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BI TP C S HU C Nguyn Hu Hiu Cu 1: Hy dung hnh v m t s xen ph trc v xen ph bn ca 2 AOp vi nhau. Nhn xt v mc xen ph trong mi trng hp. Tr li Hnh v s xen ph ca 2 AOp: Xen ph trc:

Xen ph bn:

Cc vng c t mu en chnh l khong xen ph gia 2 AOp, da vo hnh v d dng nhn thy, mc d xen ph bn c ti 2 khong xen ph so vi 1 khong xen ph ca xen ph trc, nhng th tch xen ph ca xen ph trc li ln hn nhiu so vi xen ph bn. Cu 2: Hy nu s khc nhau gia lin kt pi v lin kt sigma. Tr li Lin kt sigma Lin kt pi S hnh c hnh thnh do s xen ph trc gia cc c hnh thnh do s xen ph bn gia thnh AO vi nhau. Cc AO c th tham gia s xen cc AO vi nhau. Cc AO c th tham ph trc vi nhau l: s-s, s-p, p-p, s-d gia s xen ph trc vi nhau l: p-p, d-d, p-d S i xng Lin kt sigma c s i xng dc vi trc Lin kt pi c tnh i xng khng i xng i xuyn qua tm ca 2AO tham thng nht (c ti liu coi nh khng i gia xen ph xng). N c trc i xng nhng li khng ni tam ca cc AO lin kt li vi nhau Nng lng Nhn chung l ln, n th hin trong cc Nhn chung l nh. Trong ha hc hu phn ng ha hc l: s ph v cc lin kt c, ph v loi lin kt ny ch cc ny thng rt kh. Nu tnh trong hu c, cc tc nhn nh HCl, Cl2, Br2dd ph v lien kt sigma cn c cc cht oxi ha rt mnh oxi ha ct mch phn t th mi ph v c lin kt ny. Gi tr nng lng lien kt ph thuc vo nguyn t tham gia hnh thnh lin kt. S lng 2 nguyn t lin kt vi nhau th ch c kh 2 nguyn t lin kt vi nhau c kh nng to ra 1 lin kt sigma nng to ra ti a 2 lin kt pi Cu 3: a) Phn bit lai ha v s xen ph b) Lin kt pi c th hnh thnh t Os vi AOp c khng? Tr li

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a) S lai ha cc obitan nguyn t l s t hp tuyn tnh ca 2 hay nhiu obitan trong nguyn t c chng y obitan lai ha ging nhau nhng nh hng khc nhau trong khng gian., cc AO tham gia lai ha phi l cc AO ca cng mt nguyn t, s lai ha mi l bc u ca s hnh thnh nn lin kt, m hon ton cha to ra lin kt. Cn s xen ph l s t hp nhng khng tuyn tnh ca 2AO ca 2 nguyn t khc nhau tao nn 1 vng xen ph vo to ra lin kt. b) Do AOs l AO c cu trc hnh cu, nn n c tnh i xng ton din, tc l n c v s trc i xng. Cho nn khi tham gia xen ph, nu l s xen ph hp thc ( tc l xen ph tao lin kt) th lun tn ti 1 trc ni lin tm ca AOs vi tm ca AO tham gia xen ph cn li, nh vy s xen ph ny l s xen ph trc nn s xen ph ca AOs lun to ra lin kt sigma m khng to ra lin kt pi. Hnh minh ha:

Cu 4: Hy so snh cc AO lai ha sp, sp2, sp3, s v p v hnh dng, nng lng v kh nng xen ph. Tr li V hnh dng AO lai ha sp3 AOs AOp AO lai ha sp AO lai ha sp2

Mt khi nim khc v lai ha cho ta c s so snh nng lng cng nh kh nng xen ph ca cc AO: l s tng tc ca cc obitan c nng lng gn ging nhau to thnh cc obitan mi vi nng lng thp hn obitan ban u v c kh nng xen ph cao hn khi lin kt. Vy: V nng lng Do AOs nm pha trong so vi AOp nn AOp s c nng lng ln hn AOs. M cc AO lai ha spx l s t hp tuyn tnh ca 1AOs v xAOp nn n c nng lng nm gia s v p. Obitan sp gm 2 obitan, c bn cht ca obitan s v bn cht ca obitan p Obitan sp2 c 1/3 bn cht ca obitan s v 2/3 bn cht ca obitan p Obitan sp3 c 1/3 bn cht ca obitan s v 2/3 bn cht ca obitan p T khng nh, v nng lng: : s< sp< sp2< sp3< p V kh nng xen ph: s < p < sp < sp2 < sp3 , c th gii thch bng th tch AO c th tham gia xen ph. Cu 5: a) V sao C khng s dng cc AO trng thi c bn tham gia lin kt?

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1) Hy k cc dng th hnh ca cacbon, hy cho bit trng thi lia ha v lien kt ca cc bon trong mi dng . Tr li a) Nguyn t cacbon khng s dng cc AO trng thi c bn tham gia lin kt l v: cc AO trng thi c bn s c mc nng lng hon ton khc nhau, s chnh lch ny xem ra l kh ln. Khi chng ta nhc ti vic to lin kt gia cc nguyn t thng qua cc AO th xem nh chng ta b qua thuyt v MO nn vic s dng thuyt VB y l hp l nht. Theo VB th mun to c 1 lin kt bn vng v nhit ng th c 3 iu kin : ng nng, xen ph tt, mt xen ph ln. C 3 yu t y u c tha mn khi ta dng cc AO lai ha to lin kt, v qua qu trnh lai ha cc AO t chnh lch nng lng s tr thnh ng nng lng, t khc nhau v mt hnh dng trong khng gian 3D thnh ging nhau v hnh dng dn n yu t xen ph v mt tha mn tt b) Cc dng th hnh ca cacbon l: Dng th hnh Cacbon v nh hnh Hnh minh ha Lai ha v lin kt Khng c cu trc r rng, nn khng th bit trng thi lai ha c

Kim cng

Lai ha sp3, mi nguyn t cacbon trong kim cng lin kt vi 4 nguyn t cacbon khc.

Than ch (Graphit)

Lai ha sp2, c cu trc lp

Fuleren (C60)

Lai ha sp2, c cu trc khp kn nh qu bng

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Mt s dng th hnh khc nh: Graphence, ng nano cacbon, Lonsdaleite, C540, C70 .v..v.. Hu ht u dng lai ha sp2, nhng chng c cu trc khc nhau dn n cc tnh cht vt l khc nhau, nn chung c coi nh cc dng th hnh khc ca cacbon. ng nano cacbon

Cu 6: a) V sao trong cc hp cht hu c, cc nguyn t C, N, O thng s dng cc AO lai ha tham gia lin kt sigma? b) D on gc ha tr COH ancol, COC ete, CNH v CNC ankyl amin. Tr li a) C th tr li tng t nh a cu 5 b) i vi nguyn t O trong COH v COC, nguyn t O ny trng thi lai ha sp3, cho nn ng ra gc COH v COC phi l 109,5 , tuy nhin do O cn 2 cp e cha tham gia lin kt nn theo thuyt sc y cp e th gc lin kt s b thu hp li v c gi tr khong 105 (nh gc HOH ca nc). Theo l thuyt l nh vy tuy nhin do gc COH trong ancol cn c 1 gc R nh vo C s chim 1 khong khng gian tng i ln, nn n s lm gin khong cch cc lin kt v lm cho gc lin kt ln hn 105 . V tng t, gc COC trong ete cn ti 2 gc R nh vo 2 C v s chim khong khng gian ln hn so vi 1 gc R ca ancol nn s lm gc lin kt tng thm mt cht na, nhng ni chung l gi tr gc lien kt ca 2 gc ny s dch chuyn trong khong 105 n 109,5 Tng t vi 2 gc CNH v CNC ankyl amin, N y lai ha sp3 nn gc lien kt ng nh l 109,5 , tuy nhin N cn 1 cp e cha chia s y gc lin kt thu hp li cn 107 (nh gc lin kt ca NH3). V tng t nh trn, gc lin kt ca CNH s nh hn CNC nhng nhn chung l dch chuyn trong khong 107 n 109,5 . Cu 7: Hy cho bit trng thi lai ha ca nguyn t in m trong cc tiu phn sau: a) CH3-CH=CH2 : t tri sang: C1: sp3, C2 v C3 l sp2 b) CH3-CH=O : t tri sang: C1: sp3, C2 l sp2 c) CH2=CH-CCH : t tri sang: C1 v C2: sp2, C 3 v C4 l sp d) O=C=O: C lai ha sp e) O=S=O : S lai ha sp2 f) H2NOH : N lai ha sp3 g) HO-CN: N trng thi lai ha sp h) H2C=C=O: t tri sang: C1: sp2, C2 l sp Cu 8: Da vo tnh cht ca lin kt, hy gii thch: -V sao ankan tng i tr v mt ha hc -V sao khng th Flo ha trc tip ankan trong iu kin thng Tr li - An kan tng i tr v mt ha hc l do trong phn t ankan, cc lin kt u l lin kt sigma, m lin kt sigma l lin kt c hnh thnh do s xen ph trc ca 2AO lai ha sp3 gia 2 nguyn t C v AO lai ha sp3 ca C vi AOs ca H. Nng lng ph v lin kt ny l tng i ln nn cc phn t ankan nhn chung l tng i tr v

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mt ha hc. ph v cc lin kt trong ankan phi dung cht oxi ha rt mnh nh Oxi. V khi Oxi ha nh vy s lm t mch Cacbon. -Khng th Flo ha ankan trong iu kin bnh thng l v Flo l cht oxi ha rt mnh, vy khi phn ng vi ankan n s c xu hng oxi ha ct mch ankan nn khng th Flo ha ankan c Cu 9: Nu trt t v nguyn nhn bin i di ca cc lin kt sau: a) C-C, C=C, CC, CN b) C-H, =C-H, -C-H Tr li a) C-C > C=C > CC > CN di lin kt gim theo bi ca lin kt. Cn CC > CN l do C v N chnh lch nhau v m in cho nn s lm lin kt mang mt phn bn cht ion nh vy s lm cho lin kt b gim i v di b) C-H < =C-H < -C-H y u l cc lin kt C-H, u phn cc v pha C. tuy nhin phn cc li khc nhau da vo lin kt cn li trong C. Nu cng khng no th cng c kh nng ht e, v nh vy cng lm cho lin kt phn cc, suy ra lin kt C-H phn cc theo chiu gim dn t C-H, =C-H, -C-H m di lin kt cng gim khi phn cc cng tng. Nh vy di lin kt s bin thin theo chiu nh trn. Cu 10: Hy gii thch v sao a) CO2 = 0 trong khi SO2 = 1,6D

b) CH2Cl2 > CHCl3 Tr li

a) Xt 2 phn t: * CO2, C y lai ha sp, gc lin kt l 180o. Ta c hnh v sau y:

2 vector 1 v 2 l 2 m-men lng cc cng phng ngc chiu v cng ln = CO = x. Ta c biu thc: Chiu ln
CO = 1 = CO CO = 0 CO 2 =1 + 2
2
2

trc Ox ta c:

* SO2, S y lai ha sp2, gc lin kt l 120o. Ta c hnh v sau y:

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2 vector 1 v 2 l 2 vector m-men lng cc c phng chiu v nh hnh v v ln bng nhau = SO =3,2D . Ta c biu thc: Chiu ln Ox c:

SO = 1 + 2
2

b) SO2 = 1 cos 2 = CO cos60o CO = 0,5.3, 2 3, 2 = 1, 6 D Da vo hnh v vo s t hp cc vector m-men lng cc thnh m-men lng cc ton phn gii thch iu ny:

CH2Cl2 CHCl3

Cu 11: Nu trt t v nguyn nhn bin i m-men lng cc v phn cc ha cc lin kt C-F, C-Cl, C-Br, C-I Tr li bin thin phn cc ha da vo chnh lch gia m in ca C vi nguyn t halogen cn li, nh vy n s bin thin gim dn t: kt C-F > C-Cl > C-Br > C-I. bin thin ca m men lng cc: M men lng cc c tnh bng cng thc: = .e.l trong : : m-men lng cc; e = 1,6.10-19 C, l in tch ht nhn hay % ion ca lin kt. Nh vy m-men lng cc ph thuc nhiu vo % ion v di ca lin kt.% ion cng ln th m-men lng cc cng ln v bn knh cng ln th m-men lng cc cng cng ln. % ion ph thuc vo chnh lch ca m in v di lin kt da vo bn knh ca 2 nguyn t tham gia lin kt. Trong cc lin kt trn u l lin kt ca C vi 1 nguyn t Hal khc cho nn ch cn so snh m in v bn knh ca cc ion halogen rt ra kt lun v s bin thin ca m-men lng cc. m in ca cc nguyn t Hal gim t F n I nhng bn knh li tng. Lin kt % ion Bn knh ion halogen M-men lng cc C-F 32,68% 1,36.10-10 m 7,1.10-30 C.m -10 C-Cl 11,25% 1,81 .10 m 3,258.10-30 C.m C-Br 6,42% 1,95.10-10 m 2.10-30 C.m -10 C-I 2,087% 2,16. 10 m 7,2.10-31 C.m

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Vy th t bin thin m-men lng cc l: C-F > C-Cl > C-Br > C-I. Cu 12: a) Hy nu s ging v khc nhau gia lin kt ion v lin kt VanderWaal b) Phn tch 3 loi lc tng tc hp thnh lc VanderWaal. Tr li a) Ging: u l lc ht tnh in gia 2 cu t Khc: Lin kt ion Tng tc Vanderwaal L mt loi lin kt hp thc c hnh Khng c coi l 1 lin kt c hnh thnh t lc ht tnh in gia 2 ion tri thnh t lc ht tnh in gia 2 phn m du to thnh 1 phn t thng nht, v in hn v dng in hn ca 2 phn t mang ngha ha hc. Nng lng ca hoc 2 u trong mt phn t. Lc tng loi lin kt l rt ln tc y l kh nh v khng mang ngha ha hc, ch mang ngha vt l

b) Tng tc VanderWaal gm 3 kiu tng tc: tng tc cm ng, tng tc nh hng v tng tc khuych tn. Tng tc nh hng: l tng tc gia 2 phn t c moomen lng cc khc khng, n cng mnh khi moomen lng cc cng ln v gim khi nhit tng, v s chuyn ng nhit ph v s nh hng gia cc phn t. Tng tc ny c tnh bng cng thc sau:

U dh =

2 4 (4 o ) 3kTR 6 1 . 2

8,854.10-12

Trong : : momen lng cc ca phn t k: Hng s bolzerman =1,38.10-35 T: nhit R: khong cch gia 2 phn t o : hng s in mi trong chn khng =

Nu =0 th khng c tng tc ny Tng tc cm ng: Khi cc phn t tng tc nh hng vi nhau n s lm bin dng phn t dn n tng tc b sung gi l tng tc cm ng. Cng thc:

U CU

2 2 = . (4 o )2 R 6 1

Trong l phn cc hay bin dng ca phn t, phn t c kch thc cng ln th cng d bin dng v tng tc ny cng ln. Tuy nhin hai tng tc ny cha gii thch c s ha lng v ha rn ca cc phn t c momen lng cc bng khng. Tng tc khuych tn: S chuyn ng khng ngng ca cc e trong phn t khng phn cc lm cho thi im trng tm in tch dng v m khng trng nhau, lc phn t c momen lng cc tm thi v to ra lc ht gia cc phn t. Kiu tng tc ny l tng tc khuych tn.

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Tng tc khuch tn c tnh bng cng thc:

U KT

3I1. 2 = . 2 (4 o ) 4 R 6 1

Vi I1 l nng lng ion ha th nht ca phn t Cc phn t c = 0 th ch c tng tc khuch tn cn cc phn t c > 0 th c c 3 loi tng tc

U KT + U CU + U DH =

A d6

Tng tc Vanderwaal lm cho cc phn t li gn nhau, nhng ch ti mt gii hn no khi m cc obitan ca cc phn t xen ph nhau th xut hin lc y v cc phn t trng thi cn bng. Lc y ny l s dng, n t l vi d-12. Vy nng lng ton phn gia 2 phn t khong cch d l:

U=

A B + d 6 d 12

Cu 13: Hy gii thch s bin i ca nhit nng chy v nhit si ca cc pentan ng phn. n-pentan sopentan neopentan Nhit nng chy -130 -160 -16,5 Nhit si 36 28 9,5 Tr li Cc phn t trn u l nhng phn t c = 0, gia cc phn t ny s hnh thnh lc ht vanderwaal da vo hiu ng khuch tn. Cho nn cng knh ca mch C s quyt nh nn ln ca tng tc cm ng v lc ht VanderWaal. Mch cng cng knh th lc ht VanderWaal cng mnh V cng knh ca n-pentan > isopentan > neopentan cho nn s bin i ca nhit si gim t n-pentan > isopentan > neopentan Tng t vi nhit nng chy. Tuy nhin c s bt thng vi isopentan. Isopentan c nhit nng chy cao bt thng, l do mng tinh th ca isopentan khi trng thi rn bn hn 2 ng phn cn li.Cho nn nng lng dung ph v mng tinh th ny cao hn v dn ti s tng bt thng v nhit nng chy cua isopentan. Cu 14: a) Trnh by bn cht ca lin kt Hirdro. Th no l lin kt hidro lin phn t, ni phn t b) Nu nh hng ca lin kt hidro lin phn t v ni phn t n nhit si, nhit nng chy v tnh tan trong nc ca cc hp cht, cho v d minh ha. Tr li a) Nguyn t hidro lin kt vi nguyn t ca nguyn t c m in ln nh O, F, N..c kh nng to lin kt ph vi nguyn t ca nguyn t khc. c gi l lin kt hidro. C 2 loi lin kt hidro l lin kt hidro lin phn t v lin kt hidro ni phn t. Nu nguyn t ca nguyn t khc trn l ca nguyn t khc th lin kt hidro

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l lin kt hidro lin phn t cn nguyn t thuc cng 1 phn t th gi l lin kt hidro ni phn t. VD: Lin kt Hidro lin phn t ca nc

Lin to

Lin kt Hidro ni phn t kt hidro c bn cht tnh in. Chng hn khi lin kt cng ha tr gia nguyn t hidro v nguyn t Flo trong HF th cp e lin kt s b lch nhiu v pha F, kt qu l F tch in m hn cn H ch cn tr c proton. Gia proton tch in dng vi F tch in m ca phn t HF bn cnh xut hin lc ht. Lc ht l lin kt hidro. Lin kt hidro th hin mnh nht trong cc hp cht ca F, O v yu hn trong cc hp cht ca N, Cl, S. b) Nng lng ca lin kt Hidro nh hn nhiu so vi lin kt cng ha tr. Nng lng ca lin kt hidro t gn 8 kJ/mol trong hp cht ca N v gn 40kJ/mol trong hp cht ca Cl. Tuy nhin nng lng ny ch gy nn s lin hp cc phn t to thnh ime v polime. Chnh s lin hp ny lm cho nhit bay hi, nhit nng chy v nhit si cao bt thng so vi hp cht cng loi VD: nhm IVA t CH4 n SnH4 nhit nng chy v nhit si tng theo kch thc v khi lng phn t, v cc phn t ny c = 0, nhng kch thc v khi lng phn t tng dn dn n nng lng lin kt VanderWaal tng. Khc vi nhm IVA, cc nhm VA,VIA, VIIA, t hp cht th nht n hp cht th 2 nhit nng chy v nhit si gim, tip theo li tng dn, v cc hp cht u ca cc nhm u l: H2O, HF, NH3 c lin kt Hidro gia cc phn t nn dn n nhit si cao bt thng ca cc hp cht ny. HF tan trong nc theo t l bt k, NH3 tan nhiu trong nc, iu ny l do s ng gp ca lin kt hidro to thnh t cc cu t em ha tan vi cu t dung mi l H2O.

Cu 15: Cho cc cht lng sau: C2H5OH , (C2H5)2O ,( C2H5)2CO , C6H5CHO , C6H5NH2 , (C2H5)3N , C6H5F a) Nhng cht no c to thnh lin kt Hidro.? V sao? b) Nhng cht no to c lin kt Hidro vi Metanol.? c) Nhng cht no to lin kt hidro vi axeton.? Tr li a) Cc cht to thnh lin kt Hidro l: C2H5OH, C6H5NH2, v ch c 2 cht ny mi c cc hidro

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linh ng to thnh cc lin kt hidro lin phn t gia cc phn t ca chng. Lin kt hidro ny c biu din nh hnh v:

b) Cc phn t to lin kt H vi methanol l: C2H5OH, C6H5OH, (C2H5)2CO, (C2H5)3N, (C2H5)2 O Tuy nhin c nhng phn t to vi methanol lc lin kt H mnh c phn t li yu

c) cc cht to c lin kt Hidro vi axeton l nhng phn t phi c Hidro linh ng l: C2H5OH, C6H5NH2

Cu 16: a)Hy biu din lin kt hidro methanol v phenol b) Dung dch phenol trong methanol c nhng loi lin kt hidro no? Loi no bn nht, km bn nht? Tr li

10

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a)

b) C 3 loi lin kt Hidro trong dung dch ny. L: lin kt hidro gia phenol v phenol, ga methanol v methanol, gia phenol v methanol.

Lin kt hidro gia 2 phenol l bn nht v lin kt hidro gia 2 methanol l km bn nht. Cu 17: Hy bit cng thc Niu-men cu dng bn nht ca cc phn t sau: ClCH2CH2Cl ClCH2CH2OH HOCH2CH2OH HOCH2CH2NH2 Tr li Cng thc Niu-men dng biu din 2 cu dng l cu dng xen k v cu dng che khut. Cu dng xen k bn hn cu dng che khut do trong cu dng che khut, cc nguyn t ca hai nhm che khut nhau. Do dn ti s tng tc ln nht gia cc nguyn t khng lin kt trc tip vi nhau. cu dng xen k, cc nguyn t ca hai nhm vo ch trng ca nhau. Cc nghin cu v nhit ng hc v quang ph cho thy phn t cu dng xen k bn hn cu dng che khut

11

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