Nitrogen family

N’ non-metat ’ focnd as NaNo, (chile saltpetre), KNO, nlon saltpe tr

non-0etal ’ ’ found
found w
as
P
apatite family, Co, (PO,): Cox, (x:f,u mroH)
As
metolloid Ca, (PO,): Caf, fuorapatite
Sb
- found as Salphite minoal .
Bi ’ 0etal
Me Syntbelie Racioactive
CMoscovium)
L lectronie canfiguwratiorn; NG] ns' np
N’ [H] 2s 2p Extra stable due to bal!
P’ [N] 36 3p flled P orbitals.
As [Aj s 4s 4p
Sb’ kr] 4d 5s 5p
Bi’ xe] 4st 5d s Ge'
Me’ Rn] 5f
Atomc & oie Radi,
,N<P<As< Sb<Bi
due to poor shielding of dff obitl
Cons'derable Tos srall tes
Small size &eetaa steble a
Lo Sorisation Enthapyi G14<KK
R4 G15 G15 (Small
(
N P > As > Sb> B [1-6< I¬,<1¬]
Electrosqatid ty'N>P As> SL y Bi
Density' NP<As<sb<Bi
PHYSI CAL PROPERTI ES,
" Ale eobers are
polyatomie Soid buf nitY
Metallic chatacter increRsa doon the roup
fro Top to botto
" B.P’ increases Arsenic 4 then cupto
Biornuth
M.P+ increases upto
N< P< As)sb) Bi
allShow llo topY:
Alotropy Exca pt NitogencHEMICAL PRO PERTI
+5
Common Oxidaton stata
+ Aue to inet pau fet
du to inevtpai tability of t5 oxit
beoz tN es
tendeny to shas efect stability of +3 state decreoses
-3 Cxidstiti e
doon the gsp
oxid s{ate Jncreases
dewn thc qrep ernthegup
ondy Bif s fomed
Bi+dont shas3 oxid' st
 N’ -3, +1, +2, +3. +4 +5) AU Oxidation stati frosn 1tH4
tend t dispo poa tiona n Qods
Nhen reuct sith
ith oxygen HNOa + NO t H,o
P ’
-3,+1) +3 + 4 +5 )AL interpediiti ozid" slatt disp1op
Jnto +5 and 3 both in aeid/bas
n oxoacics

@ Covalancy H,Po’ HPO +PHa

N o vacant dorbrtal -> only S and P orbital’ ma" Co valey
1 but other menber bave
Vacant d-osbital
So,erpand thein cavaleny en Pf
N’ 5mall Size
ANOMALOUS PRoPERTY Of NITROG EN,
High EN
’High Jori zetion potenti So, Nitgen behave dilfeanty
No vacant d- from other neber
obita
N ’ foms ’ P-Pr multiple bond wth itself os otber ele men
NEN ,CEN Cso of almost samne size:
but other members
term Pr-d or d-d multiple bornd.
: R&P=o
N As Sb
forms tie+ N=N P-p
bord As-As Sb-sb metallic bonl
N-N <P-P
Weak epuion,Bo Bond strength)
Ctenation is
eaker tn rttroen'
CHEMICAL REACTION
Reacivity ith Hydrpen (EAy).
Stability i-
NH, > PH, > As H, > sbH, > BiH
Recucing ae NH, < pH, <AsHa < SbH, < Bi,
Mid RA
stog RA
Basi aty NH, > PH, > AsHy> sbH, > BiH3
MP NH, > SbH, > AsH3 > PH,
Bpi- BiH, > SbH, >NH, > As4, >PH
Bond Lengthi- NH, < PH,< Asy < sbHs
Bord Angee i- NH PH,> AsH, > ShH
 Reaction wrth ogen E,o, 4 Go) ’ acide mluc
3
|C,o,>,9|
Acidic
N,0, Acikic
characeer
decrease
douon the
As,}Anpbotene
Sb,O,
Br,o, Basie
(3 Reacton sith Haleseg (EX, e 4EX-) [NX not forned beoz nox |
(2) Exs is mere Co valent than EX,
(faan's Rute) Covalency of Nitrgen i 4J
(u) Aee other trihalide (3)
are
Nitten trihalide ue on stable (only Nf, islotil
4 other all +covaent).
Reaction with
Srth metal - voat i h metal and shoo -3 odaton stl
Ca,N, Casf No,As,. Zn,sb,
Caleium Calcium Sodiun Zinc
Maqnetium
Nitrnide Arsenide Antimonide
Bimuttide
Phosghide
6 Tbocgh gritrgen eshibite
exhibits +5 ozidation stata, t does not fem
pentahalideGive rea) bn.
Sol' Ntreen wth n2. b S and p orbitau only tt does not
hare d erbitab to epands to Covalonce beyond foer.That
noy it does not tomn pentahalie.
PH, ha looer beilig point than NHy ohy ?
se' Unuke NHy, PH, molecule are not asociateol theugh hydbgen
in auic stte. That wsthy boili point of PHs
bondigJoer than NH,:
all the
BiH, the stronget reducig gt omor
bydide of Group 15 elernents?
incteaaes
So As we NOVE deon the grp, be atoic SIze
ntsde cas
and the stability of the bydide of Grop 15 eleve
Since the stability of byida decheayes from NH, to BiH,,
B0, relu cng character of the byide incr eases o
fron NH, to BiHa
CoMeO NOS Of NITROGEN>|DINITROGEN
OPPr Connercal -i,uifaction f fractional ditllati on ef ai.
go K
Bp 77:2K
ditite eut first ¢ ia O, obtained
 laboratory preparation;- (3Ht E a)
Nitrite dichromti àzide vey pe
(Na, Bo) Nitregen
NH,a +NaNO, (NH,) NO,
ammonium nitrite
(NO ¢HNO, s aho formed here 4
hemoveo
by pasin gos through ay Hso
(NH4), Cr,0, N, +o, + 4H,0
(gecnboid)
Na Nz Na + N, ‘
ple Very
Ba(N), Ba + N, ‘
N propentiu;- Colouaes, odeuln, tasteln, non-toxe gaa
’ two stable s otopoes
Usually çnet non-reactive) at oom temp becoz bf
-’
high
Bat
bond enety o-f NN
nehen T t rea ctivity T
N, + rmetal nic
Lonec nitride

N t non-netal Cov tide

omenia (Habers procen)
Na t Hydig
773K AH = - 46"1 k/mol
Ngt 3 H
cetalyst 2NH g)
N t nitricoide (No)
N t O, 2000k
atRce3J
2NO(a)
Uses &- ma Nufacture at NH, aum yana mide CoCN,) refigant
Q Wgte the action ef ther oal decon position ofsodi orn azido o
So Thermal decormposition of sdium azide gires intgen
2 NaNg A 2Na +3y
eactine
ternperakwe?
" Dte to sroa 0 si2e f trgen t ) bosd lungh veyshot (103pm)
Dus to high bond ethelpy of NN bond.
s HeOerer rapidly nith sse i terp
AMMONJA (NH;)
PPr. decay of itrggenecus orqanic rmatter Urea
NH, coNH, + H, 0 H,Cog
On Small scale:
NHct t a(0H
(NH4),s0, + NaOH ’ NH;OH + Na,so4
On Laye Scall3- Amnonia us nanufactuied by Haber's
2o0atm pros
N2(9t3H> (9) 2 NH33) AH -4 6-1 kJ/mol
 5
Catalust ’ Iron oxde t k,0 ond A,0, ’ratt of e ‘e
Garlier Catayt Iron + Mo (PKomoter)
A/e to Lechatelier pinciple, High presune fave uy nH, fornation
prepentie: Pt eqm forwand
" Colounlen , pungent smdl (odoun)
Soid/iqud st ate + it shou0 Hydipgen Bond. so High MP 48P
-’ Trigonad Pyra midal
Wighy soluble in nater, ts aquos Solection wakly babic
NHatH0cy NH (e) + OHas)
NH4OH (soak bse)
Remction nith acid ;.
NH, +HC’ NH cQ
NHg t HaSo4 (NHa), S04
Reacti on ef NH,OH aith metal salt, t form preiprtati °f
(weak ba) hy daoide
Znso, t NH,OH ’ Zn (o), + NH), so4
metal salt white ppt
fe (oH), + NH,a
fe,og H,o
netal ion ompex
. NH, luis bcwe d onoite oneBem ppt empoun
+2
+ NH, culNHS)J
be oepbe
Aja tNH LAr (NnJ
white pt Colawlem
Notei- iq. NH iss Used as efi Arent e Jed to prep cune testuzd
3 why does NH, aot a lenis base ?
So: Nitrogen atorn NH bas one ome pa of elecrons nehied
availabe for don ation. Therefooe,t act as a leuis base.
Mention the cosnditions negiedl to mai mue the yield fomoa
E tempercitune (700K)
Hugh preow iron oicde tth mll anounto of
Proence of catalystSuh o
Qpmomig heacf th a soution ef ct
Sue to Pesenc CQ of Lone pu ofe Dn the nitregen alon
ef the DNolecule gt fos s a linkoge stth mal
ion to fos m Cornplex cosnpond tetraammine Copper(*
21
Cu?t t 4 NHg [Cu(WH),I: (e)
Cblu) (deep blue)
 Oxide of Nitroge
it torms all oxide from +1 to +5
+1 N,o dinitrogen
Cen
NH¡NO,N, +H,0 Coloues (Netial)
Gas
Nitres ozide
NH, NO. N,o + H,0 NEN>0 N=N=0
N= Lineon
+2 NO Di ttrogen Monoxide ON, +o, 20cs 2NO
Colonles Neuthe?;
Nitic oicle
2 NaN0, + fesa, H,So
te, (so),-+ Na HSO H,0 tNO odd eltron
+3
Drnitrogen
triode Blue solid (adic)
:N-N
JPlanas
+4 NO, Nitrogendigide Pb(NOJ 673K
NO, +PLo +0, Bng (Audic

+4 N,o4 initen tetode 2NO,N.Q, rAnguln (acdic

Heat

N-N
(Reomance) .
P anar
+5 N,05 dinitrogen pentaoide 2HNO +9o -H,0
N,0tHPo, Coloul Solid (acidic)
dehylratg
gent
O.

Complete Reso
Qe N-o bods
he equvalent,
wby does NO, dinerise 2 [planan
Sa NO, Cotains odd unber ßf valence electrons gt babave typias
seld molecule. On dimeruatio, t is Converted to stable N,Og molecate
ith even number f elecrons .
what the co valence of nitogen dn Ns?
Sol! N tregen shares ton pa of electss nith oygn, bence
utregen COvale noy
N

Nitogen forms oxo acids NITRIC AcID +1

HO- NN-oH
H2 N,0, ’(hyponutrous acid)
( sitres acid) +3

HNOS (nitric acid) Ho

 Oppr indiansttpetre
KNO,
Laboratory Ppr kHsoa +HNO,
This wà prepand
NaNO, NaHsO4 t HNO glas neta,t
Lage Scal. behilk saltpetie
(Qstuald proce) (Catalytie Oication of NH, by ad moophevis Dxyg)
NH5O> () Pt/Rhgay
5ook, obon
ba
+ H,0
from ci
+4 frone NO, (o) t2
NO + +,0
HNO, + NO (dispaopoti onation R:")
This NO ecycled
2 Propeties
H
qas state N
plano (Reo)

HNO3(as) t H,0(u) strorgacid

Hso tNOO
one HN, Strongoaidizing a nt (reactithall rmetal)
Ccept noble rnct
Cone HNO, ary metal NO, tH,0 + netal ritrata
Au, Pt)

Dil HN, +(P, cu Ad)

fe, Zn
Sn NH4NO t metal itrate
Vey dil HNO, +( fe, Zn ,sn/
H, + metal nitrate

Cut HNO, (dil) Cu(NO), + NO + H,0

ut HNO,(Con)’ Cu(NO), + NO, tH20
ZotHNO, (di) Zn(No,), + H,o + No
Zn t HNOz(Con) Zn(No,), + 4,0+N
/At HNO, (on) No ox ( oxide layer formaton os metal
Swface ).
non netal,
HNOg
9

H, tco)
CHao
Se Hso t O, + H,
Ha PO4 + No, t Ho
 BROWN RINGTEST
Test for ntrates (NO,)
NO react itth f e t t t 3
react th fet to fosm Broon Co lou
dilte feneu Sulphto is added to aqesu soction Comple'
Conta
nitrat ion and aseflly adding conc Hso, alos
walb of tot tae
" Broon ing torms at interfaco b/s so"
t2
4Bulphuio aid oyer.
No t fesoy t Ht. NO + fe+3 +
-+ 1

[fe CH,9)]No [ielno)N6]"

Preun Rig omgle
PHOSPHOROUS
3Alotope,
white -black
Red
elack <g-black
whto
Heatirg of she Phosphorosforat
573 K
K n inert atmosphere
P

-P- P P-P
Tetrahedral P
stran)
les stable (one Poyrer ef P
Mere reative reactive thao nehite
toAve les
80, Ctches fire un a Oo Lroo ay usture
dense whita fnes of sdeles, non-poanes
P, + 50, Po, insobu in H0 4 Cs
trasucent wohicte woy Solid
PosoNDUs,tnsolbe in H,0
but Bouble in s,.
Gl e s in cark
PatsNaoH4aH,0 PH, +3NaHPO}

K- Block B-Black
Ppa Red phosphoroun is beated per'- shua phosphoMus
n a sealed tube ct s0K. beated t 43K
does not oidize in a vnder high pes se.
" doest busn on au
Black phocphores has layered sttr.
(Gke graphite).
 (9
PHOSPHINEJ(PH3
Calciun phosphide + H,0 o dil HCA + phosphine
CyP. + H,o /dit Ha Ca(oH),
Cacl, 9

laterctery: whio P tConc Na bH PH, NaH, Po, (gortez?)

PHy t NoHPo, (disprop)
Pure forg t s no-inflannble
Becornes ènfaoable in pr caence of H or P apo
Punificatinof PHa;
PH, + absorbed in HI PH,I (phosphorium iode
PH,I + KoH ’ PHa tH,o+K
ropertie;:
Colore rotlenfsh snell highly paioaus
Ex ploles ohe) Corses in ContaA with Ojci t
Soution
Lighti (ond p+H,).
. On treatig with Copper salphati
phophioe us obtned.
Cuso, +PH
+Pa
PH, weakk basic sike NHg 4 fom phosphoniur
Coonpeund. neitt aiol.
PHt HBr PHBr.
|Phosphorow Halides

Pxy (x=f,d, Br, I)

Pr-0) white Pt+ chlorin-’ PF':) whit Pt exces chlorne.Bry
whit la t thionyI chsoride (exc ew)

t, tsoc, Pcet s0,

Propete'- yramidal shape ,se propenties:
Coloress aly lig CAj
" Tio aial bono are lony
Hydrolysi) than B-equitrial bo
SLd state:- PC
Plgt H,0- HsPO,+HCA sp
Tetrabedal aabd
al
 " yelowish whit powdr!
-Remction wth oygaic Comp |Hycrolysá
(Srtezt)
HC
HgPo,t
. Roaction with orgoçc Corp
CHCoc+POce,-+Hu
CH,CpOH + Pe,
Reaction wrth metal:

6why doa PU, fune inmaistere ?

Sol"':- Py hydroyse dn the prese NKe» af aistre
Ha
8 Are all the fre boea in Pa, olecule eivalostt ?
So-
:- Pa, has a tnyol bipyramidal structure and the
three equatorial p-ca bowds ae equvalest, tile the
tuoo aial bnos ae cfferent ond orgor thnn
equatohal boods
Oroacid of hosphoreu
Oaidation Çhemical Narme structure Reaction
State formulg whd ptalkali
H, Po, Hpopbosphorus H H,Po
(phasphintc)
+3
H
(rhsphonie)
+3
trophophoraoH
acio H

+4
Hyporhuptorie Horp Red P+ alkali
oH
+5 HsPO,
vattophapteie
+5 H4P,0, fyrohouphasie
+S (HPe), meta phaghasie
(HPO,), ycic mio phosbhauc oly mtaphophnic ( HPO),
 (11)
Cyclotimeta phophaic ac: Polyrnetaçhupheie acd

HO

Note: Oxoaicd in t3 oxidation stat dipop. to hgher 4

l o r Os.

Oroacid Cortainiy pH bond nduàg oget

NtM,0+ HPO,A tHgtHfOy
&) Ho do yeu aceont for the neducing bhaviog of
Hyro,
on the bas of ito structure ? H
dçetty to P cto)
n HPo, tyo0 H atoons are boed acid
charocfer to the
thich impts neducing
8" what a the basicy ef gfo,?
an heploce io acd.
Noof H atoy that a base

gPoy bornd 4 1Po

3P-0H
is3.
B0, H4 PO, is tibawie aid ¢ basiciby
what happeyy ben HyP o beted
Sol 4 H,ro,
(ortophaphau)
acid
(aitoghasghas
acid
(troghin)

ay n
Ca) it
t be
be poved thet PHa obasie in natyn =
A go ohat
PH, aeadts stth a cics ike HI t f n pHI hich gh
Sol'
that t is baoic dn natuee.
PH, + HI ’ PH, I
>Due to one paithe phosphasw alor) PHy s
a ws base dn above eacti o).
Q?) ohat s fosmed shen PHa eact with an add

- when phosphine heacdith an aod sat u fosmed.

PH, + Hx
(where Xz Ca, Br,r)