PART 6: THE GROUP , IS t:LCIYICl"l 1-' - .-..

~---- ---- - - -
. , and 'the rare gases~ Both are misnomers, sin
The elements of Group 18 have been called 'the merthgatses on 1·s not m· ert and argon makes up 0.9% b
'd · 1962 shows t a xen · '
the discovery of the xenon fluon es m , . r that they tend to be unreactive, in the same wa
volume of the atmosphere. The name 'noble gases unp ies ast reactive metals.
that the noble metals are often reluctant to react and are the le

Table 10.40 Electronic structures

Electronic structure
Element Symbol
Helium He ls2
Neon Ne [He] 2s22p6
Argon Ar [Ne] 3s2 3p6

Krypton Kr [Ar) 3d10 4s2 4p6

Xenon Xe [Kr) 4d 10 ss2 sp6

Radon Rn [Xe] 4f14 5d10 6s2 6p6

Helium has two electrons which form a complete shell ls2. The other noble gases have a close~ octet of
electrons in their outer shell ns2 np 6 (Table 10.40). This electronic configuration i~ very stable_ and 15 related
to their chemical inactivity. These atoms have an electron affinity of zero ( or slightly _n~gat1ve ), and have
very high ionization energies - higher than any other elements. Under normal cond1t10ns the noble gas
atoms have little tendency to gain or lose electrons. Thus they have little tendency to form bonds, and so
they exist as single atoms.

10.67 I OCCURRENCE AND RECOVERY OF THE ELEMENTS

The gases He, Ne,Ar, Kr and Xe all occur in the atmosphere. A mixture of the noble gases was first obtained
by Cavendish in 1784. Cavendish removed N 2 from air by adding excess 0 2 and sparking. The NO 2 formed
was absorbed in NaOH solution. The excess 0 2 was removed by burning with S, and absorbing the S02 in
NaOH solution. This gave a small volume of unreactive gas.
Ar is quite abundant and can be recovered by fractional distillation of liquid air It constitutes 0.93% by
volume of air (i.e. 9300 ppm). It originates in the air mostly from electron capture (/3 + decay) of potassium:
40K
19
o 40 Ar
+ -l e ~ 18

. The other noble gases are much less abundant. The non-radioactive noble gases are all produced indus-
trially by fractional distillation of liquid air. This gives large amounts of dinitrogen and dioxygen, and only
~ small_ am~unt of the noble gases. (The dioxygen is mainly used for steel making.) Of the noble gases.Ar
1s obtamed m the largest amounts, and it is the cheapest.

10.68 I USES OF THE ELEMENTS

The lar~est use of Ar is to provide an inert atmosphere for metallurgical processes.
Helium has th~ lowest boiling point of any liquid, and it is used in cryoscopy to obtain the very low
~mia:ratures requir~d for s~perconductivity, and lasers. It is used in weather balloons and airships. Though
2
f a lower den_sity an~ 1s cheaper and more readily available than He, H , is highly flammable. Thus on
sa ety grounds He 1s used m p f H · · • . -
H . re erence to 2 m airships. He 1s much less dense than air. One cubic metre of
. ethgas at at~osphenc pressure can lift 1 kg. Helium is used in preference to dinitrogen to dilute dioxygen
m e gas cylinders used by dive 1n· · b d" • . .
. rs. is 1s ecause m1trogen 1s quite soluble in blood so a sudden change
m pressure causes degass· d · b bbl . •
tion called 'b d , H r m~ an gi~es u es of N2 m the blood. This causes the painful ( or fatal) condi-
S en s. e mm is only slightly soluble so the risk of ' bends' is reduced
ma11 amounts of Ne are used in neo d" h b . . ·
'neon' signs. Th O th n isc arge tu es which give the familiar reddish orange glow of
e er gases are also used in discharge tubes to give different colours.
- - - - - - ~- ~ ~ - - ~ - - - - ~
.69
~ - - -,=-o:=-.-7--:-, I Ch em kal Pro per tie s of
the No ble Ga ses ~
10 \ PHYSICAL PROPERTIES
elements are all colourless, od
ourless mo
1ne forces holding the ato ms together. The valnua tomic .
the very weak van de r Waal gases. The enthalpy of vaporiz
are s forces. The enthalpeys arfe ve ation is a measure of
•
•\'t)' of the atoms inc ry _low because the only forces
abI I reases. 0 vaponzation · between the atoms
Because the mt. . mcreases down the group as
eratom forces are very we the polariz-
'}1le boiling point of He is 1c ak
the lowest of any elem;ntthe . .
The atomic radii of the eleme :el ;m g pomts and boiling po
1°
nts are all ve ints are also very low.
be noted that these are_ non-b Y our _degrees above absolute
zero.
\eroents rather tha n with cova
onded radii, and s~ u: \:
~~! mcreas~ on descending the gro
e lent (bonded) radii (S ~ up. It must
• ee iable pa red with the van der Waals rad
10.41.) ii of other
Table 10.41 Physical pr op ert
ies of the noble gases
First En tha lpy of
ionization Melting Boiling
vap ori zat ion Atomic
ene rgy po int Ab un dan ce in
(kJ mo1- 1 ) po int radii
(kJ mol-1) (OC) (OC) atm osp her e
(A) (% volume)
He 2372 0.08
Ne 2080 - 269.0 1.20
1.7 5.2 X 10-4
- 248.6 - 246.0
Ar 1521 1.60 1.5 X lo-3
6.5 -189.4
Kr 1351 -186.0 1.91
9.1 0.93
-1512 - 153.6
Xe 1170 2.00 1. lx l~
12.7 - 111.8
Rn 1037 - 108.1 2.20
18.1 8.7 xl ~
- 71 -62
The noble _gases are all able
~o diffuse through glass, rubbe
makes them difficult to hand r and plastic materials, and som
le m the laboratory, particula e metals. Th is
low temperature work. rly since glass Dewar flasks
cannot be used for

10.70 \ SPECIAL PROPERT

IES OF HELIUM
Helium is unique. It has the
lowest boiling point of any
solids on cooling, bu t cooling substance known. All other
only produces helium liquid elements become
25 atmospheres). There are . It only forms a solid under hig
two different liquid phases. h pressure (about
Superfluid. A superfiuid is a Helium I is a norm al liquid
most unusual state of matte , but helium II is a
move in a more restricted wa r. Normally atoms are free to
y in a liquid, and can only move in a gas. can
temperature decreases, the am vibrate about fixed positions
ount of thermal motion of ato in a solid. As the
eventually solids. When the tem ms decreases, and gases beco
perature of helium gas is low me liquids.. and
SUrprisingly the liquid continu ered to 4.2 K it liquifies as he
es to boil vigorously. At 2.2 lium I. Rather
normal materials is when a sol K, the liquid suddenly stops
id is formed). In this case he boiling (which \\it h
the interatornic forces are no lium II is forme d. This is still
t strong enough to form a sol a liquid because
st0P~ed. Helium I is a normal liq id, but t~ermal motion of ~he
uid , and wh en it changes to ato ms has actually
?hys1ca\ properties change ab hehum II at the ,l-pomt tem
ruptly. Toe specific heat cha perature. ~a~y
increases by 106 and become nges by a factor of 10. The the
s rm al
zero electn·cal • t ) Th 800 times greater than for copper. It becomes a supercondu co~ductl\'ll)
•
res1s ance . e v1scos1 ·ty beco mes effectively zero and 111 ctor (1.e. sho,,s
lt spreads to rf t t . 00th of that of gaseous h,dro~
. ratures below the 1-pomt.Th . . en .
sides of the cover a11d su acehs a dempetil .
us the l,q md can actuall\' flo·w up~ the
c vesse1an over t e e ge un the levels on bo th sides are the same. Th
ompressibility are also anom e surface tension and
alous.

10.71 \ CHEMICAL PROPE

RTIES OF TH E NOBLE GASES
lbe n bl
tho uJ t e gases were isolated . d because of their lack of rea
and_ disco_ver~ Before 2, cthi t). For a long time it wa
s
then b that they really were ch 196 the only evidence for compound forma
0 le gases
en uc ~Y me · ed in discharge tubes, and tion by
was some molecular ions for clathrote compounds.
m
- Chapter 10 I The p-Block Elements and their Compounds

Molecular ions formed under excited conditions

Several mo1ecu1ar ions. sue h as He+ 2,
HeH+, HeH2+ and Ar; are formed under high energy conditions in
.
. h arge tub es. Th ey o nl y survi·ve momentarily and are detected spectroscopically. Neutral molecules such
d isc
as He 2 are unstable.

Clathrate compounds
Cla thr a t e comPounds of the noble gases are well known. Normal
ul
chemical compounds have ionic or
f th · ·
1
covalent bonds. However, in the clathrates atoms or mo ec es o e appropnate s12e are trapped in
cavities in the crystal lattice of other compo_unds. Though the gc:ses are tr~pped, they do not fo rm bonds.
If an aqueous solution of quinol (1 ,4-dihydroxybe~zene) _is crystallized un~er a pr~ssure of 10-40
atmospheres of Ar, Kr or Xe, the gas becomes trapped m cavities of about 4 A diamet~r m the ,8-quinol
structure. When the clathrate is dissolved, the hydrogen bonded arrangement of ,8-qumol breaks down
and the noble gas escapes. Other small molecules such as 0 2 , SO 2 , HiS, MeCN and CH3 OH form clatb-
rates as well as Ar, Kr and Xe. The smaller noble gases He and Ne do not form clathrate compounds
because the gas atoms are small enough to escape from the cavities. The composition of these clathrate
compounds corresponds to 3 quinol: 1 trapped molecule, though normally all the cavities are not filled.
The gases Ar, Kr and Xe may be trapped in cavities in a similar way when water is frozen under a high
pressure of the gas. These are clathrate compounds, but are more commonly called 'the noble gas hydrates'.
They have formulae approximating to 6H2O:1 gas atom. He and Ne are not trapped because they are
too small. The heavier noble gases can also be trapped in cavities in synthetic zeolites, and samples have
been obtained containing up to 20% of Ar by weight. Clathrates provide a convenient means of storing
radioactive isotopes of Kr and Xe produced in nuclear reactors.

10.72 I CHEMISTRY OF XENON

The first real compound of the noble gases was made in 1962. Bartlett and Lohman had previously used the
highly oxidizing compound platinum hexafluoride to oxidize dioxygen.
PtF 6 + 0 2 ➔ o; [PtF r
0

The first ionization energy for 0 2 ➔ 0 ~ is 1165 kJ mo1-1, which is almost the same as the value of 1170 kJ
moi- for Xe ➔ Xe+. It was predicted that xenon should react with PtF6 • E xperiments showed that when
1

deep red PtF6 vapour was mixed with an equal volume of Xe, the gases combined immediately at room
temperature t~ produce a yellow solid. They (incorrectly) thought the product obtained was xenon
hexafluo~oplatmate(V), Xe+ [PtF6r, The reaction has since been shown to be more complicated. and the
product 1s really [XeF]+ (Pt 2F.11 ]- •

Xe[PtF6 ] + PtF6
25 0
r
c (XeFr(PtF6 + PtF5 heat 60~[XeFr[Pt:! F11 r
h Soon after thi sit · was f ound that Xe and F reacted at 400 °C to give a colourless volatile solid Xef4. This·
2
th
r.
t:s e. same ~umber of valency electrons as, and is isostructural with, the polyhalide ion [IC1 4 Following
ese dis~ov~ne~ there was a rapid extension of the chemistry of the noble gases, and in particular of xenon.
f Th~ 10mzatton energies of He, Ne and Ar are much higher than for Xe and are too high to allow the
~ormation of similar compounds. The ionization energy for Kr is a little Io~er than for Xe and Kr does
1orm KrF2 Th 10 · · · . '
"mil • e mzatton energy of Rn 1s less than for Xe, and Rn might be expected to form compounds
s1 ar
Thi h . . to those of X e. Rn · ct· ·
is ra 1oact1ve, has no stable isotopes, and all the isotopes have short half 1·1ves.
\ as limite~ work on radon compounds, and only RnF2 and a few complexes are known.
. e re~cts duectly only with F 2• However, oxygen compounds can be obtained from the fluorides. There
1s
Thsome evidence . . fo r the existence
· o f xeC12 and XeC14, and one compound is known with a Xe-N bon d·
th
us ere is qmte an extensive chemistry of Xe. The principal compounds are listed in Table 10.42.
 10.72 I Chemistry of Xenon 545 .
Structures of some xenon compounds
ble 10. 42
~
r,nu a I Name 'fi . Oxidation state
fo Xenon d1 uonde (+II) M.p. (°C) Structure
,eF,
129 Linear
(RnF2 and XeCl2
Xenon tetrafluoride are similar)
xef, (+IV)
117 Square planar
Xenon hexafluoride (XeC14 is similar)
;xef, (+VI)
Xenon trioxide 49.6
\ e0 i Distorted octahedron
(+VI)
Explodes Pyramidal (tetrahedral
with one comer
XeO:f2 unoccupied)
(+VI) 30.8 Trigonal bipyramid
(with one position
XeOF, unoccupied)
(+VI) -46 Square pyramidal
( octahedral with one
XeO, Xenon tetroxide position unoccupied)
(+VIII) -35.9
XeOl2 Tetrahedral
(+VIII) -54.1
Ba1[XeOJ4- Barium perxenate Trigonal bipyramid
(+VIII) dee.> 300 Octahedral

Xenon reacts directly with fluorine when the gases are heated at 400 ·c in a sealed nickel vessel, and
the products depend on the FJXe ratio.

_,,,,.,:,, 2: 1 Mi.xture ➔ XeF2

Xe+F2 ~ 1: 5 Mixture ➔ XeF
~ 1: 20 ➔
4
Mixture XeF.;
The compounds XeF2 , XeF4 and XeF6 are all white solids. They can be sublimed at room temperature, and
can be stored indefinitely in nickel or Monel containers. The lower fluorides form higher fluorides when
heated with F2 under pressure. The fluorides are all extremely strong oxidizing and fl.uorinating agents.
They react quantitatively with hydrogen follows:

XeF2 +H2 ➔ 2HF+Xe

XeF4 + 2H 2 ➔ 4HF + Xe
XeF6 + 3H2 ➔ 6HF + Xe
Tuey oxidize c1- to Cl2• i- to I 2 and cerium(III) to cerium(IV):

XeF2 + 2HC1 ➔ 2HF +Xe+ Cl:i

XeF4 + 4KI ➔ 4KF +Xe+ 212
So;-+ XeF2 + Ce:11 (SO4)3 ➔ 2Ce1v(SO4)2 +Xe+ Fi
Tuey fluorinate compounds:

XeF4 + 2SF4 ➔ Xe+ 2SFo

XeF4 +Pt ➔ Xe+ PtF4
2
XeF is . . •d 1 used in synthetic organic chemistry. It can oxidize and
tlu • now commercially available and is qwte wi . e Y
onnate the 'hetero element' in an organometallic compound ' but does not attack the alkyl or aryl groups.
CH ~l + XeF2 ➔ CH,IF2 + Xe
C6H.sl + XeF.~ ➔ C6HsIF2 + Xe
(C6H s)2S + XeF2 ➔ (C6Hs)2SF2+ Xe
 d their Compounds
I The p-Block Elements an
546 ChaPter 10 "bl
. f •ty is greatly increased, poss1 y due to the fonn r
. . anh drous HF its reac iv1 a Ion Of)(e •
If XeF2 is nuxed with y Pt+ 3XeF/HF ➔ PtFo + 3Xe J; .

Ss + 24XeF/HF ➔ 8SF6 + 24~e

. . ·t with water. XeF2 is soluble m water, but undergoes slow h
.d differ in therr reactlVI y Ydroty .
Toe fluon es .d with alkali. SIS,
Hydrolysis is more rapt 2XeF2 + 2H20 ➔ 2Xe + 4HF + 02 ,
. I "th water, giving xenon trioxide Xe03.
XeF reacts v10Ient y WI i
4 3XeF4 + 6H20 ➔ 2Xe + Xe03 + 12HF + 1202

. •th water but slow hydrolysis by atmospheric moisture gives the highl
XeF6 also reacts v10lent1y w1 ' y explosive
solid Xe03" XeF6 + 6H20 ➔ Xe03 + 6HF
.
With small quan t·t· of water partial hydrolysis occurs, giving a colourless liquid xenon oxofl .
I ies ' . .. 1 . uonde
XeOF4• The same pr Oduct is formed when XeF 6' reacts with silica or g ass.

XeF6 + H 20 ➔ XeOF4 + 2HF

2XeF6 + Si02 ➔ XeOF4+ SiF4
Xe0 3 is an explosive white hygroscopic solid. It reacts with XeF6 and XeOF4.
Xe03 + 2XeF6 -➔ 3XeOF4
Xe0 3 + XeOF4 ➔ 2Xe0 2F 2
Xe03 is soluble in water, but does not ionize. However, in alkaline solution above pH 10.5 it forms the
xenate ion [HXe0 4 r.
Xe0 3 + NaOH➔Na+ [HXe0 4 r
sodium xenate
Xenates contain Xe(+VI) and they slowly disproportionate in solution to perxenates (which contain
Xe(+VIII)) and Xe.
2[HXeo4r + 20H- ➔ [Xeol- +Xe+ 0 2+ 2H20
perxenate ion

Several perxenates of Group 1 and 2 metals have been isolated, and the crystal structu~s. of Na~
6H20 and _Na4Xe0 6• • 8Hz0 have been determined by X-ray crystallography. The solubility of used
perxenate m 0.5 M NaOH is only 0.2 grams per litre, so precipitation of sodium perxena1e could be ·ru·cb
as a gravimetnc
· · method of analysis for sodium. Perxenates are extremely powerful ox1"d'izmg
· agents. w ·ae
will oxi·ct·~e HCl 1
. to C 2, H20 to 0 2, and Mn +to MnO;. With concentrated H 2S04they give xe non tetroxi
2 ·
Xe0 4, which 1s volatile and explosive.

Xenon fluoride complexes d

XeF2 acts fl ·ct d . .
• ~s a uon e onor and forms complexes with covalent pentafluondes mclu
din pf5 AsFs, Sbf5...1anre
g ' thestf11C "'·
the trans1t10n metal fluorides NbF5, TaF5, RuF5, OsF5, RhF5, IrF5 and PtF5• These are thought to have

XeF,,·MF5 [XeFr [MF6 r

and XeF2 ·2MF5 [XeFr [M 2 F11 r
2XcF2 ·MF5 r
[Xe 2F3 [MF6 r
 10 73 nd
,r1, structures of som f · I Structure and Bonding in Xenon Compou s
,,,e e o the XeF
(figure 10.61 ) , the two X e-F d .st 2 complexes in the .
r.
[XeFr [Sb2F 11 However , the ~ ance_s differ greatI sobct state are known. In the complex XeF2 2S?Fs
distance of 3.50 A.This sugg t e-F distance of 2 3/ {~·84 A and 2.35 A). This suggests the formulation
the structure is inte rmediat e~ s th at one fluorine ~t ?
much less than the van der Waals (non-bonded)
bridge structure. e etwee n that expectedo:r orm~ a ~uorine bridge between Xe and Sb. In fact
th e 1oruc structure, and that for the fully covalent

F
F

figure 10.61 Structure of XeF 2·2SbF (F

.t
Ch em1s ry,
4th e d ., Bl ac k"1e, 1989 .) s· rom Mackay an d M ac k ay, Introduction to Modern Inorganic

XeF4 forms only a few complexes fo

donor, forming complexes such as: ' r example th ose wi th PFs,AsFs and SbF 5• XeF6 can act as a fluoride

XeF6 • BF3
XeF6 • GeF4
XeF6 • 2GeF4
XeF6 • 4SnF~
XeF6 ·AsF5
XeF 6 · SbF5
XeF6 may also act as a fluoride acceptor. With RbF and CsF it reacts as follows:
XeF6 + RbF ➔ Rb+(XeF7 r
On heating, the [XeF7 r ion decomposes:
r
2Cs+ [Xef7 so oc XeFO+ Cs2 (XeFR]

10.73 I STRUCTURE AND BONDING IN XENON COMPOUNDS

The structures of the more common xenon halides, oxides and oxoions are given in Table 10.43. The nature
of the bonds and the orbitals used for bonding in these compounds are of great interest and have been the
subject of considerable controversy.
_!able. 10.43 Possible explanation of structures
Number of Number of lone VSEPR
Formula Structure explanation of structure
electron pairs pairs
3 Five electron pairs fom, trigonal
XeF2 Linear 5 bipyromid with three lone pairs
in equatorial pos1hons
2 Six electron pairs form an
XeF4 6 octahedron with two positions
Square planar
occupied by lone pairs
1 Pentagonal bipyramid, or
7 capped octahedron with
Distorted octahedron
one lone air •
 Cha pte r 10 I Th
. e p-Bl ock Elen,e
nts and thei r Com pou nds
i. b
a le. 10. 43
~n;ti~n~u~e~d'!._)_ _ _ _ _ _"7 :'"_
-:- --- --- --- --- -:- :::- ::- == --- --- -
Forr nula __S(C;-;o
Stru ctur e Num ber of lone VSEPR
Num ber of
tron pair s pairs expl anat ion of struc ture
XeQ3 elec
Pyra mid al 7 J Thre e n bonds so the rer:na; .
four electron pairs fonn ning
a
tetra hedr on with one co rner
. db
occup1e y a lone pair
Xeo p2 2 One ;rbo nd, thre e sigma b
T-sh aped 6
and two Jone pairs constitu~~ds
the T-shape
Xe02 F2 See- saw 1 Two ;rbo nds so remaining fi Ve
7 . "
e Jectro n pairs 1orm trigonal
bipy. rami .
d with. one equatona
. 1
pos1t10n occupied by a Jone Pair
XeO F4 1 One ;rbo nd so remaining
Squ are pyra mid al 7 six elec tron pairs form an
octa hedr on with one position
occu pied by a Jone pair
0 Fou r ;rbo nds so remaining
Xe04 Tetr ahed ral 8
four elec tron pair s form a
tetra hedr on
0 Thre e Jr bond s so remaining five
Trig onal bipy ram id 8
elec tron pair s form a trigonal
bipy rami d
0 Two ;r bond s so remaining
Octa hedr al 8
six elec tron pair s form an
octa hedr on

Xe F2 quite simply
ecul e with both Xe- F dista nces 2.00 A. The bonding may be exp lain ed
XeF2 is a line ar mol
5d level. The two unp aire d elec tron s
form bonds
tron from the Sp leve l of Xe to the
by pro mot ing an elec bipyramid. Of these, three
pairs poin t to the corners of a trigonal
with fluo rine atom s. The five electron occ upy the apical positions.
ial positions, and two are bond pair s and
are lon e pair s and occ upy the equ ator
e (Figure 10.62).
Toe atom s thus form a line ar molecul
F

..
F

Figure 10.6 2 XeF2 molecule.

5s Sp 5d
Elec troni c stnict11re of Xe
atom - grou nd slate
[iI] [11/u/11/ [ l l l II
Xe excit ed
[iI] G1/H/tD [t I l l l I
two unpa ired eJectrons form bonds with fl .
. uon ne atoms
five electron pairs - u··1gonal b1pyramid
but an b · . 18 .
Thi s exp lain s the obs erve d structure, 1e~tw n that the 5d orb ital s of Xe app ear to be too
Jarg c for effective overlap of orbitals.
The max i·mo · tion func tion for 3 5d
· tnbu
um 10 the rad· I e Iectr on d1s
Ia
 10.73 I Structure and Bonding in Xenon Compounds
.1 8 Xe atom occurs at a distance of 4.9 A from th
1
roital0 ,n extent of d orbital participation in molecular:nu~u~. 1 It has_been noted in Chap ter 3 in the
:ectio 'Jllese a large contraction in the size of d orbitals If t~n g th a~ hi~hl~ electronegative atoms like
nuorioe
Jaoauon~au will suffice.
. . . th . . . s contraction IS big enough , the valence bond
e~ 5econd obJectton 1s over e mixmg of orbitals (sp3d h brid' . . . .
A rbitals of similar energy, and the Xe 5d orbitals id izatton). _M~ g IS only effective
i,etween oh 8 scheme of hybridization. (The difference in e:ou bseem too high m energy to contrib-
kJ sue
ute to rnol t .) ergy etween a Sp and a 5d level is about
960
){ef4
e structure of ~eF4 is squar_e planar, with Xe- F distances of 1.95 A (Figure 10.63). The valence bond
11t
theory explains this by promotmg two electrons as shown··
••
r.----1- -._F

••
Figure 10 .63 XeF4 molecule.
5s 5p 5d
Electronic structure of
Xe - excite d state
[ill [ti Iti It ] [t IIII
t

four unpaired electrons fonn bonds to four fluorine atoms

six electron pairs fonn octahedral structure
with two p osition s occupied by lone pairs

The problem of whether the size of the xenon 5d orbitals will allow effective overlap, or their energy will allow
mixing and hybridization, is the same as in XeF2 • The molecular orbital explanation of XeF is similar to that
for XeF2• Toe Xe atom bonds to four F atoms. 4
XeF 6

The structure of XeF6 is a distorte d octahedron (Figure 10.64). The bo nding in XeF has caused consider-
6
able controversy which is not completely resolved. The structu re may be explained in valence bond tem1S
by promoting three electrons in Xe:
F

F - F

Figure 10 .64 Capped octahedron.

5s 5fJ 5d
't71
Electro nic s~ructure of
xeno n - excited state ~ It II II I l1!tl ITI 1

1be si,, unpaired electrons form bonds w;lh fluodne atoms The d;suibution of seven orh>1al, giv~, cithe'.
'
h octahedron or a pentagona I b tpyr
aincapped amt'd (as in JF 7) • (A capped
• oct,,hedron has a lone· pair point
n.>d
gt rough one of the faces of the octahedron.) Since there arc s,x bonds and one 1one patr, a capr
 Chapter 10 I Th e p-Block Elements and their Compounds

. a distorted octahedral molecule. Toe molecular orbital

three ,•ould give
octahedron
since . a~proach fails With x,
shape. three-centre molecular orbital systems mutually al right angles would give a regular oct~~

10•7 4 I STRUCTURES O F SOME XENON COMPOUNDS

structures of some xenon compounds are shown in Figure 10.65 (skeleton only).
F •• 0
F
F

F
0
F 0
••
Square pyramidal
0 (octahedral with one
F position unoccupied)
Pyramidal
Sligh t1y disorted Xenon trioxide Xenon ox:yfluoride
octahedron XeOg XeOF4
Xenon hexafluoride
XeF6
0
0
F
0
••

4°
0

0
0
0
0
F Tetrahedral
Octahedral
Xenon tetroxide
Perxenate ion
Xe04
Xe0#2 [Xe06 ] 4-

Structures of some xenon compounds.

Figure 10.65

SINGLE C,ORRECT CHOICE TYPE QUESTIONS

(C) Liquid nitrogen
1. Which of the following elements has the highest ioni- (D) Liquid helium
zation energy? 4. Which of the following properties does not increase
(A) He from helium to xenon?
(B) Ne
(A) Boiling point
(C) F
(B) Atomic radius
(D) H
(C) Rate of diffusion through glass
2. The most abundant inert gas element is
(D) None of these
(A) Ne
(B) Ar 5 • When XeO3 reacts with XeOF4 , the product formed is
(C) He (A) XeO4
(D) Xe (B) XeO2F2
• Which of the following_ e!ements is used in cryoscopic (C) XeOF2
3 (D) XeO]F2
study for superconductJV1ty?
(A) Liquid bromine
(B) Mercury liquid