Nhm nit I. Mc tiu ca chng 1. V kin thc Bit: - V tr ca cc nguyn t thuc nhm nit trong bng tun ho n.

- Tnh cht ca cc n cht v hp cht ca nit v photpho. - ng dng ca cc n cht v hp cht nit. - iu ch nit, photpho v cc hp cht quan trng ca chng. Hiu: - S lin quan gia v tr nit, photpho trong bng tun ho n vi cu to nguyn t, phn t ca chng. - S lin quan gia cu to nguyn t, phn t ca nit v photpho vi tnh cht ho hc ca n cht v hp cht ca chng. 2. V k nng - T v tr, cu to nguyn t, phn t d on tnh cht ho hc ca n cht v hp cht ca nit, photpho. - Lp phng trnh phn ng ca cc n cht v hp cht ca nit v photpho. Xc nh c vai tr v so snh tnh kh, tnh oxi ho ca chng trong cc phn ng oxi ho - kh. - Vit c cc phng trnh phn ng trong cc s chuyn ho. Bit gii cc dng khc nhau ca b i tp trc nghim, b i tp t lun nh lng. - Tin h nh mt s th nghim n gin nghin cu tnh cht ho hc ca n cht nit, photpho v cc hp cht ca chng. 3. V tnh cm, thi - C thc tch cc, t gic v hp tc trong hc tp. - C thc bo v mi trng. II. Mt s im cn lu v ni dung dy hc v phng php dy hc 1. Trong nhm nit ch xt k nit v photpho, cn l m r s ging nhau v khc nhau ca cc n cht v cc hp cht ca hai nguyn t . y l nhng kin mi i vi hc sinh. Do hc sinh c hc y c s l thuyt nh cu to nguyn t, bng tun ho n, lin kt ho hc, cn bng ho hc, s in li, khi nim v axit, baz v mui, nn gio vin cn dn dt hc sinh c th da v o l thuyt ch o d on c tnh cht ca n cht nit, photpho v cc hp cht ca chng. Gio vin biu din th nghim, hc sinh quan st, nhn xt v rt ra kt lun khng nh s ng n ca nhng d on . 2. S khc nhau v cu to v bn ca phn t nit v phn t photpho. * Phn t nit N2 c kch thc nh hn phn t P4 (dN N = 0,109 nm; dp-p = 0,221nm) v v N2 trng thi kh nn lc tng tc gia cc phn t N2 nh hn nhiu so vi lc tng tc gia cc phn t P4. * Lin kt ba trong phn t N2 c nng lng ln (EN N = 946 kJ/mol), ln gp 6 ln lin kt n N - N (EN - N = 169 kJ/mol), nn l lin kt rt bn. 30000C n mi bt u b phn hu th nh nguyn t nit, do nhit thng nit phn t l mt trong nhng cht tr nht. Cn nhit cao, nit tr nn hot ng hn, nht l khi c mt cht xc tc. * Mc d photpho c m in (2,1) nh hn so vi nit (3,0), nhng iu kin thng photpho hot ng hn nit. l do lin kt n P - P trong phn t P4 km bn hn lin kt ba trong phn t nit (EP-P ~ 200 kJ/mol). trn 20000C phn t P4 b phn hu th nh cc nguyn t photpho. * nguyn t N khng c kh nng kch thch cp electron ghp i phn lp 2s chuyn sang obitan 3s ca lp th ba, v obitan n y c nng lng cao hn nhiu. V vy cng ho tr cc i ca nit trong cc hp cht bng 4: ba lin kt c to th nh theo c ch trao i, cn mt lin kt c to th nh theo c ch cho - nhn. Nit th hin cc s oxi ho: -3 (NH3), - 2(N2H4), 1(N2O), 0 (N2), +1(N2O), +2(NO), +3(N2O3), + 4(NO2, N2O4), +5 (N2O5). 3. iu ch nit trong cng nghip Nit c iu ch bng phng php chng ct phn on khng kh lng cn cha kh him v nhng vt oxi. Trong nhiu trng hp, tp cht kh him khng gy tr ngi g c, nhng oxi th khng c ln. loi tp cht oxi, ngi ta cho nit i qua mt h thng cha ng kim loi t nng. Khi tt c oxi u phn ng to th nh CuO. 4. Amoniac * Kh amoniac l mt trong nhng kh tan nhiu trong nc. Hin tng tan nhiu ca amoniac c gii thch bng s to th nh lin kt hiro gia cc phn t NH3 v H2O (c hai u l phn t c cc: momen lng cc NH3 = 1,48D, H2O = 1,86D). Lin kt n y c hnh th nh nh lc tng tc tnh in gia nguyn t H mang mt phn in tch dng ca phn t H2O v nguyn t N mang mt phn in tch m ca phn t NH3. * L hp cht c cc, NH3 d ho lng v d ha rn (tnc = -780C, ts= - 330C) cao hn nhiu so vi cc hp cht tng t nh PH3 (tnc = -1330C, ts = - 87,40C), AsH3 (tnc = -1160C, ts = -620C) v.v iu n y c gii thch l : do phn cc kh mnh, nn cc phn t NH3 d kt hp vi nhau to th nh tp hp phn t (NH3)n nh lin kt hiro. ph v tp hp phn t n y cn tiu tn nng lng. Bi vy, NH3 c tnc, ts v c nhit ho hi (22,82 kJ/mol) cao hn PH3, AsH3. nhng hp cht n y khng xy ra hin tng tp hp phn t.

* Khi tan trong nc, trong dung dch nc ca amoniac xy ra cc qu trnh sau: NH3 . H2O + NH3 + H2O NH3 . H2O NH 4 + OH-

+ Khi NH3 kt hp vi H+ ca H2O theo c ch cho - nhn, to th nh ion NH 4 v dung dch tr nn c tnh baz. Phn ng chung c vit l : + NH3(dd) + H2O NH 4 + OHy l phn ng thun nghch, lnh n chuyn dch t tri sang phi, khi un nng trong bnh h n chuyn sang dch t phi sang tri. Hng s phn li baz ca amoniac trong dung dch 250C: _ + Kb = [ NH 4 ][OH ] = 1,8. 10-5
[NH 3 ]

Trc y, ngi ta cho rng tnh baz l do NH3 kt hp vi H2O to th nh phn t NH4OH, nhng thc t khng c nhng bng chng minh s tn ti ca phn t n y. Khi nghin cu nhit ho rn ca dung dch NH3 ngi ta thy c ba dng hirat bn nhit thp l 2NH3.H2O (tnc = -78,80C); NH3.H2O (tnc = -790C) v NH3.2NH3 (tnc = -980C). Trong cc hp cht hirat , phn t + NH3 lin kt vi phn t H2O bng lin kt hiro, ch khng c cc ion NH 4 , OH- v phn t NH4OH.

cation phc (gi chung l amoniacat kim loi [Ca(NH3)8]2+, [Cu(NH3)4]2+, [Ag(NH3)2]+, v.v l do c s hnh th nh cc lin kt cho - nhn (cn gi l lin kt phi tr) gia cp electron t do cha s dng ca nguyn t N trong phn t NH3 v obitan lai ho cn trng ca ion kim loi (theo thuyt lin kt ha tr). * Amoniac cn c tnh kh, mc d khng c trng bng phn ng kt hp. Tnh kh ca NH3 l do nguyn t nit c s oxi ho thp nht (-3) gy ra. Ngo i O2 v oxit kim loi ra, clo v brom oxi ho m nh lit amoniac trng thi kh v trng thi dung dch ngay nhit thng. 2NH3 + 3Cl2 2NH3 + 3Br2 5. Mui amoni

+ * Kh nng kt hp ca amoniac vi nc v vi axit to th nh ion NH 4 v vi cc ion kim loi nh Ca2+, Zn2+, Cu2+, Ag+ v.v to th nh

N 2 + 6HCl
N 2 + 6HBr
0

+ Ging vi mui ca kim loi kim, cc mui amoni u tan nhiu trong nc v khi tan phn ly ho n th nh cc ion. Ion NH 4 cng khng c m u nh ion kim loi kim. Khc vi mui kim loi kim, dung dch mui amoni c tnh axit do ion amoni cho proton: + NH 4 + H2O NH3 + H3O, Ka = 5,5.10-10.
* Cn hiu v nm vng phn ng nhit phn ca mui amoni. Sn phm ca phn ng n y l khc nhau, tu thuc v o bn cht ca axit to nn mui. - Mui amoni to bi axit khng c tnh oxi ho, khi b nhit phn to ra amoniac v axit tng ng. V d: NH4Cl

* Cn thy r s ging nhau v khc nhau gia mui amoni v mui kim loi kim.

NH3 + HCl
t0 t0 t0

t0

(NH4)2CO3 NH4HCO3 (NH4)3PO4

t0

2NH3 + CO2 + H2O NH3 + CO2 + H2O 3NH3 + H3PO4

(NH4)2S 2NH3 + H2S - Mui amoni to bi cc axit c tnh oxi ho, khi b nhit phn th axit c to th nh s oxi ho NH3, to ra cc sn phm khc nhau.
250 0

V d:

NH4NO3

N2O + 2H2O
t0

NH4NO2

N2 + 2H2O

(NH4)2 Cr2O7

t0

N2 + Cr2O3 + 4H2O

(NH4)2SO4 NH3 + NH4HSO4 Tip tc un nng thm mui NH4HSO4 s b phn hu: 3NH4HSO4

t0

t0

N2 + NH3 + 3SO2 + 6H2O

Ch : Khi l m th nghim nhit phn mui NH4NO3 cn tun th nghim ngt ch nhit, v NH4NO3 nng chy 1690C, t khong 190 - 2600C b phn hu cho thot ra N2O. Cn nhit cao hn 3000C s phn hu n, do N2O khng bn phn hu nhanh ra N2 + O2: 2N2O 6. Axit nitric

t0

2N2 + O2.

HNO3 l axit c tnh oxi ho mnh. C t i liu ni rng nng rt lo ng v lnh HNO3 khng th hin tnh oxi ho trong dung dch nc. Khi HNO3 rt lo ng v lnh tc dng vi kim loi hot ng, v d Mg, th c H2 thot ra thi im bt u phn ng. Trong nhiu t i liu, khi ni v tnh oxi ho ca HNO3 ngi ta khng a tnh cht n y v o, thm ch c mt s t i liu cn khng nh l khi tc dng vi kim loi, HNO3 khng cho H2 thot ra. Nu s dng HNO3 c th sn phm cui cng lun lun l NO2. l v tt c cc hp cht cha oxi ca nit vi s oxi ho (+4 u b HNO3 c oxi ho n NO2). V d: 2HNO3 + NO 3NO2 + H2O Cc kim loi c tnh kh trung bnh v yu (th d Fe, Pb, Cu, Ag,) kh HNO3 lo ng ch yu n NO. Cn cc kim loi c tnh kh mnh (th d Al, Zn, Mg,) kh HNO3 lo ng ch yu n N2O hoc N2 v kh HNO3 rt lo ng n NH3 ( dng mui NH4NO3). Trong cc phn ng, kim loi b oxi ha n mc oxi ho bn, cao nht. Qu trnh kh HNO3 thng din ra theo mt s hng song song, kt qu thu c mt hn hp sn phm kh khc nhau, tu thuc v o mnh, yu ca cht kh v nng axit. Hnh di y minh ho h m lng tng i ca cc sn phm khc nhau khi kh HNO3 bng Fe tu thuc v o nng ca axit.
Axit c ng lo ng th c ng c nhiu sn phm kh su hn trong hn hp, v d NH3 ( dng NH4NO3). HNO3 "bc khi" c iu ch trong phng th nghim theo phn ng NaNO3 + H2SO4 NaHSO4 + HNO3 Phn ng n y c tin h nh trong chn khng, HNO3 bay hi ngay v t b phn hu, khi thu c HNO3 100%. Cng c th khng s dng chn khng, nhng cn ly NaNO3 rn v H2SO4 c (~ 98%). Phn ng c tin h nh khi un nng nh, gip cho HNO3 bay hi v dch chuyn cn bng sang phi (HNO3 bay hi mnh hn nhiu so vi H2SO4). un nng mnh s l m phn hu HNO3 to th nh. Nu dng dung dch lo ng, sau c c th ch thu c hn hp ng ph 68%. 7. Mui nitrat Khi un nng mui nitrat cao hn nhit nng chy ca chng (c trng hp cha t n nhit nng chy) th chng b phn hu. Tnh cht phn hu ca mui nitrat ph thuc v o bn cht ca cation. Mui ca cc kim loi hot ng nht (ng trc Mg trong d y in ho) to th nh mui nitrit tng ng v gii phng oxi. Mui ca cc kim loi hot ng km hn (Mg - Cu) b phn hu to th nh oxit. Mui ca cc kim loi km hot ng hn na (ng sau Cu) b phn hu gii phng kim loi. Tnh cht khc nhau n y khi tin h nh phn ng l do bn khc nhau ca cc mui nitrit v oxit tng ng nhit b phn hu: trong cc iu kin i vi natri th nitrit bn, i vi Mg th nitrit km bn, nn cho thot ra kim loi. Trong mi trng trung tnh, ion NO3- khng c kh nng oxi ho Trong mi trng axit, ion NO3- c kh nng oxi ho nh HNO3 V d: 3Cu + 8H+ + 2NO33Cu2+ + 2 NO + 4H2O Trong mi trng kim mnh, d, ion NO3 b Al (hoc Zn) kh n NH3 V d: 8Al + 5OH- + 3NO3- + 2H2O 8AlO2- + 3NH3 8. Cn nm vng cc iu kin chuyn ho gia hai dng th hnh ca photpho.

Khi un nng trn 2500C, khng c khng kh, P chuyn th nh hi, khi l m lnh th hi ngng t th nh P trng. Cn khi un nng P trng n 2500C khng c khng kh hoc di tc dng ca nh sng th n chuyn chm th nh P l dng bn hn. Phn ng n y c th tng nhanh khi c mt t iot l m xc tc. C th biu din cc qu trnh chuyn ho nh sau: P trng P H = - 16,7 kJ/ mol Tt c cc dng thu hnh ca photpho khi nng chy u to th nh cng mt cht lng gn nhng phn t t din P4. Dng P4 cng tn ti trng thi hi. Nhng nhit cao hn 8000C v p sut thp, P4 b phn hu to th nh cc phn t P2. Di p sut kh quyn v nhit ~ 18000C, 50% P4 phn hy th nh 2P2, cn ~ 28000C th 50% P2 phn hu th nh 2P. trng thi rn, P c cu trc polime nh sau:

P P P P P

P P P P

P P P P

P P P

9. Photpho trng rt hot ng v mt ho hc, d d ng bc chy trong khng kh nhit thng, nu dng phn tn nh. iu n y c minh ho bng th nghim sau: Ho tan mt mu nh P trng trong dung mi cacbon isunfua (CS2). Tm dung dch thu c v o mt bng giy lc cn li nhng ht P trng rt nh. Chng b oxi ho bi oxi khng kh, pht nhit mnh, l m bc chy bng giy lc. 10. Cc axit photphoric Cu to phn t ca cc axit photphoric:
O H O P O

H H

O P O O P

O O

H H

axit diphotphoric axit metaphotphoric S oxi ho ca P trong cc axit n y u l +5.

H O H O P O H O axit octophotphoric (axit photphoric)

Axit H3PO4 l axit ba ln axit c mnh trung bnh (K1 = 7,6 x 10-3; K2= 6,2 x 10-8; K3 = 4,4 x 10-13). Axit H4P2O7 mnh hn H3PO4 v l axit bn ln axit ( K1 = 3 x 10-2; K2 = 4 x 10-3; K3 = 2 x 10-7; K4 = 5 x 10-10). Tuy nhin, ch mi bit c hai loi mui ca axit n y: mui ihiroiphotphat, th d Na2H2P2O7 v mui iphotphat trung tnh, th d Na4P2O7. Axit HPO3 mnh hn c hai axit trn. Trong s cc mui metaphotphat ch c mui ca kim loi kim v magie l d tan. Trong phng th nghim thng s dng axit H3PO4 v cc mui ca n (mui photphat). Khc vi axit nitric, cc axit photphoric u khng c kh nng oxi ho. iu l do photpho c m in nh, dn n i lc vi eletron nh. 11. Mui photphat Mt trong nhng tnh cht cn bit ca mui photphat l phn ng thu phn. Trong s cc mui photphat tan, mui photphat trung tnh ca kim loi kim b thu phn mnh trong dung dch cho mi trng kim mnh. Th d: Na3PO4 + H2O Na2HPO4 + NaOH 3 + H O HPO2-4 + OHPO 2
4

Do khi kt tinh t dung dch, Na3PO4 thng c ln NaOH.

Mui hirophotphat, th d Na2HPO4 b thu phn yu hn: Na2HPO4 + H2O NaH2PO4 + NaOH 2 + H O H2PO4- + OHHPO 2
4

Qu trnh thu phn n y xy ra mnh hn so vi qu trnh phn li axit ca ion HPO2-4 HPO 2 + H2O PO43- + H3O+
4

nn dung dch c mi trng axit yu.

Mui ihirophotphat, th d NaH2PO4 b thu phn yu hn na: NaH2PO4 + H2O H3PO4 + NaOH H2PO4- + H2O H3PO4 + OH Qu trnh thu phn n y xy ra km hn so vi qu trnh phn li axit ca ion H2PO4H2PO4- + H2O H3PO4 + H3O+ nn dung dch NaH2PO4 c mi trng axit yu.