A2 Chem Group 4 (14) Candidates should be able to: describe the change in relative stability of oxidation states II and

IV down Group 4, as shown by reactions of CO as a reducing agent with oxides and Pb(IV as an oxidising agent in the reaction of PbO! with concentrated hydrochloric acid"

Element C

Oxidation State II Example CO Carbon monoxide is an exception

Si does not exist under normal
II

Oxidation State IV C
IV

Example CO2 is the stable oxidation state

Example SiCl4 SiO2

Si

conditions
Example GeCl2 IV Ge is less stable than Ge
II

Si

IV

is more stable than Si

II

Ge

Ge

IV

Example GeCl4 II is more stable than Ge

Sn

Example SnCl2 II IV Sn and Sn have similar stabilities Example PbCl2 Pb(NO !2 II IV Pb is more stable than Pb

Example SnCl4 II IV Sn and Sn have similar stabilities Example PbO2 IV Pb is more stable than Pb
II

Pb

2" Carbon monoxide is a stron# reducing agent$ It is involved in the reduction o% metallic ores$ e$#$ iron(III! oxide copper(II! oxide
II

&e2O (s! ' CO(#! CuO(s! ' CO(#!

IV

2&e(s! '

CO2(#!

Cu(s! ' CO2(#!

Since Pb is more stable than Pb ( some lead(IV! compounds are oxidisin# a#ents bein# reduced in the reaction to Pb $
)he example *uoted in the speci%ication is lead(IV! oxide$ +hen heated ,ith concentrated h-drochloric acid( lead(IV! oxide oxidises the chloride ion to #ive chlorine #as$
II

PbO2(s! ' 4.Cl(a*! (l) Carbon dioxide Candidates should be able to:

PbCl2(s! ' Cl2(#! ' 2.2O(l!

recall the nature, physical and acid#base properties of CO! and PbO" Carbon dioxide is a covalent( colourless #as$ It is readil- soluble in ,ater to #ive an acidic solution$ Solid carbon dioxide (dr- ice! sublimes at /" C$ +hen passed into a*ueous sodium h-droxide( sodium carbonate is %ormed i% the al0ali is in excess$ CO2(#! ' 2NaO.(a*! Na2CO (a*! ' .2O(l!
o

I% carbon dioxide is in excess then sodium h-dro#encarbonate is %ormed CO2(#! ' NaO.(a*!
Na.CO (a*!

)his acidic nature is used in the lime,ater test %or carbon dioxide$ 1ime,ater is a saturated solution o% calcium h-droxide( ,hich is onl- sli#htl- soluble in ,ater$ On passin# carbon dioxide into lime,ater( calcium carbonate is %ormed as a ,hite precipitate$ Scienti%icall- it is more correct to state that a ,hite precipitate is %ormed( rather than usin# the common expression 2the li$ewater turns $il%y3$ CO2(#! ' Ca(O.!2(a*!
2

CaCO (s! ' .2O(l!

On continuin# to pass carbon dioxide throu#h the mixture( a colourless solution %orms$ CO ' CO2(#! ' .2O(l!
2.CO (a*!

24 It is incorrect to sa- the calcium h-dro#encarbonate is %ormed$ 5 solution containin# calcium ions and h-dro#encarbonate ions is %ormed$ 5n- attempt to isolate calcium h-dro#encarbonate results in the decomposition o% the h-dro#encarbonate ion and the precipitation o% calcium carbonate$ 2.CO (a*!
CO
2

' CO2(#! ' .2O(l!

)his reaction ta0es place in the %ormation o% 0ettle %ur and stalactites and stala#mites$ Lead(II) oxide 1ead(II! oxide( PbO( has predominantl- ionic character and exists in t,o %orms 6 one a red solid and the other a -ello, solid$ )he di%%erence lies in the cr-stal structures o% the t,o %orms$ )he red %orm is called lithar#e and the -ello, %orm massicot$ 1ead(II! oxide is amphoteric as can be illustrated b- its reaction ,ith nitric acid$ Since lead(II! sul%ate is insoluble and lead(II! chloride onl- sparin#l- soluble in the cold( it is best to %orm the soluble lead(II! nitrate$ PbO(s! ' 2.NO (a*! Pb(NO !2(a*! ' .2O(l!

+hen heated ,ith a*ueous sodium h-droxide( sodium plumbate(II! is %ormed as a colourless solution$ PbO(s! ' 2NaO.(a*! ' .2O(l! )he plumbate(II! ion is Pb(O.!4 the %ormula Na2PbO2$ (m) Some chlorides o Group 4 Candidates should be able to:
describe the types of bonding in the chlorides CCl 4, &iCl4 and PbCl! and their reactions with water "
26

Na2Pb(O.!4(a*!

althou#h PbO2

26

,ill be acceptable #ivin# sodium plumbate(II!

)etrachloromethane( CCl4 Sometimes called carbon tetrachloride( tetrachloromethane is a colourless li*uid ,hich is more dense than ,ater and immiscible ,ith it$ 7nli0e all the other tetrachlorides o% the #roup it is not h-drol-sed b,ater$ 8ein# in the %irst period( carbon cannot utilise d orbitals %or attac0 b- the nucleophilic ,ater molecule$ )he molecule( as predicted b- VSEP9 theor-( is tetrahedral$ Silicon tetrachloride( SiCl4 Cl Cl Cl C Cl

: )his is a colourless li*uid ,hich %umes on contact ,ith air as it is h-drol-sed b- atmospheric moisture$ Silicon tetrachloride reacts vi#orousl- ,ith ,ater bein# h-drol-sed to silicon dioxide$ )he lone pair %rom a ,ater molecule can attac0 the silicon atom ,hich can expand its octet bein# in the second period$ SiCl4(l! ' 2.2O(l! )he SiCl4 molecule is tetrahedral$ 1ead(II! chloride( PbCl2 1ead(II! chloride is a ,hite solid ,hich is sparin#l- soluble in cold ,ater but much more soluble in hot ,ater$ )he compound has a si#ni%icant amount o% ionic character( its a*ueous solutions containin# the Pb
2'

SiO2(s! ' 4.Cl(a*!

ion$

1ead(II! chloride ,ill dissolve in concentrated h-drochloric acid %ormin# a tetrachlorolead(II! ion$ .-drochloric acid provides ,ater and a hi#h concentration o% chloride ions$
2'

PbCl2(s! ' a* Pb (a*! ' 2Cl (a*! Pb (a*! ' 4Cl (a*! PbCl4 (a*!
2# 2' 2

(n) Some reactions o the a!ueous "b Candidates should be able to:

ion

recall the reactions of Pb! (a( with a(ueous )aO*, Cl and I + +ith a*ueous sodium h-droxide +hen a*ueous sodium h-droxide is added to a*ueous lead(II! nitrate( a ,hite precipitate is %ormed ,hich reacts ,ith excess sodium h-droxide to %orm a colourless solution$ Pb (a*! ' 2O. (a*!
; 2'

'

Pb(O.!2(s! lead(II! h-droxide

2

Pb(O.!2(s! ' 2O. (a*!

Pb(O.!4

plumbate(II! ion +ith a*ueous chloride ions +hen a*ueous sodium chloride is added to a*ueous lead(II! nitrate( a ,hite precipitate is %ormed$ )his precipitate o% lead(II! chloride is more soluble in hot ,ater than in cold$

< Pb (a*! ' 2Cl (a*!

2'

PbCl2(s!

)he ,hite precipitate is soluble in concentrated h-drochloric acid as sho,n previousl- in (m!$ +ith a*ueous iodide ions +hen a*ueous potassium iodide is added to a*ueous lead(II! nitrate( a bri#ht -ello, precipitate is %ormed$ )his precipitate o% lead(II! iodide is soluble in hot ,ater to #ive a colourless solution$ Pb (a*! ' 2I (a*!
2'

PbI2(s!