cc phng trnh phn ng: Vit phng trnh ho hc cho mi trng hp sau: a) Cho kh amoniac (d) tc dng vi CuSO4.5H2 O. b) Trong mi trng baz, H2O2 oxi ho Mn2+ thnh MnO2. Trong mi trng axit, H2O2 kh MnO4- thnh Mn2+. BI GII: a) C th vit CuSO4.5H2O dng [Cu(H2O)4] SO4.H2O. Do khi phn ng xy ra, NH3 s th cc phn t H2O cu ni: [Cu(H2O)4] SO4.H2O + 4 NH 3 b) H2O2 + 2e Mn2+ + 4 OH 2 e Mn2+ + H2O2 + 2 OH c) 2 5 MnO4 + 8 H3O+ + 5 e H2O2
-

[Cu(NH3)4] SO4.H2O + 4 H2O 2 OH MnO2 + 2 H2O MnO2 + 2 H2O Mn2+ + 12 H2O O2 2 Mn + 2 H3O
2+ +

S kh S oxi ho S kh S oxi ho 14 H2O

+ 2 H2O 2 e 6 H3O
+

2MnO4 + 5 H2O2 +

+ 5 O2 +

K THI CHN HC SINH GII QUC GIA NM 2005 (BNG A) Nhng hai tm km, mi tm c khi lng 10 gam vo hai dung dch mui kim loi ho tr hai. Sau mt thi gian xc nh, ly hai tm km ra khi dung dch, ra sch, lm kh ri cn li. Kt qa cho thy mt tm c khi lng 9,5235 gam, tm kia c khi lng 17,091 gam. Cho bit: Mt trong hai dung dch mui kim loi ho tr hai l mui st (II); lng km tham gia phn ng hai dung dch l nh nhau. 1. Gii thch hin tng xy ra mi dung dch. 2. Cho bit kim loi no tham gia vo thnh phn dung dch mui th hai. BI GII: 1. Khi nhng tm km vo dung dch mui Fe(II): Zn2+ + Fe (1) Zn + Fe2+ V: MFe < MZn nn khi lng tm km gim i. Khi nhng tm km vo dung dch mui th hai X2+ Zn + X2+ Zn2+ + X (2) V: MZn < MX nn khi lng tm km tng ln. 2. Gi x l s mol Zn phn ng, theo (1) ta c: (10 65,38 x) + 55,85 x = 9,5235 x = 0,05 (mol) V lng Zn tham gia phn ng 2 trng hp l nh nhau, theo (2) ta c: (10 65,38 0,05) + MX 0,05 = 17,091 MX = 207,2.

Vy X2+ l Pb2+, X l Pb Zn + Pb2+

Zn2+ + Pb

K THI CHN HC SINH GII QUC GIA NM 2005 (BNG A) Hon thnh cc phng trnh phn ng sau y: 1. NaCl + H2SO4 c, nng 2. NaBr + H2SO4 c, nng 3. NaClO + PbS 4. FeSO4 + H2SO4 + HNO2 5. KMnO4 + H2SO4 + HNO2 6. NaNO2 + H2SO4 long BI GII: 1. NaCl + H2SO4 (c, nng) hoc 2. 2 NaCl + H2SO4 (c, nng) 2 NaBr + 2 H2SO4 (c, nng) 2 HBr + H2SO4 (c, nng)

HCl

+ NaHSO4

2 HCl + Na2SO4 2 NaHSO4 + 2 HBr SO2 + 2 H2O + Br2

3. 4. 5. 6.

2 NaBr + 3 H2SO4 (c, nng) 2 NaHSO4 + SO2 + 2 H2O + Br2 4 NaClO + PbS 4 NaCl + PbSO4 2 FeSO4 + H2SO4 + 2 HNO2 Fe2(SO4)3 + 2 NO + 2 H2O 2 KMnO4 + 3 H2SO4 + 5 HNO2 K2SO4 + 2 MnSO4 + 5 HNO3 + 3 H2O 3 NaNO2 + H2SO4 (long) Na2SO4 + NaNO3 + 2 NO + H2O

K THI CHN HC SINH GII QUC GIA NM 2005 (BNG A) t chy kim loi magie trong khng kh. Cho sn phm thu c tc dng vi mt lng d dung dch axit clohidric, un nng ri c dung dch n cn kh. Nung nng sn phm mi ny v lm ngng t nhng cht bay hi sinh ra trong qa trnh nung. Hy vit cc phng trnh phn ng xy ra trong th nghim trn v cho bit c nhng cht g trong sn phm ngng t c. BI GII: Cc phn ng: 2 Mg + O2 2 MgO 3 Mg + N2 Mg3N2 MgCl2 + t
o o

MgO + 2 HCl Mg3N2 + 8 HCl MgCl2.6 H2O NH4Cl II. t

H2O 2 HCl + 5 H2O NH4Cl

3 MgCl2 + 2 NH4Cl MgO NH3 + + HCl

Sn phm c ngng t: NH4Cl ; H2O ; HCl. OLYMPIC HA HC QUC T:

OLYMPIC HA HC QUC T LN TH 28: S polime ha lp th ca hydrocacbon cha no thng c coi l mt trong nhng phn ng quan trng trong ha hc hu c cng nghip. Mui ca cc cation ln khng thng hng mang in tch ln tn cng vo mt electron phn b dc theo cc lin kt ca phn t olefin thng c dng lm cht xc tc trong cc qa trnh ny. Anion cloroaluminat (AlCl4-) thng c dng do c n tch m c bt nh cao. Nhu cu pht trin cht xc tc mi thuc loi ny thc y cc nh ha hc kho st tng tc trong h thng A B, trong A = Te (kt tinh) v B = TeCl4 + 4AlCl3. Hp phn th hai B - c coi nh l mt cht tng t Te(IV) cloroaluminat Te[AlCl4]4, nhng li khng th c lp c hp cht ny di dng hp cht ring bit. Ngwofi ta thy rng tng tc ca cc hp phn A v B c th dn n s to thnh ba hp cht mi I, II v III trong cc h thng lc u c cha theo th t 77,8; 87,5 v +1,7% theo s mol ca hp phn A. Ngi ta cng nhn thy trong trng hp cc hp cht II v III khng c s to thnh sn phm ph km theo, nhng s hnh thnh hp cht I c km theo s gii phng 1 mol TeCl4 d bay hi ng vi 2 mol I. C hai hp cht u c mu tm hng v c hai phn li thnh 3 ion m kho st tnh dn in trong NaAlCl4 cho thy: T php o nghim lnh tng NaAlCl4 nng chy cho php tnh c khi lng mol phn t ca I v II ln lt bng 112643g/mol v 86748g/mol. Ph hng ngoi IR ca c hai hp cht ch quan st c c mt di c th c gn cho kiu rung ca lin kt tOo bi mt nguyn t Te. Di ny nm tjai 133cm-1 v v vy c nng lng thp n ni khng nghi ng g na lin kt ny l mt loi Te-Te. S liu ph cng hng t ht nhn 27Al NMR ca cc phc I v II cho thy ch c mt loi nhm ph tr t din trong mi hp cht. Tuy nhin di ha hc quan st c ca nhm vi cc hp cht I v II khc nhua, nh th cho thy cc nguyn t Al trong cc mi trng khc nhau. 1. Hy xc nh t l nguyn t ti thiu ca Te:Al:Cl vi cc phc I, II v III. 2. Vit cng thc phn t ca cc hp cht I v II. 3. Vit cng thc cc anion v cation trong hp cht I v II. 4. Vit cng thc ha lp th ca cc cation v anion trong cu to ca I v II. Gi thit rng cc cation trong I v II l nhng v d ca h thng thm v c. 5. I hay II c bn nhit cao hn. Bit rng AlCl3 l mt cht cc k d bay hi. 6. Nu mt trong cc hp cht I v II c th chuyn thnh cht kia khi un nng th hy vit phng trnh phn ng tng ng. BI GII: 1. C th dng s lu v hm lng Te(kt tinh) xc nh cc t l Te:Al:Cl, nh vy: 77,8% Te (kt tinh) tng ng vi: 7Te (kt tinh) + 2TeCl4 + 8AlCl3 v t l nguyn t b nht cho thnh phn m khng tch lng d TeCl4 l Te:Al:Cl = 9:8:32, trong hm lng Al v Cl l chn v c th chia ht cho 4. tng lc hm lng Te vt qa bi s ca 4 l 1. Tr mt mol TeCl4 t t l thu c ri chia cho 2 ta c 4Te+4Al+14Cl v t l l Te:Al:Cl = 2:2:7, t l ny c th c kim tra li bng cch so snh vi khi lng phn t cho. 87,5% Te(kt tinh) ng vi: 7Te (kt tinh) + TeCl4 + 4AlCl3 = 8Te + 4Al + 16Cl v t l l: Te:Al:Cl = 2:1:4 91,7% Te(kt tinh) ng vi: 11Te (kt tinh) + TeCl4 + 4AlCl3 = 12Te + 4Al + 16Cl v t l l Te:Al:Cl = 3:1:4 2. Cng thc phn t c th c suy t cc khi lng phn t. C hai u ng vi gp i cng thc n gin nht: Vi cht I: Te4Al4Cl14. Vi cht II: Te4Al2Cl8.

3. Thnh phn ca cc ion c trong cu to ca I v II c th c xc nh bng cch da trn c im l c hai cht I v II u l nhng cht in ly to bi 3 ion v tt c nhng nguyn t telu phi tng ng theo ph IR v ch c lin kt vi nhau, cng nh l cc nguyn t Al trong c hai hp cht l tng t v c phi tr t din. t nht trong mt trng hp, c th l anion AlCl4- ph hp vi cht II nn v th c cng thc l [Te4]2+[AlCl4]2-. Do mu tng t nn cc cation trong c hai trng hp l tng t, cu to I phi cha cation [Te4]2+ v anion [Al2Cl7]-, iu ny ph hp vi cc s liu ph NMR, gn cho cc nguyn t Al trong cht I c hnh hc t din khc so vi hnh hc t din ca cht II. Anion [Al2Cl7]Hp cht I: Cation [Te4]2+ Hp cht II: Cation [Te4]2+ Anion [AlCl4]4. Hnh hc ca cc anion: AlCl4- c cu to t din n
Cl Cl Cl Al Cl

Al2Cl7- gm hai t din c chung nh mt nguyn t clo

Cl Cl Cl Al Cl Al Cl Cl Cl

Hnh hc ca cation: [Te4]2+ c cu trc vung phng do c tnh thm. Cu hnh vung phng l u i v cation c tnh thm, c ngha l ng phng v c bn lin kt bng nhau cho cc cnh ca vng thm tng ng:
Te
2+

Te Te

Te

5. bn nhit ca cht II phi cao hn cht I; c hai u l cc hp cht ion vi im nng chy cao, nhng hp cht I c th chuyn thnh II bng phn ng tch AlCl3, l mt cht rn d tch ra khi bay hi v c th tch ra mt cch tng i d dng nh un nng. 6. Te4[Al2Cl7]2 = Te4[AlCl4]2 + AlCl3. OLYMPIC HA HC QUC T LN TH 28: Gii hn d l mt trong nhng tham s c bn tng vic phn tch nh lng mt lng rt nh (vt) ca cc nguyn t. Gii hn d c m t l khi lng nguyn t b nht c th c xc nh bng mt phng php cho trc vi mt mc chnh xc cho trc. V d, xt hai phng php c dng xc nh vi lng ca bitmut. Nm 1927, Bergh, nh ha hc ngi c, ngh rng bitmut c th c kt ta di dng mui khng tan: 8-hydroxiqiunonlin tetraiodobitmutat [C9H6(OH)NH][BiI4] c M = 862.7g/mol. 1) a) Vit cng thc cu to cation v anion ca mui ny. b) Mc oxy ha ca nguyn t Bi trong hp cht ny l bao nhiu? 2) Xc nh khi lng nguyn t b nht ca bitmut (theo mg) c th c xc nh mt cch ng tin cy bng phng php Bergh, nu khi lng b nht ca cht kt ta c th o c mt cch ng tin cy l 50,0mg.

Mt phng php khc do R.Belcher v cng s t Birmingham pht trin xc nh hm lng vt ca bitmut c gi l phng php a bi. Theo phng php ny, ngi ta tin hnh mt chui cc phn ng ri tin hnh chun sn phm cui c m t chi tit di y. Bc 1: Thm 50mg kali hexathioxianatocromat (III), K3[Cr(SCN)6] vo mt lng nh khong 2mL dung dch lnh c axit ho c cha mt lng vt Bi3+ dn n kt ta nh lng ca bitmut. 3) Vit v cn bng phng trnh phn ng di dng ion thu gn. Bc 2: Lc ly kt ta, ra bng nc lnh v x l vi 5mL dung dch natri hydrocacbonat 10%. Vic x l ny gip chuyn kt ta ban u thnh mt kt ta khc oxobitmut cacbonat (BiO)2CO3 vi s gii phng ion hexathioxianatocromat (III) vo dung dch. 4) Vit v cn bng phng trnh phn ng ny di dng ion thu gn. Bc 3: Nc lc c axit ha nh v chuyn sang phu tch, sau thm 0,5mL dung dch iot bo ho trong clorofom v lc mnh hn hp. Iot tin hnh phn ng oxi ha - kh vi ligand ca ion phc v to thnh sn phm c c xianogen iodua [ICN] v ion sunfat. 5) Vit v cn bng phng trnh phn ng ny di dng ion thu gn. Bc 4: Sau 5 pht, thm 4mL dung dch H2SO4 2M vo hn hp. S axit ha ny dn n phn ng oxy ha - kh vi s to thnh iot phn t. 6) Vit v cn bng phng trnh phn ng ny di dng ion thu gn. Bc 5: Tch nh lng iot bng 4 phn clorofom. Lp dung dch nc c chuyn vo mt bnh cha, thm vo 1mL nc brom v lc hn hp trong 5 pht. Brom ly d c th phn ng c vi hydro xianua to thnh xianogen bromua BrCN v vi iot to thnh IO3-. 7) Vit v cn bng phng trnh phn ng ny di dng ion thu gn. Bc 6: loi lng d brom phn t, thm 3mL dung dch axit fomic 90% vo hn hp. 8) Vit v cn bng phng trnh phn ng ny di dng ion thu gn. Bc 7: Thm lng d kali iodua (khong 1,5g) vo dung dch hi axit ny. Iot c th phn ng vi BrCN theo cch tng t nh vi ICN to thnh iot phn t. 9) Vit v cn bng phng trnh phn ng ny di dng ion thu gn. Bc 8: Chun dung dch thu c bng dung dch Na2S2O3 0,00200M tiu chun. Nh vy kt qa thu c s dng tnh hm lng bitmut trong mu em phn tch. 10) a) Vi mi mol bitmut c bao nhiu mol thiosunfat trong mu ban u? b) Hm lng b nht ca bitmut c th xc nh c bng phng php Belcher l bao nhiu? Gi thit rng s xc nh ny l ng tin cy nu dng khng di 1mL dung dch Na2S2O3 0,00200M tiu chun. 11) Phng php phn tch a bi ny ca Belcher nhy hn phng php phn tch trng lng ca Bergh bao nhiu ln? BI GII: 1) a) Cng thc cu to ca cation v anion: Cation:

N H OH

Anion:

I I Bi I I

hay:
I Bi I I I

Mc oxy ha ca bitmut: +3 2) m = 12,1mg 3) Bi3+ + [Cr(SCN)6]3+ = Bi[Cr(SCN)6] 4) 2Bi[Cr(SCN)6] + 6HCO3- = (BiO)2CO3 + 2[Cr(SCN)6]3- + 3H2O + 5CO2. 2Bi[Cr(SCN)6] + 5HCO3- + 5OH- = (BiO)2CO3 + 2[Cr(SCN)6]3- + 3H2O v.v (C th cn c nhng dng khc) 5) [Cr(SCN)6]3- + 24I2 + 24H2O = Cr3+ + 6SO42- + 6ICN + 42I- + 48H+ 6) ICN + I- + H+ = I2 + HCN 7) a) 3Br2 + I- + 3H2O = IO3- + 6Br- + 6H+. b) Br2 + HCN = BrCN + Br- + H+. 8) Br2 + HCOOH = 2Br- + CO2 + 2H+. 9) a) IO3- + 5I- + 6H+ = 3I2 + 3H2O b) BrCN + 2I- + H+ = I2 + HCN + Br10) a) Chun iot bng thiosunfat theo phn ng: I2 + 2S2O32- = S4O62- + 2IGi thit rng dung dch ban u cha 1mol Bi. Trong phn ng (5) mi mol Bi dn n s hnh thnh 42 mol ion iodua ( thun tin, chia tt c cc h s ca phn ng cho 2), trong 6 mol ion Ic tiu th phn ng (6). Nh vy 36 mol iodua phn ng theo phng trnh 7a to 36mol IO3m vi phn ng 9a cho 108 mol I2 nn cn 216 mol thiosunfat chun . Mt khc mt mol Bi3+ to ra 6 mol HCN theo cc phn ng (5) v (6). Brom oxy ha HCN trong phn ng 7b cho 6 mol BrCN, m theo phn ng 9b to 6 mol iot nn cn thm 12 mol thiosunfat na. Nh vy, tng s mol thiosunfat cn thit l 228mol. b) ta c th tnh c kt qa l: 1,83.10-3mg = 1,83g 11) 6600 OLYMPIC HA HC QUC T LN TH 31: Ligand (L) c th to phc c vi nhiu kim loi chuyn tip. L c tng hp do s un nng hn hp gm bipiridin, axit axetic bng v hydro peoxit n 70-80oC trong 3 gi. Sn phm cui L kt tinh di dng hnh kim nhuyn v c khi lng phn t bng 188. Mt phn ng tng t vi piridin l:

b)

[O]
N N O

Phc ca L vi Fe v Cr c cng thc l FeLm(ClO4)n.3H2O (A) v CrLxCly(ClO4)z.H2O (B). Thnh phn phn tch nguyn t v tnh cht l hc ca chng c cho trong bng 1 v 2. Quan h gia mu v bc sng cho trong bng 3: Bng 1: Thnh phn phn tch nguyn t: Phc Phn tch nguyn t (% khi lng) A Fe: 5,740; C: 37,030; H: 3,090; Cl: 10,940; N: 8,640 Cr: 8,440; C: 38,930; H: 2,920; Cl: 17,250; N: 9,080 B Dng cc s liu sau: S hiu nguyn t: Cr = 24; Fe = 26 Khi lng nguyn t: H = 1; C = 12; O = 16; Cl = 35,45; Cr = 52; Fe = 55,8 Bng 2: Tnh cht vt l: Phc Mu Momen t (B.M) A 6,13 Vng B Khng o Tm Bng 3: Quan h gia bc sng v mu: Bc sng (nm) v mu hp th Mu b sung (mu b) 400 (tm) Lc vng 450 (xanh) Vng 490 (lc xanh lam) Vng cam 500 (lc) 570 (lc vng) Tm 580 (vng) Xanh lam 600( Vng cam) Lc xanh lam 650 () Lc 1. Vit cng thc phn t ca L. 2. Nu L l mt ligand cng cua hai rng, vit cu tjao ca bipiridin dng. Vit cu to ca L 3. Ligand L c in tch tng cng l bao nhiu? 4. Vit cu to khi mt phn t L lin kt vi mt ion kim loi M 5. T cc s lu ghi trong bng 1 hy xc nh cng thc thc nghm ca A. Ga tr ca m v n trong FeLm(ClO4)n.3H2O l bao nhiu?. Vit tn y ca A theo quy tn\c IUPAC. Khi A ho tan trong nc th t l gia cation v anion l bao nhiu? 6. S oxy ha ca Fe trong A l bao nhiu? C bao nhiu electron d c mt trong ion Fe ca phc? Vit cu hnh spin cao v spin thp c th tn ti c i vi phc ny. Cu hnh no, cao hay thp l cu hnh ng? C chng c no l tt nht minh ho kt lun chn? 7. T bng 3, c lng bc sng (nm) ca A. 8. Phn tch chi tit B cho thy n c cha ion Cr3+. Hy tnh momen t ch vi spin ca hp cht ny. 9. Hp cht B l loi cht in phn 1:1. Hy xc nh cng thc thc nghim ca B v cc ga tr ca x, y, z trong CrLxCly(ClO4)z.H2O.

BI GII: 1. Bit L c tng hp t bipiridin v trong phn ng bipiridin b oxy ha n gin thnh bipiridin oxit.Khi lng phn t ca bipiridin l 156 (ca C10H8N2) trong khi khi lng phn t ca L l 188. Khc bit 32 do hai nguyn t oxy. V vy cng thc phn t ca L l C10H8N2O2. 2. Cu to ca bipiridin:

Cu to c th c ca L:

N O O

N O O

N O O

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

N O M

N O

5. Cng thc thc nghm ca A l: FeC30H30Cl3N6O21 m = 3; n = 3 Cng thc ca phc: [FeL3](ClO4)3.3H2O T l cation v anion l: 1:3 6. S oxy ha ca Fe: +3 S electron d trong ion Fe ca phc: 5 Cu hnh spin cao: (t2g)3(eg)2 Cu hnh spin thp: (t2g)5(eg)0 Cu hnh ng: spin cao do c momen t tnh c da vo s e c thn l 5,92B.M cn spin thp l 1,73B.M. So snh vi ga tr momen t o c trong bng 2 ta rt ra c kt lun trn. 7. 450nm 8. 3,87B.M 9. CrC20H18N4Cl3O9 x=2

y=2 z=1 OLYMPIC HA HC QUC T LN TH 32:

Phc vung phng cis-diaminodicloroplatin (II) l mt dc phm quan trng iu tr ung th. 1. Vit cc ng phn cis v trans ca phc. Mt s ion cng c cng thc nguyn Pt(NH3)2Cl2. 2. Vit tt c cng thc c th c ca ion trn nhng phi tha mn cc iu kin sau: - C cng thc nguyn Pt(NH3)2Cl2. - Anion v cation phi c vit r v tt c phi c cu trc vung phng. - Anion v cation phi th hin c s tn ti ca mi phc platin (II) ring bit ca mi hp cht. 3. Lp 5d ca platin c bao nhiu electron? S tch mc nng lng trong gin nng lng obitan d ca phc vung phng lin quan n phc bt din do lien kt kim loi ligand: Nu cc ligand nm trn trc z bin mt m lin kt kim loi ligand vi cc ligand nm trn trc x v y tr nn mnh hn. 4. Trong s 5 obitan 5d ca platin, trong phc Pt vung phng th obitan no c mc nng lng cao nht?
BI GII:

1. Cng thc cu to cc dng ng phn ca phn t cis-diaminodicloroplatin (II): (1 im) H3N Cl Cl NH3 Pt Pt Cl NH3 Cl NH3 trans cis 2. [Pt(NH3)4][PtCl4]. [Pt(NH3)3Cl][Pt(NH3)Cl3] [Pt(NH3)3Cl]2[PtCl4]

[Pt(NH3)4][Pt(NH3)Cl3]2 3. 8 4. 5d x 2 y 2 . Trong phc t din 4 ligand u nm trn ng phn gic ca hai trc x v y.

Nu c y electron th mt electron s cao hn.

OLYMPIC HA HC QUC T LN TH 33: Phim en trng cha lp ph bc bromua trn nn l xenluloz axetat. 1. Vit phn ng quang ha xy ra khi chiu nh sng vo lp AgBr ph trn phim. 2. Trong qu trnh ny th lng AgBr khng c chiu sng s b ra bng cch cho to phc bi dung dch natri thiosunfat. Vit phng trnh phn ng. 3. Ta c th thu hi bc t dung dch nc thi bng cch thm ion xianua vo, tip theo l km. Vit cc phn ng xy ra. BI GII: h 1. Phn ng: 2 AgBr (r ) 2 Ag (r ) + Br2 / 2 Br 2. AgBr(r) + 2Na2S2O3 Na3[Ag(S2O3)2] + NaBr 3. [Ag(S2O3)2]3- + 2CN- [Ag(CN)2]- + 2S2O3-

2[Ag(CN)2]- + Zn [Zn(CN)4]2- + 2Ag+ OLYMPIC HA HC QUC T LN TH 36: Trong qa kh c mt s cng trnh v vic iu ch cc hp cht ca canxi ha tr 1. Mc d bn cht ca cc hp cht y vn cha c bit nhng chng to ra c mt s quan tm rt ln i vi cc nh ha tinh th. C th chuyn CaCl2 thnh CaCl bng: canxi, hydro, cacbon. 1. Vit cc phn ng xy ra. Cho CaCl2 phn ng vi Ca theo t l 1:1 ta ch nhn c mt cht mu xm khng ng nht. Nhn di knh hin vi ta thy c mt phn mu bc v tinh th khng mu. 2. Tinh th khng mu v phn c nh kim l ca cht no? Cho CaCl2 phn ng vi hydro nguyn t ngi ta thu c sn phm mu trng cha 52,36% Ca v 46,32% Cl v khi lng. 3. Xy dng cng thc thc nghim cho hp cht trn. Khi CaCl2 tc dng vi cacbon nguyn t ta thu c tinh th mu . T l s lng nguyn t xc nh c bng php phn tch nguyn t l n(Ca):n(Cl) = 1,5:1. Thu phn cht ny thi thu c sn phm nh thy phn Mg2C3. 4. a) Vit hai ng phn (mch khng vng) ca cht sinh ra khi thy phn. b) Vit phng trnh phn ng xy ra (gi s khng sinh ra CaCl) Khng phn ng no trong cc phn ng trn cho php ta xc nh c cu trc ca CaCl. C th gi thit rng CaCl c mng tinh th tng t nh cu trc tinh th n gin. Cho bit t l bn knh cation ca cc hp cht MX c cho bng: S phi tr ca M Hnh dng ca cc T l bn knh: Kiu cu trc Nng lng mng nhm X bao quanh rM/rX li ca CaCl LHo 3 Tam gic 0,155-0,225 BN -663,8 kJ.mol-1 4 T din 0,225-0,414 ZnS -704,8 kJ.mol-1 6 Bt din 0,414-0,732 NaCl -751,9 kJ.mol-1 8 Lp phng 0,732-1,000 CsCl -758,4 kJ.mol-1 5. a) CaCl c kiu cu trc tinh th no?. Bit r(Ca2+) 120pm; r(Cl-) 167pm Mun bit CaCl c bn nhit ng hay khng ta khng ch s dng LHo m cn s dng Hs. b) Tnh Hs ca CaCl vi cc s liu cho xc nh CaCl c bn nhit ng hay khng ta phi tnh Ho ca qa trnh 2CaCl Ca + CaCl2 (b qua S). 6. S dng tnh ton cho bit phn ng trn c xy ra hay khng? BI GII: 1. CaCl2 + Ca = 2CaCl. 2CaCl2 + H2 = 2CaCl + 2HCl 4CaCl2 + C = 4CaCl + CCl4. 2. Tiu phn c nh kim mu bc: Ca Tinh th khng mu: CaCl2. 3. n(Ca) : n(Cl): n(H) = 1 : 1 : 1 Cng thc thc nghim: CaClH Lu rng phn ng gia CaCl2 v hydro khng th no dn n CaCl m thay vo l hydrua CaClH. Cu trc ca hp cht ny c xc nh php phn tch ph tia X nhng phng php ny khng phi l mt phng php tt tm thy cc nguyn t nh nh hydro. Chnh v s bin mt ca hydro trn ph tia X m trong mt thi gian di CaClH b tng lm l CaCl.

4. a) Cc cu trc ng phn:
C H C C H H C C CH3

b) Cng thc thc nghim: Ca3C3Cl2. Lu rng: Nu t l s nguyn t n(Ca):n(Cl) = 1,5:1 (hay tt hn l 3:2 v c th vit li l CaCl2.2Ca2+ = Ca3Cl44+) v sn phm kh phi cha anion C34- nn phi cn hai cation Ca2+ trung ho in nn chnh v vy nn cng thc Ca3C3Cl2 c chp nhn. 5. a) T l bn knh l r(Ca2+)/r(Cl-) = 0,719. Vy kiu tinh th s l kiu NaCl. b) Tnh nhit sinh ca phn ng hnh thnh CaCl da vo chu trnh Born Haber: LHo Ca+(k) + I1 Cl-(r) CaCl(r)

ECl

Hs Ca(k) Hthng hoa Cl(k) 0,5Hphn ly

Ca(r) + 0,5Cl2(k) Thay s vo ta tnh c: Hs = -231,9kJ/mol 6. 2CaCl Ca + CaCl2 c Hs = -332,2kJ/mol. Vy phn ng trn khng xy ra. OLYMPIC HA HC QUC T LN TH 37: S tng hp v xc nh tnh cht ca vng kch thc nano l mt lnh vc ang rt pht trin. Phng php Bruff Schiffrin tng hp vng kch thc nano (AuNP) da vo s bn nhit ng v bn khng kh ca AuNP ta c th iu ch AuNP dng a phn tn c kch thc nm trong khong t 1,5 v 5,2nm. Phng php ny c ni dung nh sau: Dung dch HAuCl4 c trn ln vi toluen trong dung mi tetra n octylamoni bromua. Dung dch thu c em trn ln vi dodecanthiol v c un nng vi NaBH4. Nhng ht AuNP mu ti c sinh ra v nm pha hu c. Sau 24 gi th dung mi toluen s c cho bay hi v khi rn thu c c ra vi hn hp dung mi etanol v hexan tch thiol. Cc ht AuNP c th c phn lp v ho tan tr li trong dung mi hu c thng thng m khng b phn hy hay t hp thun nghch (irrvesible aggregation). 1. Phng php ny cn s tip cn t trn xung hay t di ln? a) Tip cn t trn xung lm cho ht nano c kch thc nh nht. b) Tip cn t di ln c th bin cc phn t v nguyn t ring l thnh cu trc nano. 2. Trimetyl n octylamin bromua cn c th c s dng nh l mt cht chuyn pha. N c th chuyn AuCl4- t pha nc sang pha hu c. Tnh cht no gip cho n c th lm c iu ny?

a) Mt pha ca phn t mang in dng, u cn li mang in m. b) Mt pha c tnh a nc, mt pha c tnh k nc. c) Mt pha mang tnh axit, mt pha mang tnh baz. 3. Vai tr ca NaBH4 trong qa trnh iu ch ny l g? a) Tc nhn kh ha. b) Tc nhn oxy ha. c) Tc nhn trung tnh. d) Tc nhn to phc. 4. Nu ng knh trung bnh ca ht vng kch thc nano l 3nm th s nguyn t vng s l bao nhiu trong mi phn nano? (bn knh nguyn t ca vng l 0,144nm). Ch ra bng tnh ton a) 102 b) 103 c) 104 d) 105 5. Bng tnh ton hy ch ra phn trm s nguyn t vng trn b mt l bao nhiu v cho bit cu tr li no ng. a) 20 30% b) 40 50% c) 60 70% d) 80 90% BI GII: 1: b) 2: b) 3: a) 4: b) 4 3 V AuNP = . .rAuNP 3 4 3 V Au = . .rAu 3

r3 V N = AuNP = AuNP = 1000 = 10 3 r3 V Au Au 5: b) 4/3..rAuNP3 = 4/3..rAu3.NAu. Din tch b mt ca mt tiu phn nano cu vng: S = 4..rAuNP2 S = 4..rAu2.NAu2/3 NS SAuNP/.rAu2 = 4NAu2/3. P = NS/NAu = 4NAu1/3. NAu = 1000 P = 40% III. BI TO CHUN B CHO OLYMPIC HA HC QUC T: OLYMPIC HA HC QUC T LN TH 30: Mt c nghin cu sinh nhn mt l hng gm cc halognua kim loi kim nhng cc bnh u mt nhn tr mt bnh cha kali bromua. Phng th nghim ni c lm vic khng h c bt k loi ph k no v vy c dng ct trao i ion nhn bit cc mu halogenua kim loi kim mt nhn . Loi nha c chn l loi nha polystiren mng li kiu axit mnh, cha cc nhm axit sunfonic (-SO3H)

nn ch cc proton c th trao i. C phn tch c su mu kim loi kim (v c KBr kim chng phng php) theo cch sau: C cn 5,00 0,01g mi mu, ri ho tan vi nc ct trong ng ong 100mL. Cho 40mL mi dung dch qua ct; dung dch ra c thu vo ng ong c th tch 250mL, ra ct hai ln vi nc ct; dung dch ra ny c thm nc c 250mL. Trc khi mu k tip c cho vo ct, c ti to proton cho nha trong ct bng cch ra vi lng cn thit HCl 1M ri vi nc ct. C chun cc mu 50mL ca mi dung dch ra, lm ba ln vi dung dch NaOH (nng l thuyt 3,26.10-2M) dng cht ch th l phenolphtalein thu c cc kt qa sau: Mu th nghim Th tch chun trung bnh A 21,15 0,1mL B 29,30 0,1mL C 7,40 0,1mL D 21,20 0,1mL E 10,30 0,1mL F 29,15 0,1mL KBr 10,25 0,1mL phn tch cc kt qa ny ta c th gi thit rng: Mi mu th t >99% tinh khit. Mi bnh u y cht, khng b nhim nc v khng kh Khng c trng hp hai bnh cha cng mt kim loi kim halogenua; l ha cht ch gm florua, clorua, bromua v iodua, khng c hp cht ca atatin. a) Hy cho bit l do v sao phi tin hnh cc th tc nu trn? Vit phng trnh phn ng ho hc ca bt k phn ng no xy ra. b) Mu th no c th chc chn c nhn bit t s phn tch ny? Mu th no c th gii hn kt qa ch cn hai hoc ba kh nng? c) Dng cc dng c c trong phng th nghim: knh thy tinh, giy qy, dung dch natri pesunfat (Na2S2O8) trong mi trng axit v mt l cha dung dch h tinh bt c c th nhn bit c c su mu th. Khng cn bit kt qa th nghim ca c vi cc ha cht nu trn, hy gii thch lm th no vi cc vt liu trn l nhn bit c tt c cc mu th cha nhn bit c cu b). d) Tnh cht no ca kim loi kim halogenua ngn cn khng th nhn bit r rng mt s mu nhn bit bng k thut trao i ion dng y? Liu mt hiu ng nh th c phi l tr ngi ng k trong mt n lc tng t nhn bit mt s halogenua ca kim loi kim th MX2 chng hn? BI GII: a) Hin nhin, cn xc nh khi lng mol phn t ca mi mu th Mr(MX) bng cch trao i M+ vi H+ nh ct trao i ion v bng cch chun xc nh lng H+. Cc phn ng gm: M+ + [RSO3H] H+ + [RSO3-M+] H+ + OH- H2O b) Phn tch kt qa: S mol M+ trong 5g = s mol OH- .(250/50).(100/40) = th tch chun .0,326.5.2,5 M(r)(MX) = khi lng mu th (5g)/s mol M+ trong 5g Thu c cc kt qa sau:

Mu th nghim Mr(g/mol) D on cht MX c th l: A 58,01 NaCl(58,44); KF(58,10) B 41,88 LiCl(42,39); NaF(41,99) C 165,81 KI(166,00); RbBr(165,37); CsCl(168,36) D 57,88 NaCl(58,44); KF (58,10) E 119,13 KBr(119,00); RbCl(120,92) F 42,09 LiCl(42,39); NaF(41,99) KBr 119,71 KBr(119,00); RbCl(120,92) Cc kt qa trn cho thy, k thut th nghim hin nhin cha chnh xc c th xc nh r rng tng mui. V d: nu mi mu u khc nhau, nu bit c mt mu chc chn l KBr th khi y mu E chc chn phi l RbCl. Khi lng phn t ca RbCl ln hn KBr vy m mu E li c Mr hi nh hn da trn kt qa chun . Cn thy rng khi lng mol phn t qa gn nhau ca hai (c khi ba halogenua) ca kim loi kim loi tr kh nng xc nh A, B, C, D, F. c) Knh thy tinh: Cc mui liti ht m mnh, do li mt lng nh B v F trn cc knh thy tinh k cn s cho php xc nh liti clorua: n s ht m v chy ra (nho) trong mt thi gian ngn (tr khi khng kh trong phng th nghim qa kh). Giy qy: Ion florua l mt ion lin hp ca axit yu HF nn dung dch mui florua c tnh kim. Do giy qy s xc nh c dung dch long no ca B hoc F l NaF v dung dch long no ca A hoc D l KF. Pesunfat axit ha + h tinh bt: Pesunfat oxy ha I- thnh I2, to phc mu xanh thm vi h tinh bt. Nh vy, nu C l KI s cho mu xanh thm ca phc vi tinh bt. Pesunfat cng oxy ha Clhoc Br- nhng khng c ch th c trng vi h tinh bt nn tc nhn ny khng gip phn bit RbBr v CsCl (Tuy nhin, c th xc nh C vi cc phng php nu nn C l KI) Khng c php th tm NaCl: bng phng php loi tr, cht no trong hai cht A v D khng lm xanh qy tm l NaCl. d) iu ngn cn vic xc nh r rng cc halogenua khc nhau ca cc kim loi kim MX bng s trao i ion chnh l khi lng mol phn t gn trng nhau ca cc halogenua y. Nguyn nhn l v cc hp cht ny c hai tiu phn u c ha tr I, ng thi cc kim loi kim c s hiu nguyn t ch hn cc nguyn t halogen ng trc hai n v: do vy, bt i mt lp y ca kim loi (chng hn K Na) v thm mt lp y vo halogen (nh F Cl) s cho hp cht c khi lng phn t gn nh ging ht hp cht ban u. Cc halogenua kim loi kim th ni chung khng c tr ngi ny, nu cng xt nh trn: bt i mt lp y ca M (nh Ca Mg) v thm mt lp y vo halogen (nh F Cl) cho ra cc cht c khi lng phn t hon ton khc nhau (78,08 v 95,21 g.mol-1 theo th t cho CaF2 v MgCl2). OLYMPIC HA HC QUC T LN TH 30: S kho st cc phn ng to phc ca cc ion kim loi chuyn tip. Mn+ + mL- MLm(n-m)+ thng tr nn phc tp do s ccnh tranh ng thi ca cc qa trnh cn bng khc: v d nh ligand L- thng l baz lin hp ca mt axit yu nn nng ca n trong dung dch ty thuc nhiu vo pH. Trong trng hp ny, thng phi vit li hng s to phc ca cc kim loi chuyn tip m. n ML(m m ) + m = n M n + L bng cch thay [L-] bng L CT(L), trong CT(L) l nng tng cng ca L tt c cc dng trong dung dch (nh djang HL hay L- hoc MLi(n-i)+) v L l t l ca dng thch hp L- so vi L tng

[ ] [ ][ ]

cng. Phng php ny thng c dng, v d nh trong phn tch bng php o chun dng EDTA, v EDTA (H4Y) l mt axit bn chc yu ch c kh nng cho phn ng to phc dng hon ton mt proton Y4-. Khi y: K a1 K a 2 K a 3 K a 4 Y 4 = 4 3 2 H + + K a1 H + + K a1 K a 2 H + + K a1 K a 2 K a 3 H + + K a1 K a 2 K a 3 K a 4 Vi Ka,i l hng s ion ha th i ca EDTA (vi tr s ln lt bng 1,02.10-2;2,14.10-3; 6,92.10-7 v 5,50.10-11). a) Xc nh cc tr s ca (Y4-) pH ln lt bng 2, 6, 10. Tnh nng d ca anion Y4- hon ton mt proton trong 500mL dung dch c cha 3,252g EDTA tr s pH nu trn. b) Hng s to phc KY cho s to phc ca Mn+ vi Y4-, c ga tr 6,3.1021 (Hg2+); 2,1.1014 (Fe2+) v 5,0.1010 (Ca2+). Ion kim loi no s tp phc vi EDTA c hu sut hn 99,9% trong dung dch c cha 5,00.10-3 M EDTA tng cng, c m vi pH l: i) 2 ii) 6 iii) 10 c) Ion thu ngn (II) Hg2+ c i lc mnh vi clorua:

[ ]

[ ]

[ ]

[ ]

Hg2+ + 4Cl- HgCl42Vi hng s to phc l Cl = 3,98.1015. Vi dung dch clorua 0,5M tng cng v 5,00.10-3M dung dch EDTA tng cng, hy xc nh t l thu ngn tn ti di dng ion t do, di dng anion tetraclorua v di dng phc EDTA ti pH bng: i) 2 ii) 6 iii) 10 (Nn ga thit rng nng kim loi tng cng rt nh hn 0,05M) e) Mt loi hn hng ch cha thu ngn, natri v canxi. Cho 5,218g mu ny tc dng vi mt tc nhn oxy ha thch hp ri pha thnh 500mL. Ly 25mL dung dch ny; m ti pH = 2,6; em chun vi dung dch 0,0122M dung dch MgY2-: tr s chun trung bnh l 44,19 mol.L-1. Khi ly 10mL mu dung dch, m ti pH = 9,5 c tr s chun 57,43mol.L-1. Hy xc nh phn trm khi lng ca thu ngn, canxi, natri trong hn hng. BI GII: a) Tnh c cc tr s sau: pH [Y4-](M) (Y4-) 2 3,712.10-14 8,26.10-16 -6 6 2,249.10 5,01.10-8 10 0,3548 7,90.10-3 Cc nng ca anion c xc nh nh CT(EDTA) = 0,02226M Mr(C10H16N2O8) = 292,25g.mol-1 b) Ta cn xc nh t l [MY2-]/[M2+], t l ny (nh xc nh hng s to phc) c tr s KY[Y4-]. Ta c th xc nh [Y4-] t x bit cu a. Tnh c cc tr s sau: pH [Y4-] [HgY2-]/[Hg2+] [FeY2-]/[Fe2+] [CaY2-]/[Ca2+] -16 6 2 1,856.10 1,17.10 0,039 9,28.10-6 6 1,1245.10-8 7,08.1013 2,36.106 562 -3 19 11 10 1,774.10 1,12.10 3,73.10 8,87.107 C th thy rng, ti pH = 2, ch Hg2+ to phc vi lng ng k; ti pH = 6, c Hg2+ v Fe2+ u to phc, trong khi ti pH = 10, c ba ion kim loi u to phc vi hiu qa cao.

c) Do HCl l axit mnh, cn bng gia Hg2+ v Cl- phi khng ph thuc pH; ta c th tnh c t s [HgCl42-]/[Hg2+] bng 2,488.1014 vi [Cl-] = 0,5M. Dng cc tr s [HgY2-]/[Hg2+] c c t cu b) ta tnh c: pH [HgY2-]/[Hg2+] %(Hg2+) %(HgY2-) %(HgCl42-) 2 1,17.106 4.10-13 5.10-7 >99,9 13 -13 6 7,08.10 3.10 22,2 78,8 10 1,12.1019 9.10-18 >99,9 2,2.10-3 d) Cc kt qa thu c t cu b) ch ra rng, ti pH = 2, s to phc EDTA ca Ca2+ l b qua c: ta c th gi thit iu y vn ng ti pH = 2,6; v nh th EDTA ch phn ng vi Hg2+ ti pH thp nh vy. Ti pH = 10, s to phc ca c Hg2+ cng nh Ca2+ l ng k, v ti pH = 9,5 s chun cho bit lng tng cng ca Hg2+ v Ca2+. Ta phi gi thit rng EDTA khng phn ng ng k vi Na+.Ti pH = 2,6, s mol Y4- = 5,391.10-4M S mol ny bng s mol (Hg2+) trong 25mL; nn s mol Hg2+ trong 500mL = 1,078.10-4 mol. V khi lng nguyn t ca Hg l 200,59g.mol-1, cho php xc nh khi lng thu ngn trong mu th l 2,163g. Ti pH = 9,5; s mol Y4- = 5,391.10-4 mol. S mol ny bng tng s mol (Hg2+ + Ca2+) trong 10mL, nn tng s mol (Hg2+ + Ca2+) trong 50mL = 3,503.10-2 mol, v v vy s mol Ca2+ trong 500mL = 2,425.10-2 mol tng ng vi 0,972g canxi trong mu th. Suy ra khi lng natri trong mu th (gi s khng ln tp cht khc) l 2,083g. Nh vy hm lng cc cht trong mu th l: Hg (41,45%); Na (39,32%), Ca (18,63%). OLYMPIC HA HC QUC T LN TH 30: S bc x kh nh knh (Greenhouse gas) l mt mi quan tm hng u v mi trung. S gia tng nng kh nh knh (CO2) trong kh quyn c ghi nhn vi thp nin qua. a) Ta s c lng s phn b cc kh nh knh trong kh quyn tri t bng cch gi thit rng nhng kh ny (CO2, hi H2O..) c khoanh vng trong tng c cao 10 11km (Cch m t nh th khng chnh xc, nhng c mc ch minh ho mt s khi nim). nh hnng ca tng kh - nh knh nh trn s ra sao i vi nhit kh quyn ti cao 5km? b) nh hng ca tng kh nh knh ln nhit kh quyn ti 15km. Gii thch mt cch nh tnh hiu ng ph ny ca tng nh knh (greenhouse layer). c) S bin i nhit ti phn thp hn ca kh quyn s nh hng ra sao n cn bng ca CO2 v ca H2O gia pha kh v pha ho tan trong nc? Liu s dch chuyn cn bng ca cc tiu phn ny, t n, c nh hng g n nhit ca phn thp hn ca kh quyn? d) Nay xt n tng cao hn tng nh knh l tng ozon. Ozon c to thnh cng nh b phn hy u do cc qa trnh quang ha (photochemical). ngh mt c ch gii thch s to thnh v phn hy ozon trong mt kh quyn cha oxy tinh khit. e) Entanpy to thnh ca O v O3 l Hof(O) = 249kJ.mol-1 v Hof(O3) = 143kJ.mol-1. Xc nh phtn vi di sng ln nht c kh nng quang phn oxy v ozon, theo th t. f) Trong vng cc, s tan r ca ozon ti tng bnh lu quan st c trong ma xun. Ngi ta ngh rng iu kin dn n s tan r tai ho ny (c bit di tn l thng ozon) ty mt s yu t, trong c cn bng sau: HCl(k) + PSC = HCl*PSC (1) ClONO2(k) + PSC = ClONO2*PSC (2) ClO(k) + ClO(k) = ClOOCl (3) PSC (vit tt ca Polar Stratospheric Cloud) ch my bnh lu ti cc vng cc to thnh t s ngng t hi nc v cc cht bay hi khc ti tng rt cao ny. S to thnh PSC thng xy ra

ti tng bnh lu Nam Cc trong ma ng v u ma xun, nhng t hn ti cc Bc v nhit khng qa thp. c bit rng s tan r ozon cng nghim trng khi cc cn bng trn di theo chiu thun. Cn nh rng s to thnh lin kt thng l to nhit, vy nhit s nh hng th no n cc cn bng trn? g) S to thnh ozon trong tng bnh lu ti cc Bc l mt hin tng c ghi nhn gn y: thot u, ngi ta hy vng cc Bc c min nhim vi s to thnh l thng ozon, nhng tht ra khng phi vy. Cn c trn cc thng tin c trn y, ngh xem l gii no c th ng tin cy c gii thch cho s pht trin l thng ozon ti cc Bc. i) Mc CFC trong tng bnh lu ti Bc bn cu gn y tng ln bng mc CFC m tng bnh lu ca Nam cc t trong thp nin trc. ii) S trn xung lin tc ca cc kh nh knh vo phn thp hn ca kh quyn cng lm gim lin tc nht tng bnh lu ti cc Bc. iii) S gia tng nng hi nc trong tng bnh lu ti cc Bc lm cho s to thnh PSC d dng hn trc y. iv) S gia tng lng phng x hng ngoi n tng bnh lu ti cc Bc gy ra s gia tng quang phn ca ozon ti cc Bc. BI GII: a) Cc kh nh knh lm nng h tng kh quyn, v mt s photon hng ngoi (IR) c ngun gc t b mt tri t l ra thot khi kh quyn li b hp th v bn tr li; s bn tr li v b mt tri t tng t nh khi bn i, lm cho h tng kh quyn nng ln. b) Cc kh nh knh lm lnh thng tng kh quyn: v c t photon hng ngoi n c cao ny t b mt, s hp th hng ngoi ny xy ra t cao 15km t hn l ra phi c. Hp th hng ngoi t dn n nhit gim. c) Cn bng xy ra l: V H2O(l) H2O(h). C hai cn bng ny u di theo chiu thun khi nhit tng: vy nng hi nc v CO2 s tng theo T. Do c hai u l kh nh knh, nn dn n hiu ng nh knh dng. d) Trong kh quyn oxy tinh khit, s hnh thnh ozon bng qa trnh quang ha dn n s quang phn oxy: O2 + h O + O (i) Sau : O + O2 O3 (ii) S quang phn cng ph hy ozon: O3 + h O2 + O (iii) (Mt qa trnh phn hy ozon khc c th l: O3 + O O2 + O2 (iv)) e) T entanpy to thnh cho sn (Hof(O2) = 0kJ.mol-1), tnh c entanpy ca phn ng (i) v (iii): Hoi = 498kJ/mol = 8,27.10-19J/phn t Hoiii = 106kJ/mol = 1,76.10-19J/phn t Vi E = h = hc/ ta c: 1 = 2,40.10-7m = 240nm 2 = 1,129.10-6m = 1129nm CO2(aq) CO2(k)

y l cc photon c di sng di nht c nng lng quang phn O2 v O3 theo th t (thc t, s quang phn c hiu qa ozon cn di sng ngn hn ga tr ngh, v nhng l do khng xt n trong phm vi cu hi ny). f) C ba cn bng ny khi xt theo chiu thun u c s to thm mt lin kt, nn nhit cao, cn bng s di qua tri v di qua phi khi nhit h thp. g) Ba gi thuyt c th b bc b nh sau: i. Khi nim rng mc CFC Bc bn cu t hn Nam Bn cu l iu khng tng: mc cng nghip ha mnh nht, v phng thch CFC nhiu nht l Bc bn cu (Thc vy, nng CFC h tng kh quyn l tng t nhau trn ton a cu: chng c trn rt u) iii. Trong khi s gia tng hi nc lm tng kh nng to PSC, khng c chng c g v s chuyn dch hi nc n tng Bnh cc Bc (c chng ch l chuyn n h tng kh quyn). iv. nh hng ca s gia tng nng cc kh nh knh (v chng vn ang gia tng!) l lm gim lng hng ngoi n c tng bnh lu. Ngoi ra d cc photon gn - hng - ngoi c nng lng cao hn mnh lin kt O2 O, chng thc s khng quang phn ozon. Gi thuyt ii) l cu tr li c ngha nht cc kh nh knh s lm nng h tng kh quyn v lm lnh thng tng kh quyn (Tuy nhin, iu khng c ngha l c ch ny l nguyn nhn ng thin nhin lun phc tp hn ta mong i). OLYMPIC HA HC QUC T LN TH 31: Tng hp mt hp cht ca crom. S phn tch nguyn t cho thy rng thnh phn c Cr (27,1%); C (25,2%), H(4,25%) theo khi lng, cn li l oxy. a) Tm cng thc thc nghim ca hp cht ny. b) Nu cng thc thc nghim gm mt phn t nc, ligand kia l g? Mc oxy ha ca Cr l bao nhiu? c) Kho st t tnh cho thy hp cht ny l nghch t, phi gii thch t tnh ca hp cht ny nh th no? V th cu to ph hp ca cht ny. BI GII: a) Cng thc thc nghim CrC4H8O5. b) T cng thc thc nghim CrC4H8O5, hp cht l [Cr(CH3COO)2(H2O)]. Nh vy, ligand l cc nhm axetat. Do nhm (CH3COO-) c in tch 1 nn mc oxy ha ca Cr l +2. c) Ion Cr2+ l h d4, ngha l h c 4e thuc obitan d. S phn b 4 electron phi thuc loi spin nng lng cao do ligand yu. Ch yu t ny cho thy [Cr(CH3COO)2(H2O)] c tnh thun t. Tuy nhin t cc kt qa thc nghim, hp cht ny li c tnh nghch t l do hp cht ny dng nh hp c cu to nh sau:

CH3 C OO OH2 O C H3C Cr C

CH3

O O Cr H2O

O O O C CH3

Trong cu to ny, hai nguyn t Cr to lin kt bn, bao gm mt sigma, hai pi v mt delta, vi bc lin kt tng cng l 4. S hnh thnh lin kt bn i hi tt c cc electron thuc obitan d u phi cp i. V vy da theo tnh cht t, hp cht dng nh hp l nghch t. OLYMPIC HA HC QUC T LN TH 32: Clorat v peclorat c s dng trong s ch to dim qut, pho v cht n. Bc th nht trong vic sn xut kali clorat l s in phn dung dch nc ca kali clorua. a) Vit cc phng trnh phn ng xy ra ti hai in cc. Cl2 c to thnh anot v OH- c to thnh catot b) Clo to thnh phn ng vi ion hydroxit to thnh clorat. Vit phng trnh phn ng. c) Hy tnh khi lng kali clorua v in lng (theo Ah, ampe gi) cn thu c 100g KClO3. BI GII: a) Catot: 2H2O(l) + 2e = 2OH-(aq) + H2(k) Anot: 2Cl-(aq) = Cl2(aq) + 2e b) Phn ng: 3Cl2(k) + 6OH-(aq) = ClO3-(aq) + 5Cl-(aq) + 3H2O(l) c) mKCl = 60,83g Q = 131Ah OLYMPIC HA HC QUC T LN TH 32: Mi trng d nhim ch lun l mt iu ng lo ngi. Trong c th con ngi, mc c hi ca ch c th c gim bt vi liu php chelat bng cch s dng cc ligand c tim nng hnh thnh cc phc Pb2+ bn c th c thn bi tit. Ligand EDTA4- c dng cho mc ch ny nh s hnh thnh phc [Pb(EDTA)]2- rt bn vng (hng s bn vng, K(Pb) = 1018M-1). Ligand c cung cp bng cch tim truyn dung dch Na2[Ca(EDTA)], mui natri ca phc canxi tng i km bn (K(Ca) = 1010,7M-1). S trao i ca canxi vi ch ch yu din ra trong mch mu. a) Mc ch c trong mu ca mt bnh nhn l 83g/dL. Hy tnh nng mol ca ch trong mu bnh nhn ny. b) Trong mt th nghim lm mu, ngi ta iu ch mt dung dch cha Ca(NO3)2.4H2O v Na2[Ca(EDTA)] c nng mi cht theo th t bng 2,5mM v 1,0mM. Thm Pb(NO3)2 rn vo t c nng ch tng ng vi nng ch trong mu bnh nhn nu trn. Hy tnh tr s gn ng ca t l [Pb(EDTA)]2-/Pb2+ trong dung dch thu c ti cn bng. Khng xt tnh cht axit baz ca cc tiu phn c lin quan v s thay i th tch dung dch coi nh khng ng k.

c) S bi tit ca phc [Pb(EDTA)]2- qua thn hin nhin l mt qa trnh bc nht theo nng [Pb(EDTA)]2- trong mu. Sau 2 gi, nng ca phc [Pb(EDTA)]2- trong mu ca hu ht cc bnh nhn thng gim 60%. Hy tnh chu k bn hy sinh hc ca phc [Pb(EDTA)]2BI GII: a) [Pb2+] = 83/(207,2.0,10) = 4,00M b) Xt phn ng: [Ca(EDTA)]2-(aq) + Pb2+(aq) [Pb(EDTA)]2-(aq) + Ca2+(aq) Vi hng s cn bng K = K(Pb)/K(Ca) = 107,3. Do kh nng to phc mnh v ion Ca2+ c d so vi tng lng ligand EDTA4-, hin nhin tt c ligand s ni kt trong phc ch hoc phc canxi. V [Pb(EDTA)2-] << [Ca(EDTA)2-] nn nng thc ca cc ion Ca2+ v [Ca(EDTA)]2s phi rt gn vi nng hnh thc v biu thc tnh K cho: Pb( EDTA) 2 Ca 2 + K= Ca( EDTA) 2 Pb 2 +

c) Nng ca phc [Pb(EDTA)]2- l 40% lng ban u sau 2 gi. Nh vy 0,4 = e-2k cho kt qu l k = 0,458gi-1. Nh vy ta c th tnh c t1/2 = 1,5 gi. OLYMPIC HA HC QUC T LN TH 32: Ureaza l mt enzym c cha niken lm xc tc cho phn ng thu phn ure (H2NCONH2) thnh ion amoni v ion cacbamat (H2NCOO-). Ion cacbamat b thu phn tip sau trong mt qa trnh t xy ra khng xc tc bi ureaza. a) Vit phng trnh phn ng thu phn ion cacbamat. b) Mi n v cu trc cp ba ca protein ureaza c cha hai ion niken(II). Nhng ion kim loi ny phi tr vi cc nguyn t cho tng ng nhnh ca cc aminoaxit trong cu trc cp mt ca protein. Hy vit cng thc cu to cc nhnh ca aspartat, histidin v khoanh trn nhng nguyn t ng vai tr cho ca mi nhnh. c) Hai tm niken (II) ca ureaza cng c ni li bng cc nhm cacboxylat cu ni v mt phn t nc cu ni. Nhm cacboxylat cu ni thuc nhnh ca lysin c chuyn thnh mt dn xut cacbamat. Hy vit cng thc cu to dn xut cacbamat ca nhnh lysin. d) Vit cu hnh electron ca ion niken (II). e) bit c mt s hnh hc phi tr ca niken (II). Trong hp cht phi tr bt din, cc obitan d c phn b gia hai mc nng lng. Hy cho bit obitan no trong s 5 obitan d chim cc mc nng lng theo th t cao hn hoc thp hn trong hnh hc bt din. Gii thch nh lng kt qa tm c bng cch so snh s phn b trong khng gian ca cc obitan d. f) Mt s phc ca niken (II) li c hnh hc vung phng, l c cu ch yu trong cc phc ca ion kim loi paladi (II) v platin (II). Hy v hai ng phn ca [Ni(SCH2CH2NH2)2] vung phng v ghi r ng phn no l cis hoc trans. g) V tt c ng phn hnh hc ca [Pt(NH3)(pyridin)ClBr] vung phng. BI GII: a) H2NCOO-(aq) + H2O(l) = NH3(aq) + HCO3-(aq) b) Cu to ca cc nhnh:

[Pb( EDTA) ] = K [Ca( EDTA) ] = 8,0.10 [Pb ] [Ca ]

2 2 2+ 2+

[ [

][ ][

] ]

O H2 C C O

H2 C

H N CH HC N

aspartat c) Cu to ca dn xut cacbamat:

H2 C C H2
2 2 6 2 6 8

histidin
OC O

H2 C C H2
2

H N

d) 1s 2s 2p 3s 3p 3d 4s . e) Mc nng lng cao hn d(z2) v d(x2 y2). Mc nng lng thp hn dxy, dxz v dyz. Trong mt trng ligand bt din, cc trc vung x, y, z (gc ti tm kim loi) c hng sao cho mi nguyn t trong 6 nguyn t lin kt thuc ligand phi nm trn cc trc ny. Nh vy cc electron ca cc nguyn t trong ligand hnh thnh cch sp xp cc in tch m quanh nguyn t kim loi. Cch sp xp ny c nh hng khc nhau trn cc obitan d khc nhau. Cc obitan dxy, dxz v dyz u c mt electron tp trung ch yu trong vng gia in tch cc ligand. Trong khi , cc obitan d(z2) v d(x2 y2) c mt electron tp trung trong vng gn in tch ca cc ligand hn so vi cc obitan dxy, dxz v dyz. Tng tc y electron lm tng nng lng ca cc obitan d(z2) v d(x2 y2) so vi nng lng ca cc obitan dxy, dxz v dyz. f) Cng thc ca phc:
H2 C H2C N H2 S H2 C S CH2 H2N C H2 H2C N H2 S

Ni

Ni
S

H2S N CH2 C H2

cis g) Cng thc cu to ca phc:

trans

H2N Pt Br

Cl N

H2N Pt Br

N Cl

NH2 Pt N

Cl Br

OLYMPIC HA HC QUC T LN TH 33: Mt vi tnh cht ca mt hp cht v c cha bit A c lit k di y:

A l mt cht rn mu trng hi vng, d chy ra v thng hoa khi un nng. A c khi lng phn t l 266. A phn ng mnh lit vi nc cho dung dch B. Khi mt dung dch hn hp gm NH4OH v NH4Cl c thm vo dung dch B th nhn c kt ta keo mu trng. Mt mu dung dch B phn ng vi dung dch hn hp nitric axit v bc nitrat cho kt ta vn cc mu trng C. Kt ta trng ny nhanh chng tan i khi thm vo dung dch NH4OH mc d khi ta cho d NH4OH th li xut hin kt ta trng D. Kt ta D c lc v ho tan trong NaOH thu c dung dch trong sut E. Khi cho kh CO2 li qua dung dch E th li sinh ra kt ta D. Cht A ho tan khng in ly trong ete khng ln nc. Khi dung dch ny phn ng vi LiH th s to thnh sn phm F. Nu dng d LiH th F s chuyn thnh G. a) Xc nh cht A. b) Xc nh cc cht t B n G v vit tt c cc phng trnh phn ng xy ra. BI GII: a) Trong bc th ba ca php phn tch ta thu c kt ta trng keo, iu ny chng t rng dung dch B c cha Al3+ v dung dch B cng to kt ta trng vi AgNO3, kt ta ny tan i khi ta thm NH4OH vo chng t rng dung dch B c cha Cl-. Vy cht A s l Al2Cl6 (MA = 266). b) Cc phn ng xy ra: Al2Cl6 + 12H2O = 2[Al(H2O)6]3+ + 6Cl6AgNO3 + 6Cl- = 6AgCl + 6NO3AgCl + 2NH4OH = [Ag(NH3)2]+Cl- + H2O Al3+ + 3NH4OH = Al(OH)3 + 3NH4+ Al(OH)3 + NaOH = Na+[Al(OH)4-] [Al(OH)4]- + CO2 = Al(OH)3 + HCO3Al2Cl6 + LiH = (AlH3)n + LiHd = LiAlH4 OLYMPIC HA HC QUC T LN TH 33: a) Nit c rt nhiu oxit. Mt trong s nhng oxit quan trng ca nit l NO2, mt kh mu nu rt hot ng ha hc. (i) V cng thc Lewis ca NO2 v hy xc nh hnh dng ca n da trn thuyt VSEPR. (ii) S dng thuyt VSEPR hy xc nh hnh dng ca hai ion NO2- v NO2+. So snh hnh dng ca hai ion trn vi NO2. b) Xem xt hai hp cht khc ca nit l trimetylamin (Me3N) v trisiliylamin (H3Si)3N. Gc lin kt o c ca hai hp cht ny ln lt l 108o v 120o. Hy gii thch s khc nhau ny. c) By gi ta tip tc xt nit v bo triflorua. Nng lng lin kt ca BF3 l 646kJ/mol v trong NF3 l 280kJ/mol. Gii thch s khc nhau ny. d) Nhit si ca NF3 l 129oC trong khi vi NH3 l 33oC. Amoniac phn ng nh l mt baz Lewis trong khi NF3 th khng. Ga tr momen lng cc ca mi cht tng ng l 0,24D v 1,48D mc d flo c m in ln hn nit. Gii thch ti sao: (i) C s khc bit qa ln ca nhit si. (ii) Momen lng cc ca NF3 qa nh. e) Phn ng ca dung dch natri nitrat vi hn hng natri cng nh phn ng gia etyl nitrit vi hydroxylamin di s c mt ca natri etylat u cho cng mt sn phm. Sn phm ny l mui ca mt axit yu khng bn ca nit. Xc nh axit ny v vit cng thc cu to ca n. Axit

ny d dng ng phn ha to thnh mt hp cht c s dng lm nhin liu cho ng c phn lc. Vit cng thc cu to ca cht ny. BI GII: a) (i) S electron xung quanh nguyn t nit: 7 Vy NO2 c cng thc cu to: O N O Nhng theo thuyt VSEPR th do phn t c mt electron c thn nn do sc y ca electron ny vi hai cp electron lin kt nn phn t NO2 khng th c cu to thng nh trn m phi c cu to gc (132o). Nh vy cu to ca NO2 s l:
O N
132o

(ii) Xt NO2+: S electron xung quanh nguyn t N = 5 + 2 + 2 1 = 8 (Mi nguyn t oxy xung quanh gp 2e) Cu trc Lewis s l: O ::N::O Nh vy s khng c sc y ca cc eletron khng tham gia lin kt trn nguyn t nit. Hai lin kt sigma s c phn b ph hp nht l 180o lm gim ti a sc cng v gc cn cc lin kt pi th khng lm nh hng n hnh dng ca phn t. Vy NO2+ s c cu to:
O N
-

Xt NO2 : S electron xung quanh nguyn t N: 5 + 2 + 1 = 8 Cc cu trc Lewis ca NO2-:

O

O N O

115o

i vi NO2- th do cn mt cp electron cha lin kt c sc y mnh hn mt electron nn gc lin kt s gim xung so vi phn t NO2. b) Vi trng hp trimetylamin th dng hnh hc l thp tam gic bi v trn nguyn t nit c mt cp electron cha lin kt lm gc lin kt gim xung t 109,4o cn 108o:
H3Si N H3C H3C CH3 N SiH3 SiH3

Tuy nhin i vi (SiH3)3N th do c s tham gia ca obitan d vo lin kt, n s xen ph cng vi obitan p ca nguyn t N to cho lin kt N-Si c tnh cht gn nh ca mt lin kt i nn cp electron t do trn nguyn t nit s tr nn nh x v khng nh hng n dng hnh hc ca phn t. Kt qa l phn t s c dng tam gic phng vi gc lin kt l 120o.

obitan p day
obitan d trong N Si

c) C NF3 v BF3 u l nhng hp cht mang tnh cng ha tr. NF3 th dng thp tam gic tuy nhin BF3 th dng tam gic phng do trong lin kt B F c mt phn lin kt i (bi v c su xen ph gia obitan p ca bo v flo). Nh vy nng lng lin kt N-F phi ln hn B-F
F N F F F F B F

d) (i) Nhit si ca cc cht khc nhau tu thuc vo lin kt hydro. NH3 c to thnh lin kt hydro cn NF3 th khng. Kh nng ht electron v ca F rt cao nn lm gim tnh baz ca N trong NF3, chnh v vy NF3 khng phn ng nh mt baz. (ii) m in ca NF3 lun b hn NH3 do:

N H H H F

N F F

Chnh v tng cc momen lng cc ngc hng nh vy cho nn momen lng cc ca NF3 lun b hn NH3. e) 2NaNO3 + 8Na(Hg) + 4H2O = Na2N2O2 + 8H2O + 8Hg NH2OH + EtNO2 + 2NaOEt = Na2N2O2 + 3EtOH Na2N2O2 l mui ca axit hyponitr c cu trc nh sau:
HO N N HO OH N N OH

ng phn ca n l H2N NO2 (Nitramit) c cng thc cu to:

H N H N O O

OLYMPIC HA HC QUC T LN TH 34: Mt s ln cc qa trnh to thnh cc mui v cc tinh th c th c hiu ra bng cch xc nh nng lng vi cc m hnh ion n gin trong ion c bn knh n gin v in tch ca ion phi l mt s nguyn. M hnh ny c s dng m t s phn ly ca cc hp cht ion trong pha kh. Thng cc qa trnh phn ly u dn trc tip n cc nguyn t trung ho nhng nng lng phn ly c th c tnh bng cch ta gi s c mt qa trnh m trong cc hp cht ion b phn ly ra cc ion t do v tip theo l s trung ho in tch. chnh l chu trnh Born Haber. Nng lng lin kt, i lc electron v nng lng ion ha ca cc phn t hai nguyn t sau c cho sn di y: Nng lng lin kt ca KCl = -464kJ.mol-1 Nng lng lin kt ca NaCl = -423kJ.mol-1 Nng lng lin kt ca MgCl = -406kJ.mol-1 Nng lng lin kt ca CaCl = -429kJ.mol-1 i lc electron ca Cl = -360kJ.mol-1 Nng lng ion ha ca Na = +496kJ.mol-1 Nng lng ion ha th nht ca Ca = +592kJ.mol-1 Nng lng ion ha th hai ca Ca = +1184kJ.mol-1 a) Thit lp chu trnh Born Haber cho s phn ly ca NaCl thnh cc nguyn t v tnh nng lng phn ly ca NaCl. Gi thit rng lin kt l 100% ion. b) Thit lp mt chu trnh Born Haber cho s phn ly ca CaCl2 thnh ba nguyn t v tnh nng lng phn ly ca CaCl2, gi s rng di lin kt trong phn t ba nguyn t th ngn hn 9% so vi cc phn t hai nguyn t. BI GII: a) Chu trnh Born Haber cho s phn ly thnh cc nguyn t ca NaCl: NaCl Na+ + ClNa+ + Cl- Na + Cl Nng lng mt i bc 1 l 464kJ.mol-1. Nng lng thu vo bc 2 l (nng lng ion ha ca Na + i lc electron ca Cl)=136kJ.mol-1 Vy nng lng phn ly l 328kJ.mol-1. b) Chu trnh Born Haber cho s phn ly ca CaCl2. CaCl2 Ca2+ + 2ClCa2+ + 2Cl- Ca + 2Cl Nng lng lin kt ca Ca2+Cl- = -429.2/0,91 = -943kJ.mol-1. (Ga tr o c i vi CaCl l 429 nhng in tch ca Ca l +2 v di lin kt gim mt lng l 0,91 ln) Nng lng mt bc u = -(nng lng lin kt ca CaCl2) = 2.942 nng lng cp ha ca Cl-Cl Nng lng cp ha ca Cl-Cl = (429/2).(1/0,91) = 236kJ.mol-1. Vy nng lng mt i bc 1 s bng = +1650kJ.mol-1. Nng lng thu vo bc 2 s bng -(2 i lc electron Cl + tng nng lng ion ha ca Ca) = -1020kJ.mol-1. Vy nng lng phn ly s l: 630kJ.mol-1

OLYMPIC HA HC QUC T LN TH 35: Cc ion kim loi mang in tch 2+ trong dy u tin ca kim loi chuyn tip vi cc cu hnh d1, d2, , d9 to ra ch yu l phc bt din c cng thc chung l ML6 (L: phi t mt rng). Kho st tnh cht t ca cc phc ny ta c th chia ra lm hai loi. Mt loi c s electron khng tham gia lin kt bng vi s electron trong M2+(k) th phc ny c gi l phc spin cao v mt loi c s electrong khng tham gia lin kt nh hoc bng 0 th gi l phc spin thp. Nu s chnh lch gia hai mc nng lng t2g v eg l v nng lng cp ha l P. Hy d on cu hnh electron c bn ca cc phc trn. Bit rng nguyn l Aufbau v nguyn l loi tr Pauli u c tun theo. BI GII: d1 : tg1ego d2 : tg2ego d3 : tg3ego d4 : tg4ego (>P) hay tg3eg1 (<P) d5 : tg5ego (>P) hay tg3eg2 (<P) d6 : tg6ego (>P) hay tg4eg2 (<P) d7 : tg6eg1 (>P) hay tg5eg2 (<P) d8 : tg6eg2 d9 : tg6eg3 OLYMPIC HA HC QUC T LN TH 36: Canxi xianamit (CaCN2) l mt loi phn bn a nng v c tc dng tt. N c th c sn xut rt d dng t cc loi ha cht thng thng nh CaCO3. Qa trnh nhit phn ca CaCO3 cho ra mt cht rn mu trng XA v mt kh khng mu XB khng duy tr s chy. Mt cht rn mu xm XC v kh XD c hnh thnh bi phn ng kh XA vi cacbon. XC v XD cn c th b oxy ha to thnh cc sn phm c mc oxy ha cao hn. Phn ng ca XC vi nit cui cng cng dn ti vic to thnh CaCN2. 1. Vit tt c cc phng trnh phn ng xy ra. 2. Khi thu phn CaCN2 th thu c cht g? Vit phng trnh phn ng 3. Trong ha hc cht rn th ion CN22- c th c ng phn. Axit ca c hai anion u c bit (ch tn ti trong pha kh). Vit cng thc cu to ca c hai axit v cho bit cn bng chuyn ha gia hai axit trn dch chuyn v pha no? BI GII: T 1) CaCO3 CaO + CO2 CaO + 3C CaC2 + CO CaC2 + N2 CaCN2 + C Qa trnh trn c gi l qa trnh Frank Caro. Qa trnh ny rt quan trng trong k thut. 2) CaCN2 + 3H2O CaCO3 + 2NH3 3) Cng th ca hai ng phn l: HN = C = NH N C NH2 Hp cht u tin l axit ca anion cacbondiimit v hp cht th hai l xianamit. Cn bng s chuyn dch v pha to thnh hp cht c tnh i xng cao hn. OLYMPIC HA HC QUC T LN TH 37: Cc nguyn t kim loi chuyn tip c phn b rt rng ri trong v tri t. Rt nhiu trong s c rt nhiu ng dng trong i sng hng ngy, chng ta d dng bt gp chng mi lc mi ni nh: ng nc bng st, dy ng v cc chi tit t ng bng crom

Crom l mt kim loi mu trng bc, c tn bt ngun t ting Hy Lp chroma c ngha l mu sc do hp cht ca crom c rt nhiu mu khc nhau. Mu sng ca hp cht crom(VI) dn n nhng ng dng ca n lm cht mu trong mu v v knh mu. 1. Trong dung dch axit, th ion cromat c mu vng s chuyn thnh ion dicromat c mu cam. Vit phng trnh phn ng. 2. S oxy ha ca crom trong hai hp cht trn l bao nhiu? 3. y c phi l phn ng kh khng? Hy gii thch. 4. ng lc lm dch chuyn cn bng ca phn ng trn l g? 5. Vit cng thc khng gian ca CrO42- v Cr2O72-. BI GII: 1. 2. 3. 4. 5. 2CrO42-(aq) + 2H+(aq) Cr2O72-(aq) + H2O +6 Khng phi, bi v s oxy ha ca nguyn t kim loi khng thay i. Nng ion H+ (hay pH ca dung dch) Cc cng thc:
O Cr O O 2O O Cr O O Cr O O O 2-

IV. OLYMPIC HA HC CC NC TRN TH GII: OLYMPIC HA HC O 1999: Nguyn t X (c nhiu dng th hnh) c mt anion cha oxy ng vai tr quan trng trong nhum nc. m in ca n nh hn oxy. N ch to hp cht phn t vi halogen. Ngoi hai oxit n phn t cn c nhng oxit cao phn t. X codn coa vai tr rt quan trng trong sinh ha. Cc obitan p ca n ch c mt electron. 1. l nguyn t no?. Vit cu hnh ca n. X c th to c vi hydro nhiu hp cht cng ha tr c cng thc chung l XaHb; dy hp cht ny tng t nh dy ng ng ca ankan. 2. Vit cng thc cu to 4 cht u ca dy. Mt trong s 4 hp cht trn c ba ng phn lp th (tng t axit tactric) 3. Xc nh hp cht ny. Nguyn t X to c nhng axit c cha oxy (oxoaxit) c cng thc chung l H3XOn vi n = 2, 3 v 4. 4. Vit cng thc cu to ca 3 axit ny. nh du (du sao hoc mi tn) cc nguyn t H v ghi s oxy ha ca X trong cc hp cht ny. Mt hp cht d vng ca X, vi cu trc phng do J. Liebig v F.Wohler tng hp t nm 1834, c to thnh t NH4Cl vi mt cht pentacloro ca X; sn phm ph ca phn ng ny l mt kh d tan trong nc v phn ng nh mt axit mnh 5) a) Vit phng trnh phn ng. b) Vit cng thc cu to ca hp cht (NXCl2)3. Hp cht v c va nu trn c tnh cht khc thng khi b un nng: n si 256oC khi b un nng nhanh. Nu un nng chm n bt u nng chy 250oC; lm ngui nhanh cht lng ny th ta c mt cht tng t cao su. 6) Gii thch tnh cht c bit ny.

BI GII: 1) Photpho. Cu hnh [Ne]3s23p3 2) Cng thc cu to ca 4 cht u tin:

H H P H H H H P P H H H P H P P H H H P H P P H P H H H

3) 4 4) Cng thc cu to ca cc cht:

OH O
+1

OH H O
+3

OH H O
+5

OH

OH

OH

5) a) 3NH4Cl + 3PCl5 = (NPCl2)3 + 12HCl b) Cng thc cu to:

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

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

OLYMPIC HA HC O 2001: A. Thuyt Pauling Thm dung dch kali hydroxit vo dung dch nc ca Co2+, mt kt ta mu xanh c hnh thnh. Trong dung dch KOH c th s hnh thnh phc spin cao c s phi tr 6.

a) b) c)
B.

Vit phng trnh ion ca cc phn ng Cho bit tn ca phc Vit s lai ha cho phc v cho bit kiu lai ha
Thuyt trng phi t

Ion phc bis(terpyridyl)coban(II) tn ti mt phn trng thi spin cao, mt phn trng thi spin thp ph thuc vo cc ion lin kt trc tip vi nguyn t trung tm ClO4-/Cl-/NCS-/Br-. a) Cho bit ba dng hnh hc c th c ca phc b) Da vo thuyt trng phi t hy v gin obitan cho cc trng hp phc spin cao v thp c) Tnh momen t (M.B) ca cc phc trn Xt cc phc sau: [Co(CN)6]3-, [Co(CO3)2(NH3)2]-, [Co(CO3)3]3- and [Co(NO2)6]3-. Mu ca cc ion phc ny s l: xanh, vng, cam v da tri (khng nht thit l phi cng djng vi cc phc trn) d) Hy cho bit tn ca tng phc v xc nh mu ca chng: BI GII: A. Thuyt Pauling a) Co2+ + 2 OH- Co(OH)2 Co2+ + 6 OH- [Co(OH)6]4b) hexahydroxocobaltat(II) c) 3d 4s 2 3 Kiu lai ha: d sp B. Thuyt trng phi t: a) Bt din b) Ta c: eg 4p 4d

eg

t2g

Spin cao c) Phc spin thp: mag = B 3 = 1.73 B spin cao: mag = B 15 = 3.87 B d) Ta c bng:

Spin thp

t2g

Cng thc Tn gi Mu sc 3[Co(CN)6] Hexaxianocobantat(III) Vng 3[Co(NO2)6] Hexa-N-nitritocobantat(III) Cam [Co(CO3)3]3Tricacbonatocobantat(III) Xanh [Co(CO3)2(NH3)2] Dicacbonatodiamincobantat(III) Xanh da tri OLYMPIC HA HC O 2004: Kim loi A c tm thy trong t nhin di dng hp cht, ch yu l khong vt orthosilicat vi cng thc chung l Mx(SiO4)y, ngoi ra n cng cn c tm thy di dng oxit. Oxit cua n c nhiu dng th hnh v n thng c kt tinh dng n ta bin dng vi s phi tr7. nhit trn 1100oC cu trc tinh th ca n s c chuyn sang dng t phng. Trn 2000oC cu trc ca oxit s l lp phng bin dng. Kiu mng li ca dng sau cng ging nh mng kiu florit trong ion kim loi c cu trc lp phng tm din vi hng s mng ao = 5,07pm. Anion O2- chim cc hc t din. Cu trc trn c th c bn ha nhit phng bng cch s dng CaO. Khi lng ring ca oxit kim loi tinh khit (cu trc lp phng) l 6,27g/cm3

V cu trc mng c s ca oxit. Cng thc hp thc ca oxit. Cho bit s oxy ha ca kim loi trong oxit Trong orthosilicat th kim loi cng c s oxy ha nh trong oxit. Hy cho bit cng thc phn t ca orthosilicat. 5. Xc nh A 6. Vit cu hnh electron ca A. 7. Cho bit s phi tr ca cation v anion trong oxit. 8. Tnh i lc electron ca oxy trong qa trnh: O(k) + 2e O2Cho bit: HoS(A) = 609kJ/mol, In(A/An+) = 7482kJ/mol, Hophn ly (O2 2O) = 498kJ/mol U (oxit) = -10945kJ/mol, Hosinh(oxit) = -11000kJ/mol C hai bc iu ch kim loi ny. Bc 1: cacbon v clo s phn ng vi silicat nhit cao v s sinh ra clorua ca A (s oxy ha ca A trong clorua khng i) cng vi oxit cacbon v silic tetraclorua. Bc 2: clorua ca A s phn ng vi Mg sinh ra kim loi. Thu phn clorua s thu c oxit trn. 9. Vit cc phng trnh phn ng xy ra. 10. Vit phng trnh phn ng thy phn clorua ca A A c th to c cc phc cht bn vng vi cc halogen vi s phi tr 6, 7, 8 c bit. Chng ta s kho st phc [ACl2F4]m+/- vi s oxy ha ca A khng i so vi oxit. 11. Cho bit cng thc ca phc v tn ca n. 12. C bao nhiu cht ng phn ca ion phc (ng phn cu to v ng phn lp th). V cng thc cu to ca cc cht i nh. BI GII: 1. Mng tinh th oxit: Mn+ ; O2

1. 2. 3. 4.

2. Cng thc ca oxit: MO2 3. S oxy ho ca kim loi: +4. 4. Cng thc ca orthosilicat: MSiO4 5. Ta c: d = m(nguyn t)/V( mng) =

4.M M + 2M O
3 N A .a 0

3 d .N A .a 0 2M O = 91,22 g / mol 4 Vy kim loi l zirconi (Zr) 6. Cu hnh electron ca Zirconi [Kr]4d25s2. 7. S phi tr ca cation: 8 S phi tr ca anion: 4 8. Xy dng chu trnh Born Haber tnh v thu c kt qa l A = 628kJ/mol 9. Cc phng trnh phn ng xy ra l: ZrSiO4 + 4C + 4Cl2 ZrCl4 + SiCl4 + 4CO ZrCl4 + 2Mg Zr + 2MgCl2 10. Phng trnh phn ng thu phn: ZrCl4 + 2H2O ZrO2 + 4HCl 11. in tch ca ion phc: +2 Tn ca ion phc: diclotetraflozirconat: 12. S ng phn: 6 Mt cp ng phn i quang: Cl Cl F F

MM =

F Zr F F Cl F

F Zr F Cl

OLYMPIC HA HC O 2004: Polysunfuapolynitrua (polythioazyl) l hp cht c mu ng, n c tnh dn in rt tt v tr thnh vng dn di 0,33K. Hp cht ny c iu ch bng cch: Bc 1: iu ch disunfuadiclorua bng cch cho kh clo kh tc dng vi lu hunh nng chy 240oC. Bc 2: Disunfuadiclorua phn ng vi clo v amoniac trong CCl4 20 25oC thu c tetrasunfuatetranitrua (S4N4). 1. Vit cc phng trnh phn ng xy ra 2. Tetrasunfuatetranitrua c cu trc dng vng. Vit cng thc cu to ca n. Tetrasunfuatetranitrua dng tinh th c mu cam, trn 130oC d phn hy n khi va p v gii phng nguyn t. Trong sn phm c hnh thnh l hunh nitrua SN, n c th ng vai tr nh mt phi t trong phc [RuCl4(H2O)NS]-. 3. V gin MO ca SN 4. Tnh bi lin kt v momen t ca SN 5. Cho bit tn ca phc nu tn ca phi t SN l thionitrosyl Nu tetrasunfuatetranitrua c bc bo v v em nung nng n 300oC trong chn khng th ta thu c disunfuadinitrua. Hp cht ny tn ti lu di nhit thp v b polyme ha chm nhit phng to ra polythioazyl (SN)x. 6. S2N2 c tnh thm. V hai cng thc cng hng ca cht ny. 7. V gin Frost Musulin cho h thm v xc nh bc lin kt pi.

BI GII: 1. Cc phn ng xy ra: 2S + Cl2 = S2Cl2 S2Cl2 + 4NH3 + 4Cl2 = S4N4 + 12HCl 2. Cu to ca S4N4:
S N N N S S S N

3. Gin MO ca SN:
x*

y* 2p

z*

2p xb yb s* 2s 2s zb

sb

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

7. Gin Frost Musulin ca S2N2:

bi lin kt pi = 0,25 OLYMPIC HA HC O 2005: Nguyn t Me, c tn ca n thn sc p do s phong ph mu sc ca cc hp cht ca n nm nhm cc nguyn t d. Trong k thun th s iu ch Me bt u t mt trong s cc oxit A ca n. Qung tng ng cha oxit b oxy ha trong mt qa trnh nung chy sau cho phn ng vi mui ca kim loi kim v cui cng kim loi Me c phn lp bng cch ngm chit Oxit ca A cha 43,98% oxy v khi lng. Trong hp cht ny nguyn t Me cho s oxy ha l. Me c iu ch bng cch cho oxit A phn ng vi Canxi kim loi 950oC. 1. Hy s dng tnh ton xc nh nguyn t ny l nguyn t no? 2. Vit cu hnh lp v ngoi cng ca nguyn t trng thi c bn. 3. Vit cng thc v cho bit tn ca A. 4. Vit phn ng gia A vi canxi Trong qa trnh trn th nguyn t c ho tan vo trong NaCl nng chy ng vai tr nh cht in phn (phn lng cha ion Me3+). S dng mt hiu in th l 60V, kim loi tinh khit b kt ta in cc lm bng tantan. Trc khi in phn khi lng in cc ny l 500g. Sau khi in phn 16 gi th qa trnh in phn xy ra vi cng dng in l 50,0A. 5. Kim loi no catot v anot trong qa trnh in phn. 6. Tnh khi lng kim loi kt ta. Nu hiu sut ca qa trnh in phn l 90% 7. Tnh tinh khit (%) trong kim loi th s dng in phn Nguyn t Me c kiu mng tinh th lp phng tm khi. Khi nghin cu cu trc bng phng php ph tia X vi bc sng = 71,1pm th b nhiu x khi tip xc vi mt phng tinh th (111). Gc nhiu x o c c gii tr l 11,7o 8. Tnh hng s mng ao 9. Tnh bn knh nguyn t ca nguyn t Me. 10.Tnh t khi ca nguyn t Me un nng oxit lng tnh A vi dung dch NaOH c th ta thu c mui B (ng hnh vi mui ortho photphat) v kt tinh dng decahydrat. Thm axit mnh vo dung dch mui B bo ha, th anion s b proton ha cho ra dng axit lin hp. Nu tip tc thm proton khc th s dn n kt qa l s c s tch ra hai phn t nc. nu tip tc thm proton th mt cation C c mu vng s c hnh thnh. 11. Vit cng thc cu to ca mui B. 12 Cho bit cng thc ca cation C? Cation C c th b kh dn tng bc. Nu ln lt mt i mt e th mt cation D mu xanh da tri c hnh thnh, sau s l cation E v cui cng l cation F. Trong hai bc u tin th c s tch ra nguyn t oxy. Cc ga tr th kh chun ca cc bc c cp trn, k c th kh ca s kh to thnh Me c cho di (trong mi trng axit): E(C/D) = 1.00 V

E(D/E) = 0.359 V E(E/F) = -0.256 V E (F/Me) = -1.186 V 13. Vit cng thc cu to ca cc cation D, E v F . 14. Vit na phn ng ca cp oxy ha kh C/D. 15. V gin Frost ca cc tiu phn ca Me c cp trn. 16. Tiu phn no bn vng nht? 17. Di iu kin ca phn ng d ly th tiu phn no s phn ng? Nguyn t Me to ra cc hp cht phc c cc s phi tr v s oxy ha khc nhau. V d: 1) [Me(bipyr)3]+ 2) [Me(CO)6]3) [MeO(O2)2ox]34) [MeOCl2(N(CH3)3)2] 18. V gin MO cho phi t peroxo c hai rng. 19. Xc nh bc lin kt v tnh cht.t ca anion ny 20. Cho bit tn h thng ca cc phc s 2 v 3. 21. Xc nh s oxy ha ca nguyn t trung tm ca mi phc v ng thi da vo thuyt VSEPR xc nh dng hnh hc ca phc v t xc nh xem c phc no bt i xng. BI GII: 1. oxit A: 56.02% Me, 43.98% O 56.02 16 b Vi cng thc Me2Ob ta c: M ( Me) = . 43.98 2 b = 1, Me2O M(Me) = 10.19 g/mol (loi) b = 3, Me2O3 M(Me) = 30.57 g/mol (loi) b = 5, Me2O5 M(Me) = 50.95 g/mol: vanadi 2. Electron ha tr ca lp ngoi cng: 3d34s2 3. Cng thc phn t A: V2O5: vanadi(V)-oxide 4. Phng trnh phn ng: V2O5 + 5Ca 2V + 5CaO 5. catot: tantalum anot: vanadi khng tinh khit 6. Khi lng kim loi gii phng: I t M 50 57600 50.95 0.9 m= = 456 g = z F 3 96485 7. tinh khit: 91,2% 8. Hng s mng: a 71.1 1012 = d= 0 3 = = 175 1012 m 3 2sin 2sin11.7 3 175 1012 a0 = = 303 1012m = 303 pm 3 9. Bn knh nguyn t r = 3d/4 = 131pm 10. Khi lng ring: 50.95 2 2 m( V ) 6.022 1023 = 6.08 gcm3 = = a3 (303 10 10 )3 0

11. Cng thc ca B: Na3VO4.10H2O 12. Cng thc ca C: VO2+ 13. D: VO2+; E: V3+; F: V2+ 14. Na phn ng: VO2+ +2H++ e- VO2+ + H2O 15. Gin Frost:
0 0 1 2 3 4 5 6

V
-0,5

-1

VO2+
zE -1,5

-2

V2+
-2,5

VO2+ V3+
OZ

-3

16. Tiu phn bn vng nht: V3+. 17. Khng. 18. Gin MO:
2x* 2y 2z

2y 2xb

2z

2* 2b

19. Bc lin kt: 1. T tnh: nghch t 20. Tn h thng ca 2: hexacacbonylvanadat(-I)

Tn h thng ca 3: oxalatooxodiperoxovanadat(V). 21. Kt qa thu c cho bng: Phc S oxy ha Dng hnh hc [Me(bipyr)3]+ [Me(CO)6][MeO(O2)2ox]3[MeOCl2(NMe3)2] +I -I +V +IV Bt din Bt din Lng thp ng gic Lng thp tam gic

Tnh bt i xng

c Khng c C

OLYMPIC HA HC BUNGARI 1999: Theo l thuyt cng thc ca khong pyrit l FeS2. Trong thc t, mt phn ion disunfua (S22-) b thay th bi ion sunfua (S2-) v cng thc tng ca pyrit c th c biu din l FeS2-x. Nh vy ta c th coi pyrit nh l mt hn hp ca FeS2 v FeS. Khi x l mt mu khong vi brom trong KOH d th xy ra cc phn ng sau: FeS2 + Br2 + KOH Fe(OH)3 + KBr + K2SO4 + H2O FeS + Br2 + KOH Fe(OH)3 + KBr + K2SO4 + H2O Sau khi lc th cht khng tan c tch khi dung dch v: - Fe(OH)3 trong phn rn c kt ta li v nung nng chuyn thnh Fe2O3 c khi lng l 0,2g - Cho d dung dch BaCl2 vo pha lng c 1,1087g kt ta BaSO4. a) Xc nh cng thc tng ca pyrit b) Xc nh s oxy ha ca cc nguyn t tham gia vo qa trnh xc nh cht kh v cht oxy ha. c) Vit cc phng trnh ca hai phn ng trn, nu r cn bng electron. d) Tnh lng brom (theo gam) cn thit oxy ha mu khong. BI GII: a) n(S) = 1,1087/233,4 = 4,75.10-3mol; n(Fe) = 0,2.2/160 = 2,5.10-3mol n(Fe) : n(S) = 1 : 1,9 cng thc l FeS1,9 b) Fe2+; S1- ; Br0 Fe3+; S6+; Br1Fe2+; S2- ; Br0 Fe3+; S6+; Br1Fe2+; S1- ; S2-: cht kh; Br0: cht oxy ha Fe2+ - e = Fe3+ c) Fe2+ - e = Fe3+ 26+ S2 - 14e = 2S 15 2 S2- - 8e = S6+ 9 2 2 15 Br2 + 2e = Br- 2 9 Br2 + 2e = Br 2FeS2 + 15Br2 + 38KOH 2Fe(OH)3 + 30KBr + 4K2SO4 + 16H2O 2FeS + 9Br2 + 22KOH 2Fe(OH)3 + 18KBr + 2K2SO4 + 8H2O d) 2 x = 1,9 x = 0,1: 90% mol FeS v 10% mol FeS2 m1(Br2) = 2,7g m2(Br2) = 0,18g

m(Br2) = m1 + m2 = 2,88g OLYMPIC HA HC BUNGARI 1999: Ion nitrit l c t cho nhiu vi sinh vt v vy n thng c dng lm tc nhn bo qun trong cng nghip thc phm. Nhng c nhng vi khun Nibacter c th oxy ha tng hp ATP. Khi oxy ha xy ra cc phn ng sau: NO2- + H2O NO3- + 2H+ + 2e 81,06kJ O2 + 4H+ + 4e 2H2O + 316,52kJ a) Tnh lng ATP to thnh theo l thuyt nu khi chuyn 1mol ATP thnh ADP (v photphat v c) pht ra nng lng l 30,6kJ. b) Gii thch con ng m hydro v electron c chuyn t c cht ti oxy nhng c th eucariot ho kh. c) Gi tn qa trnh sinh tng hp to thnh nhng chui vi nng lng. Lng cc i ATP thu c l bao nhiu? d) S oxy ha sinh hc trong t bo eucariot v lin hp vi sinh tng hp ATP c thc hin u? e) ATP l loi hp cht ha hc no?. Vit cng th cu to ca ATP. BI GII: a) Phn ng tng hp khi oxy ha nitrit thnh nitrat l: 2NO2- + O2 = 2NO3- + Q Q = 158,26 - 81,06 = 77,2 kJ/mol Lng cc i ATP l: 77,2/30,6 = 2,52mol b) Do mt dy nhng cht mang trung gian trong chui h hp. c) Oxy ha photphoryl ha: Lng cc i ATP l 3 mol. d) Trong tinh th (mitochondria) e) Nucleotit to lp t nit, riboza v P: aenin riboza P P P: OLYMPIC HA HC BUNGARI 1999: Trong cng nghip, sn xut ng c tin hnh qua nhiu giai on, trong s c giai on gi l ng. N l hn hp ca CuS v FeS. Cho mt mu 4,1865g ng tc dng vi HNO3 c, cc qa trnh l: CuS + HNO3 = Cu(NO3)2 + H2SO4 + NO + H2O FeS + HNO3 = Fe(NO3)3 + H2SO4 + NO + H2O Khi thm mt lng d dung dch BaCl2, s to thnh 10,5030 gam kt ta. 1. Cn bng cc phng trnh phn ng trn, nu r s trao i electron v cn bng electron. 2. Phn trm mol ca CuS trong ng l bao nhiu?. 3. Tnh phn trm ca khi lng ng trong mu. BI GII: 1. 3CuS + 14HNO3 = 3Cu(NO3)2 + 3H2SO4 + 8NO + 4H2O S2- + 8e = S6+ 3 N5+ + 3e = N2+ 8 FeS + 6HNO3 = Fe(NO3)3 + H2SO4 + 3NO + 2H2O = Fe3+ Fe2+ - e 9e 1 = S6+ S2- + 8e N5+ + 3e = N2+ 3 BaCl2 + H2SO4 = BaSO4 + 2HCl 2. n(CuS) + n(FeS) = n(BaSO4) = 0,045mol (1)

m(CuS) + m(FeS) = 4,1865g (2) T (1) v (2) ta thu c kt qa: n(CuS) = 0,03 mol %CuS = 66,67% 3. %Cu = 45,54% OLYMPIC HA HC UCRAINA 1999: Hai cht A v B cha anion phc bt din c cng thnh phn nguyn t nhng chng khc nhau v momen t ( = [n(n +2)]1/2 trong n l s electron khng cp i): A = 0, B = 1,72D. Khi cho 20mL dung dch 0,1M ca A tc dng vi 1,3240g Pb(NO3)2 th to thnh 1,2520g kt ta trng v trong dung dch ch cn li mui kali. Khi cho 1,2700g FeCl3 vo mt lng d dung dch ca A th to thnh 1,6200g kt ta trng C (51,85% khi lng l st). Khi ra ngoi khng kh C tr thnh xanh l v chuyn thnh D. Dung dch ca B tc dng vi FeCl2 to thnh ngay mt kt ta xanh l E c thnh phn ging ht D. a) Cc cht A, B, C, D, E l nhng cht g?. Tnh ga tr ca n i vi cht B. b) Vit cc phng trnh phn ng. c) S khc nhau gia D v E l g ? BI GII: a) n(Pb(NO3)2) : n(A) = 1,3240/331:0,1 .0,02 = 2:1 Anion trong A l X42Pb2+ + X4= Pb2X -3 2.10-3 2.10-3 4.10 M(Pb2X) = 1,252/2.10-3 = 626 M(X4-) = 212 2Fe2+ + X4= Fe2X 0,01 0,005 n(FeCl2) = 0,01; M(FeX2) = 324 n(Fe) = 324.0,5185/56 = 3; C l Fe2[FeY6] 1,72 = [n(n+2)]1/2 n 1; = 0; Fe3+. Vy Y l CN; A l K4[Fe(CN)6]; B: K3[Fe(CN)6]; C: Fe2[Fe(CN)6]; D v E: KFe[Fe(CN)6] b) K4[Fe(CN)6] + 2Pb(NO3)2 = Pb2[Fe(CN)6] + 4KNO3 K4[Fe(CN)6] + 2FeCl2 = Fe2[Fe(CN)6] + 4KCl 2Fe2[Fe(CN)6] + 2K4[Fe(CN)6] + O2 + H2O = 4KFe[Fe(CN)6] + 4KOH K3[Fe(CN)6] + FeCl2 = KFe[Fe(CN)6] + 2KCl c) KFe2+[Fe3+(CN)6] v KFe3+[Fe3+(CN)6] ch l cng mt hp cht. OLYMPIC HA HC UCRAINA 1999: 83,3g mt hn hp hai nitrat A(NO3)2 v B(NO3)2 (A l kim loi kim th, B l kim loi d) c nung ti khi to thnh nhng oxit, th tch hn hp kh thu c gm NO2 v O2 l 26,88L (0oC v 1atm). Sau khi cho hn hp kh ny qua dung dch NaOH d th th tch ca hn hp kh gim 6 ln. a) A v B l nhng kim loi no?. b) Tnh thnh phn ca hn hp nitrat. c) Vit cc phng trnh phn ng. d) Nu nung nhit cao hn na th c th thu c nhng mui g?. BI GII: a) n(NO2 + O2) = 1,2mol n(O2) = 0,2mol n(NO2) = 1mol %NO2 = 83,3% v %O2 = 16,7% n(NO2) : n(O2) = 5 : 1 2Me(NO3)2 = 2MeO + 4NO2 + O2; n(NO2) : n(O2) = 4 : 1 O2 oxy ha BO thnh B2OX

2A(NO3)2 = 2AO + 4NO2 + O2 a a 2a 0,5a 2B(NO3)2 = 2BO + 4NO2 + O2 b b 2b 0,5b 2BO + (x 2)/2O2 = B2OX; n(O2) = 0,05mol b b(x 2)/4 b(x 2)/4 = 0,05 b = 0,2/(x 2) Me(NO3)2 NO2 M(trung bnh) = 167g/mol Vy M(trung bnh) ca c hai kim loi = 43g/mol Vy A l Canxi (Ca) (MA = 40g/mol) M(trung bnh) = 40a + b.MB/0,5 2a + 2b = 1 a = (1 2b)/2 = 0,5 0,2/(x 2) = (0,5x 1,2)/(x 2) 43 = (40(0,5x 1,2) + 0,2MB))/((x 2) .0,5)) x = 4; MB = 55g/mol Vy B l Mn. b) %Ca(NO3)2 = 80%; %Mn(NO3)2 = 20% c) Cc phn ng xy ra: 2Ca(NO3)2 = 2CaO + 4NO2 + O2 2Mn(NO3)2 = 2MnO + 4NO2 + O2 2NO2 + 2NaOH = NaNO2 + NaNO3 + H2O d) xCaO + MnO2 = CaxOx-1MnO3: manganat kim (1 x 4) OLYMPIC HA HC UCRAINA 1999: Cho 6,84g oxiclorua A(tinh th ) tc dng vi nc nng to thnh tinh th ngm nc B. Nung B thu c 4,64g C c mu vng. 300oC, C phn ng vi CCl4 cho 7,94g D mu tm. un nng D trong HI kh thu c bt E l mt cht nghch t, v nh hnh mu nu. a) Xc nh cc cht A, B, C, D, E bit rng ch c 1/3 s nguyn t iot trong E l to kt ta vi Ag+. b) Vit cc phng trnh phn ng. c) Vit cng thc cu to ca A v D. Nguyn t trung tm, c cc lin kt cng di vi clo l trng thi lai ha no?. d) Th ngh cu to ca E trng thi rn v gii thch v sao ch c 4 ch khng phi tm nguyn t iot tham gia phn ng trao i?. BI GII: a) 2MOxCln-2x M2On 68,4/(A + 35,5n 55x) = 4,64/(2A 16n) A = 50n 116x M2On 2MCl2 4,64.2/(2A +16n) = 7,94/(A + 35,5n) A = 30,67n 50n 116x = 30,67n n = 6x v A = 184g/mol Vy A l WOCl4; B l WO3.H2O; C: WO3; D l WCl6; E l [W6I8]I4 b) WOCl4 + 3H2O = WO3.H2O + 4HCl WO3.H2O = WO3 + H2O 2WO3 + 3CCl4 = 2WCl6 + 3CO2 6WCl6 + 36HI = [W6I8]I4 + 36HCl + 12I2

[W6I8]I4 + 4AgX = 4AgI + [W6I8]X4. c) Ion trung tm W cc trng thi lai ha sau: dsp3 (WOCl4); d2sp3(WCl6) OLYMPIC HA HC C 1999: Nhng hp cht ha hc no c th c tng hp ch t khng kh (c xem l hn hp ca oxi v nit) v nc?. Bn hy vit cc phng trnh phn ng c cn bng. C th k n qa trnh nhiu bc, ngha l cc sn phm c th tng hp c t khng kh cng c th tip tc phn ng vi nhau. Nng lng, cc dng c bt k v cc cht xc tc thng dng c xem nh cho sn nhng khng phi l cc cht khc (nh ng, halogen) BI GII: Nc c th c phn tch thnh hydro v oxy nh in phn: 1. Nit v oxy tc dng vi nhau to thnh nit dioxit: N2 + 2O2 = 2NO2 2. Nit dioxit cn bng vi Nit tetraoxit: 2NO2 = N2O4 3. Tng hp amoniac: N2 + 3H2 = 2NH3 4. Oxy ha amoniac thnh nit monoxit: 4NH3 + 5O2 = 4NO + 6H2O 5. Tng hp dinit trioxit bng cch lm bo ho NO2 lng (hay N2O4) vi NO: NO + NO2(l) = N2O3. 6. Axit nitric: 2N2O4 + O2 + H2O = 4HNO3 7. Amoni nitrat: HNO3 + NH3 = NH4NO3 8. iu ch dinit monooxit bn cch un nng amoni nitrat: NH4NO3 = N2O + H2O 9. Kh oxy ca axit nitric to thnh hydroxilamin: HNO3 + 6H+ + 6e = NH2OH + 2H2O 10. Dn hn hp ng lng mol ca NO v NO2 vo dung dch amoniac to thnh amoni nitrit: NO + NO2 + 2NH4+ + 2OH- = 2NH4NO2 + H2O OLYMPIC HA HC C 1999: 420,0g mt hn hp gm (NH4)2CO3.H2O, FeCO3 v NaCl c un nng. Cht kh hnh thnh c lm kh v sau chim mt th tch l 124,0dm3 ( nhit 22oC v p sut 1021hPa). Cng khi lng ca hn hp c x l bng mt lng d axit clohydric long. Mt phn trm ca dung dch hnh thnh c chun bng dung dch kali dicromat 0,1M. Sau khi chun xong tn ht 27,2cm3. Bn hy tnh khi lng ca tng mui trong hn hp. BI GII: St cacbonat phn ly da vo phng trnh: FeCO3 = FeO + CO2 Amoni cacbonat hydrat phn ly theo phng trnh: (NH4)2CO3.H2O = 2NH3 + CO2 + H2O Mui n khng phn ly. Da vo nh lut kh ta c th tnh c ton b lng cc cht kh hnh thnh NH3 v CO2. Php chun cho ta lng Fe2+ v nh vy l c lng cacbon dioxit hnh thnh t st cacbonat. Ly tng lng cc cht kh hnh thnh tr i lng cht ny ta s c lng cc cht kh hnh thnh t

amoni cacbonat hydrat (bao gm 2/3 l NH3 v 1/3 l CO2). 1/3 lng cht cn li ny l lng cht amoni cacbonat hydrat. Bng cch nhn vi cc khi lng. Bng cch nhn vi cc khi lng mol tng ng ta c khi lng ca cc cht cn tm. Tng lng cc cht kh c hnh thnh c tnh theo pV = nRT n = 5,16mol Chun : 6Fe2+ + Cr2O72- + 14H+(nc) = 6Fe3+ + 2Cr3+ + 7H2O Lng cht dicromat trong mt mu th: 2,72.10-3 mol Lng cht st trong mt mu th: 6.2,72.10-3 = 1,632.10-2 mol Tng lng cht st: 1,632mol Tng khi lng st cacbonat: 1,632.115,86 = 189,1g Lng cht kh hnh thnh t amoni cacboant hydrat = 3,53mol Lng cht amoni cacbonat hydrat = 3,53: 3 = 1,18 mol Tng khi lng amoni cacbonat hydrat = 134,2g Tng khi lng mui n = 96,7g OLYMPIC HA HC C 2000: Ch c sn xut t loi qung hay gp nht trong thin nhin ca n: galen. Thnh phn chnh ca galen l ch (II) sunfua nhng trong qung vn cn nhiu thnh phn kim loi khc trong c ch nguyn t. iu ny rt cn thit xc nh tinh khit ca mu qung, n c tnh bi t l ca lng ch c mt dng nguyn t so vi tng lng ch c mt trong qung. Vic sn xut ch t qung galen c bt u t vic nung chy galen trong mt lng gii hn khng kh to ra ch (II) oxit v gii phng ra l hunh dioxit. a) Vit phng trnh phn ng. b) Ti sao vic phn ng xy ra vi mt lng gii hn khng kh li quan trng? c) Vi ch nguyn t th trong iu kin chuyn g s xy ra?. Hy vit tt cc phn ng lin quan. d) Hy vit phng trnh biu din s ph thuc lng ch c mt trong galen (dng PbS) so vi lng SO2 thot ra (o 298K v 101,3kPa) Ch (II) oxit hnh thnh trong iu kin trn li tip tc c kh bng galen nhit cao sinh ra ch lng v li tip tc gii phng lu hunh dioxit. e) Vit phng trnh phn ng xy ra. f) Ch r cht oxy ha. Mt mu gm 10,45g qung giu galen c phn tch xc nh hm lng ch. 2/3 mu c nung chy vi mt lng gii hn khng kh sinh ra PbO v gii phng 66,2mL SO2 (o 298K v 101,3kPa). g) Tnh s mol ch sunfua c trong mu galen ban u. h) Tnh tinh khit ca galen. i) Tnh khi lng ch oxit sinh ra. Lng ch oxit ny c nung chy vi 1/3 lng galen cn li. Ch lng sinh ra c lm lnh v em cn c 0,8663g j) Tnh % ch nguyn t trong mu. 100,0mL dung dch ch nitrat c pha ch chnh xc bng s mol ch c trong mu galen c cp trn. Sau ta thm dung dch NaOH 0,200M. Sau khi thm vo th ch hydroxit c kt ta v khi thm lng d NaOH th kt ta b ha tan tr li. Sau khi kt ta b ho tan hon ton ta thy tn ht 83,3mL dung dch NaOH. k) Bng nhng d kin cho. Hy s dng xc nh cng thc cu to ca phc ch.

BI GII: a) 2PbS(r) + 3SO2(k) = 2PbO(r) + 2SO2(k) b) trnh b oxy ha xa hn. c) 2PbO(r) + O2(k) = 2PbO2(r) d) n(PbS) = 0,0409.V(SO2) e) 2PbO(r) + PbS(r) = 3Pb(r) + SO2(k) f) Pb2+ l tc nhn oxy ha. g) 4,06.10-3mol h) 92,9% (93%) i) 0,605g j) 2,9% k) [Pb(OH)4]2- (n(Pb2+) : n(OH-) = 1 : 4) OLYMPIC HA HC C 2001: S kh ton phn l mt phn rt quan trng trong ha v c, cc tiu phn hu c nh etanol v andehit tng ng ca n l etanal c th tham gia vo phn ng kh. Axit ha dung dch c cha ion dicromat c th oxy ha c hai cht trn thnh axit etanoic trong khi anion dicromat chuyn v dng Cr3+. Dung dch bc nitrat trong amoniac ch c th oxy ho etanal to ra axit etanoic v trong qa trnh ny ion Ag+ b kh ha v Ag. Mt nh ha hc tr chun b 500,0mL dung dch hn hp gm etanol v etanal (cha bit c th lng ca mi cht). xc nh hm lng ca tng cht trong hn hp th anh ta truc tin phi tiu chun ha dung dch K2Cr2O7 0,05M sau axit ho bng cch chun n vi dung dch st (II) sunfat. Dung dch st (II) sunfat ny c chun b bng cch ho tan 7,43g FeSO4.7H2O vo lng chnh xc 100,0mL nc. 25,0mL dung dch ny phn ng ht vi 23,12mL dung dch dicromat v 22,45mL dung dch dicromat ny sau khi c tiu chun ha th phn ng ht vi 50,0mL hn hp etanol v etanal. Cui cng, mt lng d dung dch bc nitrat trong amoniac c thm vo 50,0mL dung dch hn hp etanol/etanal khc v nh ha hc ny nhn thy rng kt ta bc kim loi thu c l 0,234g. Ngi ny nhn thy rng by gi c d kin xc nh c hm lng etanol v etanal trong dung dch hn hp. a) Vit na phn ng ca cc qa trnh: i. S kh Cr2O72-. ii. S oxy ha etanol. iii. S oxy ha etanal. iv. S kh Ag+ v. S oxy ha Fe2+. b) S dng cc d kin phn trn hy cn bng cc phn ng sau: Cr2O72- vi etanol. i. Cr2O72- vi etanal. ii. Cr2O72- vi Fe2+ iii. Ag+ vi etanal. iv. c) Ti sao ta buc phi axit ha dung dch dicromat? d) Tnh nng ca dung dch K2Cr2O7 s dng trong php phn tch trn. e) Tnh s mol bc nitrat cn tm oxy ha etanal trong dung dch hn hp v t tnh s mol ca etanal trong 50,0mL dung dch hn hp ny. f) S dng cu e hy tnh nng ca ion dicromat cn thit oxy ha etanol trong 50,0mL dung dch hn hp.

g) Tnh hm lng ca etanol v etanal trong 500,0mL dung dch ban u. BI GII: a) i. Cr2O72- + 14H+ + 6e = 2Cr3+ + 7H2O ii. CH3CH2OH + H2O = CH3COOH + 4e + 4H+. iii. CH3CHO + H2O = CH3COOH + 2e + 2H+ iv. Ag+ + e = Ag v. Fe2+ = Fe3+ + e b) i. 2Cr2O72- + 3CH3CH2OH + 16H+ = 4Cr3+ + 3CH3COOH + 11H2O ii. Cr2O72- + 3CH3CHO + 8H+ = 2Cr3+ + 3CH3COOH + 4H2O iii. Cr2O72- + 6Fe2+ + 14H+ = 2Cr3+ + 6Fe3+ + 7H2O iv. CH3CHO + 2Ag+ + H2O = CH3COOH + 2Ag(r) + 2H+ c) Cn bng ca cc phn ng c s tham gia ca proton chuyn dch v pha tri. Chnh v vy, vic tng thm nng proton lm chuyn dch cn bng v pha phi. d) 0,0482M e) 0,00108mol f) 0,000720mol g) netanol = netanal = 0,0108mol OLYMPIC HA HC C 2001: Oxit c th c phn loi thnh oxit axit, oxit baz hay oxit lng tnh. Cc oxit ion u l oxit baz, n phn ng vi nc cho ra dung dch baz. V d nh Li2O: Li2O(r) + H2O(l) = 2Li+(aq) + 2OH-(aq) iu ny c gii thch l anion O2-(aq) c tnh oxy ha rt mnh v n d dng phn ng vi nc sinh ra ion OHO2-(aq) + H2O(l) = 2OH-(aq) Oxit ca cc phi kim l cc oxit axit: V d: CO2. CO2(aq) + H2O(l) = H2CO3(aq) Oxit cha cc nguyn t c trng thi chuyn tip m in u l nhng oxit lng tnh. N c y tnh cht ca oxit axit v oxit baz. V d: Al2O3. Al2O3(r) + 6H+(aq) = 2Al3+(aq) + 3H2O(l). Al2O3(r) + 2OH-(aq) + 3H2O(l) = 2[Al(OH)4]-(aq) a) Vit cc phn ng ca bari oxit v indi oxit vi nc (y l cc oxit baz). b) L hunh dioxit v trioxit u l nhng oxit axit. Vit cc phng trnh phn ng ca cc oxit ny vi nc. c) Trong cu b th axit no s c tnh axit mnh hn. Hy nu ra quy lut. d) Hy sp xp cc oxyaxit ca clo theo chiu tng dn tnh axit. e) Trong hai oxit ca thic l SnO v SnO2 th oxit no c tnh baz mnh hn. Gii thch. f) Beri oxit v asen(III)oxit u l nhng oxit lng tnh. Hy vit cc cn bng axit v baz cho mi cht. Cc peroxit(O22-), supeoxit(O2-) v nitrua (N3-) ion (ca kim loi) th hin tnh baz rt mnh khi chng phn ng vi nc v trong mi trng hp chng u sinh ra dung dch kim. Hydro peoxit l sn phm sinh ra khi cho peoxit v supeoxit phn ng vi nc, sn phm ph l oxy. g) Vit cc phn ng xy ra khi cho bari peoxit v kali supeoxit phn ng vi nc. h) Khi cc nitrin phn ng vi nc th ngoi dung dch kim ra cn thu c cht no? i) Tng t nh vy vi trng hp ca photphin. j) Trong hai sn phm hai cu h v i th sn phm no c tnh baz mnh hn. Gii thch.

BI GII: a) BaO(r) + H2O(l) = Ba2+(aq) + 2OH-(aq) In2O3 + 3H2O(l) = 2In3+ + 6OH-(aq) (hay In(OH)3(r)) b) SO2(aq) + H2O(l) = H2SO3(aq) SO3(aq) + H2O(l) = H2SO4(aq) c) SO3 c tnh axit mnh hn, nh vy H2SO4 c tnh axit mnh hn. i vi mt dy cc axit th axit mnh hn s l axit c nhiu nguyn t oxy gn vi nguyn t trung tm hn. Zumdahl gi thit rng iu ny xy ra do nguyn t oxy c tnh m in cao th c kh nng rt electron ra khi nguyn t trung tm v c lin kt O H. Kt qa l lin kt O H tr nn phn cc hn v yu i. Chnh iu lm tng tnh axit ca cc axit c cha nhiu nguyn t oxy lin kt vi nguyn t trung tm. Cng c th gii thch nh sau: S c s oxy ha +6 trong SO3 v H2SO4 cn trong SO2 v H2SO3 th lu hunh c s oxy ha +4. trng thi oxy ha +6 th lu hung c kh nng ht electron t cc nguyn t O ln cn. Nh vy lin kt O H s b yu i v tnh axit s tng ln. d) HClO < HClO2 < HClO3 < HClO4. e) SnO c tnh baz mnh hn. Do trng thi oxy ha +2 th Sn t c kh nng ht e cc nguyn t O ln cn hn l khi trng thi c s oxy ha +4. f) BeO(r) + 2H+(aq) = Be2+(aq) + H2O(l) BeO + 2OH-(aq) + H2O(l) = [Be(OH)4]2-(aq) As2O3(r) + 6H+(aq) = 2As3+(aq) + 3H2O(l). Al2O3(r) + 6OH-(aq) = 2AsO33-(aq) + 3H2O(l) g) BaO2(r) + 2H2O = Ba2+(aq) + 2OH-(aq) + H2O2(aq) + O2(k) 2KO2(r) + 2H2O(l) = 2K+(aq) + 2OH-(aq) + H2O2(aq) + O2(k) h) Mg3N2(r) + 6H2O(l) = 3Mg2+(aq) + 6OH-(aq) + 2NH3(aq) i) Na3P(r) + 3H2O(l) = 3Na+(aq) + OH-(aq) + PH3(k) j) NH3 l baz mnh hn, N c m in ln hn P nn nguyn t N trong NH3 s kt hp vi proton d dng hn nguyn t P trong PH3.