GROUP15ELEMENTS

At
omi
candi
oni
cradi
i:
Cov
alentandi
oni
cradi
ii
ncr
easedownt
he
gr
oup.Ther
eisappr
eci
abl
eincr
easei
ncov
alentr
adi
ifr
om Nt
oP.
Ther
ei ssmal
li
ncr
easef
rom Ast
oBiduet
opr
esenceof
completel
y
f
il
leddorfor
bit
alsi
nheav
yel
ement
s.
I
oni
sat
ionener
gy:
Itgoesondecreasi
ngdownt hegroupduet oincreaseinatomi c
si
ze.Group15elementshav ehigherioni
sati
onener gythangr oup
14elementsduetosmallersizeofgroup15el ement s.Group15
el
ement shavehi
gheri
onizati
onener gythangroup16el ements
becausetheyhavest
ableelectr
onicconfigur
ationi.e.
,halffi
l
ledp-
orbi
tal
s.

Al
lot
ropy
:
Al
lel
ement
sofGr
oup15exceptni
tr
ogenshowal
l
otr
opy
.

Cat
enat
ion:
Nitr
ogenshowscatenationtosomeextentduetotri
plebondbut
phosphor
usshowscat enati
ontomaximum extent
.Thetendency
toshowcatenat
iondecreasesdownthegroup.13.
Oxi
dat
ionst
ates:
Thecommonoxi dationst atesar e+3, +5,
–3.Thet endencyt o
show–3oxi dat
ionst atedecr easesdownt hegroupduet o
decr easeinelectr
onegat i
vitywhichi sduetoincreaseinat omic
si
ze.Thest abil
i
tyof+5oxi dati
onst atedecreaseswher eas
stabili
tyof+3oxi dati
onst ateincreasesduet oinertpaireffect
.
Nitrogenshowsoxi dationst atesfrom –3t o+5.Nitrogenand
phosphor uswi t
hoxi dationst atesfrom +1t o+4under go
oxidationaswel lasr educt i
oni nacidicmedium.Thi sprocessi s
call
eddi sproporti
onat i
on

3HNO2→ HNO3+H2O+2NO

React
ivi
tyt
owar
dshy
drogen:

Allgroup15el ement sfrom tri

hydri
des,MH3.Hy bri
disation-sp3
Thest abil
it
yofhy dri
desdecr easedownt hegr oupduet o
decreaseinbonddi ssociati
onener gydownt hegroup.NH3>PH3
>AsH3>SbH3>Bi H3Boi l
ingpoint:
PH3<AsH3<NH3<SbH3<
BiH3Boi l
ingpointincreaseswi t
hincreaseinsizeduet oincr
ease
i
nv anderWaal sf orces.Boili
ngpointofNH3i smor ebecauseof
hydrogenbondi ng.Bondangl e:NH3( 107.8°)>PH3( 99.5°)>
AsH3( 91.8°)≈SbH3( 91.3°
)>Bi H3(90°)Electronegativi
tyofNis
hi
ghest .Theref
ore,thelonepai r
swi l
lbetowar dsnitr
ogenand
hencemor
erepul
si weenbondpai
onbet rs.

Ther
eforebondangleist
hehighest.Af
ternit
rogen,the
el
ect
ronegat
ivi
tydecr
easesdownt hegroup.Basici
tydecr
eases
asNH3>PH3>AsH3>SbH3<Bi H3.

Thisisbecausethelonepairofel
ectr
onsareconcentratedmore
onnitrogenandhencet hebasi
cit
ywil
lbemaximum i nthecaseof
NH3.I twil
ldecr
easedownt hegroupastheel
ectronegativ
ity
decreasesdownt hegroup.
Thereduci
ngpowerofhy
dri
desincreasesdownthegr
oupduet
o
decr
easeinbonddi
ssoci
ati
onenergydownt hegr
oup.

React
ivi
tyt
owar
dsoxy
gen:
Allgr
oup15el ement sfrom tr
ioxi
des(M2O3)andpent oxides
(M2O5) .Aci diccharacterofoxidesdecreasesandbasi ci
ty
i
ncreasesdownt hegroup.Thisisbecauset hesizeofnit
rogenis
verysmal l.I
thasast rongpositiv
efi
eldinav er
ysmallarea.
Theref
or e, i
tat t
ractstheelect
ronsofwat er’
sO- Hbondt oitsel
f
andreleaseH+i onseasily
.Aswemov edownt hegroup,the
atomicsi zei ncreases.
Hence,t
heaci
dicchar
act
erofoxi
desdecr
easesandbasi
cit
y
i
ncr
easesaswemov edownthegroup.
React
ivi
tyt
owar
dshal
ogen:

Gr
oup15el
ement
sfor
mtr
ihal
i
desandpent
ahal
i
des.
Tr
ihal
i
des–cov
alentcompoundsandbecomei
oni
cdownt
he
gr
oup.
sp3hy
bri
disat
ion,
pyr
ami
dalshape
Pent
ahal
i
des-sp3dhy
bri
disat
ion,
TBPshape.
Theyarel
ewi
saci
dsbecauseoft
hepr
esenceofv
acantd–
orbi
tal
s.
PCl
5+Cl
-→ [
PCl
6]-

PCl
5isi
oni
cinsol
i
dst
ateandexi
stas[
PCl
4]+[
PCl
6]-
InPCl5,ther
earethr
eeequat or
ialbondsandt woaxialbonds.
Theaxialbondsar
elongerthanequat or
ialbondsbecauseof
great
errepul
sionf
rom equatori
albonds.
Ni
tr
ogendoesnotf
orm pent
ahal
i
desduet
oabsenceofd-or
bit
als.

React
ivi
tyt
owar
dsmet
als:
Allel
ement
sreactwi
thmet
alst
ofor
m bi
nar
ycompoundsi
n–3
oxi
dati
onst
ate.

Anomal
ousbehavi
ourofni
tr
ogen:
Thebehav
iourofni
tr
ogendi
ff
ersf
rom r
estoft
heel
ement
s.

Reason:
i
.Ithasasmal
lsi
ze.

i
i
.Itdoesnothav
ed–or
bit
als

i
i
i.I
thashi
ghel
ect
ronegat
ivi
ty

i
v.I
thashi
ghi
oni
zat
ionent
hal
py

Di
nit
rogen:

Pr
epar
ati
on:
NH4Cl
(aq)
+NaNO2(
aq)⎯⎯⎯⎯→N2(
g)2H2O(
l)+NaCl
(aq)
(
NH4)
2Cr
2O7⎯⎯⎯⎯→N2+4H2O+Cr
2O3
Ba(
N3)
2⎯⎯⎯⎯→ Ba+3N2
Pr
oper
ti
es:
I
tisacol
oul
ess,
odour
less,
tast
elessandnon–t
oxi
cgas.
I
tischemi
cal
l
yun-
react
iveator
dinar
ytemper
atur
eduet
otr
ipl
e
bondi
n(N≡N)whi
chhashi
ghbonddi
ssoci
ati
onener
gy.

Ammoni
a:
Ammoni amolecul
eist
ri
gonalpy
rami
dalwi
thni
tr
ogenatom at
theapex.I
thas3bondpair
sand1lonepai
r.Ni
ssp3hybri
dised.
Pr
epar
ati
on:
Haber
’spr
ocess:
N2(
g)3H2(
g)⎯⎯⎯⎯→ 2NH3(
g)
Pr
essur
e=200x10^
5Pa
Temper
atur
e=773K
Cat
aly
sti
sFeOwi
thsmal
lamount
sofK2OandAl2O3.

Ni
tr
icAci
d:
a.Ost
wal
dPr
ocess:
Pt/
Rhgauge4NH5O32500K,
9bar4NO6HO.
..
..
.(
i)2+
⎯⎯⎯⎯⎯⎯⎯→ +
2NOO2NO.
..
..
.(
ii
)22+YZZZZZZZXZ
3NO(
g)HO(
l)2HNO(
aq)NO(
g).
..
..
.(
ii
i)223+→ +

NOt husformedi
srecycl
edandtheaqueousHNO3canbe
concentr
atedbydi
sti
ll
ati
onupt
o~68%bymass.Fur t
her
concentr
ati
onto98%canbeachievedbydehydr
ati
onwit
h
concentr
atedH2SO4.
Ni
tr
icaci
disstrongoxi
dizi
ngagenti
ntheconcent
rat
edaswel
las
i
nthedil
utest
ate.

Phosphor
us:
a.I
tshowsthepr
oper
tyofcat
enat
iont
omaxi
mum ext
entduet
o
moststabl
eP–Pbond.
b.I
thasmanyal
l
otr
opes,
thei
mpor
tantonesar
e:
i
.Whi
tephosphor
us
i
i
.Redphosphor
us
i
i
i.Bl
ackphosphor
us
Pr
epar
ati
on:

Phosphi
ne:
Pr
epar
ati
on:

Phosphi
neishi
ghl
ypoi
sonous,
col
our
lessgasandhasasmel
lof
rot
tenfi
sh.
Chl
ori
desofPhosphor
ous: