,.

..

~

Rai 1-5:

Bai 6-14:

Bai 15-20:

Rai 21-34: che cac

Hili 35- 40:

Hili 41-50:

Rai 51-99:

Rai 100:

NQi dung

Danh phap hidrocacbon

M¢t so khai ni¢m C<1 beln : chi so octan; chi s6 axit, chi so xa phong hoa, chi s6 b~c cua nguyen tv cacbon; b~c cua ruqu, b~c clla amin; dong phan; d¢ linh dQng cua nguyen tlr hidro; tfnh baz<1 cua amin

C<1 che CLla the cua ank[m; philn lO1g c¢ng van anken; phim lrng the vao vang tham, phim lrng este hoa. Cau t<:t0 cua monosaccarft; disaccarft

Nh~n biet cac chat; phan tach hon hqp; s<1 do dieu

che1t hUll C<1

M(>t so bai trac nghi¢rn

MlI0i bai t~p danh cho h9c sinh gibi

Cae bili loan hoa hCfU c<1

M<)t de thi ki~m tra

!lli.L Trinh bay nhung nguyen tac quan trf;mg nhat vi' each g'}i ten hidrocacbon

no ml;lch hi! va goc c,ia chung theo llJPAC.

LOi giai --.............~

1. Ten cua hidrocacbon no m~ch hrJ khong co nhanh

- Mn cMit dau c6 ten la metan. etan. propan. butan.

- Ten cac d6ng dfu1g cao hem g6m phAn n~n d~ chi r6 s6 hrc;mg nguyen ttr cacbon va phtln du()i "an" d~c tnrng chb ankan. ThlICmg c6 them tiep dau la "n" va

each ten m¢t g~ch ngan "-".

- Ten cua g6c hidrocacbon no kh6ng nhanh. hoa tri m¢t dlIQ'C thi€t l~p bang each d6i du6i "an" hidrocacbon tlI<mg U'ng thanh "yl". Vi the g6c lo~i nay duQ'c g9i chung l~ ankyl.

2. Hidrocacbon no m(}ch nhemh:,t ­Ch9n m~ch chinh la m~ch chua s6 11Iqng nguyen tlt cacbon nhi~u nha't. N€u :, cac m~ch c6 56 11Iqng nguyen tlt cacbon btmg nhau thl m'.lch chinh la ml;\ch c6 nhitu ~ m~ch nhanh nha't.

- Danh 56 thtl tt! nhfrng nguyen tlt cacbon cua m~ch chinh ttr dfiu nao g~n

m~ch nhanh va eho t6ng 56 cae s6 chi vj trf nhanh la nho nh{\'t.

- G9i t~n tmae he't g9i vi trio dO bOi va ten cua tUng IO<;li m~cll nhanh theo vtin A.B.C. ...sau do g9i t~n cua m~ch chinh c6 t~n cung bMtg du6i II an" . Chu y cae tie'p dftu di-, tri-, tetra- ... Kh6ng duqe dlIa vilo trlnh tl! chft cai khi g9i ten. Khi viet ten thi cac 56 chi vj trf cach nhau m¢t dau ".", cae s6 chi vi tri cach tl1 chi ten ml?t net g~eh

ng~n "_",

- Ne'u g6e co m<.teh nhanh phl,l thl khi gQi t~n g6c ciing ti€n h?mh cae buC1c nhu tr?n. nhl1ng 56 ttl tl! cacbon cua g6e dlIQ'C d:inh bat d1iu ttr nguyen tu cacbon lien ket vo; m~ch chinh.

3. Chll Y. -Ml)t 56 ten kh6ng h¢ th6ng nhl1ng IUPAC vAn cho dung

(CH)hCH-t.:::H) isobutan (CH)4C neopentan

(CH)2CH-CH2-CH) isopentan (CH)hCH-CH2-CH) isohexan

CHr0I-CH3 isopropyl CHrCHr CfI-CH3 sec-butyl

(CH))2CH-CH2­ isobutyl (CH3))C­ tert-butyl

N€u m6t d~n xu~t ella ankan c6 chua halogen(X), uhom nitro nhom amino viL c~c nbom ankyl tbl )chi goi t~n ta goi theo trioh ~: Tnr6c ti~o la halogen sau den ten nhom NO:!. ti€p d€n NH l . r6i den t~n cac g6c ankyl xep theo v~Jt~hM' caiLeu6j cling den t~n mach chinh v{ri du6i "ao"

ct.' z/ ,ht" 3 ..~'t~j 1

LOi giai.HfJi 2. ;r'~.'··~Ten nao cua hrm chat sau duac goi theo IUPAC. Gilli thich.

,:,y ., I 3, 2,5-Dimetylhcxan d, 3-Metylpentan '\,

b, 2,2,4-trimetylpcntan c, 4,4-Di£ropylheptan(\ Y'j s" l.~H.r' \ : r;! .. ,.CH)-CH2-CH2--CH2-CH-CH2-C-CH2-CH)

~ ~ 1- It; , ,I I 1

C, 2,4-Dimetylhexan f, 5-Isobutyl-2- etylnonan CH3-CH2-CH-CH7 CH)

I ­ lIY~'1e~ CHJ :)I(;Cl

Bai4.-.-., ­a, 5-Butyl-3,7,7-trimctylnonan Trinh bay nguyen tde Cd ban glJi ten hidrocaebon khong no mCfch hu theo b, 5-Butyl-3,3,7-trimetylnonan 4r ; IUPAC. Chp thi dl;l minh hf10

c, 5-(2'-Mctylbutyl)-3,3-dimetylnonan

d, 5-(2'2'-dimctylbutyl)-3-metylnonan LUi giai

LUi giai Hidrocacbon kh6ng no la nhfmg hidrocacbon co chua li~n ket dOi ho~c li~n

"b" dung nhat thea IUPAC. Vi: Chat do co~ch m6i m~ch co 9 nguyen tti ke't ba giiIa nhiing nguy~n ttt cacbon VOl nhau.

cacbon: nhl1ng co m~ch chi c6 2 nhanh, co~h co 3'-nMI:!!l, cpn m~ch b "b" da 1, Ten cua Hidtocacbon mCJch ha co m¢t hay nhie'u no1 dbi: chon co 4 nhanh; tOng s6 cae s6 chi vi tri mach nhanh b "b" Iii 5 it 3 + 3 + 7 = 18 Iii TA' h'd b h' Ot h . b A' dA' ~t hl'.t t' A • ankh ~ h' . . ~n cua I rocac on c ua m., ai, a... nvl vi xu I P i1 tI kn cua an non fit. ttIcmg U'ng bllng cach thay du6i "an" bang "en" (n€u co m¢t n6i dOi); "adien" (n€u co1

hai n6i d6i); "atrien" (neu co ba noi dOi) ... , co kern theo d chii' s6 chi ro V! tn cua tUng noi dOi b~t dAu tu nguyen tu cacbon nao cua m~ch chfnh. M<;tch chfnh Iii m~chBfli 3. cacbon dili nhAt co chua nhieu n6i doi nhAt duqc danh s6 tu dau nao co the eho tcingIHay gf1i ten cae chat eho dum day thea lUPAC. s6 de s6 chi V! tn eua cae li~n k€t doi Iii nho nhat. Gic s6 chi vi tri cae n6i doi e6 th~

I d~t tnr6c ho~e sau ten eua m<;leh ehfnh. N€u co m~ch nhanh thi each d~t cae s6 chi V!

~HJ ~HJ CH)-CH2"" tri b phia sau ten m~ch chinh dUgc1SU dl;lng r¢ng rai han.

a) CH)-CH-CH2-CH2-CH-CH) . d) !/CH-C;:H3 l ;$" ~ CH)-CH2CH CH r ; I : (;/ (11/ III' Thf dy: CH2=CH-CHr CH=CH2 c6 the g9i pentadien-l ,4

" I J ( I i-IJ }" I

ho*c l,4~pentadienb) CH)-C-CH2-CH~CHJ e) (CHJ-CH2-tCH2)4C I ICHJ I. I , I" CH2=CH-CH2~C=CH2 ten thOng dl;lng han la 2-Metylpentadien-l,4

" ~,! II! i!/ I ('j' :' I ,I,

r I CH)v) \~(

I

If'l I1

r ,c) CH)-CH2"" ,I' '4 'll /CH) /CH-CH2-CH", I

! ~H) _~ :V _ICHJ ,CH) I­

I CH3-~-CH2-CH=CH-CH) 5.5-Dimetylhexen-2/,', ,1"" I /, I' ~H)

I

CH3f) CHJ-CH2-CH2-CH2-CH-CH2-CH2-CH " Cl-h ~ ( Ib_l]

- cae ttn khl'>ng h~ th6ng vAn dugc SlI dl;lng. Etylen CHz=CHz¢H~ CHJ

Allen CH2=C=CHz Isopren CH2=C-CH=CHz

I CH3

2. Hidrocacbon kh6ng no chua mcj( hay nhilr..: noi ba:

7

~--

III

,I,

i

I

i

,II

I :1

1\,

Twmg tlf nhl1 tcn clla 10'.li hidrocacbon CO chua lien ket d6i, chi vi~c thay du6i "an" clla ankan thanh "in" (m¢t n6i ba); adiin (hai n6i ba); atriin (ba n6i ba)...Cach danh s6 va each viet tl1ang t~t nhl1 hidrocacbon chua lien ket d6i. M~ch chlnh la m<;\ch chua nhi~u kien ket b¢i nhat. Hqp chat CH=CH theo h~ th6ng nhl1 v~y phai lA etin, \

nhlIng IUPAC vlin eho phep sir dl;lng ten kh6ng h~ th6ng la axetilen.

3. Tefl cua hidrocacbon co chLla cd lien kef d6i va lien kef ba:

M~ch chlnh la mqch chua nhi~u lil~n ket b¢i nh111. M~ch cacbon dl1qc danh F

s6 sao cho t6ng s6 cac 56 chi vi tri Clla cac n6i d6i va noi ba lil nho nhat. N6i d6i co; d¢ hem cap cao hem n6i ba, tuc la khi c6 st.J' Ilfa chQn thl uu tien d~ cho n6i d6i c6 s6 ' chi vi trl thap, ttn ciIa n6i d6i "en" gQi tru6c t~n n6i ba "in"; Vi trt cac lien ket viet·

ngay 'sau ten clla chung. '

432 1 g9i ten la Buten-l-in-3CH;;'C - CH=CH2Thf d':1: kh6ng gQi la Butin-l-en-3 ho~c Butin-3-en-l

6 5 4 3 2 1 gQi 13 hexadlen-l ,3-in-5CH~C -CH=CH-fH=CH2

CH -CH) gQi la 4-Etyl-3-propylhexadien-1 ,3-in-5 2

I ) 2 ICH=C-C==~-CH=CH2 kh6ng chQn m~ch c6 7 cacbon la m~ch

6 5 4 CH2-CH2-CH3 dai nhat lam m~ch chinh de danh s6 thll' til·

CH2-CH) ttt do gQi ten lil 3-Etyl-4-vinylhepten-3-in-lnhl1 : I 4 , --..CH::C-C=C-CH=CH2

I 2) 1Cl-h-CH2- CH3 5 6 7

4. Ten gqi ~~~a'goc-kh-6rig,1Ohoa trl m¢t.

Ten g6c hidrocacbon kh6ng no h6a tIi 1 dl1qc thiet l~p bang each them du6i "yl" vao ten clla hidrocacbon k.h6ng no tuemg lIng. Do v~y c6 cac ten chung la ankenyI (m¢t n6i d6i); ankinyl (m¢t n6i ba); ankadienyl (hai n6i d6i) ankadiinyl (hai n6i ba)... 56 thll' tlf caebon m~ch chlnh ella g6c duqc danh b~t dAu tir nguyen ttr

caebon c6 h6a tri tlf do.

cae ttn thubng: Vinyl CH2=CH- ; Allyl CH2==CH-CH­

150propenyl CH2=~H-

CH)

ThiJL.l:

CR=C- Etinyl CH 2==CH- Etenyl

3 2 1 CH3·-CH=CH- Propen-l-yl

321 ClbC-CHr Propin-2-yl

Bai 5.

Trinh bay nguyen tac g{)i ten Hidrocacbon m~ch Yang. Cho thE dlJ min} h{)a

LOi giai

1. Hidrocacbon dan yang:

Ten clla hidrocacbon dan yang no va kh6ng no, cling nhu t~n gQi cac g6c h6, tri m¢t tuang U'ng clla chung duqc gQi bang each them tie'p dAu xiclo- vao t~n ell;' hidrocacbon m~eh h6 co cung s6 luqng nguyen ttt caebol1 so v6i Yang.

Thfd':1:

6 I I o o o o Xic1opropan Xic10butan Xic10pentan Xiclohexan Xiclohexen Xiclohexadien-l,3

Ne'u co nh6m the lien ke't v6'i dem yang no thl s6 thli W cacbon trang yang duqc danh b~t dAu ttt m¢t eacbon co nhom the, sao eho t6ng s6 de chfr s6 chi vi trf lil nho nha:t.

Ne'u nhom the' lien ke't vrn dan yang kh6ng no thl s6 thli tt.J' cacbon cua yang phai danh b~t dt\u ttt eacbon ella lien ket d6i, ehi~u danh s6 phai di qua n6i d6i, sao eho t6ng 56 cae s6 chi vi trl clla nhom the la nh6 nhA't.

56 thll' tlf eacbon ella g6c hidrocacbon dem yang cung danh bAt dau ttt cacbon co h6a tri tJ,t do.

Thl dl):

\ ~CH)

V CH)

CH3

0CH'

CHXH)

lJ-CH2-CH)

l,l-dimetylxiclohexan 1,3-dimetylxiclohexan 3-Etyl-I,I-dimetylxiclohexan

Thl dy: :i''

cr~3 ~:;i

I8 6 6 ¢~ : 607~113 2 rf.:1

i CH)

6r1;l2 ~~f Xiclohexyl Xiclopenten-2-yl-1 I,

3-metylxicloh~ xen S 4 ) ~1 2,5-dimetylxiclohexa~ien-1 ,3 o sV)

108CH-CH) ,L.I2. Ten Clia hidrocacbon chu-a hai vong. /Ct:

9CH) CH) CH) l:' Hidrocacbon chua hai vong dl1qc gQi 13. Hidrocacbon bixiclic. pic f'p-Mentan p-Menten-l Norbommhidrocacbon bixiclic c6 chung nhau m¢t nguyen tll cacbon 0 m¢t m~t vang gQi Hi h~

spiro, ten cua lo~i nay dl1<;1c gQi b~ng each them tiep da.u spiro cung cac s6 chi s6 I"'>r"CH)111qng nguyen ttt cacbon am6i vang vao ten clla hidrocacbon m~qh hb c6 cung s6 I;,I",luqng cacbon. ) 6 )CHrf]2

6 ~~ ~~'i

Thid':l: :!j

CH) 7 4

i S I S

/~4,./j6 a-pinen Pinan Bonan tt~~6, 4<] f 4

2VC~ 'J

2 6 ) g 7 II

.1 , Bai 6.

5pirop¢ntan5piro[2,3Jhexan spiro[3,41sx: tan Chi so oclan lii

l gi? Niu khai qual m6i' liin quan gifia ch,' 56' oclan va ctfu

tf!.o cua hidrocacbon. Tt;li sao ngzrOi. ta noi rling Irong xang co chua chi?

P-:

.~~:

" b b" r ' chung du n6i dUC1C goi ten bc1lilg cach them tiep : LOi .•. cac hldrocac on IXIC!C ~o _ ' . . . b • !m6i cfiu theo thu ! g131. I~da.u "bixiclo" cung cac chii s6 chi ro 56 luqn,g nguyen t~ cac on C1

j b: A•

.. b h ho c6 cung s6 lucmg nguyen tu cac on. Sv tu nho dAn vao ten cua hldrocac on m~c dt( 'hA~" ,Thanh pha.n chinh cua cac loai nhien lieu long dung I cho cac dOng ca d6t'i . - 6 [ I va cach nhau mN aU C .u11 ,! _ "• 1. •

nay duqc d~t trong ngo~c vu ng ... . I ! trong, d¢ng ca dj~zen ... la h6n hqp nhieu hidrocacbon. Chi 56 octan la m¢t trong

2 1 2 ~

,] nhling tieu chuan d~ danh gia chat lU<;1Og cua xang, n6 d~c tnmg cho tinh nO cua

7 7 ;..' xang khi bi ncn. He;tp chat:<]D.'! 3 ~ : 6 ! CH)CO CD 3

6 5 4 5 '4J CH)-¢-CH2-yH-CH) 2,2,4-trimety1penta . I I CH3 CH3

Bixiclo[2.2.1 ]heptan Bixiclo[3.2.0}heptan Bixlclo[3.2.!_l]oc~an ,.' ~ •

, thu tu dl1<:1C danh b~t diiu tiI m¢t nguyen ttt cacbon b da.u di~ n61, dl qua ~ thuCmg gQi 1a iso-octan 1a lo~i nhien li~u t6t, chi n6 khi nen d~n CI!C d'.li va dU<;1c quy dc d~heo trl~h tv s6111qng cacbon giam dAn, sao cho nhling nguyen ttl cacbon c6:j116c c6 chi s6 octan Iii 100. Conn-heptan la lo~i nhien li~u t6i Ilh~t, khi b! nen nht? la

mach phu c6 s6 thu tV nhonhat.;da n6 va dU<;1c guy uoc co-chi s6 octan b~ng O. H6n hqp g6m iso-octan va n-heptan c6 . ~ieu hidrocacbon la tecpen rna IUPAC chap nh~n co th6 g<;>i ten thee h~ ~ chi s6 octan tu 0 d6n 100 tuy theo ti I~ ph1n tram cua iso-octan c6 trong h6n hqp ay.

th6ng ho~c thea ten thuCmg. f Ne'u_ ~,¢t lo~i ~ang nao do co C?I s6 oct~n bang 90 ch~ng_ h<;tn, thl l<?<:,i xang ,nay co l

! d~c diem n6 nhu m¢t hOn hqp g6m 90 % lso-octan va 10 % n-heptan.

: - Ok n-parafin co chi s6 oetan tha'p, m~ch cacbon dng dili chi 56 octan cang thap.

1110

iii

----

• •

M,.\ch hidrocacbon dug phrtn nhanh lhl chi 86 <.>clan cang c~o.

SI! co m~t CUEl nbi d6i lam taug chi so octan,nhfll 1a.khi ndi d6i avao phan o Hgiva cua m~ch cacbon. CII -O-C-R

0Ole cycloankan co chi s6 oclan cao han cac ankan tuang Ung. I z

II cac g6c R, R',.R" c6 th~

gi6ng nhau ho~c khacfH-O- C- R' Cac hidrocacbon tham co chi s6 octan d~c bi¢t CJf\. nhall.

CHz-0-~-R" C6 tht tham khao de kh~ng djnh cac ket lu~11 trcn thea bang sau: o Hidrocacbon Chi 56 octan Hidrocacbsm Chi s6 octan

n-Butan

n-Pentan

n-Hexan

n-Heptan

n-Oclan

2,3-dimetyl hexan

2,2,4-trimetyl hexan

(isooctan)

92

62

26

0

-17

79

100

2,2,3-trimetyIbutan

2,~;3,3-

tetrametylpentan

Heplen-l

IIeptan-2

Hepten-3

Xiclohexan

.benzen

p-xylen

112

125

54

70

84

78

102

100

D~u lhI!c v~t nhv driu dua, dfi~ ~~c .r. dtu IhuQc lo~i chal beo. Con dau rna h6i tran thong thuang ( nhv vazalin) la h6n hgp hidrocacbon. VI v~y chung co lhanh

phan h6a h9c hoan to?l.I1 khac nhau. Vi dftu th~rc v~t la este, con dflll boi tron IA hidrocacbon.

*- Trang chat beo chva tinh kJlict thuong co Ian m(lt IV~1Ilg nho axit cacboxylic tv do. ~gam KOH dn dlmg M trung hoa axit co trang m¢t gam

i chat ben g<;>i Iii chi s6 axit cua chatJ?eA ;

- Tclng s6 miligam KOB dn dllllg de (rung hoa'axit cacboxyhc tI! do va xa phong hoa hoan toan glixerit c6 trang mQt gam ch:lt beo dV<;1c g9i Ii\ chi so xii phong

, hoa.

- Chi s6 iot d~c tnmg cho mlre do kh6ng no clla chtlt beo S6 . 'I " . "" .,' . , " , . ' . i c(lng hqp voi'} 00 l chtlt be . I ,... , . ..: . gam lOt co t le

_ Khl chlIng cM dfiu mo ta thu dV<Jc cac lo"u xang co chva nhltu 10<;11 n- [ g 0 g91 achI s6 lot cu" chilt beo do.

parafin, chi s6 octan cU;l chung thtlp (tnvang khong Vllgt qua. 60) n~n chung d~ n6. i . *- Chat beo ran thvOng chua g6c axit no, con chat beo Ion thvOn chua '.l

Ngvoi ta lam tang chi s6 octan cua cpnng btmg .erich th~m vao xang cac chat khang ~ aXIl ~ong .no, do v~y ml.lc dfch quan tr9ng nhat ella vi~c hidro hO: chilt b~o r I~6c I n6.M¢t trong nhfrng chat khang n6 d~qcdung ph6 bien nhat 1a tetraetyl chi, chat nay:1 chuy~n chat beo long thanh chiit beo ran. a n lam

~ :

i khi dvg~ pha v_ao xfmg vm n6ng d¢'tU,.O,2 den,O,8 ml~ se Uu::, t~~g.chi s6 ~ta~,~ua~~8.1 ~~' ­I I xang tm 93 ho~c cao han. Tetraetyl chI dvgc dung dvm d~ng chM long ety1 g6m c6:~ .• •

tetraetyl chi (chiem 63%), dibrametan (26%);dic1oetan. (9%) va. phAro nhu¢m (2%)." h' ~~c cua n~IlY~~ t~ cacbon, clla ruflU, clla amin la gi? Cho bie! phuang Khi bi d6t thl chi trang xang bie'n thanh chi oxit kh6 bay hCfj deF. d6 ,d\.lflg;~ P ap hoa hfJc phan b'rf cac rUi;m co bl,ic khac nhau, cac am;n co bljc khac nhall.

dibrametan nhtIm ml}c dfch chuy~n chi oxit thanh chi bromuadt-Jxty h.criva th6at ra'£ LOi ghli. ngoai d¢ng ca, Vi cac 11 do tren nen trang xang luon luon c6 chu~ chi:

nai 7. B~c ella m<)t nguyen tu cacbon bang s6 IvO'ng nhfrng n J h k' lien ke"t truc tie m ~' , . guyen tu cac on hac

Chlft beD La gi? Dli'U thl!C vtJt, dau mil boi tron thong thuimg co thllnh pha'n . p v nguy n tv cacbon do.

hoa hqc gom nhiing gi? The' nilO Iil chi s6 axit, chi so xd phdng hoa vd chi so iot. Thf dl}: Trang hgp chat

cua chat bio. Cho hiet m~c dich cua qua trinh hidro h6a chat bio. 'r cae nguyen ttT caebon trang cac nhem CH)­CH3 dtu Iii cacbon bac 1.

Lffigiai I 2 I 3 4 j " ,

Cl-h-C-CHz-CH-CH Nguyen ttr cachon.s6 3 la bik 2.\,1 I , .

i '; CH3 eH3 Nguyen ttl cae bon 564 In bik 3. il *- Chftt beo 1a este cua g1ixerin ven cac axit c6 m<;\<:h cacqon dai nhu ~xit{ 'Nguyen tiI cacbon s6 2 la h~c 4.

I,

1,panmitic C lsH31 COOH, axit stearic Cl1H1SCOOH, axit oleic CI1H33COOH... (thvang);Chinh VI v~y rna ten g6c hidrocacbon sinh ra do m{(t nguyen tir hidro acaebon b~c 2,

i ~ oi la axit beo). Cong thuc t6ng quat chung 1a: ):b~c 3 ta them tiep d~u sec-, tert- vao t~n g6c ankyl. ( sec-, tert- xuilt phat ttr lieng g. !;Anh: Secondary, tertiary nghia la b~c 2, b~c 3).

, ::[!t l?

Theo d~nh nghia tren thl nguyen tll cacbon trong pMn tll metan c6 nguyen ttr CHJ-CH-CH) + HCI ~ CHrC,H-CH) + H20 philO U'ng sau

Jcacbon b~c kh6ng, nhung ta van guy uoc n6 c6 b~c 1. OH CI 5 phut

_Bac cua nrqu la b~c ella nguyen tv cacbon lien ket trlfc tiep ~61 nhom OH. Nhu the c6 nghia la neu nh6m OH lien ket vm nguyen tii cacbon b~d may thl b~e cua ZnCl,CHr CH2-CHr OH + HC} -~ kh6ng phein Ung ruqu 1ft ba'y nhieu.

Thl dl;J: Ru9U b~c I: CHJ-OH, CHJ-CH2-OH, CH2=CH-CH~OH - Amin la dAn xu~t eua amoniac trong d6 1, 2, h<ty d. 3 nguyen tii hidra cua Ruqu b~e 2:

amoniac bi thay th€ b~ng g6c hidrocaebon. B~e cua amin baAg 56 IU<;111g nguyen tiIOH I hidra eua amoniac da bi thay the, d6 cling ehinh la 56 lugng g6c hidrocacbon h6a tr~

CH3-CH-CH-OH3CH3-yH-CH3 , I lien ket tl}'c tiep v6i nguyen tii nita. OH CHJ

Ruqu b~e 3: H-N-H R-N-H R-N-H R-N-R" all I I I J L',OH I II H H R" R'CH3-CH2-y-CH3CH3-~-Cfl] CH3 1

} amoniac amin b~e I amin b~c 2 amin b~e 3CHJ 1 I

.De ph;.1n bi~t dic rl19U c6 b~c khac nhau ta co the oxi h6a cac nr<;1U bling CuO, sau d6 nghien CtIu san phfun t'.l0 ra; Neu ~an phfun t~o ra la andchit ho~e xct6n thl Dt phan bi~t cae amin e6 b~e khac nhau ta dung phan lmg eua amin v6j axit

1 nitrC1. 010 amin phan lIng v6i NaN02 va HCI anhi~t d¢'tLr DoC den jOe. Khi d6 amill ruau ban dAu Iii b~c I ho~c b~c 2. . 0; b~c 3 k.h6ng phan t1'ng, Amin b~c 2 t~o ra hqp eha"t N-nitrazo thuang la chat long to ~ mau vang, it tan trang nuoc.

R-CH - OH + CuO - R-C + Cu + H202 --'H

r R-CH 2 - C -CH 3 + cJ + H 0, ! R-~H + NaN02 + HCI R-~-N:::O + NaCI + H20 + euo 2R-CH2- CH -CH -­I 3 II R R

OH ° Hqp chat N-nitrolo

NeU nrqtl khOng bj CuO oxi hoa thl no la nr<;1U b~c 3. :

EPhuang phap n~u trcn xity ra ltiu, han nua b nhi~t d¢ cao thl cac chat hUll CO Amin b~c m¢t phein tlng t<;\o ra mu6i diazoni: co th~ tac dyng v6i CuO t~o ra CO2 va H20 theo phucmg tdnh phan Itlng chung:

aOC-5° C C"HyO + (2x+y/2-7,) CuO - x CO2 + yl2 H20 R-NH2 + NaN02 + 2 HCI ) R-N2+CI- + NaCl + 2 H 0

z I 2

_-~ Phucmg phap thu~n ti¢n va nhanh chong pha.n bi~t cae ruqu FO b~c khac nhau ~ Iii dl}'a vuo t6c d¢ philO tlng thay the nh6m -OH cua nrqu bang do trang phan tlng): . gifra n1qu voi dung dic~ ella ZnCl

2khan trang axit HC} d~ d~c. Khi d6 ruqu b~c 3~ Neu la amin b~c ,m¢t thl mu6i diazoni se phAn huy n a iai h' ,

ph (mg ilgay tuc khac, tao d~n xua't halogen lam van d~c dung dieh; rUqu b~c 21 t~o fa nrqu. g y g pong kh. N, va im ~ R-OH + N2 i +\ Phim~ung t~o ,a san phAm sau vai ph"t; Ruqu bac I kh6ng phan (mg. ! RN,Cl + H-OH HCI t '---.

~ CH3 CH3 I ZnClz I phan (rng ngay Neu la amin tham b~c 1 thi mu6i diazoni ben aO°C_ j0C, c6 th~ tic'n h?mh+ H20Cll)-C-OH I- HCI ---- CH)-C-C1 , I phim lIng ghCp d6i vm p-naphtoll'.lo ph~rn mau" C1I3 CH3

< "

+NaO +HP NuOH + Ar-N,Cl + ~ --+

~OH @X$lOH N=N-Ar

Mu6n phan huy mu6i diazoni tharn phiii dun n6ng nh<::. khi do thu dLIqc

~phenol, N2.

---1- ArOB + N2 + HCIAr-N2Cl + H20

Bai 9. • _ ' . . [' '? C ' .' [ . dong p'han Cho thi du minh hoa va chI TO ..

D6ng phan a gl. 0 may Of;ll • .'

III danh phtip ella chung.

I:: LOi giai ;: , ' if:11·'

I)- * D6ng phan la nhfrng hqp chat co cung eong thuc phftn tu nhung khae nhau .~ .I,ll': ' v~ clIng thue diu t~o nen tfnh eMit h6a h9c khac nhau.

Thi du: cac h<;1p chat CHr CH2-OH va CHrO-CH) la d6ng phftn ci\a nhau,vI

chung co cu~g eong thue phAn tir C2H60. ,

Vi cae d6ng phtln co cung .cong thue phftn t~ d~ d6 :0 kh6i lu~g phtln. tu ' h' 0' tha'nh ph~n dinh tinh va dinh luang phAn tram cae nguyen to nhu nh<1u.bangn au,c . . '

* Co hai 10'.li d6ng phftn chinh la d6ng phlln eau t~o va d6ng phan kh6ng gian.

D .' han call laO: La nhfrng dong pMn khac nhau ve trlnh n.r sap xe"p cac - ongp. , ., h' h d ' htl

, h a-c nh6m nguyen tv . Trong d6ng philn cAu t~o 1<;11 ehla t an ong p n nguyen tU o. . . ' h' h' h e . 'dA hAn lien ke"t·, d6ng phan ve mach cacbon; dong phan ve c uc oa g . VI tn; vng p a .

. Thi dl): CH CH -CH=CH va CH)-CH=CH-CH) chi khac nhau v~ vi tn lien r 2 2

k€t doi trong phAn tv. CH -CH -CH -OH va CHrCH-CH) chi khac nhau v~ vi tn cua nh6m OH

2 2) I OHi':,'

i i chung la nhCi'ng e*p d6ng ph:ln vi tn.

va CH3-CH-CH3CH3-Cl-h-CH2-CH3 CH3

CHz / " CH3-CH=CH2 va CH2-CH2

chung la nhtrng c~p d6ng phlln v~ m<;1ch cacbon.I;:

CH =CH-CH=CH2 va CHr CH2-C == CH la d6ng phan lien ket. 2

I,:: CH)-C=O va HCOOCH) va HO-CH2-C=O I I _ H H

)11:

In nhfrng h<;1p chat co cong thuc phftn tir ~H402 nhung khac nhau v~ 10'.li nhom chuc do do g9i la d6ng phtln v~ chuc hoa h9c.

- Dong phan klzong gian: La 10<;1i d6ng phan c6 tnnh tlf s~p xtp cac nguyen tv gi6ng nhau nhung chi khac nhau ve SIf phftn b6 cac nguyen tii xung quanh ph~ cU'ng nhk ho~c phfin bat d6i XUng cua phftn tir. D6ng phftn khong gian co hai lo~i chinh 13 d6ng phftn hlnh h9C va d6ng phAn quang h9C.

- Dong phdn hinh hQC: La cae d6ng phan khac nhau v~ sIf phan b6 cac nguyen ttt va nh6m nguy~n tl'r trong khong gian cua cae nh6m tht d6i v6i lien ktt doi ho~c d6i veJi m~t ph~ng clla yang ( trucmg hqp cac chit c6 cAu t~o Yang). G9i fa d6ng phtln hlnh h9C bbi VI sIf phftn b6 khac nhau se diln den khoang each giiia cac nh6m se khac nhau. D6ng phlln hlnh h9c thucmg g9i la d6ng ph~n cis-,trans-.

',., ,.". " •Neu co hal nhom nguy~n tu lI~n ket v6i hal nguyen tLI khac nhau cua m~eh

vang, thl dong phftn cis- dt chi d6ng phftn co hai nh6m phan b6 aeong m¢t phfa eila m~ll ph~ng trung blnh eua Yang. Nguqc I~i la dong phan trans-.

H]C~H~H]LAH] f~H] cis-l,4-dimetylxicIohexan trans-J ,4-dimetylxicIohexan

Xung quanh li~n ktt d6i C=C chi e6 d6ng phtln hlnh h9c neu m6i nguyen tv eacbon cua n6i doi lien ke't vO'i hai nguyen ttl ho~e hai nh6m nguyen tv khac nhau.

(ibC=C.cd ho~e abC=Cab

Neu m6i nguyen tii caebon deu can mC,'>r nguyen tl'r hidro thl din cu theo sl! phtln b6 eua hai nguyen tii hidro d6 acung phia hay khac phia xung quanh.lien ke"( doi rna ta c6 d6ng phan cis- hay trans-.

1

H" t. ~/H CH~ i- l/H

/ c = C=C >C '{ )~ va '-CI-h " If/ "C"'II -CHCHz-CH3 z 3

. \cls-penten-2 trans-penten-2

Neu khong the dl!a vao slf phAn b6 eoa cac nguyen tl'r hidro thl ta dlfa theo hai dAu ellll m'.lch chfnh trang anken duqc phan b6 acung m¢t phia hay khac phia ella n6i doi rna co tuang t'mg d6ng phAn cis- hay trans-.

Thi dt,J: \ 1 CH3-CH2" 2) 4 /CH2-CH]

C = C , _/ "S -' '1ell] CH2-Cl 12-CH] .......

~ Ne'u hai d6ng pha.n quang hQe khOng phai lit v?t va anh qua guuug rh~ng th1

g9i la 4-etyl-3-rnetyl-trans-heptcn-3 rn~c du hai nh6m gi6ng nhau a eung rn¢t phfa ~ 89i la d6ng pha.n qua~g hge khOng dOi quang hay g9i If! d6ng phan dia.

ella n6i doi kh6ng goi la eis- bOi VI hai dUu eua mach ehfnh akhae phfa. r\ . ~ .. Tnremg hqp tOng quat nhat ta dln xae dinh d¢ hem d'ip ell4 cae nh6m nguyen ~ I I

CHO CHO ttr lie,n ~€t v6i m6i ~guyc~ t~ eaebo~ ella n6i doi, ,n€u, cae, nho,'n; I e6 d? ~em e~p <:ao j 21 '21

H-C~OH H-C-OHhan cr eung m¢t phm ta kl hl~u la dOng phAn Z; con cr khae phl~ ta kl hl~u la dOng": 31

va JIphan E. I . fi H-C-OH HO-C-H

4 I 4 INguyen tit co di~n tich h~t nhan dlUg i6n thl d¢ han cffp [ding cao. N~u d~a ! CHJ CH3

vao d<) han ~ap eua nguyen ttr y~n k€t, tIl!~: ~~~p vCri n6i dOi khongl pha.n bi~t dll'qe thu ~ D-· L­H!. thi xet tiep nhling nguyen tlI hen ket ke hep. I ,~;

~

i ~; Khi bitu dit:n cae d6ng pha.n quang h9C ta d~ m<;l.eh caebon thea ehi~u th~ng B~ /H B~ CHJ :~ dlmg. nh6m ehue chua nguyen ttr eaebon e6 s6 oxi h6a eaa nhat quay I~n phla tn~n.

C=C ~ C=c! '.i Khi d6 ne"u nh6m -OH eua nguyen ttr eaeban bAt d6i, vCri s6 thl! tt! eao nhat. nam a" va ('" M(C CHJ C H J phfa tay phai eua ngum quan sat thi g9i lil d6ng pha.n 0-, aphfa tay trai g9i la L-.

E Z ~\

i ,~

DOi vCri cae a-laminoaxit thl d6ng phan e6 nhom -NH2 aphla tay tnii lil d6ng Brom c6 s6 thu tt! trong h~ th6ng tuAn hoim Iii 35; con clo 0 thu 17, eaebon a~. phJm L-, aphfa tay pl}ai Hi d6ng pha.n D­

() 16. v~y d¢ hem cap la Br > CI > C> H.

Neu lien kit doi kh6ng phai la h~ C::::C ma la h~ C=N thilU'ng vCri dOng philn-.' CiS- ta dlmg thu~t ngii syn-; va trans- dOi la anti. 1

I I H~CH~HCOOH: COOH

f-!O H

\ iI'

~hN-C-H va H-C-NH2 C6H~ _ /OH . C6H~ i 1 - I I :~ g~

CHJ CH3C - N va C =N ,. Cl-hOH/ / ,

IC~ C~ 10H IL-alanin D-alanin D-glueozcr• I ;

syn- antl- ~ ~

_Dong phon quang h9C: La nhling d6ng pht'tn khac nhau v~ 51! phAn b6 cae ~ DOi vCri glue6zcr trang stich giao khoa ph6 th6ng noi den la Io~i d6ng pha.n 0­

nh6m nguyen ttr xung quanh nguyen ttr eaebon bat d6i xllng, , ~ glueow, tl!e la chi eho bi€t nh6m -OH ella nguyen tir C3 (caebon bat d6i e6 s6 thu tt!

Nguy~n ttI eaebon bat doi xUng la nhling nguyen ItT caeb!on lien ket v6i b611f eao nhat) nlun aphla tay phai. Khi ehuyen ttr d~ng m~eh ha sang d<:mg m~ch yang thl nguyen tir eua bOn nguyen to ha~c ",(Ii bOn nh6m nguyen ttI khac ilhau. ~ cae nhorn -OH aphia tay phai deu aphia dum Yang. nh6m CH2 0H atren vong.

b ~ I t

a-C-d ~ I ~ Hili 10. b i N1zi~1 d(J s6i (con gfJi Id dilm s6i) cua mrJI chat phl;l thurJc vdo nhilng ytu t6'

Ntu ha} don~ pha~ quang h9C rna dOng pMn nay la ilUhi cua dOng .~hAn kia ,I ndo? cho biet cO" sO- khoa hl!c dl! doan 51! xap ~ip cac chat'lheo Ih'-, II! nhi~1 drJ s6i

tang da'n hOlJC giam dii'n?qua guemg phang thl g91 la hal dong phAn quang h9C dOl yuang ~o~e dem gl311 la hal ,~" I ~J

d6iquang. m LOi giaiI ~

COOH ~ I COOH

I ~ + Nhi~t d¢ s6i cUa rn<)t hqp chAt If! nhi~t dl;> t~i d6 tip suat hoi eua eha't b~ng ap H-C-OH HO-C-H ~ sU:ll khi quy~n tren be m~t chat long. Nhl! the' ta thily ngay nhi~t d(> s6i phl} thu¢eII ~

CH3 ~. vao:CH3 ;~

- A.p su:il khi quytn-lfcn ~ mal ch~l Ilmg. ap su:fl canglhjp thi nhi¢l c1<) SCJi cang axit D-Iactie axit L-Iactic lha"p.

19

~~~.

:"":,!}.

';.'

If - Kh6i ltrqng phftn tir ella ehtll. VI kh6i h.rqng phan ttl ella ehftt eang Ian thl

chat cang kh6 boc hcri, ap suat hoi ri~ng ph~n eua chat tren b~ m~t cang kh6 dL,\t tm con cac d6ng phfl.n meta-dihidraxybenzen (Rezoxinol) va d6ng phfin para-dihidraxy­

gia tr, ap suat khi quy~n, nhi~t d(> s6i dng cao. benzen (hidroquinon) chi co lien ket cAu hidro giua cae phftn tu, nhffilg lien ket eua

- Lien kct hidro giua cae phAn ttl. d6ng phfin para m'.lnh hem do d6 nhi~t de) s6i eao han.

+ So sClnh nhi¢f d¢ s6; Clia C(Ic cJutf d~(a vao Cali t~IO elia cJlLlng.

- 01i so snoh acung m(>t gia tri ap suat ben ngoai. H"'0-fi 0", O/H-<Q)- /H."O~

- Chi so sanh cae chtit cung m¢t day d6ng d~ng ho~e c6 kh6i ltr911g phan ttl 'I .~ H· .. O 0 I ~ I HX{lp Xl nhau. :' H

Trang cung m¢t day ( thi dl;! dc ankan vai nhau; ho~c cac ru<;ru no dem chuc f bac ffi¢t v6i nhau... ) thl nhi?t d(> s6i tang khi kh6i Ivqng phftn ttl tang. ;',; Nt{ , h h' ",. ': c;U so san n I~t d¢ 561 cua eae aXIl no dan ehuc, rvQ1I no dan chue va este* Pentan (36,1 DC) < hexan (68,7°C) < heptan (98,4°C) < octan (l26°C) l: no. dcm chu~ c6, kh6i. Ivqng phfin tu btlng nhau thl este kh6ng t'.l0 du hidro n~n c6

* CH30lI (65°C) < CHJCH20H (78,SOC) < propanol (97,2°C) < butanol (l38°C) f nh..~t d¢ s6.1 thAp n~ftt: rvQ1I t?O ,lien ket cAu hidro yeu hon li~n ket du hidro trong :1"'" /' , -'", , ,. . ~ aXlt nen nhl~t d¢ s61 ella rvgu thAp han ella axil.

( Trong eung m¢t day chat thl chAt c6 ctiu t?O ding phfl.n nhanh thl nhl~t d¢ s61 :~ Leang giam. ---- ~

....-.- :~, CHJCOO~H5 < CH)(CH2)JCH20H < CHJCH2CH2COO~H II t (77°C) (l38°C) (l63.5°C)i,

il CH)CH2CH2COOH (l63,SOC) > CH 3-CH-COOH (lS4,SOC) I,':Ii ~ Chi Chtl~Cac chfr 56 d~ trang ngo~c dan la nhiet d6 s6i ella cae ehat tvang {,..,..

'I'1

CH] ~ . . ..."g. 1'11 t

1 .')

i.I:1\,. , , h" , khAo 1 h' b' h '. h h' h: x ,IBai 11.N~u cae e at co vI vqng p ftn tv ang o~c xtip XI n au, tiC at ndO co ~

il;l, kh<'t n~lIlg t<;to lien ke't du hidro giua cac ph~n ttl thl ch[(t d6 c6 nhi~t d¢ s6i caD han,'~ So sti~h dtj linh. dtjng ella nguyen t,} hUJro (so stinh tfnh axit clia ruf!U, i'\1III, lien ket diu hidro gifra cae ph~n ttl ding m~nh thi nhi~t d¢ s6i cang eao. SiJ ill nhv f;phenol va axlt eacboxylre). Cho thi dl;l minh hfJa.

1'1 v~y VI vi~c t<;to diu hidro giua cae phan ttl da gian tiep lam eho kh6i luqng pha.n ttl ~

"I tang len, do d6 phai mat nang Ivqng cal cac lien ket cau hidro, lien k€t hidro dng .~ LOi ghii

manh thl nang Ivqng tieu t6n cang 100 do d6 nhi~t d¢ s6i dngcao.:: D6 r h d ' , 0 •

A

' .~ . m yng cua nguyen tl1 hldro hay n61 eaeh khae 130 tinh axit ella m6t chat Thi dl;!: pa kha nang nhvemg proton clla chat d6. .

,I TIllr t~r nhi¢t d¢ soi clla C6HiOH)2 nhv sau: 1, . RVQ1J, phenol va axit cacboxylic deu <;6 nh6m -OH, dQ linh dQng eua nguyen

D6ng phan ortho- (240°C) < d6ng phftn meta- (273°C) < d6ng phftn para- tlv.h'd;o phy thu¢c vao ,d~ pha.~ cl!~ ella lien ket gifra oxi va hidro trang nh6m -OB, (285°C). f~u c,ac nho~ ,nguyen ttt h~n ket v6i nh6m -OH lam tang d¢ phfin el!c eua nh6m -OH

, . , . . . ". ~hl d6ng thOi lam tang d¢ hnh d¢ng ella nguyen tu hidro trong nh6m naVI d6ng ph~n ortho-dlhldroxybenzen (procatechm) chi e6 hen ket cftu hldro i' , . y.

n¢i phan ttl, li~n ket nay kh6ng lam tang kh6i Ivqng phin ttl, kh6ng n6i cac phan tlr;l, Nh6m -?H cua IDot la ~h1'1n c.l!e nhat, ,nh6~ -OH ella phenol phan el!c han lFhom

r' J OH eua rvau. Do d6 tmh axIl dVacl«ap xep nhv sau'1al· VOl n lau. ~ • • • ' ~

.~ rvgu < phenol < axitH r, , ~ d Chieu tang ella tfnh axitrQI7 h 00..H-O~O. ~ 'HII O ,rnH2n+ I-O-H g6c ankyl CnH2n+ l - dAy electron ve phia oxi Hun giarn d6 phan cue

I ~ua nhorn -0H. . ' .H "

I '"H ,I,

I· , Trong phenol c6 sv chuy~n dieh electron nhv sau:

•. J~ ...."

i

••

1 ,~

r:(J4_H SlJ tuang tac giiia dic electron chu~ t~o lien ket i. V clla oxi v6i cac electron 7t trong ~ong tharn l~ ,~

I I I'

cho m~t dQ electron tn~n oxi giam, d6i electron clla lien ket giiia ~xi va hic1ra chuy~n~ d!ch ve phfa oxi lam tang dg phftn clfc eua nh6m -OH. f.c:O 1;:

Trang axit: R-C~(' ~ "0 -- H : i

Nh6m eaebonyllam cho d6i electron Wdo clla oxi trong nh6m -OH b! chuyen} djeh nhi~u han, lam cho m~t dQ electron tr~n oxi giam hem so v61 Iphenol. '~

Thf du. minh hoa: . i ,i~ _Axil eaeboxylie lam do quy tim. phenol va ruqu khOng I~ do quy tim. I _ Phenol va axit philn (rng v6i kiem, nrqu kh6ng phan Un~ vm kitm chung tIl'

tinh axit cua ruqu Ii} yeu nhfft.

C6H~OH + NaOH -t

RCOOH + NaOH -->

C,H2n + OH + NaOH ~ I

_ Axit eaeboxylic day duqc khi CO2

RCOOH la axit manh hem axit cacbonic..

2RCOOH + Na2COJ ~

1

~H50Na + H20 I,

ReOONa + J!,o . kh6ng phim ung

.;i

ra khoi mu6i cacbonat chUngl to axil!

' '~I)~ '~

2RCOONa + H2P + CO2 , #.H Khi CO

2day dugc phenol ra khoi dung dich phcnolat chlrng to axit caeboni~

la axit m~nh hcm phenol. ]

CO + H20 + C6H50N'a .....-)- ~H50H + NaHCpJ IIj'l

2

Theo tinh chAt bk diu ~'! co: I '~ Tinh axit eua phenol < t}~h axit cua axit H2COJ < tfnh axil clla RCOOH. ~ rtI

I~

BailZ.' I; '~ Amin Ia gi ? Nhif dau amin co tfnh bazO' ? Tl;li sao ainin beo co tinh ba~

ml;lnh ha1l amoniiic? Tfnh amin cua baZ(1 beD co thay ddt thea btJc .;ua am~ khong? i

S<1 di cac amin deu c6 tfnh baz<1 vi nguyen tv nita tTOng amin vAn con m<?t doi electron' chua t~o thanh lien ke"t. nha d6i electron nay rna cac amin co kha nang nh~n proton, tlfe la c6 rinh baza gi6ng nhti amoniac:

~ - - ­.,

H-N-H H

~

H-t-;r-R2

R]

I

+ H+

I +

+ H

NIitB

H I (£) I

R-t-;r-Rz R,

LOi giai :t i ,p

_ Amm la d~n xu~t cua amoniac trong d6 1,2 hay ca 3 nguyen tv hidro cU_,} Neu cac g6c lie kAt ,. . d' 1 '" ., . , . "n (,:; VC1I nita ~u ag6c tham th' bn ' . . " , amon,ac b~ thay the bC1I g6c hldroeacbon . ~~ ,baza dng giam. (f"' H ) N < (C H ) NH rH 1 . C cua arum cang Ci10 tmhII '--{, 5 J . 6 5 2 < '-1j 5NH2' ­

v-~

- Trong phAn tir cac amin beo CnH]n+,-NH2 do cae g6c ankyl ~H2n+l- day electron g~y hi~u tlng cam U'ng duang (+1) lam cho m~t d¢ ~lectron tren nguy~n tir nita eua amin beo Ian! han m~t dQ electton tn~n nguyen ti'r nita_cu<LaIlloniac, do v!y amin bee de nh~ proton han amoniac. Tinh baza cua amin bee rni;lnh han tinh baza cua amoniac. r"1"' .... ~

Trang pha.n tir bic alOin thorn do ea(: electron tlf do clla nita lien h<;Jp v6i cae electron cua lien ke't n trong vong tnam, lam cho d6i electron tlJ do cua nita chuyen dieh rni;lnh v~ phfa vong tham, m~t khac nguyen tLr nita e6 d¢ fun di~n (3,0) lem han d¢ am di~n cua cacbon (2,2) nen d6i electron dung chung gifra cacbon va nitq pha.n ClJC ve, phfa nita. Nhtnlg trong amin tham hi~u ling litn hgp v&i yang tham m~h hem hjeu (mg cam Ung, do! d6 rn~t d¢ electron tren nita cua amm thdrn nho hem trtn nita eoa amoniac, ram giarn khci nang nh~n proton tuc la lam 'giam tfnh baza so vCti amoniac.

CnH2n+ I-+NH2 , rrYr7J_H H-N-H~I \j H ~

- Khi b~e cua amin beo cang tang tUc Iii 56 luqng g6c'ankylli~n ke't tl1!C tic'p vm nita tang. stf day electron cua cac g6c ankyl d6n ve nita cang m~nh, m~t d¢ electron trtn nita tang! do d6 tfnh baza tang.

~ - .......... Ta c6 trinh tt! sap xt'p nhu sau:

amin tham < amoniac < amin beo bftc 1 < amin beo bAc 2 . '.~

Chieu lang cua ti'lh baza

,·,,'~f, ' , irI;;~ ft",.•..'I F"T' ~.: ~ ~' t',j

f: ~.If. HI; I ~

I'i.,: !:I. , I.

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oi , ~

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( ) Bili 13.

.l1A: Chqn cau tra lUi dung va giai thich ngan gqn. Sap xlp cac chat sau theo

chilu tiing cua tinh axit tit trai sang phai. CH]-C6H4-NH2, 02N~NH2' Cl-@-NH2 , @-NH2 13A: CH2=CH-COOH, HCOOH, CH=C-COOH, CHr CH2-COOH (I) (II) • (llI) IV)

(I ) ( II ) ( Ul) ( IV ) r a, < II < III < IV( ti

b, III < II < IV < I a, "", (IV) < (III) < (II) < (I) to

,j c, II< III < IV < I d, II < IV < III < I

b, ( IV ) < (II) < (I) < (UI) ~ 14B: c, (I) < (II) < (III) < (IV) ­d, ( IV ) < (II) < (Ill) < (I) J ~NH1' CHJ-NH-@ o-NII21. o13B: ~H5-0H, p-CH3~H4-0H, (C6H5)3CHO, p-02NC6H40H n (I) (II):}; (III) 1'1 (lVt

.".., (I) . (II) (III) (IV) :~ \¢ a, II < I < III < IV b, IV < III < II < I

a, I < II < III < IV b, TIl < Il < I < IV II I~

c, I = III < IV < IIll' d, I < IV < III < II c, II < I < III < IV d, IV <: I < II < III I

r.:i "

!t .f-.,J LOi gmi I~

13C: CH3-CH-COOH CH -CH -COOH , CH,-COOH ,CI-CH-COOH ~ !4A: (c) dung. OIc nh6m hut electron !am giam t~nh bam cua anilin. ,Nh6m _- I I 2 .' 2 I I ~ N02 hut electron m<;lnh han clo rAt nhltu. cae nhom day electron (-CH ) lam lang a

CI Cl CI ~ tfnh ba1:a cua anilin. 3

I

a, I < IT < III < IV II III IV 'I. 148: (a) dung. I va II la amin thom nen linh bal" ye'" h<1n III va IV. IV la b, II < I < III < IV ~ amin b~c 2 co tfnh baza m<;lnh han III la arnin b~c I.

c, IV < III < n < I d I < III < II < IV ii

LUi giai ' ina; IS.

l , h . '€ Trinh bay cu cht phan img c(mg cac hflP chat HX VtlO anken, tit do gUii13A: (b) dung. G6c CnH2n

+ - dt\y el:ctron n~~ n dmg tang tin aXlt cang gthfch cu sO- khoa hqc cua quy tac Mac-c6p-nhi-c{ip th'!c nghi~m. Khi cho giam. Litn k€t 3 GC hut e1e.:tron m'.\~h han IItn ,ke'l d()1 c:=c. , , :~izobutil~n ~:o dung d!ch axit HEr c6 hoa tan NaCl, CHJOH c6 the tl;lO ra nhiing

13B: (b) dung. Tfnh axit cua nrqu y~~ han cua phe~ol. cac nhom day ~h£fP chat gl. i electron lien k€t v61 vang tham lam giam tfOO aXlt; Ok OOom hut electron lam tang 'a

tinh axit cua phenol. i~ LOi ghli

13C: (b) dung. cac nhom hut electron c~~ gin ~om_-C0,oH t~l SI! hut;~ Ph~n Ung c¢ng fIX vao litn k€t dlli C=C clla anken co th~ ttinh bay ngan g<;>nelectron dng m'.\Tlh; Qng nhitu nhom hut electron thl dng lam tang tmh axil. rtheo sa d() sau:

'f ',)1 XBail4. ~

j, 'I +H0 I / I I ~ : " C=C / +xG

-C-C­ -C-C-Chqn cau tra lOi dung: Sap xtp cac chat sau theo chilu tiing cua tinh bazu~ / '\, - I '\, ­ H Itil tra; qua phdi. f, anken cacbocation

~.'. Giai ~o'.\n ~¢t la phin ~~ c¢.ng proton vao I,itn k~t d()i t~o ~a cac?ocati,on',sau \;d6 cacbocatlOn ket hqp ngay VC1I anIOn X" t'.\o ra san pha.m CU()I cung cua phan ttng. .It.

1 Nh('1 51! Illtu bi6t V~ CO chc' phan t'rng nhll tren ta giai thkh dlrqe t~i sao cae ph;'m U'ngi conI' V~1O aIlkcn thvana dung axir co cO manh dt Hu:n X(IC Lie. f.: ,..1:- \0 s: \0 r 5- ('

• C' o' r I U l' r u - h CH2 == CH - C-N , . ' ._ , A'l h 'Kh' - , hA'~ CI-h=CH-C CH7=CH-N?' _ Quy tae Maee6pnhl6p thl!e I1ghl~l~ e~.ny~ ( Uj1~ '.1 V sall: ~ C9?g cae e ~lt~ - "OH - 'OH

hal d6i xlrng (HX ho~1C X-Y) V;lO 'H'.ken bllt d6~ Xling thl IOn dV~? eua ta~ n~a.n. tani ' c(mg ~ao eacb~n m,an di¢n t.leh am (n,guyen tv caebon m.'~ng ~hH~U nguyen tv hldr?~ " Thea cae ~9ngl thl1e ~ieu, ~ien ?tre,n, ,thi m~t d~ di7n tfeh a.m t~p trung nhi~u hern) Ion am eua tae

gnhan ({\n eOng vao caebon mang dl~n tier dvong (nguyen ttr~ nhat 0 nguyen tv cacbon Clla hen ket d61 hen ket v61 s6 it nguyen ttt hidro, do l?l

caebon mang it nguyen tt! hidro han). 1'111 dl;l: '[ ~ trung ~~ tan c6ng c~a ~ac tac nha.n mang di~n tfeh dvang; d~n tm san ph~m nguqc 3 2 1 ~ vm qUI tac Maecopnhlc6p:

or. . I .,~

CHJ-CI-!=:CH + HCl --+ CH1~CH-CHJ ~ CHz=CH - COOH + HEr ~ CHz- CHz- CGOH z itl ~ Br

,r ~~\. t., . - Khi eho isobutilen phan ling trong dieu kien nhu diiu, bai, ta se thu dvqe h6n

] 2 1/ ()_. 0+ ,. f hl/P gc)m: CH -CH = CIl + H---O--13r J..~. CIl3:~H-~Hz ;r

3 z CH) CH) CH) CH)IOH Br j I I I I

CH)-C-Br CHr C- OH , CH)-C-Cl, CH)-C-O-CH]I I I ~ INguyen tit hidro ciJa phM tit Hel, nguyen tit hr6m tTOng ~lBrO dii kct hqp v~ CH) CH) CH] CH)

nguyen tli eaebon sCi I clla propilcn. : ~ M~c du tt! ket qua thl!e nghi~m Mae6pnhlc6p nH ra dtrqe; guy lu~t tren, nhl1n~!~ BCri VI theo C(1 che trcn ta co cae giai dO<;ln chinh nhv sau:

til co th~ giai thich dVCJe cO sa khoa hge clla no. I .~! HEr = H+ + Dr" ; NaCl = Na+ + Cl­

. Tnr"c ticn ta dua v~o hi?u img chuytn dich~le~tTOn trOli;g phftn tit ank~n: Ci~, Nhu v~y trang h6n hqp phim ling se c6 4 lo?i tac nh~1O l?i Br", Cl-, goc ankyl gay hi~u U'ng cam U'ng dtrcmg (tHc Ii'! hl~u vng +1, day electron) lam ch~ ~ mar d6 electron Ulp trung nhieu nh;lt trcn nguy~n Iii caebon lien [ke't v6i nhi~u nguycn'i H-Q-H ' CH3- Q-H co kha nang kc't hqp vCri cacbocation: ., . . I'

tli hidro. i ~~ 8 ~ G)/CH]

i CH)-y=CHzCH -£H = Cf~2 do d6 nhung tac Ilhan mang dl¢n tfeh dVOllg se tfin eong vao nguye.~ + HGl CH]-C"CH) Cacbocation3 CH)

tli eacbon nay, t~ ThI1 hai sau khi ke't hqp V01 proton (tac nhfm mang di¢n :tieh duang) thi t~o r~ Br o I

caebocation, caebocation b~c cang cao thi eang b~n do do cang pe t<;lothanh: l~ + Br CHcy-CH) ClCH)e !" ~ Gl I+Cl­__________~ (1) CH1-~H-CHz -, kem ben ~.·.i CH -C-CH CH)-C-CH lI ./" ~\ Y CH

3 t{ ) I ,)

CH)CH)-~H = CHz + 1-( "-.. e CJI _ ~ CH)I.

CH) CH)CH) (2)""-. CH)-C:: ) - :ben, de I~O ra :~~ CH)+CH)-OH ~ Gl/ I HGlCJ~ ~ ----+ CH)-c-n - CH)-C-O-CH) +

I "'" H I Ciin ehu y r~ng: Quy tac Mac6pnhie6~ ch~. ap, dl;ln~ eh~cac p~an lIng x~y n.l CH) CH)

tr~ng moi truang phftn cl!e, eho cae anken bat d61 :<If!1g va eho e~e tac nhan ba.t d61 CH) H CH)

+H-OH I Gl/ I e CH)-c-n - CH -C-OH + H x~g I

IDl!a van SI! ehuy~n d!eh electron trong phlln tli, ta d~ hieu cae phan lIng ngu~ I ""'H )CH3 CH

I

3voi qlly lAc Macc)pnhic6p: Khi co dc nhom hilt electron manh (-NOz; -COOH;;~ COH; COOCH ) lien ket v6'i n6i doi thl sim phftm t'.10 ra ngvqc v6i guy d~.Ij;>J

Macopnhicclp: ;~u' ~ ;~ ~

I

~~ I"r".··.·.·,'~>.

I.,

:~ 'l H2S04 :::: H'" + HSO~- llS04- :::: H'" + SO}­(

Rai lti: 1, a H 0 oKhi cho metan tac dlfng vOi do duOi tac dl}ng cua aull sang, tlli co mqt ~ ~ o I ~ 81' H-R-N~O + H H--O-N~ H20 + N~lUq7lg nho elan dUl!c If.lo Ihi11lh. Hay giai thich tiJ i sao. \' e 0 o

LOi giai ~~ t Cation til N01 g<;>i III calion nilroni, va chfllh no In. tac nhftn tan e6ng vao van~

Phan lIng gifra an~~n ,~a do khi c6 ~h~eu sang thl,Il?C.lo~i phan lrng the xay ra ~ tham. Trong yang lham c6 (4n + 2) electron 11:, nen m~l d<') di~n lfeh fun Ian: v

thea co ch€ g6c IV do. D61 vm melan, cac glat dO':ln nhu sall. ~ '. ., ~ W-.e ~N02 ~N02:-1 0 8

Ciai do~m bar dau (khm mao): ~ 1S?.) + N02 ~ ~ -N02 ==: ~ H - 0 + H i~

(1)~ 2el· PlnIc 1! phu-c aCl:Cl ti ~ Luc d~u do sV tuemg tac gifra cac eleclron n cua yang benzen v6i cation ~

Ciai dO(lll phat trjen m(lch: ilroni t<;to ra phuc n, sau d6 Il!c hut llnh di~n lam eho cation nitroni ding tien gfin h~i

."..' H yong lham ya Ia:y fa 2 electron cua vong tham t~o thanh lien ket (') gifra l nguyen llfI~ ~ HCl + H-C' (2) ~~c;icbon cua yang ym nguyen ltl nita cua cation nitroni. Do \lang tham ma:l di 2 CI· + H:C-H I i~ !ectron nen dien lfch duemg cua cation nilroni nay di ehuy~n V~IO Yang, nguyen tu I It

HH

'-', acbon cua vang t~o li~n k€t 0 y6i nguyen tu nita chuyen thilnh tr~ng thai lai hoa Sp3 ech ra khoi m~t phAng cua Yang, 4 electron rr con phai giai toa tren 5 nguyen tll

H~ . i, :acbon Sp2 ella Yang. H~ yang kh6ng con la vang tham mla, tr,!-ng thai nay rat kern

H-C' + (3 ) ~~n va con g9i la phlfC b. Phue nay nhanh chong tach di proton de tai t~o I~i yang

II r \CI: Cl CHJCl + Cl'

HI .tfhurn.

'; Ql!y-Ill~t the trong "aog tham: Khi vang lham lien ket v&i m¢t nhom th€ X nao cae phan (mg (2) va (3) luftn phien nhau. I{J, thl-nam nguyen tlf cacbon can I~i cua, vang kh6ng can haan toan giong nhau, rna Cia; dO~ll ktl thuc (eftt m~ch): cae g6c t'! do ket h(Jp v&i nhau: tUgC chia lilln 3 lo~i:

2 Clh + Cl. -7 CH3C1 '..("j X Vj tr~ 2 va 6 g9~ Ia. ortho.6@2Cl. + Cl. -7 CI 2 ~ 0 V! tn 3 va 5 g<;>1 lit meta

CI1j-CHJ ;~ 5 3 Vi trf 4 g<;>i la paraCHj + CHj (4)

Do 51! k(t hqp cua hai g6c CH3 rna t~o ra etan. ; Nh6m X ,:gay anh hll<'mg den hO~1 d0 eu. vong thom (tile la lam cho vong ;,ham tham gia phan ung lhe de hay kh6 han benzen) va imh huang dinh huang (tUe Iii. ra nh6m mm V?lO thay the nguyen ttr hidro avi lrl meta" hay acae vi trf ortho va

Rai 17. '" ., ra). Neu x lam eho kha nang tham gia phan Irng the eua vong tham 100 hem cua Ron hqp nitro hoa va phan img nitro hoa La gi? Trinh~ba.y c~ cht}'h.an ~g nzen ta g<;>i X 13. nhom hO~1 h6a, nguge I~i la nh6m phan ho<;tt hoa.

. . ~ h::- h itro hoa til do gidi thich qUI lut;lt the vao vong: . ". . ,....,nitro hoa bem:.en bang on l!P n , , Neu X dua nhom mm v?w thay th~ cac nguyen tu hldro a cae V! tn ol1ho va ben1.en. !, ra ta kf hi~u X lit nh6m the lo~i 1. Neu X dua nhom mm vao vi trf meta kf hi~u la

Lm giai. 11 om lo~i II.

, ,. ., . . _ Ph' , l~ Th,!c te cho thay dc nhom lo~i II d~u 1a cae nh6m phan ho~t h6a vong tham; H6n hgp nitro hoa la h6n hqp g6m aXlt mlnc ~a ~Xll sunfu,flc _d'!-C~ an ung,[c nh6rn lo~i I co khi I?\ de nh6m hO<;lt h6a, c6 khi 1a nh6m phan ho~t hoa. Dil rut ra

nitro hoa h'1 phim lrng dl1a nh6m nitro -N02van phftn tlf cac h~1p chat hUll c . ~i de nhu sau:

i Co ch€ phan lrng nitro hoa benzen: h

J* Nh6rn loai II: f: Ca che prlcln Ung : - Oic nhorn hut electron rfit manh nhu: -NO." -CN, -COOH, -CHO, ~ H2S04 == H~ + HSO~-

COOR, - NIf], tv RJ

; -SOJH, CF)...· Mu lam cho~kha nang tha~ gia phan (mg thJ (O~ /OH~Q_Hi OH R' , OHeua vang th01n giiul1 di so vo; benzcn va dua cac nh6m mm vao v1 tn meta. "'. ~ + If> ~ R-C0J ~. I 0/R-C "­ R-C-O I '\.OH OH V It-C-O-R' ::;=* Nhom Ioai I. ! I (H, 0 I

, • j /I 1 00 00H2- cac n09m dtly electron nhu: -CnHzn+l; -OH; -NHz; ·NHR:; -NH-C-CH3 ~

-?-CnH2n+I.•; .la ,cae ,nh~m !arn eho,kha nang phim u-ng the eua ~ang Umg len va dU~ - H20?H ° cac nh6m mm vaG cac VI tn onho va para. .' ~~ = R-C----'O-R' _~ R II 0 . , ~ 0 ~ -C-O-R' +H'" Olc nh6rn -CI, -Br, -CH2CI lilin cho kha nang phafl I1ng cua vong kern bcnze,' . nhlfllg dua nh6rn rno; VilO cac vj tff onho va para. ~ ~a che trcn. co the chUng minh duac kh' t d' , .

., stc chua nguyen tt! oxi 180 . I a !lng ruqu yal nguyen Itt 1~0 ' Cac phiin ling the vao vang bcnzcn (nhu halozcn hoa, sunfo hoa, axyl haa. . I Ihl

ankyl h6a...) d~u xay ra theo ca che t11cmg tI! nhu phan vng nitdo h6a & tren. Vai r .f'0 0

. , h' , .( h' h IA d' "h hi... Nil! . R-C I- R' O· IIeua cae c M xuc tdC C 10 d C t<.t0 r~ cac tac n !in tt!cmg tlf n 11 cation mtrom 0' '\. - - - II --. R-C-O-R' + f • 'fh h . d- d;l. .•. h' h .f I ' h t· I,. h d • h,l OH {.,Oco C(1 c c tren ta e dllg glal t IC uU<;1c qUI

• u~t an IJlwng lm o~t Q cuano. ­

the' X. Neu nh6m X day electron vao vang thOln thl lam tanglm~t elQ di~n, tich . ~eo ca c,he tren ,ta hieu ngay vai tra yuan Ir h" i

, d d'}' - I h' - h,t'A "- >.. I ,.( h ' I:I.} rotonH Jamxuetacch h' , 9ngn atcuaHso I~ h- /.trongyong, 0 0 am tang lfc ut tm ul~n gma vvng tl10m va tdC nan, ttrc d 'ha <1 ! 0 P an lIng, do vfiy co the tl 'H ~ 2' ~ <I P an I ra thu~n Iqi cho 5lf tan cong clla tac nh~n vaG vang th<1T11. Nham! hut electron g~y . c v n thu dU<;1c este. . lay z504 bang cac axit m<;Jnh

hUCmg nguqe l:;ti. . ' . '; . Cu~g th~o co ehe' tr~n ta th~ n '., .~o hen. ket de ui'n c6ng vaG nguy~n ;~~~l~ tt! OXI, clIa ~<;1U dung dOl eleclron chua

, . i ay aXIl RCOOH bang cac dan xufft ella ?on Clla nhom cacboxyl, do v/ly eo Ih6 H~I 18.

I

guycn tu cacbon a • " aXIl, sao chI) mat d6 die t' h J , ' I , ". n y cang Jan !til este can d~ d '" n le (lrang Ircn

.g RCOlf9cPhan ring esle Irau La gi? Phdn {rng este eo d{ic die'm gi va thrtcmg du(/c t' a?g ~nhldnt aXil (RCO)20 , b5ng clorua a ~~o r,a. ~~y Co the thay aXlt

hanh trong die'u ki¢n nhu the' nao, tl}i sao·? I I. ,han lIng t<,to ra cstc con x3y fa de dan ~t h Cl de Than I1llg v6'i nr(JlJ~ khi <16 I '2504' gall, t ~m chi khong dn du 1 • - ,

Trinh bay ca ehe'phdn (Lng este h6u khi eo m~t eua a:fit sunfucric dije. ng xuc tac I'~~ lro e,ua H 2 S04 , Co thi cho nlqu tac dl!ng l'(n "hfing e~J(it nao khac ma v~. q-0 o

,f CHJ-c'\. +HCI

I k: ••• I Ii Cl O-CzHj

dIeU che duVe este. i.1 CzHsOH + CHrC'\.

,VI gJaI. '

Phafl tIng este hoa lfl phan ling giua fU<;JU va axit hfru e~ I~o ra este va I1lrocJ q-O I --"- I ~ CHJ-C

RCOOH + R OH ~ R-COOR + Hl) . C21150I1 + '\.0 q-oj CHrC'\. + CHJCOOHPhall Crng cste hoa co tiIlh chit thu~n ngh!ch. rha i Crng thuang: c1uqc ~ CHrC/' 0-C2H5h?mh trong s'! c6 m;~l clla ax.it vo eu m:;J.nh (hay dung nhilt In ~2S04)' khi dun non . ~

chlTng cat ngay cstc ra khbi h6n hqp pldll1 lIng. so ill ph5i ti~n hanh tron!? dieu nhL1 tfcn Iii VI phan ling este hoa x.dy ra ch~m, vi¢e dung axit !va dun nang nham tang t6e c1() phan (mg. M~t khac VI phan Crng co tfnh thullo nghich ncn t~ch ngay hO;IC mt6e ra khol h6n hWI d~ Call bing chuytn djet> theo chi~lI thu~n. lam tang Sl\'lt cslc. Este kh011g co lien k~t du hidr6 giua de phrtll ttt do d6 thlicmg c6 nhi~

sOi th[ip han so v6i axit va nIqu va de bi ChWlg c51. I

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r I .' . 19 I , rr Trong d~g m;~ch vong, n€u nhem -oH lien ket vOi cacbon CI cua glueoz0

!b!..!..--Van mach hu eua glucozO' va JructolO' ehuyin !han~ dlJ~g m~ch v~~g nh,i, ho~c lien ket vOi c; clla fructoro cOn t6n t~i tt! do thl mOl co hi¢n tlIqng rna yang tai

tid nao? lhi hlla tan cae monosa,ecarit ~ay VtlO nz~O'c till chung ~on tiJl 0" d~m i~~;.' t~O d~ng m":,ch ho: neu nh6m_-oH d6 b! chu.ytn h6a thanh d~n xuAt thi Sl! rna van~ nao? Lam the' nao dl dlJng mlJch vong khong quay ve dlJng mlJch hO'. ;; khl'>ng tht thl!c bl~n dU'<;1C mra. Vi v~y mul'>n cho d~g m~ch yang khl'>ng quay ve

LOi giai ;~ d~ng m~ch ho. ta chuytn b6a nhem -OH nay thanh nh6m chuc kh:lc.

, ,. ,~ Ta c6 th~ chuytn h6a nh6m -OH aCl glucoza ho~c a~ clla fructoza bang

Glucoza va fructoza la 2 monosaccarit d6ng phan cua nhau, deu co c6ng thu~~ phan Ung ella cae monosaccarit v6i metanol khi c6 m*t HCl lam xuc taco Nhom

hftn ttr la Ct,H O. D~ng m~ch ha cua chung co cft.u t~o sau: .~ -OH nay thu~ lo~ nh6m -oH trong semiaxetal nen co tfnh chAt khlic vai 5 nhom p 12 6 0 i~.' -OH con l":,i. chung khl'>ng phan U'ng vai metanol trong dieu ki?n nay. '01f dl;l:

o 5 4 3 211 I ~ 6 5 4 3 2 1-;::- 6CH -CH-CH-CH-C-Clh . ~ CH -CH-CH-CH-CH-C, I 2 I I I I ., CH20H CH20H

2OH OH OH OH OH H OH OB OH OH OH ; H 1----=--0 II H J---.=.---o

Fruct6za l~ ~H HelGluc6z0 .:¥: OH H + CHJOH -~ all H +H20 , , , Un c6n v' cI

."",.,,' Nh6m -OB eua m6t s6 nguyen ttr cacbon tblCh hqp co the phan _g ,. g, i HO OH ~l /10-CH)H~ 9 H

. " h h - 6 h Kh' do he yang se ben va j r---r (nhorn cacbonyl de t~o ra h~ vong ~ c~n .o~c, c~n. I h ~an Trong dllran: H OB H OH do dang mach h6' cua monosaccant chuyen thanh d~,ng m~c g. h 0 "'J. trlnh 'ph6 thtmg ta dl1qc h9c d~ng rn~ch yang 6 c~nh cua gluc6zC1 va d~ng m~c v Bai 20.

5 qnh cua fruct6zC1. , . • " , d ',; Trinh bay ccru tt;lO clla sacearozu va MantolD" Tai sao MantolO" co phdn img , " arit atren ton tal chu yeu a L).ng m~ . • ,. ,'. .

Khi haa tan vao nl1C1C thl cac monosaec ~.' 'ti trang gllung, con saccatozu khong co phan fmg nay? TiJl sao dung d~ch thu dUf!c yang va lu6n lu6n chuyen h6a l~n nhau theo m¢t c~n bang., . sau khi dun nong saccatoIU vUi axit 11~04 loiing, va dung d!eh /ructolu trong S~I

I: co mat cua NaOH Ini tham Pin phan fmg tran u fJ'llung.CH 0 l.ilM' . b- b eI2

I~I0 OI{t,' LlJi giiii.H .~

~ OH H H'~ Ph:ln tic Mamoro dug<: t":'o ra do 2 g6c a-glucoza Ct,H 11 0 5 litn ket vOi nhau HO ~l •• 6c • C:l - • C H ttU \3 r2 .. qua nguy~n tU' OXI. ml>t g a I Vd m¢t goc a 4:

H OIl ..H OHH OH ~

. r'lucozo :i&.' ktCH10H yH20H u-Glucozo d<:lng m<:lch ho p-u j'li) H --0 H H 0 H

NhI1 va dang 6 c~nh cua glueoza dl1<;1C t~o ra do nhom O.H cua~cacb~n s H H Mfrntaz.o .Y . 6i h' deh'lt Ne'u nh6m -OH vita tao ra a C, nam phla dl· Oll tL0 ~~Hda h~m iTng c6ng v n om an . '. HO H

p. ,. , . I .• h'a tren yang ta c6 dang p. Hal d~ng mat phang vong ta co d~ng a, Ngl1qc ~l a pl., 0;,'. H OH H OH ch'uy~n hoa qua lai phai qua giai do<;\n t<;\o ra d~ng m~ch ha. ~ '..' '-------.------'

• • 1tf a-Glucozo u-Glucoza Tl100g tl1 da xay ra vCri fructoza: ~

. ~ Phftn tic saccarow dU'g<: t~o blri SI! litn kit gifra nguyen tt~ C. rn¢t g6e a-

o~n.H H Hrvlu /0........ I glucoro C6HIlOS vOi nguyen tu C; ella m¢t g6c ~-frutoza Gua nguyen ttloxi:II

1 21/;.HOCHz~ H H 5 ;r=:HIGHH ~ CH20H

3 4 6HOCH2 OH OH H I I ~OH HI p-frutoZO 11\: I ll:I d~ng m~ch hb fructozo

f~u-frutoza

i , t ~:I~il: ~

,I 'PHAN II

H ~! .~2 H ! D6 ohftn bitt, ph~n bi~t cac chat hU'u ca ta Slr dl;lng m¢t 56 chu y sau: H I Mantozo I ... ';' ., , '" • , ., ,:K;o CHkOH +) all co a.xlt mdl phan ung vm muOI cacbonat glal p!lOng khl COzbay ra.

I , H OH, . OlI .. II ,1 - Trong s6 cae axit don chtrc, chi co axit fomic co phan ling trang gucmg.

a-Gl~cow ~-frutoza! !, +) O1i c6 axit, phenol, cste phan lIng vOi ki~m t~o ra mu6i. Trong d6 este

. 0 g6c a-glucoza thu hai cu;~ phan ttr mantoza con co nHom -GH t~-,' do a ; phan li11g ch~ v~ phai dun n6ng.

do do no t6n t<:ti .a d~n.s dln b~ng vai d<:tng m~ch h& dla g6c hay, tuc la co nho ~ ~) Ruau don ch\.fc khOng h03 tan Cu(OHh. Ruqu,da chuc co It nhftt hai nh6m >, , b I ,,) .

-CHO nen c6 phan ung trang ~c. ~ OH a hai cacbon li~n nhau thl hoa tan Cu(OHh. Ruga b~c ] b! oxi hoa t<;to raI

Trong phfin ttr saccaroza deu kh6ng con nhom -OH tvl do aC, cua g6c'andehit, b~c 2 t<;to ra xeton, rugu b~c 3 kho b! oxi h6a. I

glucoza, va aC'1 cua g6c ~-f:uct?za:, nen ~aeearoza kh6ng co d~ng m,:,ch ho, kh6n , +) Lien kef d6i C=:C khi c¢ng H 0 tao ra Nqu, con li~n kc't ba C=C khi c¢ng2

co nhom -CHO nen kh6ng co phan ung trang guong. " , -I 0 tao ra andchit ho~c xclon. Nha do fa phAn bi¢t hgp chat kh6ng no chua C=C'

Khi dun nong v6'i dung dich axil thl saccarozo cung nh1 m<;>i saccarit b! th~: ' :y 0=<::, ankin-l t~o ket tua vm dung dich AgNO) tr~ng amo~iac. phArr: De pha.rl tach h6n hqp cac chfr'l hliu C(J ta dt!a vao hai d~c Idiem quan tr<;>ng:I'

Jr' /0

C12HnOIl + H20 -~ c,H I20 6 + CtJH I20 6 - cae chfi't hiiu cd- kh6ng thu¢c lo,:,i mu6i va polime thl c6 lhe s6i va bay hm a saccarazt1 glucozo fi;uctozC1 .~ nhiN d¢ kh6ng cao lfun.

I

Trang m6i lfUang kiem, fructOZd bi€n thanh glucozC1 thcolcAn bang: i ; . _cac chat hliu c& chu y€u c6 lien ket cQng hoa tr! do d6 It tan trang ntrac, de

ki~m , tan trang dung m6i hliu,ca. Do v~y khi chuyin tha-nh mu6i chung se tan trong ntr6c,Fruetoz(1 ~ glucoza

: 6ng tan trong dung mOi hliu ca. St! t6n t~i cua glucoza trong cac dun~ dich_nhu tr~n l~_cho chung co~, Khi han tach dc chat hiiu Clf ra khoi,h6n hqp, achucmg trlnh phD th6ng, ta

nang khtr duac phuc bae-amoniac t<;to ra bC;lc kim lo"u, d61a phan ung tning gucmg. ; P h. h' , h 't t'· kh' ,. h hrtn A ct tra'cA. . '. HhuCmg v~ dI;1ng p uang p ap tac aXl axe lC ra 01 un. ':':1-' gum ax on, n ,

: 'au metylic va axit ax.etic. H6n hqp nay thu dugc trong qua tnnh san xufr't axit

dx~tic b~ng phuong phap chtrng g6 (5ach giao khoa).

Ta cho h6n hgp tac dl;1ng vCti v6i, chi co axit chuyen thanh mu6i:

2CH)COOH + ~(OH)2 ~ (CH)COO)zC::a ' + 2HzO

CH)OH, c;H)COCH) kh6ng phan tIng. ~

(Chung kh6 thl dc C~ftt kh6ng phai la mu6i bay., hai di, c~n con l<;ti la mu6i

lKCH)COOhCa. 010 mu6i nay tac dl;1ng vm H2S04 d~c: ~

(CH)COOhCa + H2S04 ' ~ Caso4 + 2CH)COOH

Ta l,:,i chung cftt thl ax it axetic bay hm, lam IC;lnh ph~n hm dtrqc ch~t long

.ungung tl;1 la CH)COOH.

Nhu v~y ta ~~p l<,Ii nhi~u Ian qua tdnh: cho h6n hqp lac dl;1ng vO'i chftt nao do

~te m¢t s6 ch:it Clla h6n lJqp chuyen thanh mu6i. Oltrng cftt thl mu6i 13 phftn c~n b 1ai. cae eMit kh6ng phai 1.1 mu6i bay hcri, lam l<,Inh phftn hai dugc ehftt long. Sau d6 I ~thCit long va din mu6i dcm xtr Ii riCng.',£ • .:.l~

'1t1. ~ 15

~;

\~ :~­

\1<'­

\l'

'\1

~~;

'4t

J Hili 21. 1 ~ ° f

.. Hay ~h9n ra cae 19 chat long /chong mau, bi mat n~an, m6i 19 dung m~fc)r<. + 2 [Ag(NH,),]OH _ C.H,COONII + 2Ag + JNH, + H 0 chat sau: rlc/oheren: b~nz~n, llCOOlI, ClI,COOlI, ClI,-ClI-COOll, andeh~ II 4 2

benzoic, anco/ benzyltc va g/lxerm. "W"

1!..1.. LOi giai.

- Trang bili nay kht>ng dung phan ling vai Cu(OHh trong moi tmang kitm

iun nong d~ nhq.n ra andehit VI andehit tham_kh~~yhanling vOi Cu(OtI)z de t?o ra +) U1Y m6i cMit m¢t it cho tac dl;lng vai dung dich NaHCO), th~y ba cMlt I t 20 .. ~----- ----'--'-'-------'~

cho khf bay ra d6 Iii nh6m chat axit . C6 phuang trinh phfm Ung sau: '_ Kh6ng dung dung d~ch mr6c brt>m ho~c dung d!ch KMn0 de nh~n ra4

RCOOH + NaHCO) -} RCOONa + H20 + CO t ' iclohexen tmac, bbi VI anCtehit cling lam mftt mau cae dung djch d6:2

- 010 cac axit t.lc dl;lng vai dung dirh AgNO) trong amoniac, thay chi c6 m:J. R-C~ ° + Br2 + H20 R-COOH + HBraxit t<;lo ra Ag, d6 la tICOOH: ,r ~,.: 'H

""""I . \ HCOOH + ~[Ag(NH)h]OH -} (NH4)2CO)+ 2AgJ, + 2NH)t + H20.;,i

-,Hai axit con l~i ~ho t3c.dl;mg vai dung djch nu6c brt>m thl thay axit lam ~:i :3 R-C-7° + 2KMnO.. -+ 2 RCOOK + 2 Mn02 + RCOOH + H20 . . "Hmau mroc brt>m, d6 lil aXlt acrylIc: ,\t

C(H 2-C;:H-COOH ':

CH2=CH-COOH + Bf2 ~ +)'Hai chat con ]?i la benzen va xicloh~xen dUg<: eho phan Ung vOi dung dich Dr Br

! ' ',~U6c brt>m, thl m¢t ch~t Hun mftt fdaU nuac br6m, d6 lil xiclohexen; chat con l~i Iii : i, ,lenzen.

,I Axit kht>ng lam m~t mau nuac brt>m la CH)COOH.

(] Br +) Nh6m 5 chat con l<;li kh6ng phai Iii axit, cha tac dl;1I1g vOi Na thl co 2 chJ H20

+ Br2 --.. , Brt~o khf bay ra, d6lil hairuqu:·1 ce

ib:,1

R(OH)n + nNa --t I R(ONa)n + n/2H2t + Br2 ~ Kh6ng phan tffig

"I' 010 hai ruqu nay tac dl)ng v6i Cu(OHh thl m¢t ruqll kh6ng hoa tan Cu(OHy-' © i 1'1 d61i1 ruqu benzylic C,H,-CH,-OH; con m~1 ruqu hoa Ian Cu(OH), Ihilnh dunl,'}li 22. I

dlch mall xanh lam la gltxenn. . , 11-' h " , h .' kh •. r . ay tac neng tung c at ra or hon hf!P khi gom etan, eti/en, axeti/en. ~H~CH20H + Cu(OHh --t kht>ng phan Ung.

LOi giaii. ' i H

_ ,.;>O-CH2 'i +) Cha h?n.~9'P. ~hf di qu~ d,ung dich A,gNO) trang NH) thi etan va etilen di I CH2-OH C 1-12 O"-."Cu I f~a, con ~H2 b! g1\.11<;11 a d~ng k~t tua b~c axetilua:: I 1 / "-." f%; 2 CH-OH + Ct(OH)2~ ­

I \H-O"H O-IH + H20 ~ ,H~CH, ~2,[[A~~NH))2]]O~ ~ Ag-C=C~Ag~+4~H~+2H:!O, , CH2-OH CH20H CH -OH I~. LQc lfi.y n~ng ket tua r61 cho ket tua tac dl;lng v6i axIl clohldf'C, thu la.y khl2

.Y fa lil axetilen: tan thanh dung djch xanh lam ( ..

, . , ," 'iJ~ Ag-C=C-Ag + 2HC] -} 2AgC]J, + CH=CHt +) Ba chat con 1,!1 cho tac d~tng VOl dung d!ch AgNO) trong NH, thl m¢t chilil

phall Cmg Ian ra Ag. do la andehit btnzoic. !~ +) ~6n h~ khf eli q~a dung dich, Ag~O~H.J g6m ,C2H,J, v~ C~HI\ duqc dAn

i ~a dung d!ch nuac br6m thl C:oH4 phan lI11g b! gll1 ]~I. thu lay Lill :11 llu'l L\ C-'lBo-I

B f,1 :t

I H6n hqp g6m anilin va benzen chQ phalJ ling voi dung dich axil Hel, thl CHz==CH1 + Br2 ~H2-~H2 tanilin phan lIng t~o thanh muoi tan VelO nUDc:Br Br

I .

Phftn CH2- CH2 tach ra rOi cho eli qua b¢t Zn dot nong, .~a dl1<;fc cuicn: @-Nl-i] + HCI [§L;\1H2.HCl tan vao nuac.I : 'I

Dr Br l ~(Tach Hfy rieng phftn benzen nOi b phla tn~n. Phfln dung dich chua Inuoi eoa 2yHz - yH + Zn _'o~ CH2:::CHz +. ZntJr2 , .anilin, t~ ~c~ ~ho tac dl;lng v6i dung d!ch, NaOH (cling c6 the dung dich NH3) thl thu

Br Br I dl1C1C amlIn b!tach ra, kh6ng tm trong nl1C1C: • - h . rlJ' ), rH t'e dung "61 nl1<1c co H SO I" .' I

Cling c6 the cho hOn 9P gom "'2 1.6 Vd "'2 4 a . . I 1 4 C H -NH .HCI + NaOH ~ ~H5NH2 + NaCl + H 0 5 5 2

xuc lac: 2

CHz ::: CHz + H-OH ~ CH3-CHz-CDH Hili 24.

thu I~y CzH6 khOng phan lIng, oi qua dung dich. HtfP chat CPuP khi b! dUIJ nong vOl H2S04 dijc U 170°C IlJo ra chat A coUy nrqu CH

3-CHz-OH dem dun n6ng vOi H2S04 d~c cr! nhi~t dl?

!'Ii kha nang rom mat dlll'K dich thuoc tim va dung d!ch nuc1c brom. Khi dun nong A to ~ 170°C sc duqc khi etilen bay ra: trong dung d!ch hon hlJP gom K2Cr20 7 va H2S04 thu (Juqc axeton va axit

112S04 (d ).170" C~ Cli ::: <i:H + HzO propionic. McJt khac khi cho A hlfP nuO"c trong s'! co mijt cua! H2S04 thi dUt!c dungCH3-CHz-OH 2 z

I chat CJI140 ban diiu. !Xac d#nh tin gf?i cua CP140 va viit cae phu07Ig trinh phan img do mieu ta utren.

1.. Bam (lhtl1of lit~ L~Ji 11;;;" I

Uri giai

Co mljt han hlfP gam anilin,phenol va b'tllzen. l1(ly tri~h bay phu07Ig ph.1l.

tach rUng tung cluff. I A phai 13. hqp ch:rt kh6ng no. Suy ra Ct,H I40 phai la cuqu no dC1l1 chuc 1 ~4,HIJOH. V~y A lil Ct,8 12• Khi oxi h6a m<;tnh Ct,H 12 t<;to fa axeton o-Ir ':'CO:-CH3Lm giai

I va axit propionic: CH --eH -c..v o

V~y cau t<;to clIa A He J 2 "­010 h6n hqp tac dl;lng v6i 111Q11g dl1 dung dich NaOH, chi co phenol phan UJ CH3-C=CItI-CHz-CH3OH

! CH3

t<;to thanh mu6i tan vao nuoc, con anilin va bcnzen khOng phim U'ng, khOng tan,

len trcn. o I

. K~r:z07IHzS04 II . @-OH + NaOH --. @-ONa:+ H20 CH)-C=CH-CH2-CH) • CH~--C-CHJ + CH)-CH2-COOH

I to

.~~~ CH3

:

~l1f .Tach ritng phfuJ chua phen0_3t va phan khOng tan g6m tr:nzen va anilin. Theo qui ik Zaisep lbl co hai cuqu Ct,H1a.0H khi mAt mroc t<;to ra cMit A, d61a ~ I --- --:::;;

cae nJ(JU:llH')i khf cOz du di quan dung djch phenolat: I ~: OH

I OHOH : I CH)-~-eH2-CH2-CH3 va CH)-~H-CH -CH2-CH3~ 1 I!+ NaHC03@-ONa + C02 + H20 ­ CH) CH)

(I) (II)vAn dl,lc n6i I~n lr~n .ijl'

l~Thu lfiy phenol t'.l0 ra sau phan Img.

~. J ~ If,

i~C;1 ''1\ r!;;\

;'"

>;,~

i?/

i',

~ .

---I

Nhung khi hidrat chAt A IC6 H2SO4 lam xuc rac, chi thu dUqc (I), v~y c{')~g thuel

(1) ehfnh la diu t<;lo ella ehft't dn tIm. Theo c6ng thuc d6 lhi l~n chft'l C6H J40 ban d<1u;~ In. 2-metylpentanol-2. 1

r cae phuang trlnh phan ling: 1

~~ it

9H H2 S04 d, not: ~ CH3-~-CH2-CH2-CH3 • CH3-~=CH-eH2-CH3 + H20

C~ C~

"I A (Qui lac Zaisep)

A+H20/H~:

:'1 ,"I OH

I ~i"ICHJ-C=CH-CH2-CH3 + H-OH ~ CHr::.<;=-eH2-CH2-CHJ "rAjI

CH3 ~-'CH3

(Qui lac MaccopOOieop)

NIJ,P,T ,b) n CH2=CH-CH=CH ( -CH2-CH=CH-CH2- )n

Cao su buna

e) Lft'y vinylaxetilen ditu eh~ nhu adi~m (a) cho h9P nuac e6 xue t;1C Hg2":

HgSO, II ° CH2 = CH - C-CH + H- OB CH2 = CH- C-CH3 Metylvinylxeton

80"

c) Lft'y vinylaxetilen, nhtt tn~n ehuy~n h6a thea cae phan t!ng sau:

CH2=CH-C=CH + Hel _ CEr =CH-y=CH2 Cloropren Cl

Trung hqpCH2=CH-~=CH2 (-CH2-CH=«-CH2- )n

Cl Cl PolicloroprenA + K1Cr1oz1H1SO!

It to

CHJ-~=CH-CH2-CH3 + K2Cr20 7 + 4~S04 -CHJ--<r=O +CH3 -eH2-eOOH C~ C~ MM·

Til eM v(Ji, than dti va cae chat vo cu can thiet kh6ng chua cacbon, hay dilu+ CriS04)3 + K:! S04 + 4~O

Rai 25.

Til nhom cacbua l'll cae chiit l'O cu can thief hay viet cac phuong trinh phti~ ilng dieu chi: i~

~!

a) Cao su buna.

b) Vinylmelylxeton.

c) Cao su policloropren.

LOi giai

I

I Ban d<1u tu AI4C3 ta ditu ch~ ra axetilen theo cac phuong trioo phan U'ng sau: 1 :t

1 . AI4C3 + 12H20 ~ 4AI(OHh + 3CH4 i

jli' 1500"C.IUlJIlg nhe> O2 \' ,

"It' 2CH4 ) CH=CH + 3H2 1;1 Ilm I",h nhanh .. i' I,

i'1'.I!::i' CU2CI1.NH4Cl ), CH =CH-C=-CH Vinylaxetilena} 2CH=CH 2I', Pd

CH;z=CH-q:CH + H2 --4) CHrCH--eH=CH2 :i~ II"

,

, ~? "

'~~;III ~ ~l .

,,'" Ii' '~ :illl .

~.~:III i

a) Polivinyl c/orua d) 2-Brom-4-nitrophenol

b) m-Bromnitrobenzen e) m-Bromphenol

c) p-Bromnitrobenzen f) Axit 2,4-dic!ophenoxiaxetic (2,4-D).

Uri giai

Tru6c h€t dieu ch€ ra axelilen va bcnzen tl-teo cae phuong trinh phim U'ng sau: f· 1400· C

CaC03 ~ Cao + CO2 ; CaO + 3C --~ Ca~ + CO , 600"C J.

Ca~ + 2H20 -~ Ca(OHh + ~H2 ; 3CH=CH ) c;H6

a) Ditu ch€ polivinyl clorua:

CH=CH + HC] ~ CH2=CH Vinyl clorua I Cl

--

'iF nCH,=CH ~ I (--CH2- yH-) P.V.c. oH Cll hai nhom: NO-) 11' - (:1 \ CI n ~y.Br va PH deu dinh ­

:1\1,~ L8J-I- Brz -- -l- HEr htr<fmg cho nguyen c) Di.6u che m-Brornnitrobcnzen: I tu br6m VaG vi tIi I­

NO, N0 2 N0 2 I

@ I I

+ HNO HzS04 • H20 e) Dieu che m-B~omphenol: I3 to

@- +

Lay m-Bromnitropcnzen dieu che nhv 6 di~m b, eho chuyen h6a thee. Cc1::: N0 2 N02

@ philO lmg sau: I

Nh6m N02 duaFe, e Br I ~- + HBr Br+ Br2 nhom mm v~lO vi II~Br trf meta. ©.- + 13Fe + 7HCI­ ~+ 3FcCl:! + 2H7.0

c) Dieu che p-Bromnitrobenzcn: lSl-NH3C:

I

NOz

Br Br Br\

Fe, to@ + Be2 © + HD. ~ I + Nil, @l + N~CINguyen tit L2f-NHjCl NH2 Ihalogen dlIa

BrSr nh6m mm VaG , ,.,vi trf para. t,~ i

HzS0+ HN03 4.@ 'c$J + H20 ~ + p2 ~0NaN + 211CI 0't-5't e + NaCl + 21120

NH2 I N2 C1N02

Br Br d) Dieu che 2-Brom-4-nitrophenol.

I

toLAy p-Bromnitrobcnzen dieu cht nhu b diem (c) cho chuy(~n hoa thea cae; H2<DV@lN2ct - @lOll +HCI + ~J

Iphan U'ng sau: ; . 1­

ONa

/'1' , :7['· I,•.

i"' i i-

Amin b~c 1 phlmlU'ng v6i axit nitra HN02 (t<;\o ra nha !NaN02 + Hel) t<.t0

thanh mu6i diazoni RNlCI-. Mu6i diazoni eua amin beo bi ppfln huy ngay thanh + 2NaOH d~c t° • + NaBr + H2O nIQU; mu6i diazoni ella amin tham ben b nhi~t d¢ th~p, khi dun n6ng nh9 t<.i0 rac$J

j

phenol.N02l~2 f) Axit 2,4-diclop*noxiaxctic.OH

~a I~CI + NaCI+ HCI CII\Qj-0-CHz-COOHc$J

N02NOz +) Tnr6"c het dieu ~he ra phenol va axit monocloaxetie: I

'I Fe, t 0 ~Cl@ -+1 el2 -- L.QJ +1 HCl

~'

1

ap sU:lt cao, tOcao("nyCl , ~ONa& +2Na0H1~c l0 + NuCI + H20

_@yONa (~OH'0 + CO2 + H20 --~ & + NaIlC0 3

/-,0CH==CH + H20 , HgS04,80<t; CH)-C;' ­

"H

AO2 CH)-C ~ + 0 (CH)COOhMn 2 CH3COOH

"H 2 :, I

; I ; as'

Ci 13C001-1 + CQ CI-CH2-COOH -I- liC! I I' " '1 -L'. I'!'" I Axil monocloaxetic 1I:i ! I.

~ ~ I +) Sau do dieu ch€ 2,4-D then hai cach sau:

:(",'11:,:11 Dclll: ~ '\ It \ I,

~ \:.1 1

:

I ,"r' \ yH2-COOH + 2NaOH @-O-CH2-COON~~@-OH +ilr Cl -~-_ ...--.. -------;~-_.-~.

'-----, + NaCI + 2 H20 ill:1 ,

. " I 1·1', ".'!'

Il'\'" Cl

i'(: ' ~\-O-CI-h-COONa + 2 C~ Cl-«(j)-O-CH2-COOll

\11\I.i.' ... :.Ii::,::::: + NaCI + HCl

i, 1.1'::.11."'::,"'::'Ii Dch2: Ii" : 11I,::1, I ' . ~Clilll'l \1': ' @-OH + 2 C~ -- Cl-\Qj-0H + 2HCI

W:I:; Cl Cl.)!I,I

i I

" I CI-@-OH+ yH,-COOH + 2NaOH _CI-@~0-CH2-COONa \1:

~ Cl I' + NaCI + 2HzO:1,I

" "

1(, Cl Cl'iii jr; CI--@-O-CH2-COONa + HCl- Cl-@-o-CH2-COOH + NaCI ,

i \ I',

~i ,i

I, ,~

, ,~ i

:1,

" "? J Utu' r,\0 : (T.€~-~() itlq ~c ~.~ ,J' :~ f~Chi dung m{it~thtii !tim thu6c thu hiiy phtin bi?t ba thai long lil benw ~; toluen va stiren dl!ng trong ba It! rieng bi¢t bj mal nhtill.

~ Hal 27.

i LN: .•. ,: UI glal _.,

Dung dung d!ch KMn04 Hun thu&.: Ihu.l~.

+ Ufy m6i cha'l m¢l il l:ic dt'~ 1 v(ri dung dich lhu6c tfm loang, thay mt>t eM lam mat mau thu6c tim 0 nhi~t d¢ thuemg, d6 lil stiren:

~oCH-""CHz ~OCH-CH) QM'­3~ ,+ 2 KMn04 + 4 H20 --3~ OB L)H- + 2 Mn0 + 2KOH (1,;

2 .~!!

+ Hai chal con l'.li cho lac dl.mg vai dung d!ch lhuot.: tim, dun nang va khua'~ d~1I1ien t\lc, sau m!?t thCri gian lhl ffi!?l chat lam cho thu6c lim mat mau, d6 lil tallitH.

((;",CH3 to ~-COOK~ + 2KMn°4 _ ~ t 2. Mn02 +2KOH +H20 )i

,~ Chal kh6ng Hun m~l mau KMn04 d khi \:1 nht?t dt> thuang va khi dun n6ng Ii ,Ibenzen.

)ltBai 28.1.-- <.(

HlJP chdt C611u khi ph{in j'.'lg vOi khi clo co chilu sang tlJu ra hOIl httP hai chat J6'ng phiin CJ//JCl. Xtic dinh cong thuc cii'u t{lO, ten glli clla cac dadS

ltheo IUPAC va viei cac phu01IK trinh phdn ling:

LOi giai

Hqp chat Ct;H 14 c6 th~ c6 cac c6ng thuc ctfu l'.l0 nhu sau:

CH3-CHrCH2-CH2-CH2-CH3; CH3-CH-CH CH2-CH3;r I

(I) CH 3 (2)

CH, 3

CH3-CH2 CH-CHr CH3 ; CH]- CH -CH-Cl13; CH]-C-CH CH r 3I I I I CH3 CH3 CHJ CH

J (3) (4) (5)

O1i co hqp chat (4) khi bi thay the m<)l nguyen tlr hidfC> t~a fa hai chat donh ~I)nan, theo phU'C1ng trlnh phan ling sau:

!lS ;;~ \~ 'I.~ t-a1

}~ .:~,.

5 'CH

3--CH-CH-CH)-Cl + 2HCl

askt / I I " (6) ­

CH)-YH-1H-CH~,-. T 511 :::-<' CH3 CH) )

CH ClI) -- ~ <(IJ CH)-CH-C-CI-l) + 2HCl

I I CH3 CH3 (7)

V~y hqp chat C6H\4 da cho co ten la: 2,3-dimetylbutan.

Hai chfit ~H13Clla cac chAt (6) va (7).

(6) c6 ten la: l-clo-2,3-dimetylbutan.

(7) co ten Iii: 2-clo-2,3-dimetylbutan.

Bai 29. Hqp cJuit CJl6 eo /lim mat mau dung d!ch nuffe brom khimg ? M~t hf!A

chat A co cong thue phdll tu C116, Khi lac dl!ng vOl dung d!ch AgNO) Iron amolliac tqo ra hlJP clui! E. Kh6i IU9'1tg phan tu clla B l{m hun ella A la 158 dv Viet cong thuc ca'u Il}o vd ten gqi eua A thea danh philp IUPAC. -'-.1 J1.

L?i giai.

_Nc'u C(,H c6 c6ng thuG diu t~o l?l @. thl C,H" Iii benzen. khi do G.B.,;6

kh6ng lam mAt ml\U nuac bromo

_N~u C c6 cAu lao m?ch ha, chi d~:6H6

CHJ-C=C-Cij2~C,=CH ; CH2=CH-CH=CH-C=CH;

CH =C=CH-CH=C=CH... thl ~H6 thu,,?c lo~i hqp chAt kh6ng no, 2

Hun mAt m?lU nuac br6m nhu nnk.en va ankin, thea phucmg tr'inh phan U'ng chung:

Ct,H6 + 4Dr1 -)- ~H6Br8

_ Hidrocacbon philO dng vOi dung dich AgNOJ trong NH) thl hidrocacbon 'I phai thu¢c lo~i ankin-l. Khi thay the' m¢t nguytn ttr hidro bang; m(H nguyen ttr b~! thl Jr.h6i lUQllg phful ttr tang 80 - 1 ~ 79 dve. Ta c6 s6 nguyen til Ag trong rnQt p~ .

-, '. M B _ M A 158 lU B la. = __ = 2 .

79 79 ~

V~y A c6 d',mg tong quat: H(:=;C-~H4-(:=;CH C~u tao A cO the I" HCooC-CH,-CH,-GCH-,

HG C-CH-C=CH ! CHJ

Plllrcmg trlllh ph3n 1ing chung:

-. !' :

I-IC=C-C2 Hc C.=CH + 2lAg(NH)):dOH -) Ag-C,=C-C2H4·-GC-Ag

(11) + H20 +14NH)

(1) C6 tcn la: Hcx3uiin-l,S.

(2) C6 ten la: 3-Metylpen'adjio-l,4. I

Bai 30.

lPhenol va anilin di'u lam mal mau dung dicl, I1UOt' bram, nhung toluen khong lam mat mau mi6c bromo Tir kei qud Ih,!c Ilglzi¢m .16 co thl rut ra dUflc kitt

, Iuan gi? Anisol (metylphenyJete) co lam mat mau nu'fre br6m hay kh6ng? Nlv. cho .d~ng d{ch nude br6m lir Il( vao cac chill p-Io/udi/l (p-aminotoluen), p-cresol (p_ metylphenol), Iheo Ii l~ mol tal do lt11:1, thl'lh .. dUf/c san ph'ilm nao? Giai thich ngan gfln.

(1) "llIg vbng !ham cua anisol s- I" m~n han nhorn ·OIII.m aho rn~( dO electrone .an llcm trong yang thmn ella phenol. .

(2) /(Y In. /(Y /i!.\~O-H ~O-CHJ'i ~ .if;

- Phao ling cua p-toludin VA p-Crcsol vOi ntrO'c hr6m: ,~"ij

~

Uri giai

- Phan I1ng ella phenol, anilin, toluen vOi nLIaC br6m:

OB

@ ~

OH

+ ,3 BT2 B,~nrj t- 311Br

Br

NH 2 NH2

@ + .3 BTl ~ n'L§j-B'j + 3HRr

I Dr

CHJ

@ + Br2 ~ Kh60g phJI1 ttng

cr " .-<IC phan ung tren chUng to cae nhom -OH - , ­

cerron van yang thrnn h h ,-NH2 la nhvng nh6m daym?n on nh6m -CH).

- Anisol rHO CH - , . - d' '-{, r. - J se lam mar mail mrac brom Vi h' CH' .I se ay electron ve phfa yang thom h " I 11 om - ) lien ker v6i

,:... .~J;'

:' , ~ii~

~ NH 2

+ Br2 ~llr NH2

+ HBr

~

,

.~

~ OH

+ Bf2 ~llr OH

+ HBr ,It

Vi de oh6m -OH va -NH2 g~y anh huang m~h hem nh6m -CH3 n~n nguy.

1\1 br6m se the' nguyen tir hidro b vi tTl ortho ella nh6m -OH va ella -NH2• .:/"" Bai 3l.

Til toluen hay die'u chi'stilhen (l,2pdiphenyletilen). chat miy CO dong Ph1" cis-, trans- hay khong? '

LOi giai .~."

I

I,

~oCH2Cl~yCH3 askt ~~ + He) . il

lQ) + C~ --­n~~

f ~ Ii' '. I 1. 1

.' . .1 H C1 ~oCH,=CH2~O~oC 2 ~ ~ - ~ + 2NaCI2~ + 2Na

IiII I (§:rCH2.-CH,-@ ~ ~CH=CH~ +H,

:1 Stilben

Vi m6i nguyen tv eaebon eua lien ket d6i trong Stilben d~u lien ket vCri

nhom nguyen ttT }iliac nhau, do v~y ch~t nay co dJng phtln hlnh hQc.

L01 giai

Khi hqp ch~1 c6 nhieu lien k€1 d6i Ih. la phai bitll dien cae d\lllg d6/lg phil/l

cis-, trans- eua tat d cae lien ket d6i. D6i vOi axil linoleic VI hai lien ket doi C=C

khbng c6 de nh6m gi6ng nhau, do v~y se e6 b6n d6ng phf1n:

fl, J-f H H H H H (CHZ)7COOH" /- \. / " / " /C=C C = C C::=C C = C

/ ", / \. / \. / " CHJCCH2)4 CHz (CHzhCOOH CHJ(CHz)4 CHz H

cis-, cis­ trans- cis­

CH3(CHz)4 H II H CHJ (CHz)4 H H (CH2hCOOII" /" / \. / \. /C=C C = C C=C C = C / "/ " H/ " / \.H CHz (CHZ)7COOH CHz H

trans- trans­cis-, trans-

Bai 33. >: Viet ddy du cac phuang trill}, plllin lfng theo cac SCI do chuytn hoa sau:

a)

+ Oz + Oz CH ::=CtI Trlll1g hqp .. CH2=CHz.,· A • n ---0--· C Pohvmy

Pd~12, Cuelz (CH 3COOhMn Pd, 160 C, 5atOl axetat 100 C. 30 atm

... flNO] ..b) XicJohexanol Axit adipic CA') CN

I .. Hel . + NaCNButadicn-l,3 I,4-dlclobutan -~ (CfH2)4-)­

eN ---.!..!.!J.!!'~ Hexametilendiamin +A' ... nilon-6,6.

LOi giai .;

C6H~ /HH" /H C==C a) C phai la vinyl axetat CH)COO-CH=CH2. Giai dO<;J.n truae ella sa d6 la qua

C=C va H/ "­/ "- rIM san xuilt ax it axetie tir etilen. Do v~y A la andehit axetic; B la axit axetic. caeC6HS

C6HS C6HS .huang trlnh phan U'ng:trans-Stilbeneis-Stilben

oBai31· PdCb, CuCb 1­2CHi"'CHz + Oz . 2 CH3-C (A)Axil linoleic co eong thue eau tl}O nhu sau: 100°C, 30 atm \.H

CHr(CH2)4-CH=CH-CH2-CH=CH-CCH2)7-COOH CHrCHO + Oz (CH)COOhMn

, 2CH3COOH (B)Viet cong thue billA diin Ntu hinh cis c !ram' c cua phan til axil linoleic.

.f

C H60 co th~ la:1 Pd,160oC

J2 CH)COOH+ 2CHz=CI-'2 + 02 c _._ 2CH)-COOCH==CHz + 2 HzO (C)

,t.;0

H -CH-,-CH- ,

'-~

CHJ-CH2'-:"'C~ ° CH)-C-CH) CM2=CH-0-CH)CH2 == r Truog hqp

! " H ' "-9 ) Polivinyl axel,

I ( ° ~"1 - Theo c6n~ thue ella CJ H40 Z don chue thl c6 th~ c6:CH)-C==O CH)-C==O J n

,t.;0b) So d6 nay bieu ditn qua trinh t6ng hgp nilon-6,6 tu xiclohexanol CH3~CH2-COOH va H-C~

" ibutadien. 0-CH=CH2

VlB ~C' to

COOH I

(yH2)4 + 8 ~~2 + 5 H20 (A')+8HNO) ­ I suy fa B la CH2=CH-d'°(5 COOH "H

peoxi/ ) Cl-CH2-CHz-CHz-CHz-CI CH-,=CH-c7 °CHz=CH-CH=CHz + 2HCI C'la - "OH

N=C(CH2)rC=N + 2NaCI .:\

,t.;0 ,t.;0 O-CH2-(CH2h-CHz-Cl + 2NaCN ~

N' /0 V~y A la: <tl-h-CHTC~ va C la H-C~HzN-CHr(CHz)rCHz-NHzN=C(CHz)4-C=N + 4Hz I, )

H "O-CH=CHz

H Olc phuong ,trlnh phim ling minh h<;>a:NH [0 0 J

z rOO I z Trung ngun~ ~C-(CH2)4-< + (n+l)H O(rH2)4+ n (rH2)6 / HN -(CH: )6-N n

Z Ni.r o ,t.;0.-112 ) (\:B CH2=CH-~° + Hz ) CH)-CH-C~COOH NHz . Nilon-6,6

I J. "

B (OJ ) C': CH2=CH-JO AgNO){NH) ) CH2=CH2~° Bai 33a. "H "OH

Ba hl!]J chill A, B, C mach ho- co cong Ihuc phim IU luang itng CJH

A' la CH2=CH-CHz-OH.CJH/J, CJH 4 0 2 co cae tinh chat sau:

_ A, B kh6ng lac dlfng vOi Na; khi hl!]J vOi lIz cung I~o ra mfll san ph A' (oJ) B: CHz=CH-CHz-OH Cuf ) C~=CH-d'° + ~

nhunhau: ! "H +) Ph:tn bi~t ~ 1<;> A, A', B, C.

- B hl!]J H 2 I~o ra A. !'l

- U(y m6i c~:.'t m¢t it cho tac d'-;Ing v&i dung djch NaHCOJ , thl m¢t ch:.'t lam_A co dong phan A' khi bi oxi hoa Ihi A' I~o ra B. sui b<;>t khi, do la axit C':

_C co dong phan C' cung Ihu9C lo~i dun chile nhu C. .Wl) CHz=CH-COOH + NaHCO) ~ CHz=CH-COONa + H20 + COz t.

- Khi oxi hoa B Ihu dUl!c C'. I

~ - Ba chat con I~i cho tac d'-;Ing vo; natri, thl m¢t chSt t<;1o fa khi Hz bay ra, do la Hiiy phan bi41 A, A', B, C' trong 41fJ mat nhii". "ruqu A':

LOi giai CHz=CI-!-CH20H + Na. --) CHc=CH-CHrONa + 112Hz ~

+) Vi kh6ng phan Ung v6i Na, nen A, B kh6ng chCra llhom -OH. V~y If.t~

- Hai andehit dem cho phin ung trang glJoog, sau d6 ltiy san ph~m cho Phant ling v6i dung d!ch nlJoc br6m, Still rh~m nao lam mat mau mroc br()m la cha't co ChuaIMt,.• Xtic dl"h cong thuc clla C, B, A, D. Cho biet tinh chat hoa hoc dac trung c' { .

· I h' '. uaomiien ket d6i C=C, d6 la do B t<;iO ra. . : nhom dIII 1 C uc trong chat A. Viet cac phuong trinh phan ring. .

Rai 34. , i LOi giai

H9P chat A co cong thrlc phan tu C28H jsO/9- Khi dUll nong 1 mol A tronijff' +) A phiin ling v6i ki~m £<.10 ra haza n la khi. Suy ra A la mu6i amoni ho~cdllng djch H 2S04 loang thu dU{1c dung dlch B chrla 2 mol Cr/I/106 va 8 mo mu6i cua amin:

CHjCOOH. B phdn {(ng vOi dung djch AgNOj trong amoniac tlJo ra Ag. Mij.t kha CJ H7COONH4 ho~c RCOONH)R'.kh; dun nong 1 mol A trong dung djch NaOH thu dUf!c du.ng djch C co chua 1 mOli

CI1~II1,O/l' ~ kho~g c_o phan ung trang gU01lg. Xac dinh cong thue cau tlJo cua A ~ +) Xac dinh axit C. VI, .~c = 74 n~n C chi co I nh6m ~COOH. V~y C la

(chi dung cae chat da hiJc). ( , CH)-CH2-COOH. Suy fa B phal la CHJNH2vay Ala CH CH CO OH ~! -C'II . J 2 J JY J.

cac phlJO'I1g trinh phan l1ng :LOigiai

iV­ - l!l 0

CH J CH2CO OHJ N -CII) + NaOH ~CHJCH2COONa + CH)-NH2 t + H

20

- VI thuy phan I mol A trang m6i tNang ax it t~o ra 8 mol CH)COOH va (A) (B)mol C,H I20 o. Suy fa A chua 8 nh6m este cua saccafoza ho~c mantoza v6i axit axetic

I

2CHJCH2COONa + H2S04 ~ 2CHJ-CH2COOH + Na S0(?) H~ 2 40

C12IlI403,0-C-CH) 8 + 9H20 ~ 2 C6HI20 6 + 8 CH)COOH (C)

_.?O- Dung d!ch C chua CIlHi2011' V~y do la saccaroza ho~c rnantoza. rna fJ---. -7-°CH)CH2-C"D0H3~ -CH CH3CH2-C" + H 0kh6ng co phan lmg trang gtwng, v~y CI2HnOIl la saccaroza. 3 2NH--CH3

Cong thuc ctlu t~o cua A Ii'!.: (D) +) Trong D c6 lien ktt

thu<,>c 10'.li li~n ktt amit, li~n kct nay H20

Ac I!I kern b~1l trong ki~rn va -C-7-°:K;jAC IIAc ,

H ~o H AcO H2 ° H Ung sau; "­N- trong axit theo cac phl1C1ng trlnh phan Ac tuc In vitI tat

Iella tLr axetylHL ,/ 0 CH20Ac -7-° e fJ-:?"O R-C..... + OIl __ -7-°H OAc OAc H CH3-C" "NH-R' R-C" e + R'NH2 o

Trong rn6i tNang axit lhi d nhom chl1c este va disaccaril d~u bi thuy phAt -7-°Do do trang 2 mol ~H1206 thi co 1 mol glucozC1 va I mol fnlctozC1. Co glucoza ne:

t

R-C" + H20 + He toNH-R' -- R_c-7-° + R'NII~

co phan ling trang b~~c. "OH

Khi thllY phftn trong m6i tflJang kiem chi c6 nhom este bi thuy ph.a,

disaccarit kh6ng bi thuy phan, do do kh6ng t~o ra glucoza. Hqp chtit CI2H22~ NAM nAI TRAC NGHI~M. khong c6 phan ling trang gl1ang la saccarozC1.

,- Ch9n cdu Ird 107 ho{ic nh(m d/nh dl~ng IrOllg cae bai 19P dum ddy, Iy gidi ngall Rai 35. iJn ho{ic viet ale phuang Irinlr phdn ling minh }U)Q.

!LJlli!.HiJP chat A co cong thrtc C./ll/N02, khi cho A vao dung dlch NaOHloan

dun nong nhi! thery bay ra khi B lam xanh giay quy tim 1161. Axit hoa dung dieI'. .? M~t tht Hch hen andehit A mlJch hu cong hf!P Mi da hai thl H h H ' " '" . ~ _.' . ._ . ham R smh ra ch ' . .-, . . . . J , ,c l' san

con llJr sail phan ling vo! NaOH bang H 2S04 loang, TOI chrmg cat tllU dll11c aXlt ai andehit ban ~ tac .~l;ln~ het ;~ natTl: th,u dU,llc the tich H] dung bang thl tfch , kh -'. I h . , b ~ 74 D ' A h d h h'- D 'h' , 1,; dau. R,et cac the IICh khl va hOl durrc do I ' h " .co Ol uf!llg p an til ang . un nong t U lIf!c r;rp c at va 01 nl/a 'utit, chat A lti:' ~' rong cung n It!t diJ, rip

,

:m a) Andehit d01l chlrc.

"h ~. ;b) Andehit dun chkc chua no chua mqt no; do;.

c) Andehit no chua ha; nhom andehit nhllng khac c{mg thue ca'u tt;lo ne~. tinh chat hoa hqc khac nhau.

!iii 39.d) Andehil chua no hai Ui'n andehit.

Nhilu andehi/,khu dUl!c Ag+ thanh Ag; khu dUlfc C~+ trong Cu(OH)lva Bai 36b.

mo; truimg kUm tt;lo I!uinh CUlO. DUu do chUng to: I Niu dinh nghill d6ng phan ?

a) Andehit Ja hhimg chat khti mt;lnh, do v4y chung se- Jam mat mau dunglJ6ng phan ra nhfmg hlfP ch(i't : djen thuoc tim, mat "Jau dung dich nuO'c bromo

a) Co cung kho'; lu(f1tg phan tu. b) Axit axetic va glixerin ciing phan fmg vOi Cu(OI1JJ, v~y chung ding ltib) Co cung cong thuc phan tti.

nhilng chat khii mC;Jnh nhu andehit. I

c) Co dmg Ihanh phiin phdn tram kho; IUCfTlg eua cac nguyen to. c) Nhom chuc andehit khong cam mat mau dung djch thuoc tim va nuO'cd) Co tinh chat gi6'ng nhau.

brom, vi cac chat KM'n04 va Brlla nhfmg chat oxi hoa ylu hun Ag+ vd C~+. !lli11.

d) Andehil co Ifnh axil vi no phan ling vOi baZ(J CU(OH)l vd oxit baz(f AglO.Hai hfJP chilt A, B deu chi chua C, H, 0, deu co kh6i lurng phan tli bdn 116. Khi cho mOl chat tac d~ng vila het ven NalCOJ thi so' mol COl bay ra bling s Bai40. mol ma; chat dti phdn ung. Khi cho han hf/]1 g6m a mol chtit A va a mol chat dIng hqp hit ven cha't Xl trong dUu ki~n IhEch hlfP, la thu duqc 2a mol chat C. Trong phan tu ca'c . . h' ,.• / ' , " . ' ammoaxlt c ua mot nhom amI 0 (i' h h;': b . san pham duy nhal, khong co dong phfm quang hoc. Toan bo luung chal C kh. ' h' 0t h~ COO . no e n e ut azO" va. ., , e Ua mo n um - H co ti h 't lJ'" .*.t.

phdn ung hel ven NalCO ding Il;lo ra 2a mol khE COl" " n aXI. leu uu ram eho: J

a) A. B la axi' fumaric va axil maleic; X, Ia Br,; C Ia axil 2.3-dibrorn-sucxini . a) Cac hfJP chal do du!"c xip vdo loai chal lUiing tinh.' 8

b) A. B Ia axil fumaric va axi' maleic; X,lll H,; C III axil sucxinic. h) Cac chal do tiln I~i c1 J~ng ion IUiing clfc H3N~RCOO

r:OOH c) Cae hqp chat do co da'y du tinh chat h6a hoc clla amin v" 'tI' ' b . . a cua ax, B Ia CH =C ; X la H2; :cac oxylre.

c) Ala HOOC-CH=CH-COOH; 2 I 2

C:OOH c' d) Khi di~n phan dung dich cac aminoaxit dii hod tan trong dung dichC la HOOC-~H4-COOH.

ie'm, Ihi cac axil am;n chay ve dUn cuc duang (anol).X21a H:,: '- ."d) Ala HO-CH2-CH=CH-CH2-COOH;

B la HO-CH2-CH2-CH=CH2-COOH ;

LOI GIAI cAe BAI TRAc NGHI~M.

iii 36a.

CIa HO-CH2-CH2-CH2-CH2- COOH .

BM 38. (C) dung Khi cho etylen phdn (mg vm nUl]C br6m eo hoa tan nalri clorua, ngUlJi B' Njf'

\..thu duq-c san phdm gom l,2-d;brometan va I-brom-2-cloetaT.l. Diiu nay cho IhayJ c..H2n (CHOh + 2H2 7' c..H2n(CH~OH)2

1 mol 2mol a) Etylen va cac anken co thicqng dong thOi vo-; nhilu chat.

Cn H2n(CH20H)2 + 2Na -+ CnH2n(CH2ONa)2 + H~ t b) Phan tti brom tan cong d6ng thm vao ha; nguyen tlr( cacbon cua noi doi I mol 1 mol

c) 51! cijng hfIP brom va.o no, doi diln ra qua nhUll glai dOC;Jn. ai 36b.

d) Nalri clorua khong nhung cam xuc tac ma e(}n tham gia phdn (mg cijl, Sb) dung. cae d6ng phAn phai c6 cung c6ng thuc phAn tli nhttng khac e6ng /. lihue eau t'.lo nen tfnh cha't h6a hoc khac nhau.

l'fn elv[ell. .

a) sai VI Cu(OHh Hl>04' H2S04 dtu CO M = 98

~H50H, HCOOH, N02 deu co M = 46, rna khong phAi Ia d6ng phAn.

c) sai VI cac chilt trung cung m¢t day d6ng d~ng (vi dl;l: etylen va butyle

lu6n lu6n co % cacbon; % hidro nhu nhau.

Rai 37. (b) dung

HOO~ /H H" ,/COOH <;OOH ~ ~ <;H2

tr'C" ' C ' <;H2

COOH rr '--COOH COOH

A, B C O15:t C kh6ng co cacbon bilt d6i xUng do do kh6ng CO d6ng pht'tn quang hQc.

/_. Rai 3R. (c) dung: Phan Ung c~ng phai ditn ra qua nhi~u giai do~n thl mm co

br6m va clo trong SilO ph:\m.

Rai 39. (a) dung. VI KMn04Va Br2 lil. de chat oxi h6a rat m<;tnh, m<,lnh han r:

nhi~u so v6i Ag+ va Cu2 +.

I, I! I! -:;:;-0

R-C,-­H

1,,"

" II ! _.1 3 R_C::'

O

I ,I

':1 1)

1;1 + {

H

,: I

. R-C~ + 2HBr+ Br2 + H20 ~ '-. OH

+ 2KMn0 + H 0 ~ 3RCOOH + 2Mn02 + 2KOH4 2

2RCOOH + 2KOH ~ 2RCOOK + 2H20

2RCOOK + RCOOH + 2MN02 + H203RCHO + 2KMn04 -----7 II

!lli-4.~.

Trong dung dieh HzS04 60% isobutylen dime hoa t£}O Tn hon h£!p ha; clui! dong phan CsHJ6. HOIl hlJP nay dUflc gfJi IiI diiwbutylen, khi bi hidro hoa /l}o ,thimh 2,2,4-trimetylpen/an (thuimg gfJi m¢/ cach nhtim nhfi Iii isooctall). l/lJP "chat isooctan nay cling iJut!c tlJO ra khi cho isobutan tac d~lIlg vOl isobutylen kJri '~co mal HzSO.J ho(ic hiaroflorua khan HF lam xuc taco Viet cac phuang trinh phdn

"img ~a cO" chtcna hai phdn fmg tren.

Hai 43.

Nitro hoa diphenyl ta thu dUflc nitrodiphellyl. Ti>c d¢ cua phdn ung nhanh tip 40 liin so vOl plu;" l'rng nitro hoa benzen /l}o ra nitrobenzen. Trong hon hlfP

'sdn phdm tlJo Tn thi cac dong phan ortho-, meta- va p-nitrodiphenyl chiem tuang 1.-.-ng ra 68%, 1% va 31%. Tinh Ii s6' giiia h~ si> tOc dij cua phdn (mg the' nguyen tIt

iJro J cac vi tri or/ho, meta, para (fo, 1m' f,J va h~ Sf)' Mc dt! phdn img the' nguyen ii hiaro clla ben,un.

~.

Khi cho t-butyl axetat va etyl axetat tac d~ng vai natri metylat, dung etanollam dung moi, diu thu dUt!c metyl axe/at, nhlmg phdn flng cua etyl axetat

hLJY nhanh gap 10 liin phdn itng cua t-butyl axetat. Mijt khac, khi CO mijt mt!t uCI1Jg nho hiaroclorua thi metanol nhanh chong phdn (mg vOl t-butyl axetat tl}O 'a' axil axetic va t-butylmetylete, trong khi do metanol ll}i phan itng rift chtjm V01 tyl axe/at tl}o ra etanol va metyl axe/al.

:~ Viet cac phumg trinh phdn img bieu dien C(/ chi"cua cac phdn ung tren; co 'he sud~mg d6ng v! 180 nhu the' nao de chitng minh dUt!c ca che' tren.

llt,J]J chiit A (CTPT CJ1sOJ) quang hl!a/, tan tOt /rong nUCtc tl}o dung dich omoi truifng axit. Khi bi dilt nong A tl}o ra B (C~/60~, khong quang hqat, it tan

! ; ,.'tong nutte (dung dich co moi truo-ng axit). Chat B phdn (mg vai KMnO" de hanRai 40. T5:t d deu dung. j i' il. Khi bi oxi hoa blmg dung dich axit cromie loting thi chat A bien thanh cha't J'

'ong C (CJHtfJ) co diem soi th(fp, chat nay khong lam mat mau KMnO", nhung I MVOI BAJ T~p nANH CHO HOC SINH GIOI. I

Bai 41.

1) Cac hqp chat XYC =C = CXY (A) XYC = C = C = CXY (B)

trong do X, Y la nhUng nguyen tii ho(ic nhom nguyen tli khac nhau, co dong ph

cis- , trans- hay khong.

9 9 ,

2) So sanh tinh axit cua CH)-C-CH2-C-CH) va CH 3-CH2-OH .~

'hdn img va; I] trong dung dich NaOH tlJo ra ket tua mau vang.

Cho bitt ca'u tl}o clla A, B, C va viet cac phuung trinh phdn itng.

ai 46.

Hf!P chat quang hfJat A co cong thuc CjHIOO" phdn fmg vOl anhidrit xetic tf;lo ra este chua hai gOl: axetat. A khong cho phd", fmg trang bf;lc vOi dung 'jch AgNOJ Irong amoniac. Trong dung djch axit loting A tl}o thanh metanol 'a chat B (C4Hs0 4 ) quang hfJat, cho phdn ung trang gumg, phan ilng vOi nhidrit axetic tlJo ra este chila ba gac axetat. Khit hoa B thu dUt!c ht!P chat

. " .. 1 222 t -boxyi, hong quang hoqt C (C4H/O04)· Oxi hoa nh~ nhang B thu dUt!c ax.it cacboxylic 3) Hai chat axit 8·bromvalelc va aXIl 4-brombulc of .. Joc ancac .. ,~ (C

4HsOj). Ami! cua axit D phan ung vOi dung dich natri hipoc/orit loting tlJo

chtit nao IiI axit mf;lnh hd1Z. ." .' , _ ..' .' • _ . W

4) Til toluen va cac chat vo cO" can thlet khac, hay Viet sa d~ phan ung dl~ r ~ _~_ L_ ...... ~#.,..I ...... _

1

ra D_(+)glixerandehit (CJ1I60 J). Xac dinh cau fl;lo etta A, B, C, D va viet cal. phucmg trinh phdn ,mg. Cho hiet ecru hinh cua chung. ~

H C6HS'!!i!ill.

Thuy phan hoan Joan pentapeptit thu dUCfc 3mol glixin, lmol alanin va Can phdi tien hanh cac chuyln hoa hoa h9C nhu the nao de kh6ng dinh mol phenylamin. Mijt khac khi thuy phan khong hOlm foan pentapeptit do fa th' 'II(/C diu trUe cua sdn phdm dI! kiln lil dung. dU'fc hon hqp sdn phdm frong do co alanylglixin lI-Ala-Gli-OlI va glixylalanf H-Gli-Ala-Oll. Khi cho peptit nay roc dl;lng v61 axit lIN02 (phu07Jg phap x

LOI GIkI TOM TAT CHO 10 BAI TV 41 DEN BAI 50. d!nh nitCl trong nhom NU2

cua Van Slyke) khong tl;lo ra khi nitCl. Hay xac din'

cong thuc cua peptit.

LUi giai bfli 41.Bai 48.

Co the to'ng hqp l-D-Glucolylcitozin theo SCl d6 sau:

2,4-dietoxypirimid inHBr 1) Hqp eh~t A khOng e6 dOng phftn eis-, trans-. Theo goe lien ket t<:10 ra giiia D-GlucozC1 > tctraaxetat I··bromglucozcl .Ie obitan lai t<;to sp, thi cae nhom XY eua nguyen til cacbon Ie, nam trong m¢t m~t

(CHJCOhO hang vuOng goc v6i m~t phing chua cac nh6m XY eua nguyen til caebon CJ . + NH] dlJ

-+ 4_ctoxy_l_(tctraaxetyl-D-Glueozyl)-pirimidinon-2 -~ I-D-Glueozylcitozin

Viet cong thuc cau tl;lo cua tat cd cac chat tham gia /rang cac chuyin h_. X,, /Xtren va cCl che phdn img vOl 2,4..dietoxypirimidin. Tl;li jiaO khi te/raaxetat . ho~c Cf=C=C

y~ 'ybromglucOZCl phdn ,mg vOl 2,4-dietoxypirimidin kh6ng tl;lo ra 6-etoxy-"

(tetraaxetyl-D-Glucozyl)-pirimididon-2 ?

Bai 49. Hqp eh~t B c6 d6ng pha.n cis-, trans-; t~t eel b6n nh6m XY eua nhiing nguyen Phdn ling giila hqp chat cacbonyl (andehit hoijc xeton) vOi amin btJc m~ caebon C1 va C4 d~4 nam trang cung m¢t m~t phfmg.

co axit lilm xuc tac xdy ra theo cCl chesau: X" /X X" /y

R'NH2 + HEll RNH: (1) C=C=Cc-=C va C=C=O=C y/ "y y/ 'x(2)R COl!l H R2CO + HEll 2

2) Tinh axit eua pentandion-2,4 160 hoo eua ctanol. Trang thl!c te ch~t @

ntandion-2,4 (axetylflXcton) cling gi6ng nhu cae hqp ch~t 1,3-dixeton kh:k t6n t~iR, ~H2-R -H20 R, @/Hcd\I + H2N - R' -- C ~ C = N :;== R2C=N-R' (3) d<;tng enol b~n viing: I IR2 ~ K 'OH K 'R'

o 0 ......... H· ..(A)

Gilli dOl;ln tl;lo ra (A) lil giai dOl;ln chtJm nhat cua cd qua trinh phdn unl CH -~-CH -t-CH - ??i 50

'1;'; Ihii!l n6ng d9 cae ehal amin va hW ehal eaebonyl ban ,tdu diu 1Ji 1 mol/I. '/:' . J (15%')' J - C.", /"C, ,(8 v.) pH cua hon hqp phdn (mg de If;li do toe dq phdn img giiia mtlt hf!P chat cacbon . 0 cHi' <; CH~ co K =10-14 vOi mqt amin co KB =10-11

, dl;lt gia try clfcdl;li. Toe dq cua phdn Un H B

gia tri pH do 1611 gap bao nhiiu Uin Mc dq cua phdn u-ng u pH =0; It pH = 71.·ng ;nol c,hi€m 8~%,.,n.hG ~6 e~~t c6, tinh ax.it. (De ti¢n so sanh ta c6 the tham khao Bili 50. . chang 56 pha.n 11 aXlt k. cua cac cha.t: ka cua axit axctic Io·~I. cua ctanol 10'16.

__ . a pcntandion-2,4: 1019). "

Tiln han}, phdn {(ng hidrobo hoa J-phenylxiclohexen, sau do ox; hoa bd , 11,0" 'fn phdm Ihu dade dl! kiln co diu lao nha sau:, I 3) Axito·bromvalcic BI-CH,-CH,-CH,-CH,-COOH ~C)

,Jf

3

I'"

/CH2-CH2

Axit 4-hrombixiclo[2.2.2.]cacboxylic Br-·6--CH,--CI-h ""C-COOH"" - -/CH2-CH2 (D)

1l1i ghii hili 42.

PhU'ang trinh pld,n lIng chung:

yH) CH)-C-CH==C-CH) (20'%)

eMit D 111. axit lTl'.illh han C. Trang ca hai ch1't C, D tht nguyen ttt brom co d9 ilm dl' H2S04~ ell) eH3 . CH1=....

100, hut electron, co hi~u l'mg -I HUll tang t1nh axit clla nh6m -COOH so voi de CH3-« == CH2 -- \ ~±L' CH]-C-Clh-CH-CH tlfffilg lrng kh6ng co chua bromo Trang phnll tlr D. th! braIn hut electron lam cho ' CH1 . \H) -?,CII2 (~H] - ell dt> electron xung quanh nh6m -COOH cllUy~n dicb v~ phia brom thea ba nga, ~ . CH3-«-CH1-·C, CH (800/<) ] trong cht\t C chi co ml)t nga: ~~ 0

"diisobutylen"-£--:~ Br~COOIIBr ",,-~COOH

«H) CH3JhSO~ ..2) CH3-«-H CH3-« == CH2 CH3-C -CIL-CH-CH3l1o~c JTF1,/...·· (D) (C) CH3 CH3 CH3 ~ CH3

M~t khac do h¢ yang trang D la Clmg Bhac, nhung trong C co sv quay tv, ." · k' d ' h h . C ' h" .. . i I" che phan Img (I)xung quanh cac 1i<~n et em, lam cop An tv ,co t e t6n [~11 Cf diu ( <,mg, [rang .

nguyen tll br6m agfin nhom -COOH: . H S0 = 11+ + HS0 ­2 4 4 JjS()~- = Jj+ + so;­

b­ VI tren nguyen tll bram co m~t dl? di~n tieh ~m CH =C/CH3

I 100, tgO ra xung quanh no m9t di¢n tlUang Hun cho&OOOH ctl) n ~ CH3"e /CH3 '2 "CH CH3 CII]~ 0 C ] I /proton kh6 bj tach ra, do do lam giam tfnh axil. /C = CHz + H == -----CH3-«-CH2-C~--I

CII3 CH3 CII] CH3 \CH34) Tit toluen dieu che m-~ramtoluen:

CH3 ijCII2 CH3e I ,

-H CH3-<;-CH2- C'CH + C1h-C-CH=C-CH3©tor CH3 3 'Ctl] CH3CH] CH3 CH3 CH3

Co che phan U'ng (2).©HNO,M,SO: ~ !:efI:ICl ~ (CII,CO),~ $Br,,c H, COO,II

Ban dftu do lac dl.mg xuc rac cLla axit H;>S04 ho~c HF xay ra phan lmg polime N02 NH2 NH-Ac a coa hai phAn ttl isobutylen 1<,\0 ra cation actylic (A) nblI giai do(~n dau cLla co che

,an tlng (1):

CIi) CH) CH3 CH3 CH ('1{HF I 3 /-,r3~- NaNO/He! 2 CH)-C=CH2 --- CH3-C-CH2-C~ (A) (2.1 )I, ~~ o HPO" &" CI-I3 CH • CH]

3

Carion octylic yBr yBr O-See ~Br -N 2 ~Br

I"

NH-Ac NH2 N~Cf? QItion nay phan lmg v6i isobutan va tach di nguyen tll hidra lien ke't v6i

bon b~c ba nhl! la anion hidrua:

~ <;H3 /CH3/lr. j9H3 «H3 <;H] <;H3 . CH)-C-CHz-C e.../ t -H C- CHJ - CH3-C-CH -CH + CHJ-C 0 (2.2)I:' 2I " I' I I I

CH3 CH3 CH] CII) CH3 CII3i. '.' , I,

2,2,4-trimerylpenran (B)''': ,I; .

:d \ii I

Cation t-butylic (B) t~o ra l~i rhan (qlg vOi isobutylen, t~o ra cation (A) m6i:

yH) /CH)C(H~ /CH) CH)-C° + CHz=C . CH)-y-CHz--C~ (2.3)

I " CH) CH)CH) CH) (A)

Tu d6 die phan lIng (2.2) va (2.3) lu6n phi~n nhau t~o ra san phfun 2,2

trimcty)pcntan.

LOi giai hili 43.

Set d6 phucmg trll1h phan ling:

@-@ HNOJM,SO~ ~ NO, ,~ ~ cSr

+

C$J@-NO' NO z

p-nitrodiphcnylortho- m-

Phan ling eua bcnzcn:

©rNO HNO)'tI2S04 ,@ .

,~ 1fc' V~y k o _ ~O~ == 0,6

fm '= k; - 4.100 I

40.6k~Con d6ng phfin para chiem 31 % nen ta e6: 2kp = --.31 ! 100 i k I p 40.6.31

[Suyra pT -=---:= 37,2l,kb 2.1 00

I LOi giai bai 44.

!

Co che phan lIngr vCri natri metylat:

(00rI) ~e I rc _R00 ~ ,~ -f dH)Ol) CHJ-C"O_R CH)-C-O-R ~ CH)-C I "OCH) : O-CH]

. R I:' . b I ) yH] h' .. d d . , I h" ] ) Khl d g6e t- ~ty CH]-y- t J glal o<;ln [tu eualP an tnlg (

sc rftt ch~m vi g6e t-butyl co kfeh th~6b 100, gAy an ngii kh6ng gian m<,mh. Khi R Jil 6c etyl CH:;-CHz- th) IsV an ngfr kh6ng gian it hem rat nhitu; VI the phan ling eoa tyJ axetat xay ra nhanhlhan phan lIng ella t-butyl axetat. I

I I

Ca ch€ phiin lIng! VOl metano) khi c6 m~t xue tac axit co thi 1:1 m¢t trang cae ado sau:

[OH~ OI~+ + I .. 2) CH2-C~ ! J-f> ~ CH)-£-O-R +CHJOH I -H G>

CH3-'-C-O-R"O-R

_ Kf hi~u h~ s6 t6c d¢ phan Ung the m6i nguyen tu hidtro ella benzen lit kb~ 1 mOCH)

t6ng s6 mol nitrobenzcn tlHmg lIng vCri 6 kb• ~, OJH @

oI ,n. I -ROH /I_ Kf h!~u h¢ s6 t6e d¢ phan Ung the' m6i nguyen tti hlldro acae vi trf ort CH)-C-O-R CH)-C-O-CH)

mcta-, para- ella diphenyl tucmg lIng la ~, km va kp. Vi trong phfin tir diphenyl co:""' OCHj nguyen tir hidra ortho-, 4 nguytn ttt hiddra meta- va 2 nguytn tll hidro para-, do t6ng s6 mol san phim cua phan Ung the' a cae vi tn tucmg lmg vOi 4ko ' 4km va ':" o

i cae ti s6 dn tfnh lh f = kJkb; fm = k,jkll va fp = k/kb' ~I 3) II o 1/ G:> ~ o CI-h-C-O~~ \-R ,+ H0~ CH)-C-O-R ~ CH2-C + R0

_ VI t6e dq toan phan phan Ung the' eua diphcnyl gap 40 Ian ella benzenj H 'OH v~y: t6ng s6 s6 mol san pharo the (cac d6ng phan) ella diphenylla 40.6kb•

R° + CH)OH ~ R-O-CH] + HG:>40.6k b

~

;

_VI d6ng phan ortho chiem 68% ta c6: 4~ == ---.68100 Vi caebocation b~:c ba m6'i ben va d~ t~o thanh, do v~y khi R la g6e

va f = .~ =:: 40.6.68 := 408 butyl thl t<;to ra (CHJhC'" phan ung xay ra nhanh, t<;to ra axit va etc tuc la phan lIng .y k 4.100 'O'

b 'y fa theo sa d6 (3). Khi R Ifl g6c etyl thi vi~c t~o ra cation 40.6k b l-CH2EB Ia kh6ng thu~n lqi, khi d6 ph:ln (rng xjy ra theo ca ahc & sa d6 (2) t~o fa

_Tucmg tl! VI <.16ng phan meta chie'm J % ta c6: 4k rn .::: -~.l (ofJtc m6'i va rlCqu.

m

!Y./

D~ chung minh co ch6 nao la dung, ra dung metanal chrJu J6ng vi 18

0 PR-C NaOCI(CH1-I~O-H). Neu phfm ung x~y ra rhea CC1 che (1) va (2) thl chi c6 este t<.l0 thanh~, RNH2

m6i chua dong v~ Ilia. Nguqc l~i neu phan ling tuftn thea co che (3) thl ere t~o ~ "NH2

chlra d6ng vi Ilia. PTrong lNang h<Jp amil clla axit D. C3H70 3-C\, , NlI2Lo; giai bai 45. : phan rlng t~o ra glixerandehit, nhl! v~y

~ nh6m amino NH2 t~o ra dii bi thuy phfin t~o ra nh6m _c..0l· "HCong thrJc cae hqp chat A, n, CIa: i}ll Di lui lLr chAt cu6i la c6:

CH)-CH~CH-COOH (ll) CHO J>;JH2 CONHJ COJHCHJ-~H-(]-I2-COOH (A) I I ~NaOCIH-C-OH ~ +­I

CHOfl CHOHOB CHOH ,,~f H-C-OH H-C-OHCH20H

I I

J I H-C-OH o CB20H CH20H I

CH20HD-Glixerandehit/- II (C)va CH)-C-CH) o Qic phl10ng tdnh phan lIng: +) oru hlnh clla nguyen tli ~ cua hgp chit 0 du(.1c xac dinh dqa rheo chuy~n

to h6a sau:(I)CH)-CH=CH-COOH + IhOCH)-~H-CH2-COOH --- JQlD B ~ COH

! I

o . Hqp chfit B eho phitn Ung trang gl1ang, phan ung vOi (CH)CO)20 t~o raI, 2- + 1I "triaxetat V~lY B la mOllosaccarit c6 nh6m andehit va ba nh6m -OH, khi khu h6a flhom

3CH3-~H-Cl12-COOH +- 2C..o4 + 10 H --+0 3CH)-C-CH2-COOH andehit t~o ra chtft khc>ng quang hQat (C). OB + 2Cr 3+ -+ 8 H20 (2) C02H CI-IO

~H20H H-C-(HI rO) H-C-OH H-C-OHI ~ I l!:!L

~ H-c-oH H-C-OI I H-C-OH'I ::: o 0

I I

1::'·( CHi)H CH20H CI-I20HII to 1/ ,. r , :

CH)-C-CH2-COOH - CH)-C-CH] + C02 (3) D B C II.,

do cae phan ling (2) va (3) nen oxi h6a A bang H2Cr04 t~o ra C)H60. (khong quang hO~I) ! Khi thuy phAn trong mC>i truang axil, tv chat A thu dugc B va metanol, v~y A ! i o ·_·a meryl glicozit. Suy ra cau truc ella A, B c6 th~ la:

1/" CH)-C-CH) + 312 + 4 NaOH - CH1J~ + CH]COONa + 3Nal + J H20 (4)

.) I

vimg HO-[:l0

H-l-Oll 0[ He H-~-OC1-IJ CH]-O-c-l

I I I I IH-C-OH H'-C-OH -- H-C-OH ° hoar H-C-OH 0

I H I I ~ I -CHJOH I ~ ILOi giai bai 46. ~i H-~-O~ H-<;:-O~ H-y-O~ . H-¢-OH I .,m CH2 CH2 CH

2 CHz --' ' BD-(+)-glixerandehit co ca'u truc la:+) (A) CHO d':tng p- d~ng.a

I a-Glicozit melyl O-Glicozit melylH-C-OH

CI-I20H

LOi giai bai 47.Phim lmg cua natri hipoelorit NaOCI vai amit li'lm mat di nguyen tit cae'

clb nh6m amit va tao ra amiL: ' .~I~

~../\­

t

Pentapeptit 1110) 3g\ix.in + alanin + fcnylamin

H20 H-A:la-Gli-OH + H-Ala-Gli-OH

Tit ket qua tfen ta th~y g6c Alanin lien ket veri hai g6c glixin. Vi kh6ng t<;to N trang phan tffig Van Slyke, suy fa pentapeptit kh6ng e6 nh6m -NH2 ttl do. C6ij

1

2

c~u t~o b~e m¢t thoa man:

9Ii-Ala-Gli-Fen-jli va Gli-Ala-Gli-Gli-FenI ~ J

(B)(A)

Tuela

~ o CII, 0 0 CII, 0 0 l' I l' l' I cf l'

HN -CH'-C'NII-CII-C,Nil-CII'--C'NH-CI1- 'NII-CH,-1 (A)

I

o CH, 0 0 0 0 l' I 1'. // r! //

- HN -CII,-C'Nil-CH-C,NH-CH,-C'NH_CII,_ 'NH-CH-C va (B) ~

I

LOi giai bai 48

2,4.Dietoxypirimidin

CH20H A~OH2 .~;° CzIIsO N O~Hs

OAc • (CHJCO)20 AcO Sr1I0~1I

HBr

OAeOH tetraaxetat l-BromglueozC1 D-GlucOza

OC2H5 OCzH:s

N P-CzHs N 0A~II' ~10e 2 5 ~~H' ~.1AcO OAc Br -C H Br

OAe. -AcO

OAe OAe 4-etoxy-I-(tetraaxetyl-D­Glueozyl)-pirimidon-2

;~ CHzOH l ~

NH], • H AC Iii kf hj~u eua CHJ-C.P - C2HsOH HO "­0

0

-4CH3COOH OH

I-G-Glucozylcitizin I

Trong phc'm Ung kh6ng t~o ra 6-etoxy-l-(tetraaxetyl-D-GlueozY1)-pirinlHhn-2:

Ae-O N~ I II._.~

C2H5c:('N 0 6

z 5~NI

OAe ~_.)4 AeO C 2HsO N) OCZH5 ~

OAc 2,4-dictoxypirimidin

ue la phan lrng kh6ng dy fa tren nguyen ttl nita b vi tri 3 l,1Ua pitimidin, VI nguyen tu ay b! an ngfr kh6ng gian f~'t m~nh, han the nfra, cae nh6m ctoxy b de V! trf ortho­ua nguyen tu nita nay lam giam tfnh baza tue la giam khc'1 nangiphin Ung eua n6 v6i ae dAn xuat halogen.

LOi ghii bai 49

Kf hi~u n6ng d¢ cae chat va ion nhtt sau:

a = [(CH3hCO] e = [(CHJ)z C 0 Ell

H]

e b == [RNH2] y == [RN HJ]

x = [He) z;;: [Oir]

+) Hang s6 kb eua de chat duqc xac ltlp thea cae phtrcmg lrinh sau:

I

,o 3 1 2

e e k = [RNH]].[OH'J 1"' d~ -k (1+I0 x+I0 x )_x(I03 +2.l0 J x)\1 Nhlfvay " - .----------=---=---~-:--__~

RNH 2 + HOH ~ RNB) OH n i}/i;: . {x (I+I03x+103x2f[RNH2]

T6c d~ v c'!e d~i khi dv/dx == 0, tue la I - lO]x2 =: 0,. y. z (1)theo de ki hicu n6ng d6 nhv trcn ta e6: kB == - ­.. b rUt ra x = ~ == 3,2.1 0-2 •

Kw KW

V~y t6c d~ phan lrng d~t gia tIi Ct!C d':li a [H+] =: x =3,2.10'2.- VI [H+].[OH-] := Kw = 10'14 ~ [OH']:= [lr] tIre la z:= - X (2) Suy ra pH == -lg[JI+] := -lg(3,2. ID'2) == 1,5.

3 _Thea de bai n6ng d<! cae eMit ban dAti b~ng 1mol/! n~n ta eo: h t' IA v(pHI.5) _ 32, 10. 2+)T' Ie ---- -'--3 ­InEEl

• V(pIfO) 33 2.10[RNHzJ + [Rt:.J H J] =I tue 130 b + y == I => Y== (l - b) (3)

" V(plll.5) 32 10-4 4thay (2) (3) V~lO bi~lI thue (I) ta e6: +) TlJlh tl Ie -- == -:-- ~ 10

:..-( • v(l'lI7) 33(1- b).K<v //- K := Ix

LOi giai bili 50. B b

I Ta eho sim phdm dl! kien chuY~f1 h6a thea m¢t trang cae bien hoa sau; r~ (I)Rut ra b =: Knl ghitn Clru e:fu tnk siin pham sau cung. Nell chAt la dung nhv dl.t kien, thl san phdr

! • ';i 1+( :;Kw)'x au cung phai nhlt tren sa d6:

+) Tlroog tt! hang s6 K'bella xeton dltgc xac l~p: H2S04 d, to Nhom -OB phai bj tach ra cungC)

o • \.. vOi nguytn IiI H avi In transG = [R2COH ].[OH ']

+ OH0 -.... k'n / C6HsR2C=O ~ HOH :;:::::= R2COH [R2CO] 1

~I)CH)-@-S02.CO (CH]hCCr~0 0 H OB Ii~ 2) NaBr H II __

(K';/x,,, },x -r C H(II) 6 s 6 5Rut ra uvgc c= H C H B1" C6Hs lach v6i H avi tn trans-K' a / o .1+( /K)'x . ~)-C:CI_ ~ ~ Q

Theo gia thitt: trong phl111 tmg eua eo che (3) thl giai dogn t~o (A) la giai de CHJ~ __

eh~ nhfi't, v~y t6c d<! eua giai do~n nay quyet dinh t6c d<! chung eua toan b~ q II C6Hs C6HS

trinh. Do do ta co: .­ tach v6i H avj tn cis,IB

V == k[R C 0 rl] .[R 'NH2J == k . C . b thay cae gia tr! clla c va b a'2

(II) ta c6:

(K'j{w).x v==k. .-- (III)

1+(K'j{J-x l+(Kj{J-x I

VI K = 10'1 \; K' B == 10'14; K.J == 10'14 nen phuong trlnh t6e d9 (lII) la:I B

v=k x =k x 2

(IV) , . (I + x).(l + 103 x) '1 + 103 x + 10 3

x 1

11 : :

l:i I .' I

,I,

'tf L{"\

PRAN RAJ TOAN

lli!lRf-Cho 0,751 lit hon hl!P khi A gom COl va m¢t hidroctlcbon B vao m¢t bi~

kin co chua san 3,75 lit oxi. BrJ.t fia lua di~n de phan irng chay xay ra hoan toa: Sau phdn (mg cac chat trong binh de'u u thl khi va chiem thi tich 5,1 lit. c~ lut;mg khi nay ld'n luqt di qua binh 1 d~mg luqng du H;zS04 dijc va binh 2 dlfj' IUlfng du NaOH dij.c. Trang thi nghi~m nhij.n th{ly: khi di qua binh 1 chiem II tich 2,7 lit, khi di qua binh 2 chiel" the tich 0,75 lit. Biet cac thltich khi dul,Yc do;

cung m¢1 dilu ki~n. Xcic d~llh cong thuc cua B.

LUi giai

Vi VB + V , == 0,75 1ft nen VB va Veo, deu nho hem 0,75 ~ft suy ra khf et,i qeo

bloh 213 oxi con duo Th~ tfch oxi eta tham gia philn lrng chay liI 3, is -0,75 =3 lIt. ,I

Binh 1 giU H20. V~y V/fP =5,1 - 2,7 =2,4 lft.

Blnh 2 giu CO (gOm CO2 c6 san trang h6n hqp A va CO2 do philO frug eha. : 2

tzw fa) ,.

' . L. V , = 2,7 - 0,75 == 1,95 lit. V~y V CO2 do phan lO.1g C~1ay ~~a ra phal n eD

hem 1,95 lit tuc la nho han 2,4 1ft. suy ra 'khi hidrocacbon B h! chay thl t~o fa nCO

n H 0, v~y B l?i m¢t ankan. D~t B 1a C)-12n+2 , ta c6: \ 2

rH + ~ O2 ~ n CO2 + (n+l) H 20

'-n 2n+2 2

(n,. 1)~n+1

2

2,43

3n +~ _ n + 1 :=) n =3. V~y B 1a CJH a·

--3- - 2,4

-t xC02 + y/2H20Cach khac: D~t c6ng thue B 1a c"Hy: c"Hy + (x +y/4)°2 x y/256 1ft B trang h6n hqp A 1a V. 1 x + y/4

1,2+V 2,456 lit CO2 trong A la 0,75-V, V 3

do do V , do phan ltng chay t~o ra: 1,95 - (0,75-V) = 1,2 + V. eo

Thea sa uO phim U'ng eua B ta c6:

_ =x + y /4 (1) ~ = y /2 (III) Giai h~ (I), (11), (II!), duqc: V 3 V 2,4 -V ==0.,6

x x ::: 31 (II) _ y::: XV 1,2 +V i

Bai 52. !..::.:::=---­

Dot chay huan tuim 672 tnl (dktc) m~t hon h'!]J khf g6~ hai olefin kl tilp

nhau trong day do'ng ddng, dan hon hl/p gom CO;z va H10 di chrJ.m qua binh 1 dU71g dung djch NaOH (du) va binh 2 dlfTlg H;zS04 dijc (du). Sau thi nghifm th{fy l~tmg binh 1 tang 6,16 gam, binh 2 tting 0,66 gam. I

. ~-

1) Xac djnh cong thuc phdn tu, viet cong thuc cau tf}O va fen g9i cae olefin.

2) Lay olefin co cau tf}O mf}ch nhanh (trong so cac olefin vila xcie d!nh) dl

viii cac phuong trinh ph~n ung thea day bien hoci sau:

+Br,lH10 + NaOH loang IIzSoJ olefin A ) B --------; C

Bift kh{ii lut;rng phan tu cua C /Un htm cua olefin La 16 dvC va kh6ng lac d~mg vOi Na de Ic;zo Ta khiH1 .

Lmgiai

1) Theo dch thf nghi~m Ihl lOng kh6i luqng CO2 va kh6i luqng H20 do phein

' g chay t<;to ra bAng tcing kh6i luqnghai blnh m¢t va blnh hai tang them.

- Khi et6t ehay ankcn th) 56 Inol CO2 va 56 mol H20 t~o ra la bang nhau . D~t () mol CO2 t<;1O ra la x, th) 56 mol H20 cling la x.

ae6; m eu + mH,o == 44x + 18x = 62x = 6,16 + 0,66 =: 6,82' ­

v~y x= 0,11.

- 56 mol olefin == 0,672 : 22,4 = 0.03

- D?t s6 nguyen tii ~acbon trung b)nh eua hai olefin la n , ta e6 :

3ii _ _ CH _+-02 ~ ne02 +nH2 0 "2,, 2

- _ 0,11 _ 3,70,03 0,11 -t n - 0,03

V~y hai olefin la CJ H6 va C4Hg•

Cbng thue cAu t~o va ten gQi: CH)-CH=CH2 propylen.

H" /H H" /CH). CH)-CH2- CHi==CH2 \ C==C C=C CH)-cr=CH2

CH)/ " CHJ CH; "H CH) Buten-I cis-Buten-2 trans- Buten-2 isobutilcn

,.,n 71

--

~ The rich anken d5. phalllrng v6'i Br2= 448-280 =168 ml ~,i

2) Chi co isobuty1en 1a co diu t~o \n~ch nhanh. ~t: T6ng th~ tfeh anken ban dtiu = 112 + 168 = 280 m!. Br Br ;:tI I +) Trang 280 ml h6n hgp kh! di qua dung dich mr6'e br6m co chua: CH3-y- CH2 (A)

CH3-y=CH2 + Br2 ~ CH3 i~ 112ml CmH2mt2 } ­CH3 M = 17,8.2 = 35,6

va 280 -112 = 168 ml CnH2nt2' CH3CH3 to (D) iCH3-C-CH2 + 2 NaDr

~ \t:-: Theo e6ng thue tfnh M coa h6n hqp nay vCri thanh phan tren ta co:I ICH -t-CH2 + 2 NaOH3 I OH OH iI

Br Br (14n+2) . 168/280 + (14m+2) . 112/280 = 35,6

CH hay (14n+2) . 3/5 + (14m+2) . 2/5 == 35,6I 3 0

+ H20H SO CH3-C-C~ rue la 3n + 2m = 12 2 4 I "­H H

(C)Cl-h I 1n,ICH3-C-CH2/- I I

H2S04 CIH3 ti..,OH OH CH2=C-CH20H + H20

Lo~i, vI. co nh6m -OB nen philO {mg vm Na

2 3 4

m 4,5 3 1,5 0

Chi c6 c~p nghi~m n = 2 va m = 3 la hqp li, do do e6ng thvc cua hidrocacbon 13. ~H6 va C)H6.

112V; Bai 53. 'X V}(j == 112 ~ % H2 = -.1 00 = 20%

560 'j Co m¢t h6n ht!P khi A g6m m¢t ankan, m¢t anken va hmro. Cho 560

'\ , him h(1p A di qua 6ng SIl chilO b~1 niken MI nong Ihi chi con l~i 448 ml khi. Ch _ 168 _ 0

= 168 ~ %~H6- -.100 - 30YoVC1J1• , , lu""g khi nay lqi qua lu""g du dung dich nutic bromo Ihi chi con 280 ml khl 560 :I'I!

. i ~] qua dung di~h. co Ii khtl'i hui so vUi hidro bling 17,8. Tim cong Ihllc cua e VC1H• = 280 ---+ % C)H6 == 280.1 00 = 50%

hidrocacbon va thanh phan phdn tram theo thi tich cua moi chift trong hdn h. 560 A. Riet thl tieh cac Chi]'t khi do a cung diiu ki~n, cac phan {mg lil hoan toano

Lm giai Hr, x M¢t hdn hfJP A g~l!!-nh;eu hidrocacbon mt;lch ha. Khi cho m gam h.on h!JP

i' Khi di qua dung d~ch nu6c br6m thi the tich khf giam, do v~y hidr6 da ph !dc dl}ng vm dung dich nulYC brom 0,2¥, thi chi co 175ml dung dieh nufTc br6m

ling hel. anken con dll va bi gili I~i tfong nllOc bf6m. D~l e6ng lhirc cua ankani 'han {mg va con /{li hon hfJP hidr6cacbon B. Trong B co it h01J trong A hai h!JP hat. .CnH + va eoa anken la CmH2m (m~2).

2n 2 Ni /0

CmH + H • ~ CmH2m+2 Do't chay hoan toan hon hfJP B thu dUlfc 6,16 gam COl va 4,572 gam hoi 1) 2m 2

CmH2m duCmH2m

Neu dot chay hODn toan m gam hon hlfP A thi thu dUlfc 9,68 gam COl vaCnH2n+2 'i CnH2n+2 ,012 gam H20.

2) CmH2m + Br2 ----)- CmH2mBr2'

Co thl.rac dinh dUlfc nhiing hid!!!EE~bon ndlL~!Jg~dn hlfP A, bi~t Theo phllOOg tnnh ph. ling (1) ta e6 : s6 mol hidf6 b~ng s6 mol oiefi~n 'dng trong hon hlfP clla ha; chat dti phan itng vUi nuuc brom thi hidro~acbon co

phOn ling vm H, va bang s6 mol ankan mm t~o fa: ' hoi !Ui;mg phan tli nhd hO'n chiem dum 90% theo so mol.

VH == VC H =560 - 448 - 280 == 168 ml 1 ". 2,"..-2

~~-=--~-_..~ -

Lm\giai

+) Trang h6n hqp B phai co nhieu ankan m~ch h~f.

D~t c6ng thlrC chung clla chung la CnH2n+2 ~i\\

3n + 1CnH :l+2+ -2- O2 --* nC02 +- (n + I) H20 2

TIleo phi'm lIng tren ta th~y: 56 mol ankan ::: s6 mol H20 - s6 mol CO2,

56 mol H20::: 4,572/18::: 0,254 } 56 mol CO ::: 6,16/44:= 0,14 SO mol ankan ::: 0.254-0.14::: 0.114

2 56 gam ankan ::: sO gam cacbon + s6 gam hidra ==

::: 0,14.12 + 0,254.2::: 2,188.

if on"" = 2,188 ::: 19,19 ::::::> Trang A phai chua CH4 0,114

+) Trang A phai chua hai hidreacbon khOng no, khi I.E qua dung d!ch mlq brOm thi chung bj giiJ I~i. Vi di tl1 cung m gam clla h6n hqp A, n~n s6 gam CO2i H 0 do hidrocacbon khC'>ng no t~o ra la:

2mH,G == 6,012 - 4,572 == 1,44 ~ n H20 ::: 1,44: 18 == 0,08

mr.o ::: 9,68 - 6,16 ::: 3,52 ::::::> n col ::: 3,52: 44 = 0,08 l

Vi n == n H 0 nen hai hidrocaebon do thu¢c 10<;li anken. Thea phan lrng: C02 2

C + Brz --* Cn,HzmBrzmH2m

_Ta c6 s6 mol ankcn =56 mol Brz == 0,175.0,2 = 0,035 mol.

_Kh6i h.rqng anken = me + mH = 0,08.12 + 0,08.2 ::: 1,12 gam 1 a} a=2 hidrocacbon Iii CmHZm-2- 0,005 0,01V~y M onken == 1,12/0,035 == 32 ::::::> Trang A phai co ~H4

+) M ~= 4.9,5 =3g y~y: s6 mol h6n hgp A =0,01 + 0,005 ± 0,015Vi trong cac anken chi co ~H4C6 kh6i luqng ph~n tl1 nho hdn 32. -:: 0,0 I( I 4 n + 2) + 0,005 (14m - 2) 38 2 8Thea de bai thi ~H4 chiem dum 90% thea 56 mol clla h6n hqp g6m =

ankcn. D~t cC'>ng thuc clla anken thu hai la CmHZm (m>2), s6 mol cl~a ~H4 va CmH

la x va y, ta c6: ~ 56 mol anken : x + Y== 0,035 (I)

56 gam anken: 28x + 14my == 1,12 ::::::> 2x + my == 0,08 (II)

Giiii h~ (I), (0) ta dUqc y == 0.01/(m-2).

Vi %CzH < 90% nen %Cn,Hzm > 10% tcing s6 mol clla ankcl1, 4

suy r~ y > 10% ella 0,035, y > 0,0035. Do d6 :

y ::: 0.01/(m-2) > 0,0035 ::::::> 01 < 4,857.

V~y m == 3 hO(lC m = 4 .Tlec l?i ankcn thu hai lil C3H6 ho~c ~H8'

H6n hqp A ban d~u nhAt thiet phai chua CH4, CzH4, C3H6 ho~c C4Hg, cac ankan con l<,li khong xac dinh dngc .

lli!iE: f Cha 336 ml hon hCfP khf A g6m hai hidroeaebon ml;lch hil di qua dung dieh

nlfUc brom 0,125"1. Sau klli phan itng hoim toim ,thery hon hW chi phan itng hit 80 ml dung dieh nuac bram va con llJi 224 rnl khi di qua dung dich. Gia thie't cae thi tieh klli do iI die'u ki¢n lieu chua'n. Tl khoi hoi cua A so vOl!He bling 9,5. Xac din" eong thite va thanh plui'n p}ui'n tram theo khoi luqng eua moi chert tTong h6n

-hqpA.

LUi giai

+) 224 011 khf di qua dung dieh nuac bram phai la ankan, khi bi giiJ I~i trong dung dieh nuae br6m l?l hitlr6caebon khong no. D~t eang thl1c ella chung Iii CnHZnt2 va CmH2m+2-h (a Iii s61ugng lien ke't Tt).

+) Tht tich ankan = 224ml; the Hch chAt kia == 336 -224 == 112 ml.

+) 56 mol ankan ::: Cil,224/22,4 == 0,0 I;

56 mol hidrocacbon khC'>ng no == 0,112/22,4::: 0,005

+) 56 mol Br2 dii phan {rng htt == 0,125. 0,08 =0,01

CmHZm+2- h + aBrz --* CmH2m+z-zaBr2a

M A== ~ n+m~ 0,015

VI hidrocacbon bai eho la khf, do v~y chi~ co hai c~p ~H6 va C4H6 hp~c C3Hg va ~ CzH2Ia thoaman.

l/V1 "2 Vl •M ­56 gam A::: 0,01(l4n + 2) + 0,005 (l4m - 2) \

\" O)ei5. ') '8: ::: 14 .0,005 (2n + 01) + 0,01 = 0,57 gam) cleq 0, >7(';])

Neu la c~p e2116 va C4116 ta c6:

75 '1~

,I 0. IT _ 0,01.30 b -- S"'(J1/'i,e, '6 - ----.10 - ..... ,(no .i'm: elIJ- 0,57 klJ*

=::j %C4H6 = 100 - 52,6 =47,4% ;Ifj:, @·vaY A leU d"\JC 4 g6c hoo lfj (I) uh":

Neu III c~p CJH g va C1H:! ta e6: CI!J- CHJ ClIJ0,01.44

%CJHg = .100 = 77,2% @' @/ @l ~]0,57

=> O/OC:!H:! = 100 - 77,2 =22,8%

e) Hidrocacbon l<~o ket tlla v6i dung djch AgNOJ trong NH) phai thu¢c lo~i

ankin- 1. Khi thav :n¢t nguyen ttl hidra bang m¢t nguyen llr b'.lC, thl kh6i luqng phftnRai 56Y­ . tV tang them, I~8 - 1 = 107, do v~y s6 nguy~n ttt Ag c6 trang m¢t ph[ln ttr B la:

Dot chay hoim toan 0,46 gam chat, A co cong thuc phan tii trimg voi con MB-M A 214 thftc do:' gwn nhtit, chi thu dUl/c khi CO] va hoi nuO'c. Dan hon h([p khi san phm, n =----- = -- == 2

Ag 107 107/ ­ehay Ian luqt di qua binh 1 dltng iur;ng dll PzO j va binh 2 dztng Illf!1lg du NaO Sau thi nghi~m kho'; lur;ng binh 1 va binh 2 tang thim 0,36 va 1,54 gam. . V~y'trong A co hai nguyen ttl hidro lien ke:'t tll!e tiep vui n6i ba. Suy fa efill t\lo

'ella A e6 th~ la:a) Tim cong thuc phan tii cua cha't A

H-C=C-CH2-CH2-CI12-C=CHb) Gia su chat A khong film mal mau nuac brom thi A co thl t~o thanh bal f-1-C=C-CH2-CH -C=Cllj nhieu goc hoa tT{ mqt. i' \ C.-I)

CH) Kf hi~u chung la c) GUi sii chat A khi phdn frng vOi dung dieh AgNOJ trong NHJ tlJo ra B k~. H-C=t-CH-C=CH If-C=C-¢-C=CH H-C=:C-C)I4;-C=CII

tlia, kho'i lw;mg phan tli cua B IUn hon cua A fil 214 dYc, thi A co thl co cau t,. tl~ CHJnhu the nao? tf-G

LOi giai Phuong trlnh phan ulg ehung:

me = (1,54/44).12 =0,42 g me+ mH =0,46 g

H-C=C-C)Ht,-C=CH + 2 [Ag(NHJh]OH -- Ag-C=C-CJHt,-C=CAgLTrang 0,46 gam A co chua: \ } Suy fa A lit

mB =(0,36/18).2 = 0,04 g hidrocacbon (A) + 4 NIlJ + 2H:O (D)

"

D~t c6ng thve A la CxHy (x,y nguyen, ducmg; y ~ 2x + 2 ). ai 57. f+ Ta e6: Dot ehay holm toan mt)t hidrocacbon A r6i hap thl;l hlt san pham phan ling

0,42 0,04 hay vao mqt binh d~tng dung dieh nuac voi frong. Sau thi nghi~m thay kho, x:y= -:-- = 0,35 : 0,04 = 7: 8 uf!Tlg binh tling them 26,24 gam. L9C, thu du,!c 20 gam chal kel fIla va dUi!c dung12 1

'ich B. Khi dun soi dung dich B ",t)t thOi gian lau, I~i thu dlli!c 10 gam kel tua ua.

Cl'>ng thve dcm gian nhfit va c6ng thve ph:l.n ttl ella A deu la ~H8' Khi cho IUf/1Ig chat A dlmg bling IUlf1lg dii dot chay if tren, phan itng hel vOi k b) Thea e6ng thve C,Hg thi A thu¢c d~ng CnH2n _6 , rna A li;li kh6ng Him m hi clo a30(f!C, thu dUl!c mt)t hon hl!P C gom bo'n dan xudt chua clo cua A, la /1

mau dung dich nuac bf6m, suy fa A la taluen: lmg phan cua nhau, vOi hi~u sudt 100%. Bon hllP C co ti kho' hoi so vOi hidro II . ho h01l 93. Xac djnh cong thuc cua A va tinh thimh pha'n phdn tram thea kho'

_uf!Tlg clla moi cluil frOllg hon hl![J C.

_.~~~- . ~---

LM ghli I,lIOu .~o Cil~_~_1 TIlay I nguyen .i, hidro

~

2C02 + Ca(OHh

D~t A Hi CJ-{y, ta co:

CxHy + (x + y/4 ) COz

CO2 + Ca(OHh

-+

=

X CO2 + y/2 HzO

CaCOJ~ + HzO 20 gam

Ca(HC03)z

(1)

(2)

(3)

(113-012 -Q-Ir O~I2' Of}

I aG:I -Cl1- Glz­ . IJJ J

II GIJ I

J dong philn

' 4 dong ph:in

Thay 2H

9 dong phnnl

10 dong phani

Thay 3H

20 d6ng phful

17 dOng phan

GIJ "

Ca(HCOJh

to Cac03t + cozt + H20 (4)

Q-IJ-~-GI3 ;_1 b J

I I dong philn I 2 d6ng philn I 3 d6ng phan

IOgam

+) 'Theo dc pInrcmg tdnh IJhan (mg (2,3 va 4 ) va thea de bai ta c6: VI C chi g6m 4 cha"t d6ng/phlln cua nhau, suy fa chi co chat isope!1 tan lii thoa man va h6n hqp C chi g6m cac chat d6ng phlln C:sHIICl.

20 10 nco = -+2- == 0,4 mol

I 100 100 IKh6i IU<;fIlg blnh dung d!ch ntr6c v6i tang them brmg t6ng kh6i luqng C02~

CH3-CH-CH2-}H2-Cl hal H~O cua phim (rng chay. Suy fa s6 gam nu6c Ia: ;.

, (I) CH.1 :

CI m HID == 26,24 - mCOz = 26,24 - 0,4 x 44 =8,64 gam

CH3-CH-CH-C~-!3 ( II)/100CC: ~ CH]CH]-CH-CH 2 -CH] 2::::::> n 11,0 =8,64/18 == 0,48 mol.

ell] + el ~HCI .~ ~I "" -............ CH3-C-CH2-CH3 ( III) Khi A chay t~o ra n }/,U > tIco,' V~y A la ankan.

0,08 mol A I

CH3 n = n H 0 - n ::-:: 0,48 - 0,4 =: 0,03 mol. CI-CH2-CH-CH!2-CH3 (IV)COlA 2 I

\ 9}3 ,Theo phan ltng dOt chay ankan:

~ gam h6n hqp C: me = 0,08.106,5 == 8,52 gam3n + I --) n CO2 + (n+ l)HzO 0,08 mol CCnH zn + z + --022

1 n

0,08 0,4 . .C~n. nh6 rang a nhi~t d¢ khoang 300°C (6 "i •

V~y n = 0,4/0,08 =5. Ch~t A c6 c6ng thllc la C H , suy ra phan trng gift3 len ket v61 cacbon b?c I, qac 2, bac 3 ti I f\ ,. he d¢ ph~n ~g the nguyen tlr hidro ~ -I I' h• :~ th€ 5 J2 . ' . pm n au .heo " so 1 : 3 3 . 4 4

Vel C 0 a p an ulIg . Trang isopentan c6: ~ . ,.

300"C :> 1 9H b~c 1-+ 9xl=9C5H12 • xCIx + x HCIC:sH 12 + X Clz ~

12H h?c 2-+ 2 x 3,3 =6,6 (AI (C)

~

IIH h?c 3-+ I x 4,4 =4,4 Me = 72 + 34,5x < 93 .2== 186 => x < 3,3.

TDng =20,0V~y oa xay ra phan {rng the' 1,2 ho~c 3 nguyen tlr hidro clia CsH lz bang \

Chfl\ A co the co d"u t<;to va s6 lll'qng d6ng phftn san phim khi thay the' 1,2 ho~ nguyen tv nhll' sao:

V,'ty: SC> mol d6ng phfln (I) l?l. 0,08 .3 == 0,012:=",;> Chiem % = 0,012.100 = 15% . 20 0,08

. 0,08 ' 0,0264D()ng rhtln (II) Ih -- .2 .3,3 =O,0264mol::::) Chiem --. 100 == 33%

20 0,08

. ,0,08 . , 0,0176Dang phfUl (Ill) la--.l .4,4 = 0,0176mol =:> Chiem % = --.100 = 22%

20 0,08

, 0,024. 0,08 ::::) Chiem --.100 30%D6ng phan (IV) la -- . 6 ::: O,024moi 0,0820

/ .... ~ Rai 5X' . b' h k' d ' h 20 I' khJ: d'?' h' 96 . ,\ rong m9 t In In fing tiC It vng 01, C Ua , gam OXI va m gaT hon h9P hidrocacbon A,B,C. Nhi¢t dq va tip suat trong binh H,c dci'u la Due va '; 0,448 atm. Sau khi b(zt tia lua di¢n de phdn ung chay xdy ra hoan toan, ta giii ) Ilhi~t d¢ binh a136,soe, thi trong binh t{lV ra 4,05 gam hoi nutic va 6,16 gam C

Tinh ap mat trong binh sail kid dot chay. :: Kac dinh cong thuc phdn tu cua A,B,C, gUi thiet B va C co cimg so nguy

tu cacbon, con sf; mol eua A g~{p 4 Mn tting so' mol cua B va C.

LOi giai

+) Kf hi¢u chung cae eMit A,B,C 1h CaHb ta co:

CoHb + (a + b/4 ) O2--). a CO2 + b/2 H20

-111eo phan lrng trtn thl 56 mol O2 d5. phan lmg = 1/2 n H 2 0 + nCOl

1 4,05 6,16 1 = -.-- + -- = ~. 0225 + 0 14 == 0 2525 mol 2 I 8 44 2' , ,

" l SO mol O2 con dtf == ~ - 0,2525 = 0,0475 mol.

11 32

I" - Sau phan tmg chay s6 mol khf e6 trong blnh la:

Ii n == rzc~ + n 1110 + no) == 0,14 + 0,225 + 0,475 = 0,4125 mol

Ap dung e6ng thue:

PoVu PV , 1.0,4125.22,4 P.20 -- :::: - ta co ::: -- ­

To T 273 136,5 + 273

Boac cang thuc PV = nRT ta c6 P . 20 ::: 0,4125 .0,082 . (I 36,5 + 273)

Rut ra dU<;1c P == 0,693 atm.

* Tcing so mol khf ban dau co trang blnb:

rj.~&

.~ m

0,448.2~ == 8,96 8,96 ::: 0,4molVo ::: t no = 22,4

Do d6 so mol 3 hidrocacbon =no - n~ = 0,4 - 0,3 =0, I mol.

S6 gam 3 hidrocacbon bang tcing s6 gam cacbon trong C0 va so gam hidra2

trong H20.

m = 0,14.12 + 0,225 .2::: 2,13 gam.

V~y M.(B,C ::: 2,13/0,1 =21,3, phai c6 m¢t hidrocaebon e6 M < 21,3, chAt duy nhat III CH4va thea bai d61a A.

n A ;::; nCII. = 0,08 mol => V~y nA + I1e ::: 0, I - 0,08 ::: 0,02

mA ::: mCfI, ::: 0,08.16::: 1,28 g => rnA + me = 2,13 - 1,28 = 0,85 gam.

MB,C == 0,85/0,02 == 42,5.

Thea d~ bili: B va C ~6 cung s6 nguyen t\'r eachan, d~t c6ng thuc clla chung Ia CxHy va CxHy' ta c6:

CH4 + 2C02 -)- CO2 + 2H20 (1)

0,08 0,08

CJfy + (x +.y/4)Oz -)- xC02 + y/2 H 02 (2)

n nx

CxHy' + (x + y'/4)02 --)0 xC02 + 1''(2 H 02 (3)

n' n'x

T6ng so mol COl::: 0,08 + (n + n')x ::: 0,14 ma n + n' ::: 0,02

0,14 - 0,08ntn 0,08 + 0,02.x::: O,14 =:> x = ::: 3 0,02

V~y B, C e6 the 13 2 trang 3 chat: C)Hg (M = 44); C)H (M == 42);6

L- •

~)H4 (M = 40). Y1 MB,c ::: 42,5 do d6 c6 2 truemg hgp;

"-:I C3H g va C~H6 ho~c C3H ll va CJH4

iii sw cttu' 't • Hai hidrocacbon m{lch hu X va Y diu lil chat khi u dilu ki~n thutYng ; hiSn j.

qp A go'm H2 va X; IIt}n hqp B g6m H 2 va Y. Dot chay hoan todn 6 gam A thu 'ltl!c 17,6 gam CO2 , M(it khtic 6 gam Attic dl;lng vila du vOl dung d~'ch chua 32

m bromo

cI~t"'J I'I-,ff-."

Ti kho'i hoi cua B so vOi H 2 bling 3. Dun nong B co b~t niken lam xuc t,

thu duqc h6n h'lP khi C co ti kh{/i hoi so vOl hidro bling 4,5.

Bilt cac phan itng la hoim toan, xac d#nh cong thue X, Y va thanh phlin

theo tinh tich cua m6i khi trong cac h6n h'lP A, B.

LOi giai

D~t cOng thuc clla X la CnH2n +2-2a

Clla Y la C H2m +loA _2b, ( trong d6 a,b la 56 li'~n ket 1t ).m

* D6i v(ri A ta c6 cac phucmg trinh phan lrng sau:

3n + 1- aCnH2n +2_23 + 2 O2 -+ n CO2+ ( n + 1 - a ) H20 (l )

(2)CnH2n+2-2a + a Br24 CnH2n+2.2aBr2a

nc~ :::: 17,6/44 == 0,4; n Br2 == 32/160 == 0,2

D~t x,y la s6 mol clla X va H2· Thea (1), (2) ta c6:

a

n

X

1 2 3 == nx == 0,4 (I)n co 2

(II) } =::> n :::: 2a 2 4 6 11 Br :::: ax == 0,2

2

~H4 C4H6 Lo~i vi X la khL

Thea (II) Khi a :::: 1 ta c6 x =0,2

:::::) m :::: m~H4 == 0,2 x 28 :::: 5,6 g.ll

do d6 m H = 6 - 5,6 == 0,42

:::::) n H2== y == 0,4/2 == 0,2

% ~H4 :::: % H2:::: 0,2/0,4 x 100:::: 50%.

tucmg tt! Khi a:::: 2 ta c6 x:::: 0,1

, 6 - 0,1.54:::::) 50 mol H2== Y= :::: 0,3 mol

2

0,1 n =0,1 + 0,3 =0,4:::::) %C4H6 =-.100 == 25%;

A 0,4

%H2:::: 0,3.100 :::: 75% 0,4

+) D6i vai B: Gia 5tr co 1mol hOn hqp B, irong do co x mol Y.

Khi 10 s6 gam 1 I1101 B =3 x 2 =6 gam.

- Me = 4,5 x 2 =9 5UY ra trong C phai con H2duo "

Cn,H2m +2a. 2b + b li2 Ni, ~ CmH2m +J.

X b~ x , I

- Vi phan ling hoa~ toan, rna H2du, do d6 5au philO U'ng (3) 56 mol khi bi giam oi dung b~ng s6 mol H2dii phan tmg, tuc la giam bx mol. V~y 56 mol cua h6n hgp C la (l-bx ) mol. Phan tmg fuao toan kh6i lttgng v~y me = mB = 6 gam. Do do:

6 M == --= 9. Suy ra bx = 1/3

C 1- bx

Vi Y la chat khi nen 56 caebon trang phan ttr Y nh6 hem ho~c b~ng 4, do d6 b chi eo th~ bang 1,2,3,4. I I

I

11 2 3 4 (lIp ,x 1 1 1 1

- - ----.-, 3 6 9 12

D~t kh6i lugng ph;n ttr ella Y la M. Theo 56 gam hOn hgp 13 ta co:

mB :::: MX + 2.(1 - x)=6 (IV)

Thay cac gia tIi Ctla x abing (III) vao phuC1I1g trinh (IV) ta c6

- Khi x = 1/3 thi M == 14 lo~i vi Y In CH2 !

- Khi x = 1/6 thi M =26 ~H2 axelilen.

%H2== 1/6 x 100;: 16,7 %:::::) % ~H4 =83,3%

- Khi x = 1/9 thi ¥ ~ 38 10~i vi kh6ng eo hidrocacbon tucrg Ung.

- Khi x == 1/12 thi M == 50 C4H2 H-GC-GC-H

% H2== 11/12 x 100 =91,67 %~.:::;> % S:4H2 = 8,33%

Hai 60. ~ Chia 672 mL (dktc) h6n h9]J khi A gam hai hidrocacbon mt;lch hi! thanh lrai

han bdng nhau.

,

- Dot chay pha'n ldu(1c y gam hoi H 20 va 1,76 gam CO2 ,

- PJu:in 2 cho di qua' dung dich nUt7c brom (du) thi k~ong co khi di qua ung dich. LUlfTlg brom ali phdn Ung La 3,2 gam, kho'i [UlfTlg binh dlfng dung dich uO'c brom tang thim X gam.

Tim cong thllC cua hai hidrocacbon, tinh thimh pha'r. jJha'n tram theo tid 'eh cae khi trong Icon hffJ1 A va cac gia t~i X,Y.

I

~'. Jo..:tr '1'J.w'l' X3

~m ghli

_S6 mol hai hidrocaebon trong 1/2 h6n hqp A = 1/2 x 0,672/22,4 = 0,015mol

_S6 mol Br2 da phan Ung vai phtin 2 Hi 3,2/160 =0,02 mol

_D~t e6ng th{re eua hai hidrocaebon til:

~H2n +2-1.a v6l 56 mol trang 1/2 A la x } ,. , x+v=0.015 I

CmH2m +2_2b VOl s6 mol trong 1/2 A la y ( ) ;}

CnH2n+2-2a + a Br2~ ~H2n+2-2.Br2a (1) "

} x ax ,

m.~

HC H2m +2_2b + b Br2~ CnJI2m +2-2bBr2b (2) ~

y by -~

111eo cae phan Ung (1,2) va s6 mol Br2 ta co: ax -+- by = D,02 (II) ·r ~ ff ~y3n+ 1- a (3) \CJI2n +2_2a + 2 O 2 ~ n CO2 + ( n + 1 - a ) H20 "'.'-',

x nx ( n + 1 - a) x .i

3" -1·1-- b ,~." (4)CnH2m+2.2b + 2 O2 ~ 111 CO2 +- (m + 1 - b) H20 t i~

y my ( m + 1 - b ) Y :,I

Thea cae phan {mg (3,4) va s6 mol CO2 ta eo: .~ nx + my = 1,76/44 = 0,04 (III) f

0,02 - 0,0150 }\,; Ttl (I) va (II) ta eo: y = (IV) J

~ ~ ~

~. Vi a,b lil bfit ky n~n d~t b>a; a ~ 0; rna y In. s6 mol n~n y phai 100 han °va n~~

han t6ng d.e 56 mol, tue lil 0< Y< 0,015. Vi b> a nen b - a > 0, do v~y thea (IV) tW

y>O<=:>0,02-0,015a>O~a< 1,3. V~ya= 1 {

Suy ra M(H hidrocaebon eo e6ng thue ~,H2n (n ~ 2 ).

111ay a = 1 vao (IV) ta co:

0,005 0,005 < 0,015 y=-­ Vi Y< 0,015 n~n

b - 1b - 1

tt'rc lil b > 1,3 v~y b ~ 2

Khi b =1 ta eo y = 0,005 } Thay vao (Un duae:

x =0,01

0,01 n + 0.005m =0,04 ~2n+m= 8CmH2m -2

.J ~.

~~

Oil

H6n hqp A g6m ~H4 va C4H~ 6

m I 4 I 2 I 0 ho~c C3H6 va ~H2

Khi b = 3 ta eo y = 0,0025 }

x = 0,0125

Thay vao (III) dUCJe:

0,025 n + 0,0025 m = 0,04

~ 5n + m = 16

~ VI hai hidrocacbon Mu kh6ng no va 13 eh[it khi nen

m I 6 I 1 I <0 kh6ng eo nghi?m hgp If. Lo<;li tntang hqp nay.

* Thanh ph:ln % the tich h6n hgp A: D6i v6i eha't khi % th~ tich bftng % s6 mol. Nen:

0,01 66% ~H~n= --.100 = 6 ,7% - 0,0 15

0,005% CmH2m 2 = --.100 = 33,33%

. 0,015

* Kh6i hrqng binh br6m tang ehfnh la kh6i Iuc;mg hai hidrocacbon:

X = 14 nx + (l4m - 2 )y = 14 (nx + my) - 2y

= 14 .0,04 - 2 .0,005 = 0,55 gam

* Theo ph~Ul u-ng (3,4):

Y = 18.[(n+ l-a)x + (m + 1 - b)Yl = 18.[(nx + my) - yl = = 18.(0,04 - 0,(05) =0,63gam

Hai 61. 'i Mljt hfJP chti't hfru ClY A c1d chua Itai nguyen t6 X va Y. Kholluf/Tlg phtin hi

cua A co gia !T1' 150 < Mil < 170. Dol chay hoim toim m gam A sinh ra ciing m gam H20. A kh6ng ram mat mall nunc br6m, cung kh6ng phdn img vOi br6m khi co mil-I bqJ sal, nhllng It;li phdn img vOi brom khi ch;eu sang t(Jo thanh mljt dan xuat monobrom duy nhlft.

a) X,Y la nhfmg nguyen to gi.

b) Xac dinh cong thirc dan gidn nhat, c6ng thuc phtin tu va viet eong thire cifu tlJ-o cua A, biet rdng A ltl phan tu co tinh do; ximg cao.

I Lm ghii

a) A la ch~t hiiu co, nen A nh~t thi€t phai chua cacbon.

A chay t~o ra H 0,nen A phai ch{ra HidrO. Suy ra A la hidrocacbon, VI A2

chi chua hai nguyen t6, v~y X, Y la cacbon va hidrO.

b) D~t cOng thuc clla A la CxHy

CxHy + (x + y/4)02 ~ x.C02 + y/2H20

y/2mollmol

rn/18molm/(12x+y)mol

Taco l2x+y=9y =:> 12x=8y ~ x/y=8/12=2/3

+ CTDG clla A la ~H3

+ CTPT clla A la (~H3)n M A = 270 150 < 27n < 170.

Suy ra 5,6 < n < 6,3 v~y n = 6 A co CfPf C12H18 ·

+ COng thuc CI2

H 1S lrng vCri d~ng t6ng quat ~H2"-6' c6 hai kha nang:

-J .f; ,~

."

_ A la hidrocacbon kh6ng no thl A lam m~t mau mr6c brOm ,khOng phu hqp v

gia thit't. i:I'· _ A la d6ng d~ng cua benzen, thl khOng la mflt mall nvac brOm Iii phu hqp

vm d~u bai.

A kh6ng phan lrng v6i br6m khi co m~t b¢\ sit, chU'ng to A khOng con hidrO::

lien kt't trl!c tic'p vm vong benzen. Suy ra ctlu t~o A la :

CH3 Tuc la t~t ca 18 nguyen ttc hidro trang A

CH]~CIl] d~u gi6ng nhau. PhA-n ttc CD tinh d6i Xlrng cao. Phan lrng chi t~o ra m¢t dan xu~t

CH3YCH3 monobram. CH3

-I33

CH3 yCH2Br CH3 0 C H3 askt

+ Bli °A-. +HBI CH3 CH3

- ~~

..]ili 62.

1) Tiln hdnh phdn ling dong trung hf!P giua stjren va butadien-l,3 thu • I

dll{fC polime A. Clf 2,834 gam polime A phdn (mg vuahet vOi 1,731 gam bromo Ti~h Ii l~ so mat 'xich butadien va stiren frong lo~i polime trin, tit do viet cong thue ella A. ~ I

2) Tien hcitih clo hoci poUvinylclorua thu dUf!c m~t lo~i polime B dung de eht t{f clorin. Trong B co chua 67,18% clo theo kh611ulfng. Tinh xem trung binh m9t phdn ttl clo phdn (mg vOi bao nhieu mat xich (-Clf2-Clf-) tudo cho bitt e6ng thuc cua B. Cl

3) Tien hanh phdn (mg trung hf!P 5,2 gam stiren. Sau phdn flng ta them 400 ml dung djch nuflc br6m 0,125 M, khud'y dlu cho phdn (mg hoan tocin. Sau do fai them lUlfng du dung djch KI, todn b9 lUlfng 11 sinh ra phdn flng vua het vO'i 92 ';'1 dung djch Na1S10 J 1M. Tinh s6'gam polime tl;lo ra.

j

LOi giai.

1) nCH2=CH-CH=CH2 + m~H = CH2 --)0 t H2-o-l=CH-Cff.!++-YH-CH2-\

© ~\© JmI

- Kh6i Ivqngpolime phim lIng. vm lmol br()m:

2,834.1 60 _ 262! t?f L) 1,731 \ V

- Cu mOt pht'tn tic Br2 phan Ung vm mOt li~n ket C=C, kh6i luqng polime chua mOt lien ke't dOi la:

54n + 104m =262

Chi co n=l v~ m=2la hqp If. V~y ti l~ s6 m~t xich bu~adien va stiren la 1:2, do do cOng thuc tcing quat clla Ala'

- CH2-CH=CH-CH2-CH-CH2-CH-CHr]

". [ @ @ I

n

2) D~t x la s6 m~t xich -CH2-CHC1- hay -~H3a- tham gia phan lIng vOi CH3 CH3 ~- m¢t ph~ ttc c1o, ta c6:

CH3CH3

~~H3~Cl~ + O 2 --)0 ~~H3~.IOX+J + Hel

%0 = 35,5(x + 1) .100 = 67,8 =:> x-2 24x + (3x - I) + 35,5(x + I)

C6ng thuc cau t~o cua polimc c6 the la:

'"T1T"""'" .. ('. ~-

/

I Cl

-CH2-CH-CH-CH-) LCH2-«H-CH2-¢- ) ha~cI I I \ Cl Cl n ~ Cl Cl Cl n

3) cae phan lmg:

CH=CH2 ( ~-Cll'- t (1)n@ ~

CH=CH2

@+ ;:

~o«H-«H2 (2) ~~ Br2 ~ Br Br \1 .:.;-~

.~ ~ + 2KBr g2KI + Br2

12 (3)

,. (4) '~

~ Na2S40 6 + 2NaI2Naz~03 + 12 (,1 _Thea (4) n 1 = 1(2 nNalS1~ = 1(2 : 0,092 == 0,046 mol

1 .~

ii _Thea (3) n 8'1 du = n' l = 0,046 mol

_Thea (2) nstiren kMng trung hQ'P ::='0,4.0,125 - 0,046 =0,004 II': =nBr1 ~.' 13== rnstiren ban d~u - rnstiren dllS6 gam polime ~ \= 5,2 - 0,004 . 104 = 4,784gam. {il'

niliJ· do d6 s6 mol ~qu eon I~i trong B =0,48 - 0,15 =0,33 mol, VI v~y t6ng s6 mol hai

.

'

n.r<;ru ban dtiu = n~ coo + nolcfin + 2.nclc = 0,33 + 0,27 + 2.0,15 = 0,9 moLCho 47 gam han hl!P hai rllt!" di qua AllOJ nung nong, ta dllflc hdn h. hoi A gom ete, olefin, rllt!" con lJ;Ii va hoi nllnc. Tach hoi nllnc khoi h6n hfIP A dllflc han hl!P khi B. Lay toan phiin nllnc 11 tren cho tac d,:,ng het vm Na, thu dlJ~. 4,704 lit H (dktc). Lllqng olefin co trong B ~c d,:,ng vita du vUi 1)5 lit dung d!~

2 i ~ nlloc brom 0) molJl. Phii'n ete va rUt!" co trong B chiem thl tfch 16,128 1ft do~

~ I :1·'1 136,5°C va 1 atm. .

1. Tinh hi~u suat rllfIU bi lot;Ji nllnc thanh olefin, biet ding hi~u sua! doi ~! m6i rllfIU deu nhll nhau va so'mol cac ete ld bdng nhau.

rI -l-~~~hdn I~--;;J~C nt~ l ~ ~--;--- LUi giai

1) Vi nr<;JU bi lo<;\i nu6c t<;\o ra olefin nen nr<;JU da cho t~u¢c lo~i nr<JU no

ehue. D~t c6ng thue ella cae ruqu la: CnH2n+I OH va CmH2m+, OH, ta c6 cae phan Un~

A/,n ,t'"_'-'3 >CnII2n+,OH 0CnH2n + H2 (1)

_A-=-/2~~,t~O--+~ C 1..1 1-1 ° CmHZm+10H m r Zm + 2 (2) 2CnH2n+IOH -). CnHZn+I-O-~H:'n+l +H:,O (3)

2CmH2m+I OH (CmHZm+,hO + HzO (4)

CnHZn+I-O-CmHZm~1 + HzO (5)

~ 2NaOH+Hz (6) CnH2n + Br2 ~ CnHZnBrz (7)

CmHzm + BrZ ~ CmH2mBrz (8) 4,704Thea (6) nUlO = 2. n fl =2.-- = 0,42 mol

~ 22,4

Thea (7) nolcfin = n Br, = 1,35 . 0,2 =0,27 mol

Thea (l,2,7,8): nf{20 a(l,2) = == n [Jr2nolefin

V~y n1l20 0(3,4.5) =0,42 - 0,27 =0,15 mol

'. , I 3 _ ete bang. nhau, n~n m61-. ete e6 s6 mol == 0,15 == O,OSmol.Thea de bfu s6 rna - ­3

T6ng s6 mol ete va ruqu eon l:;ti:

- Va - 16,128.1.273 _ °48 Ia- --- - , mo 22,4 1.(273 + 136,5).22,4

YAy hi~u xuat tao thanh olefin b!ng: H = 0,27 .1 00 == 30% '" 0,9

2) lim c6ng thue ph~ tli eua nrqu.

- Kh6i humg phAn tit trung blnh eua 2 nrau M== ~ == 52,2 . . 0,9

V~y phai c6 m¢l nrqu e6 kh6i hrqng phAn tit < 52,2. Ruqu e6 KLPT < 52,2 va i lo~i nuOc t~o ra olefin. duy nhat la CzHjOH.

- D~t s6 mol ruqu thu hai la x, thl s6 mol nrqu etylie la (0,9-x). Thea kh6i uc;mg nrgu ban d~u ta c6:

46 (0,9 - x) + (14m +18)x == 47

hay 14mx - 28x =5.6 =:> mx - 2x =0,4

- -

~f,_.

0,4 rUt fa: x == m - 2

Vi x la s6 mol nrqu tl1l1 hai ncn s6 mol nay phai nho hem tOng s6 mol hai ru<;1U~ va phai 1611 hem s6 mol hai nrqu d6 d5 phan U'ng tao fa ete, t~o ra olefm.

.~!j

_ Hi?u su~t t~o olefin la 30% n~n s6 mol CmH2mtlOH da t~o olefm a (2) l~(

O,3x. _56 mol c",Hzm+\OH t~o ra ete a(4) Iii 0,15.

V~y tOng sO mol C lll H2m+,OH d5 phan U'ng Iii O,3x +0,15.

1'a c6: 0,3x + 0,15 < x < 0,9

x> 0,21.1'i'r O,3x + 0,15 < x => 0,15 < O,7x =>

04 Tuc la 0,21 < x < 0,9 vi x == -'- nen ta c6m-2

'J \ 0,4 m:= 3. =;> 2.33 <m <3,9 =>

0,21 < -- <0,9 m - 2

VI(Pl \ m> 2 n~n m -2 > 0 v~y ruqu thu bai Ja C3H70H.

-;1

V~y c6ng thuc cae nrqu Iii ~H~OH va C3H70H.

Ie Bai 64· lfP ch"at A (ch'ua C"11 0) kh'I Ph"an ung vm,. h"et Na tlilU duCfc so"ImoH

dung bling so mol A. M~t khac khi cho 6,2 gam A tac dlfng 1'mNaBr va H}SQ.

theo Ii I~ bling nhau vI so mol clla teft cd cae chat, thu dUCfc 12,5 gam cheft him ( B vOl hi~u suat 100%. Trong phan tu B co chua m9t nguyen tU oxi, m~t nguyen'

brom, con kJi Ul cucbon va hidro. "

1- Xac d~nh cong thuc ctfu tlJ.o cua A,B.

2- Hay dieu chiA tu dIl voi, than da va CCle cheft VO Cd ctin thilt.

3- Dung d!ch chat A trong nUUc co n6ng 49 28,6% se (lOng d4c Unhi~t nao? (hling s6 ngh~m kJnh Clla ntiOC K = i,86).

LOi giai

1- Ch~t hfru co chua C,H,O tac dl;lng v6i Na t<;tO fa Hz phai chua nh6m - d

7

­

hoac -COOH. VI A + NaBr + HZS04 --) B, trong B chua IJl()LngU'~~n tit oxi thl A P Iii ~<;1U. D~t A 13. R (OH)n: ~-- -------~. ­

-----'

R(OH)n + 2Na ~ R(ONa)n + n/2Hz (I)

1 mol n/2mol

VI n A = nll~ nen n = 2.

/OH /BrR + NaBr + H2S04 R + NaHS04 + H20 (2)

"OH "OH

(R + 34) gam (R + 97) gam Umg 63 gam

O,lmol "

12,5 - 6,2 = 6,3 gam

Thea (2) khi thay 1 nh6m -OH blmg 1 nguyen ttl Br thi tang 63 dve.

Suy fa nA == 0,1 mol => MA = 6,2/0,1 =62.

Suy ra R + 34 =62 => R= 28 phai la CzH 4

V~y cOng thuc ~ la HO-CHz-CHz-OH va B la Br-CH2-CHz-OH.

2- 1'u da vOi ditl\ eh€ A nhlI sau:

to CaC03 CaO + CO2

400°CCao + 3C

I \

.) CaCz + CO

Ca~ + 2HzO ~ Ca(OH)z + CzHzt.

PdCH=CHI+Hz -~ CHz=CHz

CHz =- CH.z + Clz ~ CI-CHz-CHz-CI

1° L Cl-CHz-CHz-Cl -+; 2NaOH ~ 2NaCl + HO-CHz-CHz-OH.

I

3- Thea dinh luAt RaUB ta c6: . . .- --------­~t:K.C ~~.-_} . ~:S6-g-am ch5; t~n t;o~g;~g.~~ dung m~.. )(Jf)

M: Kh6i IUQTlg phAn ttl cua chAt ~an khCmg.di¢~ (bt~ (I]A

Vi n6ng d<) dung d!ch la 28,6%~·drchw28~6g~---· - :::. 32., HO-CHz-CHz-OH va 109 - 28,6::: 71,4 gam HzO.

V~y trong m<;Jt 1000 gam dung m6i se hoa tan s6 gam chft't tan la:

II

-------

I r"

28,6 M C21f. (OIf)2 =62m = 71,4 .1000

V~y t.t = 1,86 , 2 8 ,6.1 000 = 12 71,4.62

V~y dung djch dong d~c a_l20 C.

--\ Hili 65:

Titn himh phdn lmg trung ngung gif/a phenol va andehitfomic, ben c~n~ polime con thu du<!c hai san phdm ph~ liz A va B, dlll co kh61 IUlfTIg phan tu ~ 124. Khi dot chay hoim toan 0,124 gam mai cluft dlu thu dUflc 0,308 gam CO2 V4 0,072 gam H 20. .

i';"" 1- Xac dinh cong thuc phan tii cria cac elrat A,B. ;

2- Khi cho moi chdt A va B tac d~ng vm axit CHJCOOJI thu du<!c cac Ch&.' A', B' tUl1Tlg Ung, dlu co khollulfng phdn hi bJng 166. Cac chat nay khi lac di;lllg vm dung dich nu{rc brom, diu If:lo ra sdn phdm co kh611ulf1!g phan tu liJ 324. Xd! dinh cong thuc Clfu tf:lo A,B, bitt dilm s6i cria A tJUJp hun cria B. Viet cac phuan~

- Neu 1<1 chat klldng no t11i ~6 nguyen tli brorn trong san pham phili Ia s6 c-h;-;n KLPT tang la bt)i s6 ella 80.

, 324 -166 56 nguyen ttt br6m = 80 = 1,975 (kh0ng nguyen, l0'.li).

- Ne'u 1a phenol th) xay ra phan ling the nguyen tli hidro bang nguyen tu bromo OJ 1H thay bang I Dr thl bAng 79 dve. V~y:

, 324 -16656 nguyen tt! br6m = ---- = 2.

79

Suy fa trong m6i eha't A,B d~u phai con 2 trong s6 3 vi tff ortho va para so v6i nh6m -OIl tt! do. V~y Ava B c6 ca'u t~o lil:

OH OH

~CH20I I c9JL8J 0 A B

va M = M = 124

(A) CH20H trinh phdn fmg xiiy ra. .~; (8)

~ Scufi chon A va B c6 c<i'u tao hu t ~ b" , LOi ghli , phAn t~nen nhi'et dO sOi tha" 0 ~ nn h' r n, ,01 ~l A t",~_ dU~c lien ket d.':!-hidro ndi

, _ - -'---,_',_-.:-_--. p, c n c 1 tao dIu hidLQ..E!ua cae Rh:ln tu e h" . ." . , _. '" nang luqng de car dm lien ket du .. ~ , h' , . n n P__!.!UdQ

~p an tlf lam cho B co nhl~t d(l sdi cao han _ 1- Theo bal thl A va B la ddng phan cua nhau. S6 gam OXI trong 0,124 gaiA,

m6i chat la: J' i

0,308 0,072 moxi = 0,124 -12. ~ - 2. ~ == 0,124 - 0,084 - 0,008 = 0,032. ;~

:~ D~t c6ng thuc ella A,B fa CxHyOz, dt dang t1m duqc:*

.~

x : y : z == 7 : 8 : 2 v~y A, B deu e6 e6ng thuc phful tiI la: ~H802 ~ ~l

2- Hai ch~t A,B chua oxi, phan tIng dUqc v61 CH)COOH, suy fa A,B phai ch~! nh6nJ OH ella nrqu. Theo sa d6: t

o R-O-~ CH)COOH. R-Oh

IdvC 43 dv C (ang 43-1 = 42 dvC

Khi phan tIng ven CH)COOH d Ava B t~o ra sim phAro c6 KLPT =166 tue; tang 166 - 124 = 42 dvC, suy ra trong mOi ch~t A,B chi c6 mt)t nh6m -OH thu¢e I

ruqu.

- A,B phan tIng vai dung dich nu6c brOm v~y A,B c6 the fa ch~t khong,'

ho~c ch~t phenol.

/H.. o b-H

@r~H' (A)

Ole ch<i't A' rr ,

OB

{

H

In\ H···bJ()\HO \Q;-CH,-6 ~CH2-0H...

' (B)va san pham 'phan Ung v6i Br2.·

c§y-CH,-OS-CH] va ~O CH- /IB,2 O-C-CH(A') ) J(

~_~,.,--c.-

_Phan lmg v6i nuC1c br6m: O1i co phenol va aXlt acrylic phan 6ng : 0H

CH2=CH-COOH + Bf2 --) yH2-yH-COOHall a Sr, 0 0

Br BfBr~CH7-a-~-Cl-h va II

~- CH2-O-C-CHJ c9r

Br

OH OH I

;3y + z = 0,035Br~Br

Br I (IV) _@ + 3 Br2 3HBr +~ Sf

Bai 66. Mill him hlfP X gam axil axelic, axil acrylic, rlf,," etytic va phenol. Kh1 Giai h~ (n, (II), (III), (IV1 ta duqc: x = 0,01 y = 0,01

IlIlfrIg hon hqp La 32,8 gam. a z = 0,005 t =10,03. I _ Lay 1/10 hon hqp X cho tan vao frong benzen khan, sau do cho tac dl;ln~

, 0,6 {\:Y 0 94 ~o/do do: %CH3COOH = -32 .1 Oyro= 18,3%; %Ct,HsOH = -'-.1 OU'o = 28,7%;

vm Na du, thi duq'c 0,616 lit khi. ; 8 3,28 I

_ Lay 1/10 hon hqp X cho tac dl;lng vm lut;mg du dung ,djeh NaHCOJ t/i Oj36 1,3~ 00/

%~H3COOH = --'-j .1 OO? = 11 %; %r H OH == ~.lO 1= 42%'duqc 0,336 lit khi. 328 ro ~ .5 3,28 0 ,

_ Lay 1/10 hon hqp X eho tae dl;lng v6i dung djeh nuae brDm O,lltl thi ~~ I I

350 ml dung djch Brzbj mat mau. 1 ~ Bai 67. Tim thanh phan % thea k1l6"i IIf'!1'g cua mai chat trong Mn hlfP X. Riel J

thl tich khi de'u do ti dilu ki~n tieu ehu6n. Co hai hlfP chat X,Y chi chua C,H,O, thu~c 10fli no dan!ehuc. Khi tr~n hai chat X,Y theo bat ki Ii I~ Inao ta dlu thu duq'c hon hlfP IUDn lu(m co Ii kho' hoi soLOi giai vcli khi COz la 1,682. Khi lay cimg m9t IUl!'Jg bling nhau eua ""ljt h6n hlfP grim X vaY,cho tac dl;lng het vOilNazCOJ ; vOi Na thi thi tieh khi cOz va thl tieh H] bay ra D~l s6 mol cua CH COOH, C6H50 H, CzH3COOH,CzH50H co lrong 1/10

3 do J cimg dilu ki~n kh6ng bling nhau. Xac d~nh cong thuc eua Ihai chat X va Y.luang lmg la x,y,Z,t. 56 gam 1/10X = 60x + 94y + 72z + 461 = 3,2:~ (1) I I

Lffi giai. _Phan lmg v61 Na :

Tftl ca b6n chftl dtu ph~m lrng : I Viti kh6i hoi cu~ r6n hqp kMngph~ thul)c V'IO.ti l~_cua ~ va Y. suy faX, va CH COOH + Na--)- CHJCOONa + 1f2H2t \ I Y co kh61 luqng philn lu bang nhau va bang KLPTIl3 eua h6n hqp.

3

Ct,H 0H + Na~ Ct,H50Na + 1/2H2t x + y + z + 1 =0,05 n Ta co M = M = 1,682 .44= 74.5 (II) " y 1

~HJCOOH + Na-) ~HJCOONa + lf2H2t I1 - VI h6n hgp g6m X, Y phim trng v61 Na2C03 t~o fa CO2 v~y ho~c co m¢t chftt

~H50H + Na-~ ~H50Na + 1/2H21 'l1Iho~c"c<l hai Chal deu Ifl axft. Neu d hai cha:t deu la axil thl:

ncOz = nHl

= ~ (n"+ny) => trcli gia thi€t .

_ Phan tffig v6i NaHC03 : Chi co hai aXil philn tffig : V~y co m¢t chftt la' axit va m¢l ch5l la rlTQU. D~t X la aXIL CnH2n+1COOf-l va YCHJCOOII + NaHC03 _-) CH3COONa + Hl) + CO2t }

:=:J aruqu CmHzm+,OH. ~,

C H}COOH + NaHCO:l-~ C1H3COONa + H20 + COlt 1< 2 Vi M" = l4n + 46 (III) ~x+Y= 0,015

My = 14m + 18

Q'\

;·1

.1 III!!

k;' ~

tc:r.-.' . .

:lili I' i

.-!"" i i

'III

:l~' ,

~llil },III',\:~ \

:~ I ,fi' I l!iiJ: I

tlIang t~r mx + my > nx +- my :::: 0,32 ~ m > 2,67.rna M~ = My nen 14n + 46 :=:.:

14m +1R =:> 01=0+2. V~y m = 3,4,5... VI M C",1I2 ",0 = 14m + 16 < 3.28 ::: 74

Ta d, aXlt la ~H5COOH va nrqu la C4H90H. Suyra m < 4,14. V~ym=3ho~c;n=4.

V~y h6n hgp g6m CH 3-CHO va CH --Cll CHO3 rf Bai 68. ho~c CH3CHO va H CHOC3 7

Dot chay hoiin toan a gam m~jt hon hlfP grim hai andehit thllqc day dong

ddng cua andehit lomic, thu dUl!c 14,08 gam CO2, M(il khac khi cho a gam hon Uai 69. }

h~1p andehit tac dlf.ng hit vOi lUf!1lg du dung djch AgNOJ trong amolliac, sau phan img tlw dUl!c 25,92 gam bl;lC va dUl!c dung d!ch. Khi dung d!ch nay phan itng VOl Cho m gam hlri ruf!U tty/ic di qua m(jt O/lg sri chua CuO dot n6ng, lam It;lnh lU01lg dl( axit lIel kh6ng gidi phOl1g chat khl. Viet cong thuc phan tit va cong thue' loan b(j phlln hui di ra kho~' ong sri cho ngung tl;l he'l, thu dUl/c chat lOng A. Chin

A thiinh hai ph/in thljl deu nhau.ca'u t{lO cua cac andehit, biet ti kho'i hoi cua moi andehit so VOl nitlY deu nho hun 3. .;,.. - Phtin 1 cho pllan Ung het vOj Na, dU{Jc 3,36 lit If] (dkte) . Loi gi:'ii - Phlln 2 cho phan itng hit vOi dung dieh AgNO

J trong amoniac, thu dUl/e

143,2 gam, Ag.\ Vi dung dich sau phan tffig trang glIC1l1g kh6ng t~a ra chat khf khi philn lIng

1) Tinh m.veri axit,suy ra trong dung dich do kh6ng eo (NH4hCO) tuc Iii. ban dau kh6ng c6

andehit fomie. 2) Xtic dinh hi~u sulit phdn U'ng oxi hoa rU(TU.

~ I _ D~t e6ng thuc eua hai andehit Ia CnHlnO va CmH2mO co n,m :t- 1; gia sir ;1 3) Neu hi~u suiit oxi ,hoa ruf!U tfing them 10% thi the tich khi H] uthi

nghi4m trin thay d6i nhu the nao ? m>n.

3n - 1 (1) LOi giaic"H2nO + --2- . O2 ---)- nC02 + nH20

1) A g6m andehit, H20 va eo th6 ~H50H dl1. 3m - I (2)C-mH2mO + ---. O2 -----* me02 + mH20

/02 CH3CH/)H + CuD -~ CH;I-CHO + Cu + H20 (1)

c"H2nO +2[Ag(NH)hlOH ~ c,,_ I H2n- I COONH4+ 2Ag.!. IPh~n 1. H20 + Na --) 1/2 H2 + NaOH (2)

+ 3NH)+ H20 (3) ~H50H + Na --) 1/2 H2 + ~H50Na (3)

C H2mO + 2[Ag(NH3hlOH ------» Cm_IH2m-ICOONH4 + 2Ag.!. m 'Phan 2. CH,CHO +2IAg(NH,),JOH ~ CH,COONH, + 2Ag + 3NH, + lI 0 (4)

2'!1 1 + 3NH)+ H20 (4)

Thea phan tlng (4): so mol andehit = 1/2nAg == 1/2.(43,2/108):::: 0,2mol. D~t s6 mol c"H2nO 130 x; s6 mol CmH 2mO la y.

Thea phan U'ng (I) thl nC1Hl(J1I bi oxi h6a = nandehll = nlJp = 0,2Thea phlm lIng (1, 2): nc~ == nx + my = 0,32 (I)

Thea phan lIng (3, 4): mAg = 2x + 2y == 0,24 (II) =:) x. + Y== 0,12 V~y thea cae phan ling (l, 2, 3) ta e6: nil} a(2) = 1/2 n~o = 1/2.0,2 =0,1

Vi m > n nen nx + ny < nx + my suy ra nx + ny < 0,32 Suy fa s6 mol nil & (3) = 3,36 - nH & (2) = 0,15 - 0,1 = 0,05

Tu (II), va nh~n xet tren ta c6: n(x + y) < 0,32 1•. 2 22,4 2

I Tuc la n. 0,12 < 0,32 =:) n < 2,7 Thea (3) va nH2 iJ (3) suy fa so mol ruqu d~ co trung 1/2A I;).:

=> n == 2 (vI n:t- 1). 0,05.2= 0,1 mol.

+ 56 mol rugll ball d~u ::: 2 . (0,2 +0,1) == 0.6

V~y m = 0,6.46 = 27,6 gam.

2) T6ng s6 mol ruyu ban d{iu bang 0,6.

SO mol n1QU bi oxi h6a == 2 . 0,2 = 0,4.

Vf\y: Hicll sui\t oxi h6a n = 0,4 .100= 66,67% ., 'I 0,6

3) VI nH,o = n C,H,OJl b! oxi h6a. Ma thea cac ph<Ul ling (2,3):

n HI == In n up + 1/2 nC1Jl,OH du =

== 1/2 nCllf\OH b! oxi h6a + 1(2 nell/,OFi du .\I

= ban dau. 1(2 I1 Cllf \vH

Suy ra nl/ khOng ph~ thu¢C vaa hi¢u suar oxi hoa, rna chi ph~ thu¢c van l .\

Juqng ruqll ban dau, v~.y th~ Ikh H2 khOng thay dei.

Hili 70

Dot chay hoiln toim mqt hc/p chat A chua C, H, 0 co eong (hue phdn (u ~jl trung vVi cong thuc am gUi" nhdf, ta thu du'fc thi tich khi CO2 luon luon bling i

3/4 thi tich hoi H 0 va bling 6/7 thl t(ch oxi dli phdn fmg do frong nhftng diiu :, ki~n nhu nhau.

2

J'

Dun nong chat A '1m KHS04 thu dU{1c chat B co ti kh6i /u,; so JIm nitu bdltl 2 va co khd nang tham gia phdn img frang guung. '

1) Xac dfnh cong thirc phdn (u eua A va B. ,~'i 2) Vitt phuO'ng trinh phdn fmg cua B vOi H); dung d!ch 1'\Mn04 trong mo~

truang trung hod va trong moi trllo-ng H1S04 dun nong. ,~

Lmgiai

I) D~t e6ng thue eua A la c.HyOz yy z

C H 0 + (x + -- - -)0 ~ xeo2 + -H20 ... Y L 4 2 2 2

3 3 3 y (I)\.r. V --V Suy ra nco, == 4nJl/ J V~y x = '4'2y 1 CU: - 4 HlU

6 y z - ~V Suy ra x = - (.x + - - - ) (II)

VI Vco, - 7 0, 742

3y 6 y 7.So sanh (I) v6i (II) la c(J; ---=-(x+---)

8 7 4 2

3y 6 3y y z =:;> -=-,~+----) => z= 3y (III)8 7 8 4 2 1;8

Tit (I) va (III) rut ra x =.:: Z va y == 8x/3 I IV~y A la CxHax;:Px hay CJxHsxO)x

C6ng thue dan ginn ella A trimg v6l eOng thuc phan ttt "'ai]a C)H 0).8

Tinh dl1qc MA ::: 92 , .."I'.:\llll~·1

Theo bai Me == 2 .28 =:; 56 ·I'~,1:I1

J,1'

V~y khi dun n6ng A vai KHS04 thl t':lO fa chilt c6 kh6i IU(,ng p!l~n ttt giim di<U ~I~ I 11 J}/; Iv~y A phai lil fl1((U va da1x:iy fa phan Ung lo~i H20 trong m~t phin ttt ella nt((U. 56 " :iJ

M -M 92-56 \ph;ln tlr H20 bi tach ra Jal: nllp =:; A 8 = - __ = 2 . 18 18 JJi~i i

'~Itl! do ta rut ra duqe dng B phai e6 it hem A hai nguyen ttt oxi va h6n nguyen tit hidrc COng thuc phftn ttt D la C)H40. ~!~lili

c)HsO) , KHSO. ,to) 2H 0 + C)H 0 2 4

2) VI B tham gia phan ling trang b~c, v~y B la andehit c6nfS thue cau l~o

",;:0 eua B phai la CH2=CH-C~ . Theo c6ng thue cAu t<,lo nhu trrn thl cae phim

H U'ng e6 thi x~y fa nhu sau:

- Phan lrng v6'i Hz:

q-° 0,'H + H2 -~ CHrQIz C,

1­

H

CH2=CH-C

-?,O CH2=CH-C

'H + H2 ~ CHt=CH-C~hOH

q-0

CH2=CH-C + 2 H ~ CH3-CH2-CH2~OH'H 2

Nghia la e6 thi t~o fa san phAro cua phein ting hidro h6a ho~e vao nh6m andehit, ho~c vao lien k€t C=C, ho?c vao d6ng thOi ca nh6m ande?it va ca lien ket d~. ,

. Phan lIng v6i dung dich KMn04 trong m6i truemg trung hM:

-70 ~O 3Ci-I2=CH-C + 2KMn04 + 4 H20 - CH2-CH-C:7 + 2Mn0 l + 2KOH2

" I I "H OH OH H

i

__

~R""~O~~~~=­

;1'·'" I Vi KMnO.. phan ling v6i litn kct d6i C=C nhnnh han v6'i nh6m cacbonyL Tuy

nhlen nell kh6ng tach dlt<Jc ngay san ph!lm ho~c dlmg ltrqng nhi~l1 KMn04 thl se )l.f\y

ra ph:\n ung oxi hoa ca nhom ,-CHO: __ ''-' '-------,------ , ­

f HC-11~~--CH,c;-:--4K~,0:;2112°.---~3 <;:;I;=~yH=cooK -l qMn0 + KGB)2 ~ ,h L_ Oil Oll ~

- _-Ph1;~;_v&iK-MnO~~'H;Sa;-dUn-no~-klt-d6i~~n cat, nhom -ClIO bj oxi h6a, do do t~o fa axii oxalic va axit nay b! oxi hoa tiep t<,to fa COl'

o 0

\::"CH2=CH-C~+ 14 KMn04 + 21 H2S04 .!.-ISCO~ + 14MnS04+ 7K2S0

4 + 31 ~hO v 'H

1Rai 71· Chia 3,1 gam mljt hon hf!P A glJm x mol axit cacboxylic d07l chffc, y mol

1-,~'~'1. TlilfU dcm chue va z mol iste c1l1l/C tlJo thimh tit axit va T£1{YU tren, thanh hai philn

bling nhau. Do't chay hoim tOlln pha"n thll nhlt, dUl/c 1,736 lit CO 2 (dktc) va 1,26 gam

lIlO. Phdn thit hai phdn ,mg vita het vm 125 ml dung djch NaOH O,IM, dlil/c P

gam chat B va 0,74gam chiit C. Cho toan blj chift C phdn itng vm CuD (d,') dUl/c chal D, cha't nay khi phd" (mg het vm dung dich AgND) frong amoniac thi tt;lo ra Ag. LlJc liiy Ag r6i hoa tan hft /rang HNO). thu dut;1c 0,448 lit khi N02 (dktc).

1) Tinh x, y, z, p.

2) X& dlnh cong thue clfu t~o clla cae clHft trang hon hlfP A.

3) Tiuh nhanh pha'n % thea kho'i lut;Jng cua lion hf!P A. I' ;

LOi giai

1) Tfnh kh6i ltrqng C, H, °c6 tfang gam h6n hqp A:

rnc= 1,736 . 12 . 2 == I,86; mH == -1,26 •.2 2 =0,28gam 22,4

mo =-= rnA - mc - m == 3,1 - 1,86 - 0,28

x mol RCOOH

y mol R 'QH

z mol RCOOR'

RCOOH +

x mol

RCOOR' +

H

co chua 32x gam oxi

c6 chua 16y gam oxi

c6 chua 32z gam oxi

NaOH -) RCOONa

NaOH -) RCOONa

R'OH 125m1O,IM chat B

3,1/2=1,55

18

.::: 0,96 gam

} 32x + 16y + 32z =0,96

hay: '

2(x+z) + Y== 0,06 (I) :~

+ 1120 (1)

xmol

+ R'On (2)

chat C

Chtil C g6m lugng R'OH co trang I/2A ban drill va R'OH ella phan Ung (2).

R'OH + CuO ~ R"CHO + C'\J + H 02 (3)

R"CHO + 2[Ag(NHJ)2JOH ---1 R"COONH.j + 2Ag'!' + 3NH) +H 0 (4)2

Ag + 2HNOJ '-7 AgNO) + N02 + H20 (5)

'Oleo (1) (2) t<'5ng s6 mol RCOOH va R'COOR' btmg s6 mol NaOH

= 0,1 .0,125 == 0,0125.

V~y

x + Z == 0,0125.2 == O,025mol (1I)

Theo (3) (4) s6 mol R'OH c6 trang i/2A da thuy pht'tn == s6 mol RUCIIO

l(2I1Ag == i/2 l1A,n == 1/1 ~448 =0,01 mol. Tuc IA: y/2 + 7I2 =0,01 "'l 22,4

=> Y+ Z -= 0,02 (III)

Giai h~ (I) (II) (III) ta dugc: x == 0,015; y::: 0,01; '£= 0.01

'nnhp:

Ap dl,1l1g djnh lu~t bao loan kh6i ltlqng clio philn ling cua 1/2 h6n hqp A v6i NaOH b cae phan frog (1) va (2) ta [6:

m 1nA + IllN.,,rlll Pll.COON~ + nH20 + nlR'OH

3,1/2 + 0.0125.40= P+18.(O,OISf2)+O,74 ~_P=1.17~gam

7) Xac djnh c(Jflg thuc ella die chftt·

- lTIRCOON.. ::: 1,175; nRCOONa == x/2 + z/2 ::: 0,0125

. 1,175 :=;> MRU''''N =--, = 94

JU a 0,0125

Vi ReOONa l?t m116i ella axit dan ch(rc !1t~n g6c R ehi chl1a cacoon va hidro:

l11 R ~,94 - (23 + 44) =27 4

],

K-il)~m;{ ::; 12x + Y 12x+ y ~ 27 3 <0 I R llo~i ~Hj

V~y axit ban d~u la CH,l= -COOH

- mR'()/f - 0,74 ; nWOH do I/2A t<,lo ra =y(2 + zj2 == 0,01

:::::) MR'OH::; 0,74 ::; 74. Rlfqu dem chuc nen R' 13 Cx.H ': v0,01 .

OIR' =74 - 17 ::: 57 12x' + y' =- 57 rut fa dLI0C x' =4 y'=9

V~y nrqu I~ C4H90H co lh~ c6 de cAu t<,lo sau:

1

CHcCHz-CHz-CH~-OH ho~c CHJ-C~-CHrOH

CH)

Suy ra diu t~o estc la: fH3

CHz=CH-COO-CHz-CHz-CHz-S:H) ho~c CHi=CH-COO-CHz--CH I CH)

Tbh thanh phful % theo kh6i Im;mg cua h6n hqp A:

% CH =CH-COOH = .0,015.72 . 100 ~ 34,84% 2 3,1

:::: 0,01.74 . tOO ~ 23,87%% C4H90H 3,1

% CHz==CH-COOC"H'I:::: 100 - 34,84,·23,87 =: 41,29(J'o

;,1

Dai 72. =---Co hal dung dich A va n dlu co nong dij 0,08 mol/I. Dang d#ch A lil dung

dich cua mijt chilt hilu crr X (chi clHla C, H, 0). Dung dic!, B lJ dlrJng dich KzCOJ'~) LOy SDml dung djch A chia thann hai pha'n bdng nhau AJ va Az.:;

LOy 25ml dung djch B chia lhdnh hai philn bling nhau B / va Bz·

AJphdn img vila du yQj 8/ gia; ph6ng chelt kh( COz' Cho Bzphan ilng v6j dung djch nlluc ra; frong vila du, If?c b6 kit tua, thu dUf!c d:mg d!ch BJ, thi dung djch B J chi phan img vita du v61 1/2 dung dich Az, frong cac SilJr., phdm tq.o ra ehl'

co mOt chill thuac loa; hihl cO'. .: . ";. t Chilt X co the thuijc loq.i hqp cl1lft nao? Hay ltfy chill co khat 1Tf971g phan ~

nho nhat cua 10l}i do dilliel cong thirc cefu lq.o va phucmg trinh phan fmg giiia 4;/ vm B /; A

2 vOi B J minh hoq.. ; <~

LOi giai. j:i'

_n trong AI =: n trang Az :::: 1/2.0,05 .0,08 == 0,OO2molxx

OK,CO, trong B1 = nK,m, trang TI2 = 1/2 . 0,025 . 0,08 ::: 0,00 Imol -i _VI ch:lt X (chua C, H, 0) phall lmg v6 K1CO) t~o ta ch1ft khf COlo suy ra~

phai chua nh6m COOH. d~t X la R(COOH)n ta c6: (1)

R(COOH)n + n/2K zCO) -+ R(COOK)n + n/2COzt + n/2HzO

1 mol 0/2mOI} n ::.: 1. Trang ph~n Ill' X chi co mqt O,OO2mol 0,001 mol nh6m -COOH

_~ phan lIng m!l1C v6i trong:

K2COJ + Ca(OH)z == CaCO)t + 2KOH (2) 0,001 0,002 ~~:

Dung d!ch ~ chua 0,002 mol KOH ~I - B] phan U'ng vOli Az:

RCOOH + KOH -+ RCOOK + H 02 (3) 0,002 ~ 0,002

111co (3) va 56 m<i>l cac ch~ft lrang A2 va B) thi A2va 8:J phiai phan lIng vua h~t

vCfi nhau. Dj~u nay lrai ~6i gia thi~l. , I

Thea de bai BJ chi phan Ung vita het v&i 1/2Az, suy ra 0,001 mol X phan U'ng vm 0,002 mol KOH, IUc la n" : nKOH == 1 : 2. V~y trang g6c R ella X phai con chu-a ml?l nhom chuc khac phan lIng dlrqc v&i kiern, rna X chi chua C, H, O. V~y nh6m chl1c do phii la phenol ho*c e~te. I

+ Ncu lrong R chua imOI nh6m -OH lo~j phenol thi c6ng thvc Icing quat cua X Ja OH

'R' ©--c.H , COO"

ch51 co kh6i lm;mg phan tit nho nhat khi R' =H; C":\Hykl16ng co, klii do c6 ba chat sau:

OH

@rCOOH OH

K9r hj~u chung la:©--COOH $ HO-C{,HrCOOH eOOH

Ok phein ling:

Al + HI: 2HO-Ct,Hr COOH + Y2COJ -+ 2HO-~HcCOOK + CO2

+ H20

Az+ Bl : HO-Ct,HrCOOH + 2KOH -7' 2KO-Ct,H4-COOK + 2H OzDili 73. T f.t fer -('/,,>1:1.'. Ho -- (1:-1, - coo - (H,l.. - <-DO H .

Di thuy phdn hoim toan 0,74gum h6n h!fP este cua hai axil monocacbo­xylic can 7,Ogam dung !d#eh KOll 8% dii hOG tan trong nuuc, thu du'!c muol va nJf!U dun chilc. Khi dun nong ~on h!fP este noi tren vtJi H;zSP4 80% sinh ra khf, ngum ta Jam bJ,nh phdn, hui, thu My /chi va can. sau d6 cho /chi ltji tU tit qua dung d!ch nuuc brom thi thdy kh6i IUflTIg /chi gidm 1/3, trong khi do khor lUlf1lg rieng ella /chi khong d6i. Gid thili cac phdn ,mg diu xcfy ra hoan t04n.

J) rinh kho,luf!!lg mol cua hon h!fP este.

2) Xac dinh congl/hirc cua este.

3) Tinh thanh phdn phan tram thea kho"j IUf!1tg clla rnai este trong han hf!P va sogam cua hon hqp khi.

~/' 1'-: :.:tt-.:.- _=-~-~~~~..-'

4) 116n hqp este tren co ;/1(111 ifng fl.li dung djch bt}c oxit frong dung d~ch amnlliac l!Ul!C khong ?

LOi giai.

VI cac chat este dan chue nen ki hi?u chung In RCOOR'

RCOOR' + KOB ~ RCOOK + R'OH (l)

7.8 1) Theo (1): neSle =nXOH =-- =: O,OImo!.

100.56

- 074V~y M'JI< = -'- = 74 0,01

2) Xac djnh c6ng thuc este. C6 hai khA nang xay ra:

a) Kha nang thu nh1t: Clc este co kh6i ltrqng phftn ttl bAng 74. Khi do chung la d6ng phftn clla nhau co OPT: C3H60~ va phai Iii: elyl forniat HCOOc;Hs

vA metyl axetat CH3COOCH).

b) Khil nang thu hai. M¢t este co kh6i hrqng phan ttr nlla han 74 va este tlIu hai c6 kh6i ItIl;mg ph!\n ttl Ian hem 74.

- Este c6 kh6i luqng phftn ltr nha hem 74 co the Hi: "

I,

HCOOCH) (M::: 60); HCOO-CH=CHz (f\1 = 72); HCOO-GCH (M=70)

Chi co metyl [omiat C0 th~ thoa man VI sau phim U'ng vOi KOH phai t~o ra

mu6i va mqu.

~ _Este co kh6i luqng ph:tn ttl 100 h<.11' 74 ta ki hi~u la RCOOR'.

Nhl1 v~y trong d hai kl]a nang d~u co este cua axit fomic, ta bie't rang kJ!i.4uIl n6ng_~~5un[uri.c thl cae fomiat bi thuy ~hfm sinh ra cacbonmon~ (M=28). V~y thea d~ bai thl trong khi thu duqc phiiu6 W, ngoai khi d6 d)~_ phai c6 etf (khi khac va khi nay chi c6 thti lil m¢t anken sinh ra do phan lOlg ~o~i nuOc ancol t'!-o

'I. ~au phan li'ng thuy phful este.

(;../ ~ Cho khi di qua dung djch mtac br6m thi anken b~ giii h~i het. VI kh6i luqng J r r\~ng ella khi tmac va khi sau khi di qua nHoc br6m Ii k.~t,ng d6i, nen chat khi thu

hai phai co eung kh6i hrqng phan ttr nhu CO, tue la 28dv C, suy ra do phai III etilen ~H4' va nhu v~y trong h6n hqp ban dau phai c6 este eua nIQU etyIie:

H2SO.,to

R-COO~H5 + HzO -----;;. RCOOH + ~H50H

H2SO., 80%. tU

C2H~OH ) ~H4 + H20

-- ----- - ..._-- -- - --- - .. -... __ ......... ------ .... - ----------------------- ---- - - -­\j sC00C::B -_._~ RCOOH + ~H4 t (2)

xa kh<i. nang thu nh5t ?J tr~n: --.... -------.

u

J ~., HlSO•. l '. - • _j-­/

HCO()~H5 --t cot + (~H.j t + H 0 (3)2

U\ IV'C),. t

l CHJ.COOCHJ--t CHJCOOH + CH 0H ~.n 3

Thea phan tIng (3) Ihl nco::: nC2H4 => ~- -._

Khi dun qua dung djch Bfl : CzH4 + Bf;Z ~ CzH Dr 4 2 (5)

CO di qua dung djch.

thl 56 gam khi phai gi,im 1/2. Dieu nay trai v6i giil thie't. v~y kha nang d hai este del c6 kh6i Iuqng phtln ttr bang 74 kht"mg phu hqp.

Xet khli nang thu hai. Hbn hqp g\~m x r .Jl HCOOCH) (M ::: 60) va y rno RCOOCzH~.

1I~~J.f tHCOOCHJ ~---~ CO + CH]OH (6)

x x

1I..!X),iU

RCOOCzH~ } ~H4 i + RCOOH (2)

y y

Thea 0) ta c6 x + y ~ 0,01 (I)

VI di qua dung djch Br2 thl kh6i IUQ'ng khi giam 1/3,

suy ra mm ::: 2. m(·JH. tue Ii! x = 2y (1I). Til (1) va (II) tfnh dl1gc:

0,01Y=­}56 gam h6n hqp este la 0.'74 gaIn 3

6() 0.02 0,010,02 .. --. + (R + 73). --- ::= 0 74 ~ R = 29

X=-- 33' 3 Vf.ly este thu hai 1?l CHr CH -O.l0-CH -CJI)r 2

3) Tinh .c&.

+) mllcooell :-::'60. (0,0213) =0,4 ==> %HCOUCH) = ~-.I00;.:: 54% } ~~

%c;H5COOC~Hj = 100% - 54% = 46%

+) rn khi = meo + me211 • = 2R.(O,02/3) + 28.(0,01/3) =28.0,01 = O,2Rgam

4) Phan ung vOi dung dich IAg(NHJ )2JOH: axit fornic va cae fomiat do

... 0 con nh6m cAll t~o -C: nen tham gia phan i1ng tfang b;:tc.

H

_ ........~-:-;,...-~~~-----::-r~--"'-------:"•.-~---,,~~~~_

TroIlg h6n hqp A c6 chua HCOOell), (lo do tharn gia phan lmg trang b~c.

~.O H-C ~ + 2lAg(NH)hlOH -.2Ag + CfI}OH + (Nl-4hCO ) +2NH)

a-eH)

: 74.

Dot duiy hoan toim 10ml hm' mqt este X phd; diing vila hel 115ml 0 11 h6n

i} san phtm khf thu duqc sau phdn ling chi gom khi COz vd hcri TRUaC vOi te I~ ? dch 2 : 1. ello 1I6n hrJP san phcim (ren di qua H zS04 di!c, khi tli ra chi con

Om I.

.M(;t khiic, d/ dot chay haan toan 20mI hcri. axit H, Ui axil If;W ra este tren,

n dung 90rnl ox;. Tat cd cac khi diu do J ding m{J1 diiu ki~n vi' nhi~t d6 va tip

at,

1) Xcic din" cong illite phdn Iu eua X.

2) Viet cong t/rire eefu t~o eua B, bii:t no co c,1'1l If!.o m~eh nhanh.

3) ClIO 1,62 gam X tac d,!ng vOl dun?,'dich NaOH O,SM. Tinh thi tich dung

'ch NaOH c{in dung vd so gallt muoi khan thu dUf!c.

4) Thuj plu]n hoan toan 3,24gam X b,1ng dung dIcit He/loang, ro; cho hbn

~rp thu tJu'!c sau thuy phan lac dl;lng vOi dung djeh nuac bram O,2M. Tinh thl

ch dung dieh nu6c br6m t6i da co Ihi tham Kia phdn itng,

Lm giai.

D~t c<>ng thuc ella X Iil ~HyOz

H S04 d~c gili H20.Khl di qua H2S04 d~c 11k CO~.2

V lOOml, suy fa ~/P == 1/2 VCOI =50m!.co, =

) Xae dinh cOng thve ph<1n tLr X.

CxHyOz +(x +t -~ )02 -- X C02 + ~ H20 (I)

y z 0 x X­X +4-2 2---<> 2

1J 5 100 5010

x -- Il) } I x + ,-y ----zTa co 1/10 x/I ()() =:) __ 4 2 => y=lO 1O---11-5=>Z==2

1/10 (y/2)/50

CllTf cua X la CIOHIOO]

2.) Xfic uinh CTPT ella !3..

Vi X la cstc rna trang phfu-l tv X chi c6 h3i nguyen ill axi, suy faX Ii). este dem chuc, v~y axit B la axil dan chlic. D~t CTPT eua B Iii ~Hrl,02' Ta c6:

CnHmOz + (n + (m/4)-1)02 ~ neOz + m/l H20 (2)

1 -) n+(mI4)-1 } ==:>4n+m=22~22-4nl 20 ~ 90 m:::;2n

~~--==1=iJ 3 4 5 6~~- 18 i 14 10 6 2 -2 i loai 9ung __L-----L~_i.___ --J

V~y B 1ft C4H60 Z h~y C3H5COOH. V~y B In CH2~C-COOH

CH3 m~ch nhanh

3) Theo eOng thuc I1'h!in tli ella este va CTPT eua axil &rrco w. c6 th~ x~c djnh fa cae b~ ph~n cau t~a cualeste X oht! sal!:

-90 CH.,=C-C M x =: 162; n

ll = 1,62 = O,Olmal

.. ICH) " O-C6~~5 162 I

GOe ~H5"c6 the 13 g6c,phenyl @ ,cuog eo th~ 13 goc kb6ng na, fbf

d\l: H-O=C-C=C-CH2-CH2- (va nhieu g6c khac) dau saa thl C H khOng th~ chua6 5

vugt qua 4 lien ker n.

- Neu C6H5- lil g6c' phenyl ta co phan t'rng cua X v6'i NaOH;:

CH2=C;-COO-C6Hs + 2NaOH - CH2=y-COONa ~ C6H~ONa +H20 (3) CH) CH)I

0,01 --------+ 0,02 ==:> VNaOH =0,02/0,5 =0,041;:: 40ml

- Neu Ct,H5 khOng phai 13 vong benzcn lhl co phan ll'ng:

CH2=C-COO-C6Hs + NaOH J'

CI-I) -- CH2=C-COONa

I

CH) t C6H50H (4)

0,01 ~ 0,01 !

(Ncu -OH lien ket v6i cacbon Sp2 ha~c sp se bi bien d~i ti~p thea, nhlJ'rig kh6ng phim (mg vm NaO~f).

, .' VNaOH = 0,01/0,5 :::: 0,02Iit = 20m)

i

!I

4) Tucfng (If nhu lr~n: nx =3,24/162 =O,02mal

I

""-..r-~. -......- ~,..-"":-~~,_,"':':,..-J --,-- ...--r;..-;--.-n, ~=.....-=-~~--------

llel f' (5)CIJ:;:c=c,:-COO-C 6IIs + H20 --.:.. CIhc~-C()OIl -+ CoH)OIl ell] CH3

om om om han hqp sau phan lIng thuy phfln g6m O.02mo! axil va O,02mol C(,H50H.

Ncu C(,H5

lb. goc phenyi th) philn ling vCrI Illlac bram nhll sail:

Hr (0) cn.,:=C-COOlI + 13r2 Br-Cl h-C-COOIl

- C:Hl - I

CH:\

0,02 0,02

all OJI

Hr~?r (7)©4 3Br, ~) + 3HBr

81

0,02 -~ 0,06 0,08 I

lI =:: 0,02 + 0,06 = O,OS =? V~ =:: --- = 0,4::::: 400m BrI l • "', 0,2

_ N~u C6H

5 kh6ng phai 1:1 g6c phenyl thi 16i da C",H50H con chua 4 lien klt TC

va c~ng dl1(,1c 4 mol Br2:

::! C,H 50H + 4Br2 ---+ C6H~BrllOH un 0,02 O,Oi)

I 'Thea (6; (0,08) thl I n 8r~ = O,U2 + 0,08 :::: 0, Imol

V8r, = 0,1 / 0,2 == 0,51 = SOOml

'i Hai 75.

- Co hai htfP chat hiiu C(J E va F dlu chi chua C, II, O. KJri hoa hoi i'l

O,31gam, E, fhu dUl/e the tich 1:fJ'i dllng bling the' tich e:ia 0J16 gam ox; do (1 dzng"1

r.,· ' dUil ki4n. Mij.t k!u1c, cling 0,31 gam E tac dl;iilg hit ~'Ji No tt;lO ra 112 ml khi 11];1. II (ok/c) ..

Chat F IiI m(H axit no don chuc. Tri)n 2,47gam Juri chat F v6i 0 1 thu duqc 6 lit h6n hlfP (do a546°C, 1atm). Cho hon hr;p win mot binh kin dUhg lieh 2,5Ii/ kh(mg d6i. B(U tfa Ilia dj~n de phan ling chJy F XQY Til hoan toano Sau phan irng, 'hity cae chat trong hinh de'u athi khi trong do van con oxi, tip sua! tronK biuh Ii 20rrc IiI 1644mmHg.

1) Xtic dinh ca'u tt;lo CUll E ~'a F.

2) Viet phurrng trin}, phd" IlnR giiia E va F.

LOi g;ai.

I) Vi Vr :::: Vo ~.) n E :::: no ::.:.9~;:.:; 005::::;. M " ~~ ~,_~l_ = 62 • 1 '32' i. 0,005

Vi E chi chua C, H. 0, rna E pharo IrTlg v6'i Na tao H], suy fa cClng tllue tcing

qUell clb E l?t (OH)lI-R--(COOH)IO' n" :::: _0,112 :::: 0,005 I 21,4

n+m(OH)n-R-(COOH)m + (n + M) -» (NaO)n~R-(COONa)m+ ---JJ 2 2

0,005 0,005 Suy fa n + m :.:0 2. VI ME ::: 62 nca ch i c0 de gia sIr! n := 2, rn :::: °III. Ihoa man

V~y E 13 erilenglicol C2HiOH)2'

- lb~ tich h6n h(,1p g6m F va O2 tmac khi .:hay qui 1J6 di~u ki~n lieu chuiln: V == 1.6.273

21ft o 473.760

Sau chay: 1.6.273 3 I'V =: :::: 12 It o (546 + 273).760 '

V h 'd-I' . Ikh'J' 3,12-2 005 Jay sau c ay a am rang 56 mo 1 a: n == --_ = , 010. .

- VI F Iii axit r.o dan ch(rc nen c~ng Ta co: c"H2nO:z + (3n-2)/20

Imol (3n-2)/2 mnl 2 47 -'-molI4n + 32

) O,SnV:ly == - ~ 14n + 32 ==

. ~_ 0,05 J 4n + 32

22A

thue ph"ln tl'r F la c"H2n0 • .- ­2

--;. nC02

+ nH 20

n mol fl mol =:> tang O,5nmol '--------y--- J

~- 005 I ~ ~:lng , rna

24,7n ::.-=:> n - 3.

V~y cwr clla F Ja C)H60 2hay CH)-CH2-COOH

2) Phan lIng gifra E va F: co the l~o ra mono- ho~c dieste:

o

rCH)-CH2-C "O--CHc CH2-0H +H20

CH)--CH2-COOH + I!O-CH1-O-h-OH-L

C2Hs-e" ~o ? O-CHI-eH2-0-~-C2H5 +2 Hp

B?ti 76. rr Dot chay hoan toan m gam mt)t amin A bang luang kh6ng khi vita du., Ihl

dllf!c 17,6gam CO]; 12,6gam hai nuuc va 69,44 lit niter. Cia thiit kho1lK khi ch

it(1l'tl oxi trong d6 niter ellie'm 80% thell the' riel,; cac thi tich klJi do 6 diill

eu chuJn. Xac dinh m Vl~ ten Rf!i cua amino

LOi giai.

_SCi gam cacboll trong A == (17,61'44).12 = 4,8gam

DlH:= (12,6/18).2 :::: 1,4gam

_ Lvqng oxi da dung cling chfnh la luqng CJxi co trong COIVa HlO t<;lO fa ;::::)

{l7,6/44).32 + (12,6/iS).16 == 24 gam =:> no"'i == 24/32=0,75.

V~y nni'<lCua khOng khf::; 4 . no"'i = 4.0,75 = 3mol.

. " 69,44 I_TOng sO mo;~ =. -~- == 3,lmo .

• Hz L2,4

56 mol n do phafl \l'ng chay chilt A t<;lo ra la: 3.1 - 3 = 0, 1mol liz

V~y rnnilO trong A := 0.1 . 28 == 2,8gam.

Suy fa rnA := me 1- lJlH + mN = 4,g + 1,4 -I- 2,8 = 9 gam

_D~t c6ng thue A 1;\ C",H1Nz ta co:

)( : y : z :-.: ~~.~.: .~~ == ?.: 7 : l' n 1 ]4

Ala (CzH,N)n hay ~nH7nNn

VI trops c6ng th,k c.,.H yN, thi Y~ 2x. + 2 + Z

V~y trong C-'1nH7nNn lhi 71l::; 2.2n + 2 + n =:> n -s; l.

V~y CfPT cua A 13 C'-1H7N co cae e~u l<;lo sau:

CH -CH -NB etylamin ho~e CH3-NH-CH3 dimetylarnin.13 2

1:? HlfP chdt X chua ...:, 11, 0, co KLPT = 136.. Khi dot chay hoan toim

!:."am X thu dlilfc 1,08gam H 20 va 2,2gam CO], Cho hoi cua X di qua {/ng sit I CuO diit nong thu duqc chd'! hftu cd Y co KLPT nho h(f1J KLPT cua X M 8 Khi cho 2,56gam chat Y lac d'fng het vOi dung d!ch AgNOJ trong amoniac

":4 17,28gam Ag. Cho X VtlO dung djch NaBr bao hoa, sau do them tii tii H1S04 cJt;jc vao hon

thu dl1lfC chilt him eel Z kh6ng chua oxi. Dun nong Z vm b¢t kim dlt~c chat Cd Q co tl kh{/i hoi so YIn hidro nho h(f1J 45. Hay xilc d#nh C~fll tf;!o va ten gfJi

X, Y,Z,Q.

LOi giai.

= 0,6 gam _Xac djnh ClYf e:tl<.\ X: ~1c =: (2,2/44). 12

1J1)1:= (l ,08/18).2 .=: 0,12 gam

rna = 1,36 - 0,6 - 0,12:-:: 0,64 gam I

, 0,6 0,12 (\ 64 ~ dilt X la c,..ByOz ta c6:. x: y: z = -:-:-'- = 5: 12: 4

• I 12 1 16

CfDG ella X la C5H120.\ va do ding If! CfPT eua X.

. - X lac dl!ng v6i. CuO t~o ra Y trang do My < M"" suy ra X ph!ai la nrgu. Theo sa dO: I

I ~ to ........ -CH-OH + CuG --- C=:O + H20 + Cu

I /

lhl eu m¢l nh6m CH-OH bi~n thanh m¢t nh6m C=O thl KLPT giam 2 dve. Ma My = M", - 8 suy ra trang X e6 b6h nh6m CBOH va M y :-:: 136 - 8 = 128

=:> Oy = 2,56/128 == 0;02 mol.

Y tham gia phim lIng Hang b<;lc., v~y Y 13 andchit R(CHO\,.

R(-CHO)n + 2nlAg(NH3hIOH ---t R(COONH4)n+ 2nAg + 3nNH j + nH 02

1 mol 2n mol

0,02 mol 0,16 mol

V~y 1/0,02 :-:: 2n/0,16 1:=) n = 4. Suy ra X c6 4 nh6m -CH 0H.2

Cl~OH CWOV~y ct\u t~o ella X la: HOClb-C-CU-OH IYin

~ I • £1. HOC-C~CHO CH:zOH I

CAO Ten eua X: tetrahidroxymctylmetan; Penlaeritritol.

Ten cua Y: tetrafomylmetan.

- Phan lIng cua X "01 NaBr + H2S04: cae nhom OB Mu b~ thtlyib~ng 13r.

CH20H I CH2Br

HOCHz- y-CH20H + 4NaBr+ 4HzS04 _ I

Brt::Hz-y-CHzBr + 4NaHS04 + 4 H20 CHzOH CH2Br

(Z) tetrabrammetylmtttan.

Vi MQ < 2.45 = 90, suy ra trong Q kh6ng eon chua br6m.

BrCH2"". CH2Br CHz CH2C/ to

I

+ 2 Zn/"". - J )c(1 + 2 ZnBr2 Brt::Hz CH2Br CH2 CH2

(Q) SpiropcnLm

'Fir"

J Hili 7fJ.. Hqp chiit A La m¢t a-ar.llillOaxit . Cho 0,01 mol A lac d~mg vita het vOi 80ml

dung djch lICI V,125Af, sau do co ct;ln thu dllqc 1,835gam muo'i. Mijt khac, khi trung hoa 2,94gam A bli1lg dung dlch NaOH vita dri thf dllqc 3,82gam muo'" A co cau tt;lo mqch thang, hliy g9i ten thuang dung cua A, dan xUlft nao cua A thliOng dtf~IC dung trong cu¢c sl5'ng hang ngiiy? Viet phl1ung trinh phdn {mg cua A vOi

,J, NaNO]trong S~( co mijl cua axit clohidric.

LOi gi:'li

D~t e6ng thuc ella A la (l,12N-)nR(COOlI)m (n, m ~ 0)

_Phan ling VtS'i HCl: nllo == 0,08 .0,125 == 0,01 mol.

(l12N-)Il-R(COOH),n + nBC! ~ (C1H]N-)n-R-(COOH)m (1) ~ I,

Imol n mol }

bai cha 0,01 mol 0,01 mol n == I

ll1eo (1): s6 mol mu6i =:: s6 mol A = 0,01 rna s6 gam mu6i = 1,835 . 1,835

Suy ra Mmu61 == -- = 183,50,01

V~y MA == Mrnu61 - MilO ==

nA phan lIng v6i NaOH

- Phan t'mg ella A vai NaOH:

183,5 - 36,5 = 147

= 2,94: 147 = 0,02 mol.

H2N-R(COOH)m + mNaOH -+ H2 N-R(COONa)m + mH20

1 mol 1mol ~ tang 22mgam

O,02moi tang 3,82 - 2,94 :-: O,88gam

Suy ra: 1/0,02 == 22m/O,88 => IT! == 2.

V~y A eo d"ll1g 1clng quat H2N-R~(COOHh M A =147

SuyramR = 147-16-45.2=41,v~yRlilC]H~

Vi A e6 m~ch th~ng, lil a-aminoaxit vfJ.y ciu 1'.\0 Ala:

HOOC-CH.,-CfI.,-CH-COOH ~ - Ni12 axitglutamic

dAn xuflt hay dtlng trong cu<,?e s6ng eo trang thanh ph~n ella b¢t ngQt, la mononatri

glutamat:

NaO()C-CH2-CH~-CH-C008 ... I

eon gQi la rot chfnhNHl e " - Phan (mg eua A ven NaN01 '/a He!.

\. HOOC-CH2-CH2-«II-COOIl + NaNO} + HCI --.I NH2l, - + H

)NaOOC-CIl,-CH2-'yH-COOIl + NaCI + N,I 20

OB

Hili 79

Dot chily hoan toan 0,122 gam chat hiiu cu A va cho toan bi) sdn phdn chily chi gom calVa lI20 vao mi)t binh dlf1lg IUlJ1Ig du nUlTC vo; trong. Sau tit nghi~m thay binh dzprg nutYc voi tling kJzoi lut;mg O.522gam va t{fo ra O,9gam ke tria.

1) Tim cong thuc dun gUin nhat cua A.

2) H'!P chat B co c{mg thuc phan tri nhu conK thue dun gidn nhat cua A Khi ox; hod hoan toan B bling K2Cr]O] trong ",oi Iruirng H

2S0

4 ta dUf!c xetodiaxi,

X mt;lch thdng, phdn IU X co it hun phan tit B m~t nguyen tit cacbon. Khi B hf!l. vOi hidro tlJ.O ra n-propylxiclohexan, khi cho B tac d~mg vOi dUllg d!ch KMnO, loling dUf!C chat Y co s6 nguyen tu cacbon nhu B. Riel Y co khoi IUf!1Ig phdn tri M 190 dvC; Y phdn Ung vOi CHJCOOH co II]S04 lam xuc /lic chi tq.o ra chat Z c(, cimg thuc phan tu CJSHuO]. Viet cong thuc cd'u ilJ.o va ten g9i cua B. Viet ca( phucmg trinh phdn ifng dti kltren.

LOi giai.

1) Xac d!nh crDG clla A: Kh6i hrgng blnh tang = m + mlliO C01

S6 gam CaCOJ =s6 gam ke1 tlla == 0,9 gam.

"en =:: 0,9 ;::: O,009mol => me =: 0,009. 11 = 0,108 gam. '''l 100

0,126mH 0 == 0 522 - 0 009 . 44 =0 126 => mLI == ~- • 2 =: 0 014 gam1 " , r 18 '

mOz = 0,122 - 0,108 - 0,014 == O. V~y Ala hidrocaebon.

D~t A la C"I-Iy ta co. x: y = O'II~8: O,~14 = 0,009: 0,014 == 9: 14

CfDG ella A ]a 4H14'

2) Xae djnh ciu t<;\o ella B: CfPT B la 4Hl4 => M :-:: 122B

/yCH2-CH2-CH3

- B+ Hz -+ L)

- B + K2CrZ0 1 + H2SO4 -+ X co ft hem B m<,?1 nguyen ttr eachan, v~y

dii co m¢1 eacbon tach ra thanh CO2, tuc la trong B co CH ==C2

Vi x la xetodiaxit nen trang B e6 hai lien ket aOi, va phai c6 nh6m c~u 1'.10

C-C=CH-C I

C

_ B + dung d!ch KMn()4 ----t Y co s6 luqng cacbon nhlI B.V~y da xay fa phan mg hidrat hoa ella B.VI KLPT ella Y = 190. Suy ra s6 nh6m -01:1 co trong Y Iii:

, Aiy A18 190 - 122 56 nllom OH = --- == ---- == 4

17 17

V~y Y co e6ng thve tcing quat ~HliOH)4

- Y + CHJCOOH -~ Z eo CfPT: CI5H2401

V~y Z chi chua 3 g6c axctat, tvc la co m¢t nh6m -OH b~e ba ncn kh6ng ph?m mg vm CH3COOH d~ t~o cstc.

UCH2-CH~CH2

Suy ra crcr ella B la

l-alylxiclohcxen

- cae phuong trInn philO LIne:

~CHZ-CH=CHZ ?! l~ + gKZCrZ07 + 32HzS04 _31IOOC-~l-h-CHrCHz-CHz-C-CH2-COOH

+ C02 + Cr2(504)) + K2S04 ~-1120

CHZ-CH=CH aCHrCH2-CHJaI 2 + 2l-h ~

---+ 3r-xC~I.z-YH-YH2 30CHz-CH=CHz + 4 KMn04 + 8 H20 "---( 'OH OH OH

OH + 4MnO z + 4KOH

o II

r-xCHz-yH-yHz H2S04oCHz-yH-Cl'Iz-O-'C-CHJ "---( 'OH OH OH + 3CHJCOOH - OH O-y-CHJ +3 H20

OH O-e--CHJ 0 II

o

Bai80

Dot chily hoan toan O,74gam hap chat X ta chi thu duq'c r.lhu1lg tht tich )dng nhau elia kh[ C01va hoi mftYc, trung do co 0,672 lit CO2 (,rJilu ki~n tiiu

:hudn).

I) Xac dinh c6ng th{(c phdn tei cua X, biet ti kh6, hoi cua X so vOi !leI; bling 18,5.

I I 2) Viet cong thuc ccfu tf;lo cua 6 chat Tnf;lch hu itng vUf CTPT tim dUffc.

3) Cho 0,74 g~m X VaG 100ml dung d#ch NllOH 1Mikho'i /uq'Ilg ning d = 1,0354 glml, dun n6~g chu phdn tlng hoan toan , sau do n,ang nhi~t d~ tu tU cho btic hoi den kho, /il1n It.mh cho toan b9 phdn hoi ngung tlf Ihit. SllU thi nghi~m ta dUffc chat ran khan If va chat lOng ngung tlf Z; Khollu¢rzg Z /Q 100 gam. Tim kh6,lufI1Ig chat ran Y, cong thuc ca" tf;lO va tell g{ji cua X.

Lmgiai

1) n Hp =nC~1 == 0,672 : 22,4 = 0,03moI I

I

me :::: 0,03 l 12 :::: 0,36 moxi :::: 0,74 - 0,36 - 0,06 =0.32 mH =0,03.2 :::: 0,06 ~ no = 0,32: 16 :::: 0,02

D~t X la CxHyOz: x : y : z = 0,03 : 0,06 : 0,02 :::: 3 f 6 : 2

CIYf clla X: (G::3H60 Z)n :::: 18,5. 4 :::: 74 => n:::: 1. i I I

CIYf ella X: C3Ht;Oz.

2) C6ng thtfc 6 ~h~t lTI'.ich ho: I I !

CHJ-CHz-COOH CHJ-COOCHJ HGOOCHz-CHJ

CHJ-CH-C~O ~O o 1/

HO-CHz- CH2-C" H Cl4J-c-CHz-OHOH "H I

3) Tfnh kh6i IlIl;tng ella Y va xac dinh c~u t'.io ella X:

+) Mx + mdung dich NaOH :::: my + mz

0,74 + 100.1,0354 = my + 100 => my ::::"4,28gam

+) nNaOH :..~ 0,1 . 1 = 0,1 mol

flxl :::: 0,74: 74 = 0,01 mol

VI mz :::: lOOgarn > mH10 trang dung d!ch NaOH ban dau (99,54 gam). Suy ra X va NaOH phafl lrng vOi nhau va t<;1o ra:

100 - 99,54 :::: 0,46 gam ch~t mm.

VI chua hai nguyen ttr oxi, nen X Iii estc ho~c axit dem ehuc.

nNaOH phan lrng :::: nx = 0,01. V~y nNaOHdu:::: 0,09 mol.

D~t x Iii RCOOR' trang d6 khi R' :::: H thl X Iii axit

RCOOR' + NaOH -)- RCOONa + R 'OH

0,01 0,01 0,01

0/'"i

ffiRCOONa trang Y == my - mNaOH = 4,28 - 40.0,09 =0,68gam

== 0,68 : 0,01 ::= 68MRffiON•

R + 67 == 68 =:> R =- 1 ta C0 mu6i HCOONa.

V~y X la este HCOOCHrCH).

I )! Bai 81.

Cho 2,76 gam chat hiiu C(/ A (chi chua C, H, 0 va co cong thuc phan tu trung v6i cong thuc d07l gian) tac d~mg vOl dung dich NaOH vua du> sau d6 chur.g kho thi phan bay hoi chi co nllac, phli'n chat ran khan con It;li chua hai muo, cIla nalri chiem khol111(J11g 4,44 gam. Nung nong hai muoi nay trong ox; dll, sau kh; phdn UnK hoan toiln, ta thu dUCfc 3,18 gam Na2COJ; 2,464 lit khi CO2(tfkte) va 0,9

gam nuac. .;... I: Tim cfmg thue phan W, viet cong thue Ca" tt;lo co tId co cua A thoo man

eac tinh chilt trell, dimg m¢t trong cdc clfu tt;lo d6 di vilt cdc phu01fg trinh phd"

ung dii xay ra.

Lffi gbli \.

* Ta co sCI dE> bie'n hoa:f 2,76 gam A + NaOH ~ 4,44g mu6i + H:zO (1)

t 4,44g mu6i + O2 ~ 3,18g Na2CO) + 2,464 lit CO2 + 0,9g H20 (2)

Ap dl;}ng djnh lu~t bao toan ta co:

"N.xm = 2'"Nu,co, = 2.(3,18:106) == 0,06mo!

m NaOIl == 0,06 . 40 == 2,4gam

V~y s6 gam H20 b set d6 (1) 130:

ml/p == rnA + mNaOIl - mmuO"i == 2,76 + 2,4 - 4,44 = 0,72gam

* me trang A =me trong CO:z + me trang Na2CO) =

= --.122,464 + -.123,18 == 1,32 + 036 = 1, 8 gam , 6 22,4 106

0,72 +0,9 mHtrang A == mH trang H20 - mil trang NaOH ==

18 .2 - 0,06 . 1

== 0,18 - 0,06 == 0,12 gam

rna trang A == mA - me - mB = 2,76 - 1,68 - 0,12 == 0,96gam

D~t A la CxHyOz ta co:

1,68 0,12 0,96x: y: z =--:--:-- 7:6:3

12 1 16

V~y CfDG va CfPT cua A d~u Iii C,H60) ~ M A == 138.

* S6 mol A dii phan U'ng v6i NaOH =- 2,76 : 138 = 0,02mol. 56 mol NaOH 0,06. V~y CtI lmol A phan Ung v6i 3 mol NaOH. Mft trong phan ttC A chi co nguy~n tir oxi, suy ra:

A co tht co 3 nh6m -OB IO~ti phenol.

A c6 1 nh6m OH phenol va 1 nhom este eua phenol.

Vi sau phan (rng thu dtrqc hai mu6i v~y chi co trtrCmg hqp este cib. phenol J

thoa man. C6ng thu-c cau t~o cua A:

o o OH~ ~OHII ~_

H-C-O~&-OH ; H-C-O~ ; H-rO-@ * Ki hi~u chung ba d(u tl;io cua A 1ft BCOO-C6Hc OH ta co cac phuong trin

phan 'rog nhtt sau:

A + NaOH

HCOO-C(,HcOH -+- 3NaOH -+ HCOONa + ~HiONa)2 + 2Il10

Mu6i + 0 1 ,.

2HCOONa + O2 --.~ Na2COl + CO2 + H20

," ­Cc,HiONa):z + 6,50), -----)0 Na;1CO) + 5CO~ + 2H20

Hal H2.

Ml}t lion hlJp X gij"m hai chat hiru Cd. Cho hOll hlfP X phdn {(ug vcfi NaOl ).,ua dll, ea'" dung lOOml dung djch NaOH SM. Sau phon itng thu Jut,Yc bon hl!j hai mUG! clia hai axil no d{/1l chuc va dUlJc m9t ru{lu no dOli chilc Y. Cho toan bl Y tac dlfng het v6i Na dUlJc 3,36 /it H?,.

Mijl khac neu dot ellay hoan t/Jim miJf lUlfllg khac cua he5n h!lP X, cii'n dunl het 6,496 lit khi 0 1 ~'a thu dUflc 5,824 lit khi CO;. Bilt thl tich eac khi dlu do • dieu ki#n lieu elman, hay xdc dinh c6ng Ih,tc phan Iu va cong thitc ea" t<}o ea, chilt co trong }u)n "lfP X.

LOi giai.

Dat c6ng [hue cua cae chat ~IH2n+l0H, ~nH2m+ICOOH va C'PH2p+,COOR

* nNaOH =0,1 . 5 :.= O,5mol

CnH)n+l0H + Na -+ C1,H1n +IONa + 1/2H2t (l)

_ ') _ 3,36_Theo (1) n <J1' - _.<0 n H - 2. - O,3molN . '22,4

x

1 cac chit trong X d~u la este thi s6 mollflrqu b~ng :;6 mol NaOH. ('1 d[1y s6 mol

u nho hem so mol NaOH, suy ra hOn hgp X g6m m¢t axit va m9t cste.

CmH2m+1COOCnH2n+l + NaOH -'" Cm H2m+,COONa + CnH2n +I OH (2)

0,3 0,3 ..--- 0,3

C~-{2P+1COOH + NaOH -'" c;H2p+ 1COONa + H20 (3)

0,2 ~ 0,5 - 0,3 = 0,2

Thea (1) va (2) ta c6 56 mol NaOH a (2) =s6mol este =0,3. Suy ra s6 rnol t = s6 mol NaOH a (3) = 0,5 - 0,3 = 0,2. Nhtr v~y trong h6n hqp X ti 1~ s6 mol

e/s6 mol axit =3/2.

3n + 3m + 1H2m+ICOOCnH2n+1 + O2 -'" (n+m+l)CO] + (n+m+I)Hi) (4)

2

1,5x 0,5(3n+3m+l).1,5x (n+m+l).1,5x

3p -I- 1 (p+ \)C02 + (p+l)H20 (5)H2r+ICOOH + -2- O2 -'"

0,5(3p+ l)x (p+ l)x

* D~t s6 mol axit bj d6t chay la x thl s6 moi estc la 1,5x

leo s6 mol O2: 0,5(3n+3m+1).l,5x + 0,5(3~1).x:::: 6,496 = 0,29 (1) . 22,4

. 5,824 (Il)Thea 56 mol CO2: (n+m+1).1,5x + (p+1).x =: -- =0,26

22,4

* Thea cac phuong trlnh phan U'ng (4) va (5): ta co s6 mol H20 va s6 mol CO2

b~ng nhau, do d6 s6 mol H20 = 0,26.

+ Vi s6 mol axit va 56 mol este b~ng 56 mol oxi c6 trol~g axit va trong ,te,bang tcing s6 mol oxi t:6 trong CO2 va trong H20 tro s6 mol oxi bi chay. TtIC la:

1,5x + x :::: no} trong CO2 + no, trong H20 - n~ =

= 0,26 + 1/2.0,26 - 0,29 :::: 0, 1 ~ x =0.04

TIlay x = 0,04 vao (II) ta dUlJC 3(n+m) + 2p :::: 8

Vi 2p la s6 chan, suy fa (n+m) phai la s6 chan thl 3(n+m) meri chan. Chi co

l¢t gia tIi n+m =:2 va p::: 1 la thoa man. V~y p = 1 thl axit 13 CH3COOH.

n + m = 2 nll'.mg n Ia 56 cacbon cu~ mqu n~n n "j:. 0; n,m ~ 2, nguyen

~O H-C

v

Khi n=2 =::) m = 0 este 1ft "­O-CHr-CIl:J

r~ Khi n=l => m = I ('slC la~ CHICOOB

Khi do X phan ung v6i NaOH chi t<;lo ra m¢t mu6i CHJCOONa, trai v6i giJ thiet, do d6 lo~i tnremg hgp n=m:::: 1.

Suy ra h6n hgp X g6m: CH)COOH va HCOOCH2CH)

HaiR3

Drit chay hoan toan 0,74 gam chat X chua cac nguyen Ito' C, H, °thu dU(fc 0,672 lit CO2 (q dklc) va 0,54 gam H20. Ti kh6i hoi cua X so }1m H2 being 37.

1) Xac d!nh cong thirc phon ttl, viet cong thuc call t~o aua X, hiet ding X co kha nang tham gin p],a~ img /rang gucmg va tac dl;lng dUdC vUi Na.

2) Cho x tac dl;l~g vm H2 (co niken him xuc tac) ta dUCfc chat Y.. Cho axit cacboxylic Z tac dl;lng vOi Y (co H 2S04 diJc xuc tac) ta thu dJCfc m9t so san phdm trong do co san phdm P. £)1 dot chay hit 17,2 gam chat P din dung 14,56 lit O

2 (dktc) va thu dll(fC CO2 ,va hoi nuac thea ti Ii ve thl tich I

Vc~ :VI/I0 = 7 : 4.

Xac dinh cong thuc phiin ttl, viet cong thuc cau t~o ,cua axit Z bilt rcing cong thuc dun gUin cua P cung cJrinh liz cong thuc phiin ttl va Imol P tac dl;lng vm 2molNaOH.

LUi giai.

1) Xac dinh X. me = (0,672/22,4).12 = 0,36 gam:

m B :::: ~0,54/l8).2 = 0,06 gam

rna = 0,74 - 0,36 - 0,06 = 0,32 gam

G9i CfDG clla X la CxHyOz, ta c6 ti l?:

x: y : z =' 0,36: 0,06 : 0,32 = 3 : 6 : 2 12 1 16

CfPT eua X la (<C)H60 2)n VI Mx = 37.2 = 74 =:> n:::: ~.

V~y CIPT ella xi la C)H60 2•

Vi X tham gia phan U'ng trang guong ncn X e6 nh6m -CfIO

X l~i phan U'ng vrn Na lien X con c6 nh6m -OH, v~y c60g thue eiu t~o clla Xla:

HO-CHz-CH2-CHO ho~c CH)-CH-CHO I

(j)H

2) Vi nh6m -GIO khi ~?P hidro t<,10 ra -Gl20H do d6i eiu t<,1o ella Y c6 th~

Iii:

HO-CH2-CH2-CH2-OH ho~c CH3--yH-CH2-OH

OE­

-11m OPT cua P: D~t Pia CxHyOz ta c6.

I In

V Z \iCxHyOz + x + 4 - -2 fJz -- xCOz + y/Z H20

(

Thea de hai ta co: = 7 : 4 =x: y/2 => x : y

y z 'i6 17,2(x+-·--)

14 ,- 065 4 2rJ =--=.= , = ~ 22,4 12x+ y+ 16z

thay gia tr! clla y ttr (1) vao (2), ta dl1qc x : z = 7:5

V~y CfDG clla Pia C-;HgOs

Vi CfDG cung la CDY[ etla P, suy ra CfPT clla P la ~Hg05'

_Vi P I~ slm phfun clla rl1qu Y vai axit Z, rna Y cO c6ng thue C3H6(OH)2 va lmol P + 2mol NaOH, chUng 10 trang pM.n tit P ho~c co 2 nh6m este, ho~c c6 m¢l

nhom esle va m¢t nh6m axit -COOH.

Ne'u P c6 hai nh6m este thl P chi co nguyen tit oxi. NhI1 v~y theo CfPT C HgOs va d.c nh~n xet tr~n, thi P chua 1 nh6m este, m¢t nhom axit va m¢t nhom

7

OH tL! do, cac c6ng thuc cau t~o co the clla P lil:

. «~-OH

HOOC-C=C-COO-CHHOOC-C=C-CO~yHl I

:1 H~CH CH3 I,!\ CH3

7 : g (l)

(2)

HOOC-e=:C-COO--CHlI ~

«Hz HO-C~

Va suy ra axit Z co c6ng thuc cau t~o Hi: HOOC-GC-COOH.

Bai 84. M~t hon h'!P X gom ba este mt;lch hu clla dmg m~t axil dun chuc vOi ba

n'flU d(1TJ chilc trong do co hai rUtfU no co khoi IUfITIg phdn tli hem kem nhau 28 dvC va m~t ruflU khong no chua mt}t lien ket dOi. Cho hon hf!P X tac d,!ng vtri 100gam dung dieh NaOH 10%, sau do co ct;ln thi thu JUlIc 23,6 gam chilt ran khan.Ngung tl! phan rUtfU bay hoi, tam khan, roi chia tho.",h hai phil'n bling nhau. Pha"n m9t cho tac dl!ng het vOi Na thu dUf!c 1,12 lit Hz (dkte). Phan hai dem dot chay hoan too.:'I thu dUlIc 7,04 gam CO2 va 4,32gam H 20. Gid thitt cae phan (mg df;lt hi~u cmit 100%. Vilt cong thuc cau tl;1o cua cae chat co trong hon hf!P x vo. tin" so mol mo; rUf!u tl;lo ra sau phdn (mg xo. phong hoa.

LOi ghli.

Vi cae este dl1qc t<;\o ra tlr m¢t axit dan chuc va cae nrqu dan chuc, v~y de

este e6 cOng thuc chung la ReOOR'.

ReOOR' + NaOH -~ RCOONa + R'OH (I)

R 'OH +- Na -) R' -ONa + 1/2H2 (2)

Theo(2): nWOH = 2. llH :::2},12 =2.0,05 = 0,1 1 22,4

V~y sau philO ling t£.lo ra t6ng s6 mol mqu = 0,1 .2 :=.: 0,2

Thea bili nNaOll ::: 10/40 = 0,25 mol

Thea (l) I1 N"OH dii phan uIIg = nR'Otl = 0,2 < 0,25 V~y trang 23,6 gam ch~t dn c6 nNaOIl = (0,25 - 0,2).40 = 2 gam,

V~y mRCOONa =: 23,6 - 2 :=.: 21,6 gam.

1heo (1) IlRCOONa = DR'OI1 = 0,2 ~ MRffiONa = 21,6/0,2 = 108.

M/{ :=.: mR + 44 + 23 = 108 ~ R == 41.

V~y R la C3Hs; axit 13. C3HsCOOH.

Cau t<;l-o ella axit c6 the 1a: CH3-CH=CH--LOOH,

CH2=CH-CH2-COOH, CH2=C-COOH I CH3

- Thea de bai thi c6 hai mqu dan chuc han kern nhau hai nh6m CH2• V~y

c6ng thuc hai nrqu d6 co u<.tng CnH1n+,OH va Cnt2H2n+sOH.

Axit khong no m<.tch ho chua m¢t lien kel d6i co dang CmH2m_10H

(m ~ 3, VI nhom -OH lien ke't vm n6i doi se kern ben).

Cn H2n+,OH + 3n/2 O2 -+

x

Cn+2H2n+sOH + (3n+6)/2 O2--)

y

CmH2m_.OH + (3m-l)/2 O 2 -)

z

n CO2 +

nx

(n+2)C01 +

(n+2)y

m CO2 +

mz

56 mol CO2= 7,04 : 44 = 0,16 mol ~ me =

(0+1) H 20 (3)

(n+l)x

(n+3) H20 (4)

(n+3)y

m H20 (5)

my

0,16. 12 :=.: 1,92

St) mol H20 :=.: 4,32: \8 = 0,24 mol ~ m~l = 0,24 .2 ::.: 0,48.

VI la mqu dan chuc nen s6 mol nguyen lir ella oxi lrong nrQU thl bang 56 mol nrgu. Ma 56 mol nrqu trong m6i ph:\n bzmg 0,1 mol. Suy ra 56 gam cxi tr~)fig n1qu bj d6t chay la: 16: 0,1 = 1,6 gam.

Kh6i 111qI1g nrgu bang t6ng thai Il1qng cacbon, kh6i 1l1qng hidro va oxi c:6 trong nrgu. V~y 56 gam nrqu bi chay:

mR'Ol1 = me + mil -I- rno = 1,92 + 0,48 + 1,6 == 4 gam.

I

,,'ti co nTqu c6 k.h6i ~lf<;mg ph~lIl tiI nho hem 40 dye. rtl<;ru duy nhal: thoa man IiI -I30H (M=..32), tir (16 suy ra fUQU no doo chuc thu hai phiti la CJH70H (hem hai lom CH7).

V~y hai rurJU 110 la CH)OH va CH)-CHz-CH2-OH ho~c CH3-~H-OH CH3

D~t s6 mol lrang m()i phan eua ruqu CH)OH la x; 56 mol C3 H70H Hi y va nHlm-iOH 1a z.

Ta c6: x + y + Z == 0,1 (J)

Thea s6 mol CO 2 (3) (4) (5): x + 3y + mz = 0,16 (II)

Thea s6 mol HzO (3) (4) (5): 2x + 4y + mz = 0,24 (III)

Lily (Ill) - (II) ta uuqc x + y = 0,08 r6i lhay vao (I) dltqc Z:= 0,02.

Thay tic'p Z == 0,02 vao (ll) ta duqc:

(x + y) + 2y + 0,02m = 0,16 ~ 2y + 0,02rn = 0,08 ON)

i'c la y = 0,04 - O,Olm. Vi 0< y < 0,08, suy ra 0,04 - O,Olm > °ttle lkl 4 > m. Ma leo cOng tht1l: CmH2m_10H ta d5 c6 m 2: 3.

V~y chi c6 ill == 3 la thoa man. RUqtl' khong no la C3Hj OH e6 cOng thlcc cau ~o la CHz=CH-CH2-OH.

Thay m = 3 van (IV) la UtIl!C y == 0,01 mol, suy ra x =0,07. V~y trong 1/2 h6n 1'lP nr\fU co 0,07 mol CH)OH; 0,01 mol C)H70H va 0,02 mol C)IIjOH. Do do trang lem hqp sau phan U"ng xa phong hO<l co chua:

0,14 mol CH)OH; 0,02 mol C)H,OH va 0,04 mol C,HsOH.

~ai 85.

Dot dUly homl loan 4,30 gam chat hiiu ca X chua C, /I, 0, r6i cho cae san 'Jhdm thu dlllfc l'£lO billh ch{(a dung d!ch Ba(OIl») du, thlfy kh6'i [UlfTlg binh tang (1,50gam va co 39,40gam ket tlla. Khi hoa hui I,72g11m chat X thi J'hl t{ch hoi thu 111(/c bdng thl tich ella O,56g khi nitO' t7 ciing dii'u ki~n nhi4t d~ va I~P sua!.

1) Xat; d!nh cong thlrc phdn til, viet cong thuc cau t{1o cua X, biet rdng x co cilu t{Io m{Ich nhanh }-'a khi rac dlfng lIOl Na)CO j thi giai ph6ng JChT CO2,

2) Viit ene phdn (mg dUu ehe mf)t eao phan tu quan trC!ng di tit X va mf)t

rlllfU thiel, hlJP·

3) Dung djch cua X c6 n6ng d~ O,IM tlJu ra rnoi trllirng vOipH = 3. Tinh d~

dien Ii eua X trong dung dfch .16.

4) Viet phllmlg trinh phdn ung eua X JIm KMn041H2S04 , bilt sau phan iin!: chi c6 CHJCOOlJ ia chat hii"u c(} tllly n}uft.

LOi gi:li

1) Xac djnh cOng thlle cua X: Mx ::: 1,72: (0,56 : 28)= 86.

- Kh6i lugng blnh tfing = ntq +mHp = 11,5 gam

- CO2 + Ba(OH)2::: BaCOJ-l. + H20

nc~ == nB(JC~ =39,40: 197 = O,2mol => :::: 0,2.44 ::: 8,8gm C01

mlfo == 11,5-8,8 = 2,7 gam ==> mlfo =2,7: 18 =0,15rnol 1 1 I

me = 0,2 . 12 ::: 2,40

mH ::: 0,15 .' 2::: 0,30 =:> nH = 0,3 : 1, == 0,3

rna = 4,30 - 2,40 ~ 0,30 ::: 1,6 => no ::: 1,6: 16 = 0,1 f •

D~t X Ii\. C'-xHyOz ta c6 ti l¢ x: y : z = 0,2: 0,15 : 0,1

::: 2: 3 : 1

CfDG (~H30)n == 86 ~ CTPT IiI C.t Ho0 2

VI X tac dl}ng v6"i NazCO) t~o fa CO2 nen X c6 nh6m -COpH.

X c6 cau t~o m{lnh nhanh nen crcr eua X Uc

CH2=~-cdoH axil mctacrylic tH3

2) Polirnc quan tn;>ng cila axit mctacrylic 1.1 thuy tinh plec-iXy-glat, <1vqc dieu che' nhu sau:

H2S04CH2"'y-COOH + CH30H -. CH2==y-COOCH) + H20 CHJ CH)

I

OOCH)r Trung hqp rOOCHJ.:)n CH2~C . ----- (-CH2-S:- )I ,

CHJ ' CHJ ~ n

3) Ne'u c6 mOt lit dung djch thl naxj( = 0,1 mol

RCOOH ~ ReaO - + H + pH:::: -lgfH+l :::: 3

c6 0,1 mol suy ra [H+] =0,00 1 mol/lit

phfln li 0,001 mol E 0.001 mol

D¢ di¢n Ii a = (0,001/0,1).100 = 1%

4) Ph3n lIng ven KMfIOlH)SOol!

CH 2=C-COOH + 2KMn04 + 3H2SO.; -> 2e02t + CH:;-COOH + I

2MnS04 + K2S04 + 4H20CH3

flai Ri!. Khi dun nong cluft htiu cO' X (chi child mtjt IOf;li nhom chitc) voi dung dich

axit V,) C(f thi duqc hai chat hfm;~(r Y va Z (dell chi chua C, H, O).Mijt khac khi oun 4,04 gam X vCi dung d[ch chlta O,05mol NaGll, thi dUf/c hai chitt Y va P. K!!6i IUlf1lg mol phdn tit cua P l6'il hif11 khoi IUf/Y1g mol pharr tu clia Z 1/1 44 gam. ni! ttung hod NaOH con du p!uii a'iUlg lUO ml dung dich lIel 0,11\-1.

Khi dun IZong 3,68 gam Y vUi H 2S04 dijc thi thu dUf/c 1,344 Hi kid m(it ai4i:l (dktc) vOi hi~u sud! 75%, bie! Z In m'!t dlJll phdn dung di t6ng ht:1' polimt I:(i: !l~JC. flay xae djnh cong tidle philn tit va cong thuc ci{u tCJo cua X, Y. Z.

LOi giai

TIleo eM bai Y phai la ntt,JU no dan chaco

X Ihuy phAn trang axil t<;J.o fa ruql.1 Y va ell:!t Z.

X tac d~mg "oi ki6m t~o f'a nt9u Y va eha't P.

Suy ra X Hi este, Z la axil R(COOH)n' P !a mu6i R(COONa)n·Ta c6 c6ng thue

X It R(COOC,I\H21J1+I )n'

JID·c u

R(C00CmB2m+ l )n + nH20 ---~ R(COOH)n + nC--mH2m+IOH (1)

R(COOCn,l--i2m+ I )" + nNaOH ~ R(COOH)n + nCmH~m+IOH (2)

1I/;04f .... (3)CmH2m~IOH ---~ CmH1m + H20. (m ~ 2)

(4)NaOH + Bel =NaCI + H20 => nNaDH du::: J'1 HO ::: 0,01

- S6 mol olefin thu duqe = 1,344 : 22,4 :.:: 0,06 mol.

, . 0,06 - S6 mol n1<1l1 ban d[Jl1 = --. 100 =: 0,08 mo1.

. 75

V~y M = 3,68 : 0,08:.:: 46 =-= 14m + 18 => m =: 2ruou

do d6 nrqu Y la C:<H~OH.

.. Mp = R + 67n \ Mp - Mz :-= 2211 =44 :::.:) n= 2

Mz =R + 45n ) (

v~y Z l~ diaxit R(COOHh·

- S6 mol NaOH d:, ph;~r. lWg ::: 0,05 - 0,01 = C,04 m~)l.

(/.; :<1 co nx ::: l/2nN,0H""" i/.!,l'JJ·'1 ;,: UJt:.VI n= 2 nell !~',.,.';)

V~y Mx =- 4,04 : 0,02 = 202

rna thea de bili va cae ket qua atren thl X la R(COO(~H5h

V~y Mx ::: R + 146:.:: 202 => R :.:: 56 y~y R = C4Hg

Vi Z III dan phtln d~ t6n!:; hqp f'Olime v~y Z EJ. axil adipic

HOOC-CH2- CHr CH2- CH2-COOH. polime c6 th,~ 13. nilon - 6,6

V ~y cfi'u t~1O ella X la:

o 0II l'

CI[3-CH2-0-C-(CH2)4-C"O_CH2 --Ci I J

nAJ 87.

Mtjt hon hlfP X gom hai andehit no, dun chitc.

1/ Kltii holm toim 16 gam X bling H 2 thu dl((JC him hfJP rulfU Y. Chn fu.in.

Jrf!P Y til{: d~mg het vUi Na thrfy thoat ra 3,36 lil Hz (rikle). Tinh so mol ClIO: Iwi andehil co trong 16 gam hon hlfP X.

2/ Dol cllay hoim tolm 16 gam hon h(fp X thi £hu dUf/c baa nhiell lit kM CO2

(dktc) va bac nhieu 1;am nuac.

3/ Them 6~ gam m¢t rUflll no mfJch IllY Z vao 16 gam hon hlfP X dlff/C han hlfP T, dittot chay het r;·cd'n 29,12 lit O2 (dktc).

Xac dinh cong th"e phdn tu, viet cong thire cd'u tlJ.O va ten gqi cua Z, bie! rang khi dot cluiy m¢t mol Z thu dUf/C dum 5 mol CO2,

LOi giai

D~t e6ng thue cae andehir la CnH2n+I CHO va Cn,H2m+I CHO

Ni,t O

1)CI\H2n"CHO +H2 ) CnH2n+,CH2OH (1)

Ni,cO CmH2m•1CHO + Hz > CmH2re.ICH20H (2)

CnH 2n+I CH20H + Na -------+ CnH2n+1CH20Na + 1/2H2 (3)

C'''mH2m+ICH20H + Na -------+ CrnH2m+ICH20Na + I/2H2 (4)

Thea cae phuong trinh phan Ung (1) (2) (3) (4) ta c6 s6 mol andehit b~ng so

mol ruqu va gllp d6i 56 mol H2 o V~y:

3,36 S6 mol andehil = 2. -- =200,15 == 0,3 mol

22,4

3n + 2 1 2) Cr,1I2n+ICHO + --- O2 ---) (n+1)C02 + (n+1)HzO (5)

2

3m-r 2 Cn,t12'11~,CHO + -2-02 --~ (m+l)C02 + (m+1)lhO (6)

- D~t 56 mol CnH2n+I CHO Iii x

56 mol CmH2m+1CHO 1a y ::::> x + y =0,3 (1)

56 gam X: (14n + 30)x + (14m + 30)y = 16 => nx + my =: 0,5 (If)

- Thea cac phan lIng (5) (6):

56 mol CO~::: (n+1h + (m+1)y

nx + my + x + Y '-~...J '=--y----' 0,5 + 0,3 = 0,8

V~y Vm, ::: 22,4.0,8 ::: 17 ,921it

56 mol H;& = 56 mol CO2 =0,8 => m 1I 0 = 0,8. 18 = 14,4, gam.1

D~it e6ng thlrC phftn Ilr ruqu no m<;\ch ho Z la CpH2P+20a

.., 3p+l'-a<'pHZP+20a + ---- 0 1 ~ P CO2 + (p+ 1)H20 (7)

2 6,2

~ ? 5>p>a14p + 16a + 2

- 56 mol oxi dii dung 29,12 : 22,4 = 1,3 mol ,....

- Thea de phan lrng (5) (6) s6 mol da dung cho (5) (6) fa:

3n + 2 3m + 2 1[ ) ] 1 ,--x + --y;:o: - 3(nx + my + 2(x + y) ::: -(3.0,5 + Lo,3)2 2 2 2

=1/2,2,1::: l,05mol.

V~y s6 mol oxi dung cho phan U'ng (7) Iii : 1,3 - 1,05 = 0,25 mol.

Thea phan U'ng (7) va 56 mol oxi:

6,'1. (3P +I-a) ::: 0,25 14 p + 160 + 2 2

58p + 26 Hay 5,8p + 2,6 ::: 7,la tlrC la a = -- ­

71

l :]_10 ~ t 2~8 EE

V~y Z la CzH60 2

CTPT: SHz- yH2 Etilcnglic01OH OH

Bfli 88

Cho 0,02 mol ml}t e:~te phan Ung vila het vOi 200 ml dung filch NaOl/ O,2M, sa" philm tao ra chi gam im~t muo1 va ml}t rIff!U de'u co so' mo~ bling so mol cua este, diu co cau tl;lo ml;lch thang. I

MrJ.t khac khi xa p/u'mg hoa hoa" toan 2,58 gam este do Ibang lUflng KOlI vila du, phdi dung 20 ml dung di~h KOH 1,5M, thu dUf!c 3,3 gdm muol. Hay xac dinh cong thuc cau tl;lo cua este, va tinh so gam rulfU thu dur;c Sau phdn img vOi KOB. 'I I

LOi giai

56 mol NaOH ::: 0,2.0,2 = 0,04 mol.

V~y t1 s6 mol c5lc: 56 mol NaOH = 0,04:0,02 =2: 1

Suy fa cste co hai nhom cste va co the thu¢c cac lo~i sau:

R(COOR\ ; (RCOOhR'; R(COOhR', I

VI sau phan U'ng t~o fa s6 rn~1 este = 56 mol mu6i =56 mol ruqu, neb chi co c6ng thue R(COO)2R' la thoa mal):

R(COO)2R' + 2NaOH -~ R(COONa)2 + R'(OH)2 (1)

0,02 0,04 : 0,02 0,02mol

R(COO)2R' + 2KOH· ~ R(COOK)z + R'(OH)z (2)

0,0]5 ~ 0,03 < 0,015 mol

- 56 mol KOH == 0,02.1,5 =0,03 mol

- Thea phan U'ng s6 (21) ta eo s6 mol mu6i 1/2 nKOH = 0,015.

V~y Mmu6i = 3.33: 0,015 =222 Suy fa R = 56}rna Mmu6i =R + (44 + 39).2 V~y mu6i la C4H8(<L00K)z

Suy fa axit tao fa estela C4Hg(COOH)z.

- Thea phan ling (2): 56 mol este = 0,015 mol.

V~y Me•lc = 2,58: 0,015 =172 tuc la C4Hg(COOhR' ::: 17X

V~y R' = ]72 - (56 + 2.44) = 28 ~ R' la ~H~

Ruqu Iii C2H4~ OH)2' HO-CH2-CH2-OH.

Suy ra cau t<~o dla e~te la: ? CJ-(,,/CH2-C-C( I 2 "-rH,

CH, r ­""- _ ,...cal

L:H2- y-O'

o

Hal fl9.

Co m¢t han hC!]1 X glim m¢t axit va Iwi ancr~hit de'u thu¢c IOt;li no, d01J chilC, khong chua aritJomie.

Lily m gam X cho tlic dl;lng het v6i dung dfch AgNOJ trong amonidc, sau do

l(}c, tlw aUl/c 54 g Ag va dlf~C m¢t dung dfch. axil haa dung d;ch nay bling H 2S04

dlf, sau do chung cdt thu lay axit hfru Cd, thi toon bi) axit huu CO' phan (mg hit vOl

150 ml dung drch KOfl 0,5 M.

Lay m gam X cha tac d~mg hit vOl NallCOJ thu dUl!c 0,616 lit C02 0 Mij.t

khac, phai dung vita het 10,472 lit O2 mOl dot chay hoem toim m gam X.(Clic tid tich khi du ti 27,3"C, 1 atm ).

Cia thiit hj~u sua! cac phan ung lil 100%, tim cong thuc cua cac chat co

trong han hlfp X; tinh so' gam CO2 va s6' gam H 20 tq.o ra sau phan (mg do! chay u tren.

LUi giai

- D~t c6ng thlrc clla cac andehfl chung III RCHO; c6ng thu-c coa axilla

R'COOH; 56 mol axil co trong m gam X la x mol.

- Khi cho X Inc d~ng vCri NaHCO), th'j chi co R'COOH phan U'ng:

R'COOH + NaHCO) ---» R'COOH + c02t + H20 (1)

x=O,02S O,025moi

C;( C 0,61b.273 JoU mol ,02 := := 0,025 mol := x

(273 + 27,3).22,4

RCHO + 2 [Ag(NH3)2)OH ---» RCOONH) + 2Ag + 3NH) + H20 (2)

RCOONH4 + H2S04 ~ RCOOH + NH4HS04 (3)

R"COOH + KOH ---» R"COOK + H20 (4).

- Thea (2) (3): SO mol axil m6i = ~n Ag = ~.~ = 0,25 := O,25mol 2 2 108

- Thea de bai thl axit tham gia phin lIng (4) 1:1 t<'Sng hrgng axit co trang X va

axit mm t~o rd. T6ng s6 mol axit bang s6 mol KOH = 0,15.0,5 :=. 0,075.

- Ma 56 mol axit mm thea (2) (3) = 0,25 » 0,075 mol. OIU'ng to trang X ph:ii

ChU-d andehit [arnie, khi lham gia phan ling trang b<;lc, no bien thanh (NH a4)2COJ

trang dung d!ch, va khi axil hoa dung dich bang H2S04

d5 chuy~n thanh CO bay di. 2

lI-rno + 4Ag(NH:t)20H ---» (NH4)COJ + 4Agt + 6NH) + 2H 0 (5) 2

(NH4)2COJ + 2H2S04 ~ 2NH4HS04 + CO2t + H20 (6)

- VI 56 mol axit R'COOH trong X la 0,025 mol. T6ng 56 mol axit R"COOH t<;Io ra la. 0,075 mol.

==> 56 mol axit mm la Q,075-0,025 =0,05

Thea (2) (3) ta c6 s6 mol Ag a(2) ::r:: 2.0,05 := 0,1 mol.V~y 56 mol Ag a(5) 13 0,5 - 0,1 = 0,4 mol.

I Thea (5) 56 mol HCHO = - 56 mol Ag 4I .0,4::= 0,1 mol.4

V~y lrong m gam h6n hqp X co: 0,025 mol axil R'COOH

0,05 mol andehit RCHO

0,1 mol HCHO.

VI tAt d axil andehit deu thul)c lo~i no d(/Tl ChLIC, nen d~t axit la C H 0 va n 2n 2andehit la CmH1mO (m ~ 1).

HCOH + O2 -~ CO2 + H20 (7) Q.l

3n - 2 ~H7.1102 + -- O 2 --+ nC02 + nH 0 (8)

2 2

0,025

3m-1 c",H2mO + '-2-O2 ---» mC02 + mH20 (9)

T • , 1OXI. d- h~ 10,472.273 0425 moI6ng 56 mo a C ilY:= =, (27,3 + 273),22,4

do do theo (7:8,9) ta co:

3n - 2 3m-1 0,] + 0,025. --+ 0,05. -- = 0,425 :::::> n + 2m = 10

2 2

Suy fa n = 10 - 2m ==> m < 5 v~y In = 2,3,4. (m "* I)

Khi In = 2 thi n = 6 CH3CHO va ~HI,COOH

ill =3 thl II =: 4 CHrCH:z-CHO va C3H7COOH

m =4 thl n = 2 CHr CHr CH2-CHO va CHJCOOH

- Theo (7,8,9) thl 56 mol CO2 = 56 mol H20

=0,1 + 0,025.n + 0,05m =0,1 + 0,025 (0 + 2m) = = 0,1 + 0,025.10 = 0,35 mol.

V~y ::: 0,35.44 = 15,4; = 0,35.18 = 6,3 gam.meol m H10

90

Co ba hlfP chat X,Y,Z dlu chi chua C,ll,O. X co khoiltlfJ1lg phan tli nho

! Z, nhung khoi lU([1Ig phan tu cua Y giln gap doi clla Z. Dun mlng h6n hf!P

1 X,Y vOi dung dich NaOll thu tftWc cheft D duy nhat.

Chat Z co mf;lch cacbon thang, chi chua cac nhom chue co hUro linh dljng.

~ phtIn fmg het vOl Na thi so mol H2 bay ra luon lu6n bling so" mol Z dii phan

~. Khi cho Z tac dlfng vOl CuO dot nong tao ra san phdm co kha niing tham gia in ung frang guung. Cho 1,18 gam Z tac dr;lng het vOi NallCOJ thll dUf!c khi

1 va 1,40 gam chat D. Viet cong thuc cau U;lQ clla eac chat X,Y,Z.

LOi ghii

- Xac d!nh Z: VI Z co chUa C,H,O, tac ~':lng vm Na va NaHCO), suy ra Z phai

1hom chua COOH va co the c6 OB. D~t Z Ii} (HO)n-R(COOH)m ta c6:

n+m (HO)nR(COOH)m + (n + m)Na ~ (NaO)nR(COONa)m + -"2- H 2

I (n+m)f2

56 mol Z =56 mol H2 ~ n + m =2.

Z + CuO ~ andchit; suy ra Z chua -CH20H v~y n =: m = I

HO-R-COOH + NaHC03 ~ HO-R-COONa + H20 + CO2t (Z) (D)

Cu 1 mol Z ~ I mol D thl kh6i luqng tang 22 gam.

V~y x mol Z ~ x mol D thl kh6i luqng tang 1,40 - 1,18::: 0,2,2g

Oz = x == 0,22 : 22 == 0,01 mol.

:::j Mz = 1,18: 0,01 = 118 = R + 17 +45

~ R == 118 - 62 = 56 :=j R 13 C4Hs·

ITer clla Z: m~ch th~ng, co -CH20H:

HO-CHr CHr CH2-CH2-COOH Mz = 118

- Mx < ML rna X + NaOH t<;tO fa D } duy nhat

illl y - 2rlL ~2. '! NaOH tao ra D ..1..

~ Suy ra X 13 este nOi pht\n tll clia Z, con Y la cste do hai phfm t:i Z ph~m Ung

v6i nhau. erer ella chung la:

o II o

/C"" II CH2 0 fH2-CH2-CH2-CH2-\ i I

~ !CH2 CH2 I

C-CH2-CH2-CH2-CH2 i II""CH;

(X) o (Z)

Mx = Mz - M;H10=100 Mz = 2Mx - 2MH10 = 200 I

Bai 91.

Dot chay hoan toa(l 1,31 gam chat hiiU C(J X clzua C,H,O, co cong thirc phtin tit trung vOi cong th:uc dun gidn nhtit, thu dUf!c 2,42 gam iC02 va 0,81 gam 1/20.

, I

I Cho X tac dlfng l'ln dung dich No.Oll vila du thu dUf!c mUQl natri cua axit A

va dUf!c hon hf!p B g6m hai rulfU thu9c cung mljt day d6ng ddng.'

Lay 1,24 gam h6n hlfP B cho hoa hoi hoan loan thu duqc1the tich hoi dung b{l7lg the tich cua 0,84 gam nitu do ucung dilu ki~n. '

Khi cho cung mljt /Ul;mg axil A nhu nhau phan (mg het VOl dung dich NaHCOJ hoij.c vOi Na thi the tich khi CO2 thu dUf!c /uon lu6n gap 1,5 kin the tich khi hidro do trong cung di'lu ki~n nhu nhau.

1, Xtic dinh cong thuc phan tit cua X.

2, Xac dinh cong tlz'ftc phan tu co the cua cac rulfU trong B.

3, Gill su A la hqp chat co thephan Ujp dUlfC til ngu6n th'!c vf;it, A luung do'i quen thu(k trong culjc song hang ngay, ~c bi~t duqc dung /rollg vi~c pha chi' nUt7c gid; khat co v! chua, hay viii cong thuc cau tl;lo cua A, tit ~o suy ra cau tf;lo cua X.

LOi giai

I) Xae d~nh e6ng thuc phan tt'r clla X

me = (2,42/44).12 == 0,66

mtl = (0,81/18).2 =0,09

mo = 1,31 - 0,66 - 0,09 =0,56

2) X + NaOH ---» mu6i cua axit + 2 fltqu cstc.

D~t X la C~HyOl ta co:

x : y : z = 0,055 :' 0,09: 0,035

=: 11 : 18 : 7

CfPT ella X 13: CiIH 1S0 7•

~ X la este phai co It nhfft 2 nhom

- CrPT eua X Iii CIIHIS07, m6i nhom este eo hai nguyen tu oxi, suy ra s6 nh6m cste trong X kh6ng vuqt qua 3 nh6m.

131

- S6 mol nrqu ::: 56 mol Nz = 0.&4: 28 ::: 0,03 mol.

M JUlJU ::: 1,24 : 0,03 ::: 41,33 suy ra phai e6 CH)OH

V~y hai ruqu thu<)c day d6ng dAng ruqu no dan chilc. D~t c611g lh{re nrgu t1l11 hai la CJ-lln+IOH (n > 1 ),56 mol Cll3 n61a y, 56 mol clla CH)OH 130 x, ta c6:

T6ng 56 mol hai nrqu : x + y ::: 0,03 (1)

T6ng s6 gam hai ruqu :32 x + (14n + 18 ) Y-:; 1,24 (II)

=::) In ::: (0,02/y) + 1 I III

Vi hai nrqu duQ'c t£).o ra ttr m<)t este X kh6ng vuqr qua 3 11n e5le, 5UY ra co 3 kha nang la: 2x::: y. X=y, x =2y tlrc 13.: x}y =:; 0,5; 1; 2.

Thay vao (I) ta duqc y =0,01; 0,015; 0,02. thay cae gia tJi nay clla y van (In) ta co:

y 0,01 0,015 0,02

n 3 1,3 (lO<.li) 2

V~y hai nrqu trang B co th~ la: CH)OH va C)H70H vm x ::: 2y ho~c

CH)OH va ~H50H vm 2x = y

3, Axit A chi chua C, H, 0.

A + NaIlCO) --+ VCOl Ma VC02 ::: 1,5 VB! tilc la} VCOl < 2 VHl

A+Na --+ VB 2 V~y A co th~m nhom -01-1.

D~t c6ng thuc t6ng qu;it A la (HO)m- R(COOIl)n ta co:

(HO)mR(COOH),,+ nNaHCO) --+ (HO)mR(COONa)n + nCOl + nHlO (1)

a mol na

(HO)rnR(COOH)" + (n+m) Na --+ (NaO)mR(COONa)" + (n+m)/21Ilt (2)

a mol (n+m ;.O,5.a

TIleo(1)va(2)vad~baitac6:na= 1,5(n+m).0,5.a ~ I n:::3ml

Thea c6ng thue ph~n lIi ella X thi ta c6 s6 nguy~n tIi oxi la 2n +m = 7 (sa ill nhu v~y VI ttr axit chuy~n thanh este veri fUqu dan chue thl 56 h.rqng nguy~n tIi oxi trang axit va trang e5te In bang nhau), rut ra dlI?C chi co m ::: 1 va n ::: 3 la hQP lY.

V~y A c6 3 nhom COOH va 1 nh6m OB : HO- RC (COOHh.

lneo cac ket qua atren: CTPT clla X : C11 HI70 7

Hai n1qu ho~c 2 mol CH)OH va 1mol C)B70H ( x ::: 2y )

ho~c 1 mol CH)OH va 2mol ~H50H (2x = y )

th) 56 nguyen t6 cacbon trang cac g6c n1qu lu6n lu6n btmg 50 V~y 56 nguyen tIi cacbon [rang g6c axit In 11-5=6.

V~y axit la HO-C)HiCODH»)o

- Theo d~ bai A duqc tach ra ttr thl.Jc v~t, duqc dung trong mr6c giai khat t£).o ra vi chua, v~y A la aXlt citric: '

OH I

IIOOC-C1h-y-CH2-COOH COOH

~ Suy ra crCT Clla X c6 th~ 1[1:

N€u cap nrau:

yOOCHJ «OOC]H7

1I ell ,Oll := 0,02 := x «H2 eHI 2

HO-C(-COOC]H7 ho~c HO-y-COOCI IJ r.CiJl,OJl = 0,01 := y yIl2 yH2 (x := 2y) COOClh COOCH]

N€u cap nwu~

1ICff,Off := 0,0 1 ~..: X yOOC2H5 ~~OOCHJ

yl-12 yH2 nC,lf,OIl := 0,02 = y IIO-«-COOCH] ho~c HO-y -COOC2H5

(2x::: y) yH2 yl-h COOC2H5 COOC21I5

Hili 92.

Hqp chat X chua niim nguyen Itf, tTong do co C, H, 0, N, cachon chiem ?3,166%, hidr6 chiem 1,4157% theo kh6i lUtfTlg.

Cho 1,554 gam X lac d~4ng he: );°m NaND} lId Hel thu dul,Tc 44,8ml (dktc) m(it chdt khi khong mill! ,khong mu!, khong chtiy, dt5ng thili tlJO ra chat hUll ClY Z khong chua nitu.

Nung nong 1,554 gam X vOl Na di chuyin cac nguyen t6 trong X thilnh de cluft vo cu dun gidn, sau {to hod vila nuac Ihu dUf!c dung dich Y.

• Lay m(it it dung djch Y elw p!:dn U'ng het VOl khi clo thi dUljc .!ung dich co khd nang Ia xanh ho tinn bl)t.

o. Lay m¢t it dung dfch r elw pJrdn ti'ng voi dung dlcJa dUltJ /;IU'iCti F:;3~ cht, ill;'4 dU~YC klr if.Ja miw xari.Jz kh6ng hi mat rna'u frOilg axit lIet .iming du.

_Lay 1/2 dung dich Y clw tac dl;lng vm Br2 vila du thi san phdm I'fJo ra phdn vila het vOi 40ml dung dich Na1SzO] 0,1 moUl.

1) Xac dinh cong thuc phiin tli cua X.

2) Nlu X Iii htfP chat quan tn;mg cua C(/ the con nguOi thi XCii cong thuc

tlJo nhu the1ll10?

LOi giai:

* x + NaNOz + HCi --j. Z (kh6ng chua nito) + khi khOng cha~,.

Khi d6 phai 13. Nz. =: 0,0448 : 22,4 ==0,002 mol.nN2

X phai chua nh6m amino: NHz. Ta c6 phan ung :

R-NHz + NaNOz + HCl ~ R-OH + NaCl + Nzi + H20

V~y s6 gam nita trong X bang 1(2 s6 gam nita bay ra .Ta co s6 gam

nito c6 trong 1,554g X la: (0.002.28)(2=:0.028 gam.

%Nita trong X =: (0.028/1.554).100=1.8018%

* Ok phuong trlnh philn (rng minh hQa:

fO

(C, H. N, 0, I) ;- Na ---=---t Nal + NaCN

+) 2r- + Oz ~ 12 + 2Cl- 12 lam xanh h6 tinh b¢t

2r- + 2Fe3+ --)0 12 + 2 f-c2+

Fe2+ + 6CN- --)0 Fe4[Fc(CN~6h~' mau xanh

+ 21" + Brz. --j. 2Br- + Iz

12 + 2Na2Sz03 --j. 2NaI + Na2S406

1 n/ =: -n Na so := 1/2 .0.04.0.1 ::;- 0,OO2mol

2 22 J2

Do v~y ntu cho toan b¢ dung d!ch Y phan ung s~ dU<;1c 0,002 . 2 =0.004 mol )6 gam 12co trong 1,554 gam X =. 0,004.254 := 1,016gam.

%1 = 1,016.100:::: 65 3797 1,554 '

V~y %Oxi trong X =100 - 23,166 - 1,4157 - 1,8018 - 65.3797 =B,2368%

Di;\l X 13. CxHyOzN.lp ta c6:

.. __ = 23~66.1,4157.8.2368_1.8018_65.3797 = I" -II 4'1'4 x.y.z.t.p .' -' --' ..

12 1 16 14 127

CTDGcua X lil CI5 H.,04NI4

2) Theo cCmg thuc tren thi X chua nhi~u iot Neu X co vai tro qUaIl .trQng trong (:a the con ngl101. thl c6 the X IA nhi~m Yl;l c~ng cAp iot eho co the. V~y X co the la

tyroxin:

l' I

HO'~ ~ CH2~H-Co6H0

~~ NH2 : I I

I

Bai93 i

Hf!P chat A chua C, H, 0, co CelU t{lo m{lch thdng_ Khi chb 0,52 gam chtfJ A tac dl;lTlg hit vOi dung dich AgNOJ b"ong amoniac, thu dUlfc 1~08gam Ag. Xu 1i dung d!ch thu dUlfc sau phan fmg (rang 1H;lc bling ariJ, thu dUlfC chat hiiu Cd B (chua C, H, 0). S6 nhom tacboxyl trong m9t phan tU B nhiiu hun trong m9t phan tU A lO: m9t nhom.

MiJ.t khac, cu 3,12gam chat A phan itng het vOi Na tl}o ra, 672 ml khi hi4ro (dktc). Viii cong thuc ca'u ft!-o co thlco cua A.

!

LUi giai

A tham gia phan U'ng tnlng b~c, v~y A phii chua nh6m i -CHO. D~t A la

R(CHO)n'

R(CHO)n + 2n[Ag(NH3)2]OH --j. R(COONH4)n + 2nAg -l- + 3nNH3 + HzO (1)

R(COONH4)n + nH+ -)- R(COOH)n + nN~+ (2)

Theo (1, 2) th'i cu ml)t nh6m CHO sau phan U'ng tcing b'.lc bien th3.nh ml)t nh6m COOH. V~y n = 1.

1 1,08 Vi n =1 ntn thea (1) s6 mol A == IflnAg = -.- = O,005tkol

i 2 108

Suy ra MA = 0.52 ::0,005 = 104.

- V~y s6 mol A ph~ ling v6i Nz. = 3,12 : 104 = 0,03 mol

- Vi A phan ltng vqi Na. do v~y ngoal rnl)t nh6m --ClIO thl trong A con phii

c6 OH, COOH ho~c d haillo~.

/CHO /CHO R:-fOHht + (n +'m) Na R~ONa) + (n + m)/2 H2t (3)

"(COOH)m "(COOH)m

n+m 0,03 mol O,0~'-2-

Theo bai s6 mol H2 = 0,672/22,4 = 0,03 => 0,03.(n+m)/2 =0,03

Va.y n + m =2. C6 ba kha nang xAy ra: . /CHO

R "(0H}z

11<;

--.:::­~

i

+) Neu n = 2. => m =.: 0 t.a co MA ::: 104

Suy ra R la C)Hs: C6 cae dIU t'.l0 la:

C(lIz-C(H-CH2-CI 10 ; «Il2-CHz-C(H-CHO; CH)-«H-C(H-CHO OH OU OH OH OB OH

+) Neu m::: 2 :=) n=O ta co:

/CHO R MA = 104 => R==-15 v6 Ii

'(COOW2

+) N€u n =- In :::1 ta co :

/CHO MA ::: 104 => R ::: 13 R-OH 'taGH

V~y A Hi: HOOC-CH-eHO I

OH

Rai94.

Co mt)t hOIl ht!P A gom hai axil X, Y deu thutJc day dong Mng cua axil khong no, mi;lch ha, chua mt)t lien ktt dO;. Cho a gam hon h'!P A tac d~ng vo; 500 ml dung d!ch Na1COJ 1M, sau phan fmg phai dung 350mI dung djch Hel2M mOi phan itng hit vOi luqng mlf; cacbonat con duo

Mijt khac, khi dot chtiy hodn toaTl a gam hon h'!P A, rai dan loim bi! san ph6m chay qua binh 1 chua H2S04dijc, Toi qua binh 2 chila dung d{ch NallH dijc du, thi dt) tang khoi IlllflJg cua binh 2 nhiell hrm dt) lling kh6i llllfllg cua binh 1 la 31,4 gam.

1) Tinh gia hj cua a.

2) Viet cae cong thuc Call t~o c6 thl c6 CUll X, Y. Neu gUi thitt chung liz dong d6ng lien liep cua nhall.

Liri giai.

D~t cong thue ella X la ~H21l )CQOH, cua Y la CmH2m-,COOH; n, m ~ 2.

1) 2C):l:lnolCOOH + Nai~OJ -j- 2CnH2n_,COONa + CO2 + H 20 (1)

2C,,,H1:n.;COOH + !\!«(~CO) -> 2(~H2m ICOONa + CO2 + HzO (2)

'2ECl + Na2CO} --". 2t'hC1 + CO2 + HzO (3)

C"l,H2n_1COOB -I- 311/202 --)- (n+l)C02 + nH20 (4)

CmH2m_1COOH -I- 3m/20z -7 (m+l)C02 + mH20 (5)

D~t x, y lil 56 mol ella X va Y. S6 mol HCl::: 0,35 .2::: 0,7.

S6 mol Na2CO) =: 0,5 . 1 =: 0,5 mol.

'Th~o (3): 56 mol NazCOj con thlla::: 11256 mol HCl =: 1/2.0,7 =: 0,35

Thea (1,2): 56 mol X, Y = 2.56 mol Na2CO) phan Ung v6i A :::

::: 2.(0,5 - 0,35) =: 0,3 mol

V~y theo 56 mol axit, ta c6 x + y =: 0,3mol. (I)

- S6 gam h6n hqp A:

a=: (1411 + 44)x + (14m + 4A~" =

=14(nx + my) + 44 (x + y)

- Blnh 1 giG' nuoc: S6 gam HzO ::: (nx + my).18

- Blnh 2 gifr CO2 : S6 gam COz = 44[(n +.1)x + (m + l)y]

Thea d~u bai thi s6 gam COz nhi~u han s6 gam H20 13 31,4 gam.

V~y 44[(n + l)x + (m + l)y] - 18(nx + my) = 31,4

hay nx + my = 0,7 (n)

1l1ay de gfa trj a(II), (1) vao bi~u thuc tinh a atrtn ta co:

a ::: 14(nx + my) + 44 (x + y)

a == 14.0,7 + 44 _0,3 = 9,8 + 13,2 = 23garn.

2) Xac djnh cr ella axit: M ",y ::: 23 : 0,3 = 76,67

Thea c6ng thuc ~H2n_ICOOH ta co 14n + 44 ::: 76,67

- 76,67 - 44 2 33 Suy ra n::: 14 =,

V~y chi c6 n =2 va axil thu hai m = n + 1 =3

• cac axit la CHz=CH- COOH, axit thu hai c6 th~ lA:

CH3-CH~CH-COOH; CH2=CH-CH2-COOH; CH2=C(-COOH; CH)

Hai 95.

DUll n6ng 9,7 gam h6,· hi/P' A gom hai chat x, Y tJw¢c day dong d&ng cua hrombenzen voi dung dfch fV:lOH:Yir; ~:i rip sua! cao. Sau plaIn U-flg th6i kM CO? Ili qua dung djch dln du; tJi!.~ dzi'':;'c d,,;t :f)'ili! .chua ox; cua X wi Y. Chi.l kiln hl/p }wj

dan xlUit ,wly Ili/inh h:,..; !,hdi~ /,6 'It ;<~',~~A,

'~Jra'n 1 phan "(fIg vita hit vOi 60ml dungl d!ch NaOH O,5M.

Pha'n 2 aem deit cluly holm toan, dAn cae san phtim chd.y liin luqt di qua lf11g lUling du' H2S04 d(ic, binh 2 df!1lg dung djch Ba(OH)2 duo

) T£nh 56' gam bin1l1 va binh 2 tang them.

) Tim cong thue pluin tri clla X, Y, neu Ii kho'i hoi cua X so vOi Y fa 0,92.

Lffi giaL

)~t cong thu-c cua X V3 Y !a CnH1n.7Br va c",Hzm_1Br, n, m ~ 6; rn > n.

__ 1°

:nHln- JBr + 2NaOH ---+ CnH1n_-,ONa + NaBr + H7.0 (1)

1° =m HZm_7Br + 2NaOH -~ CmHlm10Na + NaBr + HzO (2)

=n Hzn_1 0Na + CO2 + H20 -+ c"H ln_70H + NaHCOJ (3)

=rnHZm_70Na + CO2 + HzO ~ Cn,H zm_10H + NallCO) (4)

)i?-t s6 mol X, Y la x, y, thl 56 mol dAn xu~t chua oxi co trong m6i phan se la

/2. Phan (mg v(rj NaOH:

C H -70H + NaOH ~ c..H1n_70Na + H20 (5)

n Zn

C H _ 0H + NaOH ~ \-mHlm.10Na + HzO (6)m Zm 7

Thea 56 mol NaOH b (5,6) ta co:

xf2 + yf2 = 0,06. 0,5 => x +- y == 0,06 (I)

Thea s6 gam hOn hl!}J A (140 + 73)x + (14m + 73)y :::: 9,7 (II)

3n - 4C"H _ 0H + -2-- O2 ~ neoz + (n-3) H20 (7)

ln 7

3m·-4c",H _ 0H +- -2- O2 -)- mCOz + (m-3) HzO (8)

lm 7

1) Bloh 1 giii HlO. S6 gam binh 1 Uing blmg s6 gam HzO elm cae ph!m ling

56 nlol H 0:::: len - 3).x/2 + (m - 3).y/2].l8 =9[(nx + my) - 3(x t y)2

TiI phuang trlnh (II) ta co: 14 (nx 1- my) + 73(x + y) == 9,7

9,7 - 73.0,06 0 38 :::::> nx + my == == .

14 •

V~y s6 gam blnh 1 lang =: 9(0,38 - 3. 0,06) -== 1,8gam

Blnh 2 giiJ COl' S6 gam bloh 2 tang thrm bing s6 gam CO2 ella cac phan

,8).

<:::"" X y]S6 gam COz = 44. n'2 + m'2 = 22.(l/x + my) = [

== 22. 0.38 == 8,36 gam I

2) Mx.y = 9,7: 0,06 = 162 VI ta d~tm >n suy ra Mx == 140 + 73 < 162

:::::> n < 6,63, :::> n =6.

x la Ct,H5Br Mx == 157 ~ My';: 157/0,92 == 171

My::: 14m + 73 => m;: 7. Y la ~H7Br.

~Br LCH]19/ 19.J ' ~CH]' ~ X lil: va Y 13:·

CH3

Dai 96.

Cho hai chat hiiucO' X va Y lIeU chi chua C, H, 0, trong m6i chtit oxi chiem 53,33% vI kh6i IUlfTlg. ghi dot c.hay hoan toan 0,02 mol hon h(1p X va Y can 0,05 moloxi. Khollllqng phtih tu clIa Y gtip 1,5 ron kh6i lUlfYlg phdn tu cua X. Khi cho so' molbling nhau clla X vel Y tac dlfng vOi NaOH thi Y t~o ra kh6i lUf!1Jg muoi gap 1,647liin kh6i luqng mu6i tq.o ra til X.

1) Tim c6ng thucdtm gian, c6ng thuc phtin tli va cong thuc cifu ti;to clla X ...d Y, bilt rling khi dun nong Y vOi CuO l{lo ra san phdm co 1cha nang tham gia phdn ling frang glltmg. II

2) Tinh kho,luqnk ella X va Y eo frong 0,02 mol h6n hf/P c,.ia chung.

L<ri giai

I

1) D~t cOng thue ~0l1 gian ella X va Y la ~HyOz, ta eo:

16z%0 = .100 == 53,33. Suy fa y:::: 14z - 12x2

122 + Y + 16z

Khi z == 1 ~ x == 1; 'j. = 2. V~y eOng thuc dOl1 g:an clla X va Y d~u Ia CH20

+) D~t eOng thue phan tU x Ia (CHzO)n ~ Mx == 30n

£)~( cOng thue phan tir Y 130 (CH20)m =:) My = 30m

Theo dt bai My ::: 'I ,5Mx => 30m::: 1,5 . 30n => V~y m =r: l,5n (I)

+) Phan U'ng d6t chay: I

~H2nOn + nOz ~ nC02 + n H20 (1)

x nx

- I

'1\C 1I2mO rn +- 0102 -~ mCOl + m H;:O ( 4.J m

y my

D~t s6 mol X lil x, s6 mol Y Iii y, ta co: x + y:=; 0,02 (II)

Thea phan lfIlg (1, 2) va s6 mol O2 ehay: nx + my -= 0,05 (III)

0,05 - O,02n Tu cae phlto'ng trInh (II) va (In) ta co y=

m-n

Vl y la s6 mol cua Y nen 0 < Y< 0,02

. 0,05 - 0,0211Kt.!!...Y.2Jl ta c6 ---- > ° rna m -n :::; 1,5n - m :::; 0,5n > 0 m-n

n{l:n y > 0 ~ 0,05 - 0,02n > °=> n <: 2,5

. 0.05-o,n2n 0,05·-- O,02nKhl Y< 0,02 ta e6 ---=-.----- < 0,02 :=) < 0,02

m-n 0,511

:=) Il > 1,67.

V ~y 0 < Y < 0,02 :=;, 1,67 < n < 2,5 =:- n :::; 2.

CTPT ella X la (CH20h tue la ~H402'

Suy fa m == 1,5n = 1,S. 2 = 3 :=) crPT CI'Ia YIn. C3H60 3

'V} d X va Y d~u phan Ung v{1i NaOH t<;10 fa mu6i, v~y X va Y chi co th~ la

axit ho~e este.

Ma theo CD'Yf ella X thi c6 lh~ c6 hai cA'u t'.10 :

CH3COOH ho~e HCOOCH3 tue la RCOOR' trong do R == CH3; H.

Pha.n ti'r Y chi chua ba nguyen lU ox~ n~n Y ding chi co the chti'a rnl>t nhom

este. O~t Y la R 1COOR2.

RCOOR' + NaOH -+ ReOONa + R'OH (3)

arnol a

R,COOR2 + NaOH -+ R.COONa -+- R20H (4)

a mol a

'Theo d~ bili ta co: (R , + 67).a = ! ,647 .(R -I- 67).a

Hay R1 == 1,647 R + ,~3A5

}'.hi X lit CH3COO~i 'J;1P :=. 1) =:> R: = 68 :5 loZ!i VI

;~h d6 My == 68,~ Vt -I :'-'2:-;- ~02 -1- R:1, > lYl C,l'b()) :;: 90

'-·~'L~'1-. 13 HeOOe' ",,1'" ~::! '7. ~ ::: 4:=i

Khi do then e6ng thuc R,COOR 2 := 90 =-."> My = 45 + 44 + R 2 = 90 ~ R 2 = 1 tue lil H

V~y R, phai ehCfa m¢t nguyen tlr oxi. Vi Y b! oxi hoa boi CUO t~o fa :lndehit, suy fa Y co nhom -CH2--OH.

V~y eong thue cfiu t~o Cli3 Y l~ HO-CH2-CH1.--COOH

va eua ". la HCOOCH3

2) Tfnh s6 gam X, Y: thay n = 2; In = 3 v;,w phvangtrlnh (III) ta dltqc h¢:

x + Y = 0,02 (II) x =0,01 va y =: 0,01}~ S6 gam X =: 0,01 . 60 =0,6gam

2x. + 3y = 0,05 (III) S6 gam Y ~ 0,01 . 90 = 0,9gam

Hai 97.

1/0'" h'!P X gom Izai clult him Cd A, B, no m{}ch hJ chua ctit: nguyen tf)' C, 1/j 0 vd chi c6 cae nhnm chuc -0// va -COOll .Chat A co hai nhom chue va

chat B chi co m(Jt nhom chuc..Nlu cho 15 gam hon JlllP X tac dl;lng hit vm No thlfy bay fa 3,36 lit l/2 (dktc), con dl trung hoa 15 gam ho" hqp X ctin diing ,f.OO

ml dung dieh NaOl/. Khi d6t chay rnoi chat A ho~c B dlu thu JUlIc s6' mol CO}

bLing s6' mol H20. Bitt rang A va B kh6ng phai la dong phan cua nhau. g6c

Izidrocacb{)n trong A co khoi lUlJn'! Lan hem goc hidrocacbon trong B_

1) Xac dinh cong thuc pJuin tii va cau tflo cua A, B.

2) Dun /long Jujn h(jp X vOi H1S04 dijc vOi 1400C co thl xtiy ra phan ling

giua 2 phdn tit A vm nhau, ho~c mflt phdn til A vOl mflt pluin tii B, viet cac

phuong trinh phan zmg tren.

Lai giai.

Ki hi~u g6c hidrocacbon cua A la R, theo d~ bai A c6 hai nhom ehtrc, v~y A

e6 th~ 111:

R(OH)2 , R(COOHh ho~c HO-R-COOH.

Kf hieu g6c hidroc(lcbon eua B la R', th~n d~ bai thl mR > mR' ; VI B chi c6

m¢t nhom chue, v~y B co the 13 R 'OB ho~e RCOOH.

Theo cae ki Ili~u tr~n thl h6n hqp X e6 th~ 111 mllt trang cae Ic;la nang sau:

(I) R(COOH)2 va R 'OH (3) HO-R-COOB va R'COOH

(2) HO-R-COOH va R 'OH (4) R(OHh va R'COOH.

Khi phan Ung v(ri NaOH chi co nhom -COOH:

Cmg : R(COOH).. + nNaOH -+ RtCpONa)n + nH20

) phan ung tren thi s6 mol nhom -COOH == 56 mol NaOH

== 0,4 .0,05 :::: 0,2mol

him tfng vm Na thi ca nhom -COOll va -OH d~u phim ling:

,--R(COOH)m + (n+m)Na -+ (NaO)n~R-(COONa)m-I- 0,5(n+m)H 2

phan tfng tren thl t6ng 56 mol nhom -COOH va -OH gnp dOi s6 mol H2 4:::: 2.0,15 == 0,3 mol

lR-llim.l. Vi A, B. no, m<;lch ha nell ta co:

~H2n(COOH)2 khi chay t<;\o ra (n + 2)mo1C02va (n + 1)moUIl)

=mH 2m+I-Ol-l khi chay t~o ra m molC02va (m + 1)molH20

'm gia thiet VI 56 mol CO2va 56 mol H20 kbOng b~ng nhau.

~.

-JO-R-COOH l ~ICO do 56 mol OH cua A bang

J s6mol COOH.

t'OH Ma s6 mol COOH ::::.0,2 mol

6ng t6 56 mol -OH va -COOH trang A :::: 0,2 . 2:::: 0,4 rna d A va B

,3 mol tcing 56 hai nhom nay. V~y truang hqp (2) bj lo~i.

!£l!QQ.l.

I H,O-R-COOH } S6 mol-OH bang 56 mol A

R COOH :::: 0,3 - 0,2:::: 0,1 mol

[Jg 56 mol-COOH va -OIl la 0,3.

5mol COOH :::: 56 mol NaOH :::: 0,2.

ra 56 mol B :::: 0,3 - 2 . 0,1 :::: 0; 1

56 gam X :::: (R + 62) . r, i + (i<.' + 45). 0,1 :::: 15 =:> R + R' :::: 43

, /R'=H VI MR > mR' =:) R < 43(2 = 21,5

~R'::::CHJ Sco 2 car:

R'::::H= I HCOOH (B)

{ R =CJH6 :::: 42 C3H6(OH)COOH (A)

R: .- ~Hl =15 -+ CH)OOH (B)

{ R =,C1H4 = 28 -+ C1114(OH)COOH (A)

1,\'1

Truong hQQ.1.

Ala R(OH)2 } nB :::: nCOOII :::: nNaOH :::: 0,2, suy ra

B iii R 'COOH nA :::: 112noB :::: 1.'2(0,3-0,2) == (1),05 mol

mx :::: rnA + rnB :::: (R +134).0,05:::: (R' + 45).0,2 = 15

=:> R+ 4R' :::: 86

Vi R > R' =:> R' + 4R" < R + 4R' = 86

=:> 5R' < 86 =:> R' < 86/5 =:> R/ < 17,2

Chi co hai gia tr! R' == 15 ho~c R' :::: 1.

- Neu R' :::: 15 lbi R :::: 86 - 4. 15 :::: 36 khOng c6 g6c phu hqp

- Neu R' :::: 1 thi R =82 c6 g6c Ct,H IO khOng no. Lo~i.

Hili 98.

Dot chay hoan toan 8)96 lit (dktc) h6n hfIP khi A g6m hai( olefin kt tiep

nhau frong day dong ddng.Cho san phdm dot chay di qua binh 1 d,fng HzSO" diJc, sau do qua binh 2 dtptg NaOH dijc. Dtj timg kh6'j IUlf1Jg cua bz'nh 2 IUn hlYn binh 1 ld39 gam.

1) Xac d!nh cong thlle phan tu va tinh thdlZh phti'n % the,o thl tich hai olefin c6 frong h6n hfIP A.

2) Cho A hlfP nuac khi co xue tac dUlfc h6n hlfP rUflu B. Iii~u suat phdn (mg hfIP nuuc cua cd hai olefin deli bling 50%. TrQn h6" hlfP B vcn lumg du h6n

hfIP axitfomic va ax;t axetic Ijoi dun nong trung s'! co mijt eua H1S'1" dije liim xuc tac, sau phdn (mg thu dUlfC 11,811 gam h6n hfIP bon este.

H;~u sud! cz1a hai phdn fmg t!;lo thanh este cua cung mlJt IOl;li ruO'l!- bling

nhau, va bling 60% doi v6i IOl;li rulJU co it nguyen tu cacbon, bling 55% doi vOi IOl;li rUl!" co so nguyen tu cacbon nhilu hlY1J:

Tinh khtfi IUlf1Jg m6i axit dti t~'aT,:" gia phan itng este hoa.

LOi ghii

D~t c6ng thuc eua hai olefin la C,.H2n va ~+lH2n+4 (n ~ 2). S6mol hai o'ietin :::: 8,96 : 22,4::: 0,4 mol

1) Phan Ung chay:

CnH2I: + 3n/2 O2 -+ nC02 + nH20 (1)

x nx nx

1,11

l -.:::: ­

~\ "'"' ;!!il,!,li!il~ , ~1

Iii' II!

II: ;1,'\

!Ji :,}:I I i,li

I:,!! "II

Hi!'I' !'I':,I,11

1~:1

!i:ilII'

1:11

, ' "1"1,I ~ ,I p11 i ~I

1

1

'

1 ,\",,1 ,1 :

:!!Ii ~ li;'(1

l:il'l !III,:111

1'1'1

Iii i Ib: ' !II: ,

III'

) l1IIII'!II: I'111 '

lill· i'II'l1,1

:11'II,I, 'I'"I'lii,ii,

I11III

1/111

i'III/

i,,1111II II Iii

III!I

liilll 1'1'1

illl,I!1 I,! I

"I,! :

! 1':1 i 1:

1

' ')"",,:1

CIli-I H21l.4 + (3n+3)/2 O2 ---+ (n+I)CC'2 + (n+1)H20 (2)

(n+l)y (n+l)yy

D~t s6 mol CnH2n la x; s6 mol Cnt,H2n.4Ia Y, ta c6:

x + y ::..: 0,4 (I)

Kh6i luqng b111h 1 tang = mill) == L8[nx + (n+l)y]

Kh6i luqng blnh 2 ting::: mc~:= 44(nx + (n+l)y]

Theodebaitac6:44[nx+(n+l)y] - 18[nx+(n+1)y] == 39

(II)Hay 25n.(x + y) + 26y == 39

Giai h~ (1), (ll) ta duqc: y = 1,5 - O,4n

VI 0 < y < 0,4 , suy fa 2,75 < n < 3,75 V~y n == 3

_They n = 3 vao (Ill), ta dlt<;1c y == 1,5 - 0,4 . 3 == 0,3 moi

V~y x == 0,4 - 0,3 =0,1 mol

%C H ::: (0,1/0,4) .100 = 25%; %C4 Hg =: (0,3/0,4).100 == 75%3 6

2) Ph~m U'ng hqp nu6c:

C3H6 + H20 H1SO. )­ C3H70H (3)

C4Hg + H20 _!.!../O. ) C4H90H (4)

Vl bi~u sullt hqp nu& la 50% suy ra:

nc II 01( 1 1

== 0,1--.50 100

== 0,05 mol; nc I( 0 • ~

== 0,15mo1

- Phan tffig este ;:03:

C H 0H + HCGOH 117"<;0.) HCOOC3H7 + H20 (5) 3 7

C:,Hl)H + CH 300H ~ CH3COOC3H7 + H20 (6)

C4H

90H + HCOOH -» HCOOC4H9 + H20 (7)

C4H 'IOH +- CH 300H ~ CH3COOC4H9 + H20 (8)

Th~o d~ bai hi~u sullt tham gia phan {mg este hoa cua C3H70H 1:1 60%, v~y s6

mol C3H70H phan lmg := (0,05/100).60 =0,01mol.

Hi?u suftt eua C4H90H la 55%, v~y s6 nol C4H90H phan tffig 13:

0,15.55/100 = 0,0825 mol.

_Thea cae phuang tnnh ~h{m U'ng (5, 6, 7, 8) ta co tdng so mol hai axit phan

tffig b~ng tdng s6 mol hai nrqu. phan ling va btmg so mol H20.

Suy ra n HIO == na~il = 0,03 + 0,0825 = 0,105

- Ap dl;1ng dioh lu~t bao toan kh6i hrqng eha de phan U'ng (5, 6, 7, S) ta c6:

nRl1\1U + m axll =. fnC'le + ;n1I1()

0,03 .60 + 0,0825.74 + mOUil = 11,811 + 18.0,105

18 + 6,105 + muir = 11,811 + 1,89 = lJ,701

V~y m ouil phan lIng = 13,701 - 7,905 = 5,796.

- D~t s6 mol HCOOH dii phan u-ng la a; s6 mol CH3COOH la b, ta e6:

a + b == 0,105 } a = 0,036

46a + 60b = 5,796 ~ b == 0,069

mHCOOH == 0,036.46 == 1,656 gam

nlClIlCOOJl = 0,069.60 =4,14 gam

Hai 99.

Co b:l hifP chat x, Y, Z diu co clfu tl;1O mCJch thdng, trong do X la andehit no oem chilc, Y La rW!lI t101l chlie, Z La mljt ankan.

lIon hlfP A g6m cd ba chdt X, Y, Z. Khi tach Z ,.a khoi A thi dUl!c hon hl!P R g6m X va Y.

Tn?n X va Z voi nhau dU(fc hon hfJ1J C.

Cho hon hr;p A tac dl;lng vita hit v6i V lit (dktc) hidro co niken dot nong him xuc tac, toan b(l san phdm sinh ra eho tae d~mg het vat natri, dlll!c 5,04 lit hidro.

Dot ehay hoan toan 0,9 mol hon hifP B, tim dUt!c 70,2 gam nllae va 277.2 gam COz.Ltlf!1lg COz nhll v~y eung thl( dll(fc kid dot ehay het a mol chat Z.

Khi tr(ln X va l' theo bat ki Ii l~ nao, r6i dem dot choy 0,9 mol hon hlfP de"u thu dU(fc 277,2 gam CO2,

Khi dot ehay mljt thl tich hU-l xae dlnh clia hon hlfP C, eho dil ti l¢ hai chat trong C fltay doi bat ki, thay kho'i lUf;mg nlltre ;u6n luon khong d6i. (Biet eac thl tfch khi dlu do adie'u ki~n tieu chuan).

1) Tinh a

2) L¢p cong thlic phan tu cua cae ehat lid thanh pha'n phd'n tram theo so mol cua chung co frOllg luSn hfJP B.

3) Tinh V.

LOi giai. 1

) Tfnh a.

) 56 mol CO2 thu duqc khi d6t chay 0,9 mol hOn hqp g6m X,Y:

= 277,2: 44 = 6,3 mol. n eol

56 mol CO2 kh6ng phl;! thul;>C vao ti I~ X vaY. Suy faXva Y 06 cung s6 ~lJy~n lI'r cacbon trong phAn tir :

D6t chay 0,9 mol X,Y thu dUqc 6,3 mol CO2

V~y d6t 1,0 mol X.Y thu duqc (6,3.1)/0,9 =.7 mol

V~y andehft X va m9U Y deu la C;.

+) Khi J6t chay hOn hqp C thi lugng ntIC1C t~o fa kh6ng phI) thu¢c vao t; I~

ehit X va hidrocacbon Z , suy ra X va Z c6 cung s6 luang nguyen tU hidrC'

lful tv .

r. X In andehit rno dem chuc v~y c6 c6ng thuc chung 13 CnH2nO rna n = 7, ( 130 C;H I40. V~y Z c6 14 nguyen fir hidra trang pha.n tir. Thea de l:iai, Z la IC la c6 c6ng thuc chung CnH2n+2 , suy fa 2n+2 =14, tlIe n= 6.

I~y Z la ~HI4'

~a -:6 phan lIng chay Z: Ct,H 14 + 9,5 O2 ----)0 6 CO2 + 7 H20 (1)

I mol ------)0 6 mol

a mol (- 6,3 mol

I~y a ~ 6,3: 6 = 1,05 mol.

~) Xac d!uh c(')fig thl1C va thanh phful clla cac cha't trong h6n hqp B:

'-Ihu tren d1i bitt hOn hqr B g6m andehit c,H140 va nIqu m<.'ch th;~ng, dan :> 7 nguyen tv cacoon. D~t Nqu Y la C;HbO.

b J) b C,HbO + ( 7 + 4" -"2 O2 ----)0 7C02 + "2 H20 (2)

x 7x b/2y

C-']H I40 + 10 O2 ----)0 7COz + 7H20 (3) y 7y 7y

D~t s6 mol fUqu Y la x; s6 mol andehit X la y.

Thea dt bai ta c6: x + y =..: 0,9 (1)

ox 70,2 S6moIH20: 2+7Y=~=3,9 ~ bx+ 14y=7,8 (II)

lar.

- Thea phuang triah (II) nc'u b = 14 tue In khi x va Y la d6ng phful ella nhau,

thi ta eo 14x + 14y =7,8 ~ x + Y =7,8/14::: 0,56 trai vai gilt thi€t cho x + y =0,9. Ho;;tc dt;ra va-a phan lIng chay (1 )(2), khi d6 s6 mol H20 phai btmg s6 mol CO2,

Thea de bai 56 mol H20 = 3,9; s6 mol CO2 ::: 277,2/44 =6,3. ,

V~y Y la ruqu kh6ng no, hIc la b < 14. Nhu v~y, ttt phuang trlnh (II), ta co :

bx + by < bx + 14y < 14x + 14y

~ b(x + y) < 7,8 ~ b < 7,8/0,9 ::: 8,67.

Trang cae hqp chat CxHyOz thl y lU6n lu6n 13 s6 chan; v~y b Ia. s6 ehan, nho han 8,67. Suy ra c6ng thuc Y eo the 13 cae eha.'t sau :

y KhOng Ia'y gia tIi b:::~, VI khi d6

b

8 kh6ng c6 ruqu tuang U'ng. 6

4

Nhu v~y e6 ba nghi~m :

Op thu nhat: f11<JU la C;HgO x + y = 0,9 (1) - } x = 0,8 ~ 88,9%

andehit la c,HI40 8x + 14y = 7,8 (II) y =0, I=:> 11.1 % I

Op thlI hai: ruqu l~ c,H60 x + Y = 0,9 } x =0,6 ::::) 66,7%

andehit la c,H I40 6x + 14y =7,8 y =!0,3::::;. 33,3%

cap thu ba: ru<Jl1la c,H40 x + y = 0,9 } x ='0,48 ~ 53,3%

andchit 130 C,H I40 4x + 14y = 7.8 y::: 0,42 ~ 46,7%

3) Tinh V St;r fl)ng hqp H2 phl;! thu¢C vao mue d¢ khCmg no cua f11qu. V1 hOn hqp B duqc t~o ra khi tach Z ra khoi hOn hqp A, suy fa ti I¢ gilia X va. Y Lrong B, cling chinh la ti I¢ cua ehung a trong A.

N€u la cap thu nhat ta co S(J d6 sau.

4H2 ,+Na 'jc,HgO + ----)0 ,~HI60 ) c,H1sONa + I(2H;2

x' 4x' x'

H2 +Na C;H I40 + --+ c,H I60 c,H I50Na + I/2H2j

l .y' y' y' ..J

~ '----r--' l(2(x'+y') = 5,04 = 0225

4x'+y' x'+y':::0,45 22,4 ,

147

~

1,:1I: :!I

iJ ,~i

ill

,II1:1'

II iiil iiil: ~III!II: ' III,11), ii,'II:

illIi

I,'I! Iii II: !II

1

]'1Iii' ;Ii illl! II'I' ii: !I iii :11

1:'1'i'II

ill iI

:11 iII I

II 1

IIII; 1:,1' I,

III I" , Iii I

1 '

:1,:',',:1,11

"I'':;,1 I'"

1:1

1:1

I,!II" 1'1

::(,

Theo t1. 1 C so. moI'(1 C.1p- th'L1 nh'at ta co:, -X' = -0,8 = 0,8 yay } x' = 0,4

'. y' 0,1 . y' =0,05

Suy fa s6 mol II;! -= 4 . 0,4 . 0.05 = 1,65 mol

V = 1,65. 22,4 = 36,96 lit

Neu 13 c{}p thCr hai ta co sa d6 sau.

5HJ +Na j~H60 + ~ ~H160 ----.) ~H150Na + 1/2H2

x' 5x'

HI +~ j

~H140 + ~ C7H 1t,O ~ ~H150Na + InH2

y' y' '---y-----J

5x' + y' x· = 0,3

T; J¢ ac~p hai: x'/y' = 0.6/0,3 2 =:> { y' = 0,15 x'+y' = 0,45

=:> n lll = 5x' + y' = 5.0,3 .0,15 = 1,65 =:> V =36,96 11t

N~'ll Ii'! cap thu ba Tlte1ng ttf nhtr trcn ta co:

nl/ 6x'+y'l

max'+y'=0,45 x' = 0,24 n III = 1,65mol :=)

0,48 }~ Til?bc~pba: x'/y'= 0,42 y' == 0,21 V =36,96lft

~ai 100.

HlfP chat A la este chl chua m(>t lOfli nhom chuc. A dUllc tflo bOi axil J( va Uf!ll Y, diu la nhfrng hlfP chat no. Trong phiin Iii' cua A co chua hai vong d9c ~p tit 6 e~nh Ira lin). Cong thue don gidn cua A lQ (Cll,lJlJJ.7S0 7.J1I' Xac d;nh e{mg 'Iue phiin tii cua A, til d6 xcii: dinh cong Ihue phan IU cua X, Y va viet eong thitc ii'u t(,lO eua mt)t este irng vOi X, Y d6.

Lm giai.

. - Thea c6ng thtlc dan gi.l.:J clla A, ta c6 c6ng thue pha.. ti'r clia A Iii : ~11.25HI).7507.5)n'

- VI A chi c6 m¢t 10<,li chuc este, n~n c<')ng thuc trtn c6 th~ vi~t la:

(C(I t.25-).75)nHIJ.7~n(COO)J.75n hay (~.5nHJJ.75n(COO)J.75n (I)

- Vi X, Y la d.c hI!!) chat no, suy fa A Ii'! este no, do do hai yang co trong A Ia

hal yang no, hay wang dlfang v61 2 lien k~t n. V'/J.y c6ng thvc cua A co d~ng:

CpH2Pf-2_2,,(COO), hay CpH2P2(COO)1 (II)

(a 13 56 hrqng lien kc't IT trang g6c hidracacbon; theo tren ta co a = 2).

Ap d~ng c6r.g thue (1I) d6i \/6i cha't A dL1qc viet ad~ng (I), ta co:

p -7 5n }~ , =:> 2.7,5n-2=13,75n => n = 1,6

t - 3,75n .

Thay n = 1,6 v?w (I), ta duqc c6ng thli'c phan llr A 13 C lsHn OJ2 . V~y A 130 estc 6 Un. D~t c6ng thirc cua X 13. R(COOH)n ; clla Y Ii'! R'(OH)m'

Ta co:

m R(COOH)n + n R'(OH)m ~ Rm(COO)nmR'm + nrnH20 (lll)

n.m=6 n",,;, 1 2 3 6

m,,",,,, 6 3 2 1

V~y co 4 tNang hqp phai xet:

Twang haP 1.

- A d\r\1c t~o bOi ax it no don chuc (n= 1) va nrqu no 6 l~n (m =6). Khi do c6ng thli'c A theo (III) c6 d<;\ng (RCOO)6R'.

- Vi A chi co 18 cachon, suy ra R chi c6 th~ Ii'! II ho~c CHJ ­

a) Ncu R =Ji thl Ala (HCOO)6R' == C1RHn 0 J2

V~y R' la: C12H I6• VI A chua hai yang d<!c l~p kh6ng nho hem 6 c~nh, suy ra trang g6c R' phai co hai yang 6 qmh tuc la:

0-0 - V ~y N<;ru co 6 nhern -OH c6 th~ Ii'!:

Hcao oaCH OH OH

OI-I~OH SuyraA HCOo--9-----P ~H~ HCOO OOCH

b) N~u R Ii'! CHJ-:

Tucmg tt! thl R' la CfjH6 , kh6ng tht chua bai yang no ~ 10i;li.

'rttemg hop 2.

A t~o Wi axil no hai Ian axil (n = 2) va ruqu no ba IAn nrgu (m ::: 3).

Theo phim ling t~o fa estf" va e6ng thue pMm tli ella A, ta de dang tlm dugc ~H4(COOtI)2 va ruqu C)H'j(OH»). Estc c6 tht Ia:

~ 0 /C--O, Il--C"

CH ~ ~~ ''''.. I 2 ~Hz 0 0 CH2 CH

I II II J I 2CH2 CH-CH2-O-C-CH1 -CH -C-O-CH -eH

"'.. /' 2 2 . CHC-O "'.. /' 2

" O--C o " o rntO'ng hqp 3.

A t~o bCri axil no ba Uin (n == 3) va ruqu no 2 lc\n. Tuang ttf nhlf truClng hgp 1 Ig hqp 2. Ta tim dugc:

<\xil X la C3H'j(COOH)J va nrqu Y la ~H4(OH)2' Estc co the la:

b) AgClOJ + Ol2 --; AgCl + CiOz + O2

c) KC/OJ + HfSOld) ~ KClO" +KHS04 + Cl02 + H 20

d) KC/OJ + HJC20 4 -+ K2C10" + CO2 + CiOz

Ciiu 2.

1. Chi dUCfc dung Cu(Oll)z ld hoa chat duy nhat ca'n lay them, hay chi ro phuO'1Jg phap nh~n ra 4 19 d1f1Jg 4 dung djch etanol, etanal, axit a~etic, glixerin dii I hoa tan trong nwtc. I

2. Cho naphtalen tac dl;lng v6i RNO) c6 H2S04 lilm xuc tac, thu dUl!c sdn phdm chua 2 nh6m nitro. Viii cau tl}o cua san phdm. I

II3. Til toluen hily diiu chtaxit p-aminoben.r.oic. II

II Cau3. II

II:Cho hon hqp X g6m Cu20 va Fe10J vao dung dieh H 2S04 2M. khuay di'v. il :cho cac phan ling hoim toiln, sau d6 Iflc dUCfc 3,2 gam ch(ft ran kh6ng tan va du9'c I·

dung dich Y. Th6i khi NHJ du velo Y, lay ktt tua n.c ~ ngoai kh6"g khf 0- 30rrc 1m Ikh{ii 11l{11lg khong tI6i, th~ khoi IUlfng chat ran thu dUl!c 6dng 1/2 khat IUlfTIg hon CHz-COO-CH1I I CH-COO-CH2I CH2-COO-O-Iz

I CH2-COO-CH2I /CH-COO-CH2 I I

CHz-COO-CH2

Tntang hop 4.

A l~O b&i axil 6 I~n va ruqtl 1 Ian bi 10<;\1

hf.JP X dil dung. Lay 1/10 d1,mg dfch f pha loang thanh 1000mi dw!c dung dfch co !pH:O. II·

(I) Viit cac phuong tn'nh phdn (eng dii xdy ra.

b) Tinh s6' gam honi hf!iJ X va so lit dung dfch H 2S04 2M da dung. Iii .' Cdu 4.

Dot chay hOall toa), 1,34 gam chat A chi tim duc;c 2,2 gam CO2 va 0,9 gam II: I0. A co cong thuc phdn tLl trimg v6i cong thuc d(m gidn nhpt. A tac dlfrig VOlH 2 I

anhidrit axetic tl}o ra este 2 ltln este; A kh6ng phdn (mg v6i AgNO) trong NHJ. Khi tac dl}ng v,6i dung d!(;h axil vo C(f Ioang tit A chi thu dUl!c rrletllnol vel hl!P chat ill B, chat nay vua tham giaphdn ung trang gUO'ng, vlia phdn ling vOi andehit axetic t~o ra este 3 ldn. Khi bj oxi hoa llh~ nhang fhi B chuyln thanh axil cacboxylic C; ami! cua axil nay phon cmg vtri B:-2 frong 51! c6 mtJ.t cua NaOH t'?-o Tfl amoniac va

Oa. glixerandehit (CJH~J)'

Xlic dinh c6ng 11kc c:fu tl}o cua A, B, C va viit tat cd cac phuong trinl: iDe thi Mon H6a (tho; gum lam bai 180 phllt) Iphon (mg. Bilt B va C c6 cung s6luCfllg cacbon va dlu c6 it hl111 A m¢t nguyerl tu I cacbon I

Cau 1.

1. Neu cac ml;lc dich chinh cua vifC sit dl}ng Criolit trong qUii trinlr san Cho H::: 1 C::: 12 o :::!6 Cu = 64 Fe :::56 hom til qu(illg boxit. I

-~--------

2. Gidi th{ch qua trinh phd huy cua thanh nhom tTong dung djch NaOH.

3. lloan chinh cae phurmg trinh phdn ,mg sau:

a) IlgO + ell --+ HgCl + ClzOz

151 ,~!

!){&Q.~O ca.!llY.

+) C1PT eLla A Iii. C~1I1004'

1 H-loCH3 CJl,C---11 I H flO-H

t) IIi'OI I ho~)c H OB If' H OB ho~c HOBIfE----i I-l t~lttl-OH . Ir Oli -0 -eHJOH HI~~o .~~ CH2 --0

(A (8)

~o COOH C""""'NH

CHOH OH 2

H+OB Br2/NaOHIG] . - .. IItOiI

OHH-r01I ~ CH20HCJI20H CH20H (C) amit glixerandchit

100 CAU H(H vA BAI T~P IIOA JnJu CO

Tnc gia: ','RAN THJ\CHVAN

ell.ilJ.. tr6.ch nhi¢m xllat ban:

Giam doc: PI L\M VAN AN T8ng bien t¢p . NGUYEN NELl' Y

Bien t(ip : NGO NGQC Al'T

SJa h/m in.: HOANG VINll

Ve bill: IHNNH LlfdNG

In 2000 cuon , khr> 14,5 x 20,5 t~i xi ngh~~p in Qu~tn 1. S6 xuat him 214/726-97CXB. In x(,ng va n9P 1t1U chi~u thang 1/1998

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