A Level Chemistry

UNIT 2 APPLICATION OF CORE PRINCIPLES OF CHEMISTRY NOTES

Written by Mr Sergeant and Dr Lawrence
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Introduction
This unit includes the following. Shapes of molecules and ions. Intermediate bonding and bond polarity. Consideration of intermolecular forces. The study of the Periodic Table looking at Groups 2 and 7. edo! reactions" particularly those concerning Group 7 elements and their compounds. ate of reaction #kinetics$ Chemical e%uilbria &rganic chemistry' alcohols and halogenoalkanes. (echanisms (ass and infrared spectrometry Green chemistry.

Assessment
The )nit e!amination will be *hour *+ minutes. It will carry ,- marks. It will contain three sections" ." / and C. Section A is an ob0ecti1e test 2 multiple choice %uestions. Section B short3answer and e!tended answer %uestions. Section C will contain e!tended answer %uestions on contemporary conte!ts. 4uestions on the analysis and e1aluation of practical work will also be included in either section / or C. 4uality of written communication will be assessed in sections / and C.

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SHAP S !" M!L C#L S A$D I!$S

The shape of a molecule depends upon its electronic structure. It is the outer shell or 1alence shell electrons which are responsible for forming bonds and it is the arrangement of these electrons which determine molecular shape. The electrons are all negati1ely charged and so will repel each other. 5ach electron region takes up a position to minimise repulsion. /y considering the 1alence shell electron regions and their positions according to repulsi1e effects we can e!plain the shape of molecules. This is called the electron %air re%ulsion theory. Beryllium chloride& BCl' 6ot and cross diagram. /eryllium chloride has two bonding pairs in the 1alence shell. These position themsel1es as far apart as possible 2 at *,-o. The molecule is linear.

Cl

Be Cl

Cl
Boron tri(luoride& B") 6ot and cross diagram.

Be
180O

Cl

F F B F F B

F
120O

There are three bonding pairs #electron area in a bond$' these will spread the ma!imum distance apart 3 that is at an angle of *2-o. This molecule is flat" that is it lies in a plane' such a molecule is said to be planar. 7ith three bonds at an angle of *2-o /89 is said to be trigonal %lanar.

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Methane& CH* 6ot and cross diagram.

H H C H H

(ethane has four bonding electron pairs in the 1alence shell. These position themsel1es as far apart as possible to form a tetrahedral sha%e with a bond angle of *-:.+o.

H C H H
109.5O

Ammonia& $H) 6ot and cross diagram. .mmonia has three bonding electron pairs and a lone pair of electrons in the 1alence shell. These position themsel1es as far apart as possible" but the lone pair has a greater repulsion than the bonding pairs pushing the bonding pairs closer together and reducing the bond angle to *-7.+o. The molecule is %yramidal.

N H

N
Water& H'! 6ot and cross diagram.

H H

107.5O
(olecule

H O
104.5O

7ater has two bonding electron pairs and two lone pairs of electrons in the 1alence shell. The two lone pairs ha1e a greater repulsion than the bonding pairs" pushing the bonding pairs closer together and reducing the bond angle to *-;.+o. The molecule is bent.
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H H

Carbon dio+ide& C!' 6ot and cross diagram. Carbon dio!ide has two electron regions in the 1alence shell. These position themsel1es as far apart as possible. The molecule is linear. (olecule

C
180O

Phos%horus %entachloride& PCl,

Cl Cl Cl P Cl Cl

Phosphorus pentachloride has fi1e bonding electron pairs in the 1alence shell. The molecule is trigonal bi%yramidal.

Cl
90O

Cl

P Cl

Cl
120O

Two of the bonds are at *,-o. The other three are in a plane at *2-o.

Cl

Sul%hur he+a(luoride& S"6ot and cross diagram.

F F S F F F F

Sulphur he!afluoride has si! bonding electron pairs in the 1alence shell. The molecule is octahedral with bond angles of :-o

F F F F S F
90O

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.mmonium ion" <=;>

H H N H

+ H
The ammonium ion has four bonding pairs of electrons in the 1alence shell #one of theses being a dati1e bond$. The molecule is tetrahedral with bond angles of *-:.+o.

H N H H

/ond angles in C=;" <=9" =2&

It is important to note that although there are four pairs of electrons arranged appro!imately tetrahedrally around the < in <=9 and the & in =2&" the lone pairs cannot be ?seen@ e!perimentally" so the shapes of these molecules are described by the actual positions of the atomsA ammonia is pyramidal and water is bent. 7e can e!plain the differences in the bond angles in C= ;" <=9 and =2& by noting that repulsions get less along the seriesA lone %air.lone %air / lone %air.bonding %air / bonding %air.bonding %air This occurs because a lone pair is closer to the nucleus of the atom" and so takes up more room than a bonding pair. 7hen this principle is applied to C= ;" <=9 and =2&" C=; is a regular tetrahedron #angles of *-:.+o$' <=9 has one lone pair" which s%uashes the = atoms down #angles reduced to *-7o$' and =2& has two lone pairs" which repel the = atoms e1en more #angle now *-;.+o$A

N
ammonia py ami!al H "on! an#le 107 H
o

H
$a%e non-linea "on! an#le 104.5o

H H

ammonia 2 pyramidal bond angle *-7o

waterA non3linear bond angle *-;.+o

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More com%licated molecules

The shapes of more complicated molecules and ions can also be ?e!plained@ by electron pair repulsion theory" or 5P . In applying this principle" we must include both bonding and non3bonding #or ?lone@$ pairs" and we must count a double or triple bond as if it were one pair #or one region of electron density$. The table shows the shapes e!pected for different numbers of electron pairs. $umber o( electron %airs Two Three 8our Si! Sha%e linear Trigonal planar tetrahedral octahedral Bond angles *,-o *2-o *-:.+o :-o +am%les .g#<=9$2>" C&2 C=2BC=2" /89 C=;" <=9C" =2& S8D" 8e#C<$D92

7e can use ad1anced 5P theory to predict the shape of any molecule or ion. 01 '1 )1 *1 ,1 -1 Decide on the central atom 2ecord its number o( outer electrons

Count the number o( bonding atoms Add 0 e3 (or each atom I( the s%ecies is 4 charged I( the s%ecies is 5 charged Add 0 e3 (or each charge Subtract 0 e3 (or each charge

"ind the total number o( electron %airs6 Determine the sha%e o( the s%ecies7 Pairs Sha%e ' Linear ) 8rigonal Planar * 8etrahedral , 8rigonal bi%yramidal !ctahedral Show any lone %airs6 8he number o( Lone %airs : 8otal number o( %airs 4 bonding %airs

91

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5!ample

P=;

>

Central atom B P /onding atoms B ; ! = Positi1ely charged

5lectrons + ; #8orms ; bonding pairs$ 3* Total B ,

* %airs : 8etrahedral

The number of Eone pairs B Total number of pairs 2 bonding pairs B ;3; B -

H P H H
5!ample

I8

3 ;

Central atom B I /onding atoms B + ! 8 <egati1ely charged

5lectrons 7 ; # 8orms ; bonding pairs$ >* Total B *2

- %airs : !ctahderal

The number of Eone pairs B Total number of pairs 2 bonding pairs B D3; B 2

.. F F .. & F
90O

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Structures o( Carbon Allotro%es

Diamond
6iamond is composed of carbon atoms. 5ach carbon atom is connected to four other carbon atoms

5ach of these atoms is also connected to three other carbon atoms. In this way a giant structure is built up from these tetrahedral units.

This structure" held together by strong co1alent bonds" is 1ery difficult to break apart. So diamond has 1ery high melting and boiling points. It is the hardest natural substance. Since all the electrons are taken up in bonding diamond is a non3conductor. 6iamonds are attracti1e which means they are used as 0ewellery. Its hardness makes it useful for cutting instruments such as drill tips.

;ra%hite
In graphite each carbon atom has three bonds" so three of the four electrons are taken up in forming these bonds. The remaining electron is allowed to mo1e from atom to atom 3 it is delocalised. Since three bonds form" the bond angle around each carbon is *2- o and a he!agonal arrangement is set up.

These he!agons 0oin together in a plane forming a sheet of he!agonally arranged carbon atoms.

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Graphite is made up of these layers held together by Eondon forces #Fan der 7aalsG forces$. Sometimes it is referred to as a layer structure.

The carbon atoms in graphite are held together by co1alent bonds forming a giant structure" so the melting and boiling points are high. Since each atom has a free electron" graphite is able to conduct electricity. The layers held together by weak intermolecular forces can slide o1er each other" making a soft slippery substance. Graphite can be used for electrodes as it is a conductor" and unlike metals it does not react during electrolysis. It can be used as a lubricant because of its slippery nature.

"ullerenes
6iamond and graphite were thought to be the only allotropes of carbon until late in the twentieth century. In *:,+ a new form of carbon was disco1ered that consisted of spherical molecules containing D- carbon atoms.

These molecules resembled the construction of a building by an architect called /uckminster 8uller. .s a result" the molecule was named buckminsterfullerene. The molecule also resembles a football" so it is often called a ?bucky3ball@. Similar molecules ha1e since been made that contain 7- or more carbon atoms. This family of molecules are called fullerenes.

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$anotubes
.nother form of carbon de1eloped as a result of the disco1ery of fullerenes is the nanotube. The indi1idual layers in graphite are called graphemes. . nanotube can be regarded as a grapheme which has rolled up to form a cylinder. The name comes from the diameter of the cylinder. . single3walled carbon nanotube is a one3atom thick sheet of graphite rolled up into a seamless cylinder with diameter *32 nm.

Such cylindrical carbon molecules ha1e no1el properties that make them potentially useful in many applications in nanotechnology" electronics" optics and other fields of materials science. They e!hibit e!traordinary strength and uni%ue electrical properties" and are efficient conductors of heat.

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I$8 2M DIA8 B!$DI$; A$D I$8 2M!L C#LA2 "!2C S lectronegativity

5lectronegati1ity is defined as follows 5lectronegati1ity is the ability of an atom within a co1alent bond to attract the bonding pair of electrons. The table below shows electronegati1ity 1alues of main block elements = 2.* Ei /e *.- *.+ <a (g -.: *.2 H Ca -., *.b Sr -., *.Cs /a -., -.: / 2..l *.+ Ga *.D In *.7 Tl *., C 2.+ Si *., Ge *., Sn *., Pb *., < 9.P 2.* .s 2.Sb *.: /i *.: & 9.+ S 2.+ Se 2.; Te 2.* Po 2.8 ;.Cl 9./r 2., I 2.+ .t 2.2 =e <e .r Hr Ie n

Polarisation o( a covalent bond

. perfect co1alent bond would consist of the bonding electron region being shared e%ually by each atom.

This occurs if each of the atoms ha1e the same pull on the electron pair in the bond #e%ual electronegati1ity$. It can be found in molecules of elements such as & 2" /r2 and <2. Since the atoms in each of these molecules are the same they will ha1e the same electronegati1ity.

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In most compounds howe1er one atom will ha1e a greater electronegati1ity than the other" and so will ha1e a greater pull on the electrons" so distorting the electron region.

This process of mo1ing away from the perfect e!ample is called %olarisation. The e!tent of the polarisation will depend on the difference in electronegati1ity of the two atoms. The polarisation of a co1alent bond will mean that one part of the molecule is more negati1e #the most electronegati1e atom$ than the other and causing the bond to be polar. =ydrogen chloride is an e!ample of a molecule which contains a %olar bond. The chlorine possesses a higher electronegati1ity" so will draw the electron pair in the co1alent bond towards itself.

'(

Cl
3.0

'-

2.1

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Intermediate bonding
In )nit * #Ionic /onding$ it was noted that ionic compounds can be polariJed which gi1es them a co1alent character. 7hen a molecule has a polar bond" it gi1es the co1alent substance an ionic character. To regard a compound as ?co1alent@ or ?ionic@ is too simplistic for understanding .S chemistry. It is more correct to 1isualiJe type of bonding on a sliding scale where compounds can be described as ?%redominantly covalent @ or ?%redominantly ionic@. 5lectronegati1ity 1alues can be used to gi1e an appro!imate idea of the predominant type of bonding in a binary compound. 5lectronegati1ity difference Percentage ionic character 5lectronegati1ity difference Percentage ionic character 5lectronegati1ity difference Percentage ionic character 5lectronegati1ity difference Percentage ionic character -.* -.+ -.: *: *.7 +* 2.+ 7: -.2 * *.22 *., ++ 2.D ,2 -.9 2 *.* 2D *.: +: 2.7 ,; -.; ; *.2 92.D9 2., ,D -.+ D *.9 9; 2.* D7 2.: ,, -.D : *.; 9: 2.2 79.,: -.7 *2 *.+ ;9 2.9 7; 9.* :* -., *+ *.D ;7 2.; 7D 9.2 :2

Eooking at a selection of substances Substance Chlorine" Cl2 .mmonia" <=9 7ater" =2& Calcium chloride" CaCl2 Eithium o!ide" Ei2& Potassium fluoride" H8 5lectKy 1alue * 9.9.9.+ 9.9.+ ;.5lectKy 1alue 2 9.2.* 2.* *.*.-., 5lectKy difference -.: *.; 2.2.+ 9.2 L ionic chKr *: 9: D9 7: :2

If these are then plotted on the diagram below" it can be seen the type of bonding is a continuum rather than a black and white picture. *29;L ionic character +D7,:*--

=2&

Cl2

NH3

H2O

CaCl
2

)i2O

*F

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Polar bonds and Polar Molecules

The presence of a polar bond may or may not lead to the formation of a polar molecule. The carbon 2 chlorine bond is polar because the chlorine is more electronegati1e than the carbon.

'(

Cl
3.0

'-

2.5

To decide whether a molecule will be polar" it is necessary to look at where the centres of positi1e and negati1e charge are placed. . molecule of trichloromethane is polar

H '( Cl Cl C
'Cen% e o+ ne#a%i,e -.a #e

Cl

Eooking at a molecule of tetrachloromethane

Cl C Cl Cl Cl
Cen% e o+ "o%. ne#a%i,e an! po/i%i,e -.a #e

Since there is no separation of charge in tetrachloromethane this is not a polar molecule. .nother e!ample of a molecule with polar bonds" but is non3polar o1erall is carbon dio!ide.

'3.5

'( 2.5

'3.5

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&ne way of testing a substance to see if it is composed of polar molecules is to place an electrostatic charge near a 0et of the li%uid.

B0 e%%e no11le C.a #e! o! 2.e -.a #e on %.e pola mole-0le -a0/e/ %.e mole-0le/ %o "e a%% a-%e! %o %.e -.a #e! o!.
The greater the angle of deflection the more polar the molecule.

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'6,

I$8 2M!L C#LA2 "!2C S

8orces of attraction must e!ist between atoms and molecules which are not chemically bonded because at a low enough temperature all substances become li%uids or solids 2 e1en helium" which consists of inert" uncombined atoms. The three types of Intermolecular force to be considered areA Di%ole 3 di%ole attractions London or van der Waals< (orces& and Hydrogen bonding.

Di%ole 3 di%ole attractions

These occur when a molecule has a permanent dipole. It has been seen that in a molecule such as trichloromethane" C=Cl 9" the electronic charge is pulled towards the chlorine atoms because they ha1e a greater electronegati1ity. This results in a molecule which has a partial positi1e charge at one end and a partial negati1e charge at the other. This type of molecule is described as %olar.

H '( C

Cl Cl

The separation of charge which e!ists in a polar molecule is called a di%lole.

'-

Cl

In a polar material there is an attraction between the positi1e charge in one molecule and the negati1e charge in the other.

+ - + + +- + + + +

This type of force between molecules is referred to as di%ole3di%ole attractions.

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van der Waals< (orces

.lso called 3 Eondon forces" instantaneous dipole 3 induced dipole interactions and dispersion forces. 7hen noble gases are cooled sufficiently they will condense. This shows that there must be some forces acting between the atoms. These forces are called van der Waals< (orces. The random motion of electrons around a nucleus produces a fluctuating dipole" which changes from one instant to the ne!t. 5ach instantaneous di%ole influences its neighbours" tending to induce a di%ole in them" and this leads to an attraction. In general a larger atom will ha1e a greater number of electrons around it" leading to a larger fluctuating dipole. This means that 1an der 7aals forces generally increase with relati1e molecular mass. 8or e!ample" in the alkanes boiling points increase steadily as 8( rises. (olecules like li%uid bromine" /r2" and li%uid argon" .r #monatomic$" can only ha1e 1an der 7aals forces since they ha1e no permanent dipoles. =owe1er" e1en in polar molecules like =Cl the 1an der 7aals are the most important factor" as can be seen from the increasing boiling points of the hydrogen halidesA =Cl #*,,H' dipole *.-+6$ M =/r #2-DH' -.,-6$ M =I #29,H' -.;26$ .long this series" boiling points rise with 8( because of the increased 1an der 7aals forces" e1en though dipole moments are getting less. Fan der 7aalsK forces are generally weak #of energy up to + kN mol 2*" compared to *+-2;-kN mol2* for most co1alent single bonds$ but they increase as molecular mass increases and as the number of electrons in the molecule increases so with large molecules the forces become large.

Boiling %oints o( the noble gases

The boiling points of the noble gases illustrate this increase in strength of Fan der 7aalGs forces with molecular mass. <oble gas <eon .rgon Hrypton Ienon adon (olecular mass 2;,; *9* 222 /oiling point 32;D 3*,D 3*+2 3*-, 3D2

.s the molecular mass of the gases increases" the atoms contain more electrons and so the siJe of the 1an der 7aalKs forces increases. .s the attracti1e forces between the molecules increases" it becomes more difficult to separate the molecules from each other and so the boiling points increase.

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Hydrogen Bonding
=ydrogen bonds" with energies usually in the range from 2-3;- kN mol 2*" are typically ten times as strong as 1an der 7aalsK forces" and about one3tenth as strong as co1alent bonds. Two conditions are necessary for formation of hydrogen bondsA #i$ . = atom must be co1alently bonded to a highly electronegati1e atom usually <" & or 8. =ydrogen only has one electron which is used when hydrogen bonds to another element. The elements listed abo1e are highly electronegati1e and so draw the electron pair in the bond towards themsel1es. This lea1es the proton on the hydrogen e!posed. ( -

H
P o%on e4po/e!

#ii$ The ad0acent molecule must ha1e a lone pair of electrons on an <" & or 8 atom. The hydrogen" with its > charge" is strongly attracted to the ad0acent lone pair. This is more than 0ust a polar attraction" and is strongly directional #along the line of the lone pair$. Oou need to draw it with the polar bonds and lone pairs marked. ( ( -

H
)one pai

3
Hy! o#en "on!

H
P o%on e4po/e!

(olecules which show hydrogen bonding between molecules includeA i$ =8' ii$ all compounds with 2&= groups" including water' iii$ all compounds with 2<=2 groups" including <= 9. In addition these molecules can all hydrogen3bond to water.

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+am%les o( hydrogen bonding Ammonia ( ( (

H N

H N

H
(

Water

H
-

O
Hydrogen (luoride

H O
-

F F
( (

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Intermolecular (orces and %hysical %ro%erties

The greater the intermolecular force strength" the more difficult it is to separate the molecules and so the higher the melting and boiling points. The strengths of the intermolecular forces are summariJed below. 1an der 7aalKs 8ound in all molecular substances 7eakest 6ipole3dipole 8ound in polar substances =ydrogen bonding 8ound in compounds where = id directly bonded to <"& or 8 Strongest

The three molecules below illustrate the 1arious strengths of these intermolecular forces.

H 3C

CH2

CH3

P opane7 ".p. 8 -42.2 oC

Propane is composed of non3polar molecules and so only has van der Waals (orces between the molecules.

H3C '( CH3 O '9e%.o4yme%.ane7 ".p. 8 -24.8oC

(etho!ymethane has a similar molecular mass to propane" but has a higher boiling point because the molecules are polar" so there are di%ole3di%ole attractions as well as 1an der 7aals forces.

- + H3C OH CH2
:%.anol7 ".p. 8 78oC

5thanol has hydrogen bonding which is significantly stronger than the other intermolecular forces and so a much higher boiling point than metho!ymethane e1en though they ha1e the same molecular mass.

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Boiling Points o( the Al=anes

. graph plotting the boiling points of the alkanes is shown below.
Boiling Points o( Al=anes
D--

+--

;--

Boiling Point .o>

9--

2--

*--

The boiling points of the alkanes increases with molecular mass. This happens because the higher the molecular mass" the greater the number of electrons and so the greater the chance of an imbalance and formation of an instantaneous dipole. The 1an der 7aalsK forces #Eondon forces$ increase.

* 2 9 ; + D 7 , : *** *2

$umber o( carbon atoms

The melting point of the alkanes increases with molecular mass for the same reason" but the pattern is not so straightforward as the different packing of molecules in the solid according to whether the number of carbon atoms is odd or e1en causes an additional factor in the determination of the melting points. The closer the molecules are able to approach each other" the greater the induction effect and so the greater the 1an der 7aalsK forces. 7hen an alkane has branching present" the molecules cannot approach each other so closely and there is less area o1er which contact can occur" so branched alkanes ha1e lower boiling points. The table below illustrates the effect of branching in alkane molecules on the boiling point. .lkane /utane (ethylpropane (olecular mass +D +D Structural formula C=9C=2C=2C=9 C=9C=#C=9$C=9 Skeletal formula /oiling point 3-.+oC 3**.7 oC

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Boiling Points o( the alcohols

The 2&= group in alcohols causes hydrogen bonding between the molecules. Therefore an alcohol will ha1e a much higher boiling point than an alkane with a similar number of electrons. .lkanes 8ormula C=9C=2C=9 C=9C=2C=2C=9 5lectron number 2; 92 /oiling point 3;2 oC 3-.+oC alcohol 8ormula C=9C=2&= C=9C=2C=2&= 5lectron number 2; 92 /oiling point 7,.+ oC :7oC

Boiling Points o( the hydrogen halides

The boiling points of =Cl" =/r and =I increase with molecular mass. This is because as the number of electrons increases so does the chance of an electron imbalance and the formation of instantaneous dipoles and so greater 1an der 7aalsK or Eondon forces. It might be e!pected that =8 ha1ing a smaller molecular mass than =Cl would ha1e a lower boiling point. This is not the case. =ydrogen fluoride has the highest boiling point of this group because =8 molecules form hydrogen bonds. The graph plotting the boiling points of hydrogen halides is shown below.
Boiling Points o( hydrogen halides
;-

2-

* Boiling %oint .oC 322 9 ;

3;-

3D-

3,-

3*-%eriod in Periodic 8able

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Boiling Points o( other hydrides

/ecause hydrogen bonds are the strongest of the intermolecular forces" molecules with hydrogen bonding ha1e higher boiling points" and higher enthalpies of 1aporisation" than would otherwise be e!pected for molecules of similar molar masses. 7e see this in the boiling points of the hydrides in groups +" D and 7A in each case the first member #in the second period$ is much higher than e+%ected #see graph$A
400

H2 O
300

Boilin# Poin%/ o+ .y! i!e/ ; o0p 6 5 7

Boilin# Poin%5*

HF NH 3

200

100

Pe io!

#nusual %ro%erties o( water

The unusual properties of water are caused by hydrogen bondingA #i$ it has a much higher freeJing and boiling point than e!pected for such a small molecule" because it needs more energy to separate the molecules' #ii$ ice is less dense than water" whereas most solids are denser than their li%uid phase. In the structure of ice" for each water molecule the o!ygen is bonded co1alently to two hydrogens" and the two lone pairs of electrons each accept a hydrogen bond" so that the structure is = tetrahedral #and not unlike that for diamond" though note that the = & = & &P=33333& distances are not the same as each other$. The = = = result is that ice has a rather o%en structure" with some empty & = & space trapped in the lattice. This gi1es it a lower density than = li%uid water.
= & =

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Solubility
In general a sol1ent will dissol1e a substance that contains similar intermolecular forces.

Solubility o( ionic com%ounds in water

7hen an ionic substance is placed in water" the water molecules" being highly polar" are attracted to the ions. The o!ygen in the water molecule carries a partial negati1e charge and is attracted to cations. The hydrogen in the water molecule carries a partial positi1e charge and is attracted to anions. The process of water molecules linking to ions is called hydration o( ions #as bonds are formed hydration is always e!othermic$. The water molecules are 1ibrating" so as they bond to the ions they shake the ions free from the lattice. The process of dissol1ing is shown below.

+ +

+ + -

+ +

+ + -

+ +

+ + -

+ - + + -

Some ionic compounds do not dissol1e in water because the electrostatic attraction between the ions" the Lattice enthal%y" is too great for the water molecules to o1ercome. To be soluble the energy produced by hydrating the ions # the hydration enthal%y$ must be more negati1e than the energy holding the ion together # the lattice enthal%y$.

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8he solubility o( organic com%ounds in water

.lcohols possess the 3&= group and so can form hydrogen bonds. .lcohols are soluble in water because they are capable of forming hydrogen bonds with water molecules. &ther organic compounds" which are not able to form hydrogen bonds do not dissol1e in water. =alogenoalkanes for e!ample" although polar" are not able to form hydrogen bonds with water" and therefore are unable to interact with the water molecules and such compounds are conse%uently not soluble in water. The reason that water will not dissol1e substances which are not ionic or able to form hydrogen bonds is that the dissol1ing process in1ol1es molecules of the dissol1ing substance to intersperse themsel1es between the water molecules. The strong hydrogen bonds cause strong attractions between the water molecules" pre1enting other molecules from mo1ing between them unless they are able to form e%ually strong interactions with water molecules. To be soluble in water the organic substance must be able to form strong hydrogen bonds with the water molecules.

Solubility in $on3a?ueous solvents

<on3polar sol1ents will dissol1e non3polar materials. Sol1ents such as he!ane will dissol1e substances such as iodine. =e!ane and iodine are both non3polar and so ha1e similar forces between their molecules #1an der 7aals forces$. This means that the molecules are able to interact with each other easily and allow solubility. To be soluble in a non3a%ueous sol1ent the substance must ha1e similar strength intermolecular forces to those in the non3a%ueous sol1ent.

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2edo+
The term 56&I stands for 2 D)CTI&<3!@ID.TI&<. &!idation can be defined as gain of o!ygen or loss of hydrogen. eduction can be defined as loss of o!ygen or gain of hydrogen. The most important definition is gi1en in terms of electrons. &II6.TI&< is E&SS of 5E5CT &<S 56)CTI&< is G.I< of 5E5CT &<S &ne way of accounting for electrons is to use !@IDA8I!$ $#MB 2S.

!+idation number
The o!idation number of an atom shows the number of electrons which it has lost or gained as a result of forming a compound e.g. 8e2> needs to gain two electrons for it to become neutral iron atom therefore its o!idation number is >2. )sing o!idation numbers it is possible to decide whether redo! has occurred. Increase in o!idation number is o!idation. 6ecrease in o!idation number is reduction. 7e can apply a series of rules to assign an o!idation state to each atom in a substance.

!+idation $umber 2ules

*. The o!idation number of an uncombined element is -. 2. Certain elements ha1e fi!ed o!idation numbers. .ll group * elements are >*. .ll group 2 elements are >2. =ydrogen is always >* e!cept in hydrides. 8luorine is always 2*. &!ygen is always 22 e!cept in pero!ides" supero!ides and when combined with fluorine. Chlorine is always 2* e!cept when combined with fluorine and o!ygen. 9. The sum of o!idation numbers in a compound is always -. ;. The sum of o!idation numbers in an ion always adds up to the charge on the ion.

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5!amples *. The o!idation number of S in =2S&; =2 S &; 2 ! >* Q ; ! 32 >2 Q 3, >2 >D 3, s B >D 2. The o!idation number of S in S2&,23 S2 &; Q , ! 32 B 32 Q 3*D B 32 >*; 3*D B 32 S B >7 9. The o!idation number of Cl in <aCl&9. <a Cl &9 >* Q 9 ! 32 >* Q 3D >* >+ 3D Cl B >+ ;. The o!idation number of (n in (n&;3 (n &; Q ; ! 32 B 3* Q 3, B 3* >7 3, B 3* (n B >7

BBB-

BBB-

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2edo+ 2eactions
7hen magnesium is placed into a solution of copper sulphate" a reaction occurs which in simple terms is called a ?dis%lacement reaction@. Chemical e%uationA Ionic e%uationA (g > CuS&; (gS&; > Cu (g#s$ > Cu2>#a%$ (g2>#a%$ > Cu#s$

The copper in this reaction is taking electrons from the magnesium. The copper gains electrons 3 it is 2 D#C D The magnesium loses electrons 3 it is !@IDIS D So this is a 2 D!@ reaction. 7hene1er one substance gains an electron another substance must lose an electron" so reduction and o!idation always go together.

!+idising and reducing reagents

.n o!idising agent causes another material to become o!idised. In the abo1e e!ample of adding magnesium to copper sulphate" the magnesium is o!idised. Since the copper ions in the copper sulphate cause this o!idation" they are the o+idising agent. In the same way the (g causes the reduction of copper ions so it is the reducing agent. (g#s$ > Cu2>#a%$ (g2>#a%$ > Cu#s$

e!0-in# a#en%

o4i!i/in# a#en%

In this e!ample the o!idising agent #copper ions$ is reduced and the reducing agent #magnesium$ is o!idised. This always happens with redo! reactionsA3 in a redo! reaction the o!idising agent is reduced and the reducing agent is o!idised.

ele-% on/
56)CI<G .G5<T > (.T5 I.E The reducing agent loses electrons and so is o!idised.

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!+idation number and redo+ reactions

7hen a redo! reaction occurs an electron transfer takes place and so the o!idation numbers of the substances in1ol1ed changes. Consider the following reactionA eactants Species = in =&/r & in =&/r /r in =&/r => I3 &!idKn <o >* 32 >* >* 3* 'H!Br 5 'H5 5 'I3 Products Species /r in /r2 I in I2 = in =2& & in =2& Br' 5 I' 5 'H'! &!idKn <o >* 32

The table shows us that the o!idation number of /r goes from >* to -" so it is reduced. The iodine goes from 3* to -" so this is o!idised. .nother e!ample eactants Species <a in <a&Cl & in <a&Cl Cl in <a&Cl &!idKn <o >* 32 >* )$a!Cl '$aCl 5 $aCl!) &!idKn <o >* >* 3* >+ 32

Products Species <a in <aCl <a in <aCl&9 Cl in <aCl Cl in <aCl&9 & in <aCl&9

In this reaction the Cl in <a&Cl is o!idised in one reaction to >+ and in another reaction is reduced to 3*. Such an occurrence is called dis%ro%ortionation. 6isproportionation takes place a particular species undergoes simultaneous o!idation and reduction.

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Hal( ?uations
7hen a redo! reaction occurs" one substance gains electrons and one substance losed electrons. These two processes can be considered separately. )sing the e!ample of magnesium and copper sulphateA 5lectron gain 5lectron loss Cu2>#a%$ > 2e3 (g#s$ Cu#s$

(g2>#a%$ > 2e3

These are called hal( e?uations.

Constructing Hal( ?uations

=alf e%uations can be constructed as followsA a$ .dd =2& molecules to balance any o!ygen atoms b$ .dd => ions to balance any hydrogen atoms c$ .dd electrons to balance any charge in the e%uation. </ 2 To write a balanced half e%uation you may only add' =2& molecules => ions &=3 ions #not usually done$ 5lectrons e.g. Construct a half e%uation forA <&93 <=;> a$ balance o!ygen atoms with water <!)3 <=;> > )=2!

b$ balance hydrogen atoms with hydrogen ions <&93 > 0AH5 <H*> > )H'& c$ balance the charges using electrons 8urther e!ample. Construct a half e%uation forA Cr2&723 2Cr9> a$ balance o!ygen atoms with water Cr2!923 2Cr9> > 9H'! Be3 > <&93 > 0A=5 <=;5 > 9=2&

b$ balance hydrogen atoms with hydrogen ions 0*H5 > Cr2&723 2Cr9> > 9H'& c$ balance the charges using electrons -e3 5 0*=5 > Cr2&7'3 'Cr9> > 7=2&

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Constructing (ull e?uations (rom hal( e?uations

. (ull e?uation is written by adding two half e%uations together. The process is as followsA 7rite first half e%uation 7rite second half e%uation /alance in terms of electrons .dd e%uations together 5!ample 3 Potassium reacts with fluorine to form potassium fluoride. 7rite the half e%uation for the o!idation of potassium H H> > e3 7rite the half e%uation for the reduction of fluorine 82 > 2e3 283 To balance for electrons" the first e%uation must be multiplied by 2 2H 2H> > 2e3 3 82 > 2e 283 .dding the e%uations together'
2* ( F 2*( ( 2F-

&ther e!amples *. Chlorine reacts with potassium iodide to form potassium chloride and iodine. (a) 7rite the half e%uation for the o!idation of iodide 2I3 I2 > 2e3 (b) (c) 2Cl3 7rite the half e%uation for the reduction of chlorine Combine the two half e%uations. Cl 2 > 2e3 2Cl3

2I3 > Cl2 I2 >

2. /romine reacts with iron#II$ to form iron#III$ and bromide. (a) 7rite the half e%uation for the o!idation of iiron#II$ 3 e (b) (c) > e3 7rite the half e%uation for the reduction of bromine Combine the two half e%uations

8e2> 8e9> > /r 2 > 2e3 28e2> 2/r3 28e9>

/r2 > 2e3 /r2 > 28e2> 2/r3

2/r3 28e9> >

9. Chlorine reacts with a solution of sulphur dio!ide to form sulphate and chloride ions. #a$ The half e%uation for the o!idation of sulphur dio!ide isA
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S&2 > 2=2& S&;23 > ;=> > 2e3 #b$ 7rite the half e%uation for the reduction of bromine. /r 2 > 2e3 2/r3
(c) Combine the two half equations. 4H+ + 2Br
-

SO2

2H2O

Br2

SO42-

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8H P 2I!DIC 8ABL
;rou% '
8he %hysical %ro%erties o( the elements6 5lements of group 2 e!ist as solids at room temperature due to the strength of metallic bonding. The delocalised electrons in the structures gi1e each element a sil1ery sheen and causes them to be good electrical conductors. They differ from other metals of the periodic table in a number of waysA i$ They are soft. ii$ They ha1e low melting points" boiling points and low densities. &n descending the group" the atomic radii become bigger but the number of delocalised electrons remain the same. The metallic bonds then become weaker as delocalised electrons become more thinly spread as metallic radius increases. This is why the hardness" melting and boiling points decrease from top to bottom. 6ensities increase down a group due to the mass of the nuclei increasing faster than the atomic radii and therefore the atomic 1olumes. "lame colours 7hen group * or 2 metals or their compounds are placed in a flame" their electrons are pushed to a higher energy le1el. .s the electrons drop back to a lower le1el again they gi1e out energy in the form of light. The light is characteristic of each particular metal and gi1es the flame a certain colour. The energy emitted is only of certain allowed fre%uencies which correspond to certain electronic transitions. 8or groups * and 2 this happens to be in the 1isible region. Eithium Sodium Potassium red yellow lilac calcium strontium barium C brick red crimson R red apple green

These can be used in analysis to detect the presence of these elements. C <ote 2 Calcium gi1es a red flame if there arenKt any sodium impurities present. 7hen 1iewed through a diffraction grating the colours are seen as bands of coloured lines. 5ach element has a specific set of lines and so can be identified in the emission s%ectrum e1en if other elements are present. Eight coming from a gas in the laboratory or from a distant star can be analysed in this way.

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"irst ioniDation energy 5lement /eryllium (agnesium Calcium Strontium /arium 8irst Ionisation 5nergy RkNmol3* :-7;+:+++--

-.**2 -.*D-.*:7 -.2*+ -.2*7

The first IoniJation energies drop down the group as the outer electron is further away from the nucleus and the inner shielding increases. The drop in ioniJation energy down the group means that the metals become more reacti1e down the group. Successive ionisation energies6 The second ionisation energy of group 2 elements is higher than the first as the second electron is remo1ed from an already positi1e ion. There is greater attraction to as the effecti1e nuclear charge attracting the outer electron has increased. The third ionisation energy of group 2 elements is much higher than the second. The third electron must be remo1ed from an doubly positi1ely charged ion and from a stable full energy le1el closer to the nucleus. ;rou% ' lement (g at.no. *2 Ca at.no. 2Sr at.no. 9, /a at.no. +D configuration S<eT 9s S.rT ;s2 SHrT +s2 SIeT Ds2
2

I.5.s in kN mol2* first second 79D *;++:**++;, *-D+-2 :DD

Third 7799 ;:*2 ;2*-

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2eactions o( grou% ' elements

2eactions with o+ygen Group 2 elements form the o!ide of formula (& when heated in o!ygen. 8or e!ample magnesium' 2(g > &2 2(g& &n prolonged heating in o!ygen" Sr and /a can go on to form the pero!ide #containing the &223 ion" which is stabilised by large cations$A 2/a& > &2 2/a&2 #prolonged heating$ 2eactions with chlorine .ll the group 2 metals react when heated in chlorine to form chlorides. (agnesium for e!ampleA (g > Cl2 (gCl2

2eactions with water Group 2 elements are less reacti1e than the corresponding group * element. /eryllium does not react e1en in steam. (agnesium burns when heated in steam to form magnesium o!ide and hydrogen. (g > =2& (g& > =2 Calcium" strontium and barium all react with cold water with increasing 1igour to form the metal hydro!ide and hydrogen. Calcium hydro!ide is only sparingly soluble in water" so this reaction produces effer1escence and a thick white suspension. Ca > 2=2& Ca#&=$2 > =2 Sr > 2=2& Sr#&=$2 > =2 /a > 2=2& /a#&=$2 > =2

2eactions o( the o+ides o( grou% ' elements

2eactions with water /e& is not attacked by water. The o!ides of the other group 2 elements are ionic and react with water to form hydro!ides. Ca& > =2& Ca#&=$2 2eactions with dilute acid The o!ides of group 2 are bases and so react with acids to form salt and water. (g& > =2S&; (gS&; > =2& Ca& > 2=<&9 Ca#<&9$2 > =2& /a& > 2=Cl /aCl2 > =2&
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2eactions o( the hydo+o+ides o( grou% ' elements

=ydro!ides of group 2 are also bases and so react with acids to form salts and water' Ca#&=$2 > 2=<&9 Ca#<&9$2 > 2=2&

Solubility o( grou% ' sul%hates and hydro+ides The table below shows the trend in the solubilities of group 2 sulphates. Sulphate (agnesium Calcium Strontium /arium description Soluble Slightly soluble Insoluble Insoluble Solubility molR*--g water 9D-- ! *-3; ** ! *-3; -.D2 ! *-3; -.--: ! *-3;

It can be seen that the sulphates become less soluble down the group. (agnesium sulphate is 1ery soluble" barium sulphate is insoluble and is part of the test for sulphates. The hydro!ides show the re1erse of this trend with the compounds in general becoming more soluble down the group. Calcium hydro!ide is only slightly soluble in limewater but barium hydro!ide is a 1ery soluble alkali which can be used in titrations. . =ydro!ide Solubility molR*--g water (agnesium -.2 ! *-3; Calcium *D ! *-3; Strontium 99- ! *-3; /arium 2;- ! *-3;

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8hermal stability Carbonates and $itrates

6ecomposition of certain carbonates and nitrates of groups * and 2 occurs when the compounds are heated. .ll group * carbonates are thermally stable up to /unsen temperatures. Eithium and group 2 carbonates decompose when heated to form the metal o!ide and carbon dio!ide. Ei2C&9 Ei2& > C&2 (gC&9 (g& > C&2 The carbonates become less stable on ascending the group. Carbonate /eryllium (agnesium Calcium Strontium /arium 6ecomposition temperature RoC *-+;:-*2:*9D-

The decomposition is a result of the polarising power of the cation. .s polarising power of the cation increases" compounds become more co1alent in character and less stable to heat. Going down the group the cations become larger" so their polaring power decreases. The smallest ion" (g2>" has the highest charge density #is the most polarising$" and forms the compound with the small anion most readily #i.e. at the lowest temperature$. . large anion like C&923 or <&93 is %olarisable& and is decomposed most readily by a polarising cation. Group * compounds are more stable because the cation has only one positi1e charge and so it is less polarising. It is the polarising power of the cation that causes decomposition of the nitrates also. .ll the nitrates decompose. Group * nitrates" e!cept for lithium break down to form metal nitrite and o!ygen. Eithium and group 2 elements" ha1ing a more polarising cation break down to a greater e!tent into metal o!ide" nitrogen dio!ide and o!ygen.

)i Na * >" C/

Be 9# Ca S Ba

4)iNO3 29<NO3=2 2)iNO3

2)i2O ( 4NO2 ( O2 29O ( 4NO2 ( O2 2)iNO2 ( O2

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;rou% 9
Physical Pro%erties
Halogen Chlorine /romine Iodine A%%earance o( element at room tem%erature Green gas ed3brown li%uid Grey3black solid A%%earance o( element in a?ueous solution Pale green #almost colourless$ &range or yellow /rown A%%earance o( element in hydrocarbon solution Pale green #almost colourless$ ed Fiolet

.ll halogens are diatomic #I2$A as they contain more electrons going down the group" the dispersion forces between the molecules increase" so the melting and boiling %oints increase. The colour depends on the absorption of light" which in turn depends on an electron 0umping to a higher3energy orbital. .s the atoms get larger" less energy is needed for an electron to 0ump into the lowest unoccupied orbital" and so the element absorbs more strongly at longer wa1elengths #i.e. in the 1isible region$" and appears darker. .ll halogens are soluble in non3polar sol1ents like he!ane. Chlorine is slightly soluble in water" bromine e1en less" and iodine 1irtually insoluble.

8ests (or Halogens

Chlorine turns blue litmus red then bleaches it. Chlorine displaces bromine and iodine from bromide or iodide solutions. Cl2#a%$ > 2H/r#a%$ 2HCl#a%$ > /r2#a%$ Cl2#a%$ > 2HI#a%$ 2HCl#a%$ > I2#a%$ /romine is orangeRred if dissol1ed in an organic sol1ent. /romine displaces iodine from an iodide solution. /r2#a%$ > 2HI#a%$ 2H/r#a%$ > I2#a%$ Iodine turns starch black" is decolourised by thiosulphate solution and is brown in water but purple in organic sol1ents.

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Chemical reactions
The halogens tend to gain electrons to form halide ions& @3. In the process of gaining an electron" the electron is remo1ed from some other substance" so the halogens tend to be o!idising agents.

2eaction with Metals

The reacti1ity of the halogens increases up the group. They tend to be reacti1e with metals" but the 1igour of the reaction decreases going down the group. Sodium will burn 1iolently in chorine' 2<a > Cl2 2<aCl Sodium will also ha1e 1igorous reactions with gaseous bromine and iodine" but the reaction becomes less e!othermic as the atomic number of the halogen increases. The heat energy gi1en out in the reaction between sodium and the halogen is shown in the table below. Halogen Chlorine /romine Iodine nthal%y o( (ormation& EH(F G$a@1 . =Hmol30 3;*; 39D* 32,,

2eaction with non3metals

=alogens also react with non3metals. The reaction with hydrogen illustrates the decreasing reacti1ity down the group. Chlorine and hydrogen e!plode in the presence of sunlight' Cl2 > =2 2=Cl /romine re%uires heat and the presence of a platinum catalyst to react" while iodine only reacts slowly and the reaction does not go to completion.

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2eactions o( Halogens as o+idising agents

The reacti1ity of the halogens increases up the group as they gain electrons more easily. The electron is gained more easily as the empty position it fills is closer to the nucleus and there is less inner shielding electron shielding with the elements high in the group. This means that the elements become stronger o!idising agents going up the group.

Dis%lacement reactions
The potassium halides indicate the o!idising powers of the =alogens. =alogen displacement reactions using potassium halides illustrate the increasing strength of o!idising power of the halogen going up the group. Chlorine will o!idise bromide and iodide ions' bromine will o!idise iodide ions' and iodine will not react with either Cl 2 or /r2. The reactions are illustrated in the table below (i!ture Potassium iodide > chlorine Potassium bromide > chlorine Potassium iodide > bromine 5%uationsA .ppearance of potassium halide solution Colourless Colourless Colourless .ppearance of halogen solution Colourless Colourless orange .ppearance after mi!ing brown orange brown Conclusion Iodine displaced /romine displaced Iodine displaced

Cl2#g$ > 2/r2#a%$ 2Cl2#a%$ > /r2#a%$ Cl2#g$ > 2I2#a%$ 2Cl2#a%$ > I2#a%$ /r2#a%$ > 2I2#a%$ 2/r2#a%$ > I2#a%$

turns orange turns redRbrown turns redRbrown

The salt solutions" e.g. <aCl" <a/r and <aI" are initially colourless.

!+idation o( ironGII1
Iron is a transition metal and it can form compounds of iron#II$ and iron#III$. Chorine is capable of o!idising iron#II$ to iron#III$. If chlorine water is added to a pale green solution of containing 8e 2>" a yellow solution containing 8e9> is formed. Cl2 > 28e2> 2Cl3 > 28e9> /romine is also able to o!idise iron#II$ to iron#III$" but iodine is not a strong enough o!idising reagent to carry out this reaction.

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Iodine titrations
Thiosulphate and iodine titrations are used to determine the concentration of o!idising agents. 8irst of all the o!idising agent is added to a solution containing e!cess iodide ions. This o!idises the iodide ions to iodine gi1ing a brown colour. 2I3 I2 > 2e3 #the electrons go to the o!idising agent$ Thiosulphate #usually as sodium thiosulphate$ is then added from a burette' this reacts with the iodine to form colourless products. 2S2&923 > I2 2I3 > S;&D2 6uring the titration" the colour intensity decreases" e1entually reaching a pale yellow colour. .t this point" a few drops of starch solution are added to gi1e the deep blue comple! showing the last traces of iodine. Thiosulphate is then added dropwise" until the mi!ture becomes colourless. 8rom a known concentration of thiosulphate" it is possible to determine the number of moles of chemical in1ol1ed in the reaction.

5!ample . -.,--g of a contaminated sample of potassium iodate" HI& 9" was dissol1ed in 2+-cm9 of solution. 2+cm9 of this solution was added to an e!cess of potassium iodide and dilute sulphuric acid. The mi!ture re%uired 2*.D-cm9 of -.*mol dm39 sodium thiosulphate solution to remo1e the iodine released. Calculate the percentage purity of the potassium iodate. (oles of sodium thiosulphate B 2*.D- R *--- ! -.* B -.--2*D mol 5%uation for the titrationA 2S2&923 > I2 2I3 > S;&D23

(oles of iodine B -.--2*D R 2 B -.--*-, mol 5%uation for the formation of iodineA +I3 > I&93 > D=> 9I2 > 9=2&

(oles of iodate in the 2+cm9 sample B -.--*-, R 9 B -.---9D mol (oles of iodate in the 2+-cm9 solution B -.---9D ! 2+- R2+ B -.--9D (ass of pure potassium iodate B -.--9D ! 2*; B -.77-;g Percentage purity B -.77-; R -.,--- ! *-- B :D.9L

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2eactions with Concentrated Sul%huric Acid

7hen concentrated sulphuric acid is added to a potassium halide" hydrogen halide is formed. 7ith a chloride misty white fumes appear. HCl > =2S&; H=S&; > =Cl The chloride ion is not a strong enough reducing agent to ha1e a further reaction. Concentrated sulphuric acid is an o!idising agent and reacts further with the bromide and iodide. /romide ions reduce the sulphuric acid to sulphur dio!ide. &range3brown misty fumes appear. 2=/r > =2S&; /r2 > 2=2& > S&2 Iodide ions can produce a 1ariety of reactions forming sulphur dio!ide" sulphur and hydrogen sulphide. 2=I > =2S&; I2 > 2=2& > S&2

Identi(ication o( halide ions

To test a substance to see if it contains chloride" bromide or iodide ions" the substance is dissol1ed in water" acidified with dilute nitric acid" and then sil1er nitrate solution is added. . precipitate of sil1er halide forms" and from its colour it is possible to identify the halide. .g>#a%$ > I3#a%$ .gI#s$ The effect of sunlight on the precipitate or addition of ammonia solution to the precipitate can then be used to confirm the result. Halide Chloride Silver nitrate 7hite precipitate Cream precipitate /romide ((ect o( sunlight 7hite precipitate turns purple3grey Cream precipitate turns green3yellow Ammonia solution Precipitate dissol1es. In dilute ammonia" precipitate partially dissol1es. In concentrated ammonia precipitate dissol1es. Precipitate does not dissol1e.

Iodide

Oellow precipitate

<o effect

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2eactions o( hydrogen halides

In water The hydrogen halides are soluble in water" and when dissol1ed in they split up #dissociate$ into ions forming an acidic solution. =I#a%$ =>#a%$ > I3#a%$ =Cl is strongly acidic due to complete dissociation. =I#a%$ > =2&#l$ =9&>#a%$ > I3#a%$ =ydrogen ions => or hydro!onium ions" =9&>" pro1ide the acidity. The relati1e acid strength is =8 MM =Cl M =/r M =I. =I is the strongest acid as it has the weakest bond #=3I$. It is therefore more easily dissociated into => or =9&> ions. With ammonia 7hen gaseous hydrogen halides come into contact wit gaseous ammonia" dense white smoke of ammonium halide is produced. =I#g$ > <=9#g$ <=;I#s$

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8he 50 and 5, o+idation states o( chlorine

.ll the halogens e!cept for fluorine e!hibit a number of positi1e o!idation states. These are due to the promotion of electrons from p orbitals into 1acant d orbitals. Chloric #I$ acid =Cl& forms salts called chlorate#I$Gs e.g. <aCl&. which contain the ion Cl&3 . Chloric acid #F$ =Cl&9 forms a series of salts called chlorate#F$Gs. 8or e!ample <aCl&9 contains the ion Cl&93. These salts and acids are all good o!idising agents.

Chlorine as a bleach
Chlorine is sparingly soluble in water. Some of the dissol1ed chlorine reacts in a dis%ro%ortionation reaction #one in which an element is simultaneously o!idised and reduced$A Cl2#g$ > =2&#l$ =Cl&#a%$ > =>#a%$ > Cl2#a%$ o!idation states S-T S>*T S2*T =Cl&" or chloric#I$ acid" is called a bleach" since it is able to o!idise coloured compounds such as litmus. It will also kill bacteria by o!idising them. This is made use of in water purification. The water supply is treated with sufficient chlorine to gi1e a concentration of about -.+ mg dm 29. .t this le1el" harmful organisms are killed" but humans can drink the water without effect #other than a slight odour$.

Chlorine and al=ali

7hen chlorine is passed into cold dilute sodium hydro!ide solution" it disproportionates to chlorate#I$ and chlorideA Cl > 2&=2 Cl&2 > Cl 2 > = &
2 2

If" instead" chlorine is passed into a hot" concentrated solution of sodium hydro!ide" the disproportionation goes further" forming chlorate#F$ and chloride 2 note that one Cl goes up by + o!idation numbers #- to >+$" and fi1e Cls go down by one #- to 2*$A 9Cl > D&=2 Cl& 2 > +Cl 2 > 9= &
2 9 2

The chlorate#F$ can be e!tracted by filtration and purified by recrystallisation as it is less soluble in water than the chloride. Similar reactions occur for bromine and iodineA these go all the way to /r& 93 and I&93 e1en in dilute solution.

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2A8 S
8he Collision theory
The collision theory e!plains rates of reaction in terms of colliding particles. 5ssentially it says that before two particles can react they ha1e to undergo a collision with each other. =owe1er" if the rate of a reaction is compared to the number of collisions which take place it is found that only certain collisions produce a reaction. In order to produce a reaction" the molecules must ha1e the correct orientation and sufficient energy' If the orientation is not correct then nor reaction occurs when molecules collide.

If a collision does not ha1e the acti1ation energy" molecules do not react.

7ith correct orientation and acti1ation energy a reaction can occur.

The factors which determine the rate of a chemical reaction are the following. *. Concentration' the higher the concentration" the more there are in a gi1en 1olume and so the more often the particles will collide in a set time. 2. Pressure in a gas' for a gas increase in pressure increases the number of particles in a gi1en 1olume and so this is the same as concentration. 9. 8em%erature' the higher the temperature" the faster the particles mo1e and so the greater the number of collisions in a set time. .lso the energy of the particles increases" so more effecti1e collisions take place. ;. Sur(ace area for solid and li%uidRgas' the reaction will occur where the two types of particle meet" at the surface" so the greater the surface area" the greater the number of collisions in a set time. +. . catalyst pro1ides an alternate reaction route of lower acti1ation energy allowing more collisions in a set time to produce a reaction.
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2ate and Molecular nergy

The collision theory states that when two particles collide" they will only react if they ha1e sufficient energy. Since" often only one collision in *- *; produces a reaction" this factor is 1ery significant. . Ma+well3BoltDmann gra%h shows the distribution of molecular energies

<umber of molecules

21

Temperature T9 U T2 U T*

22 23

(olecular energy This type of graph is called a (a!well3/oltJmann distribution. It shows the distribution of molecular energy within a gas. The horiJontal a!is shows the energy le1el and the 1ertical is the number of particles that ha1e that energy. .t a higher temperature the a1erage energy of the molecules increases. The area under each cur1e is the same" as this represents the total number of molecules" it does not of course change with temperature.

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Activation nergy
8or molecules to react bonds ha1e to first be broken. This means energy is taken in. 7hen molecules collide and react" they mo1e through a state of high potential energy. This can be pictured as an energy barrier. The energy re%uired for a reaction to take place is called the activation energy& A.

5nergy

>ea-%an%/ /

:? P o!0-%/

Path of reaction Products of a reaction will only form if the particles ha1e sufficient energy to o1ercome this energy barrier" the siJe of this barrier being the acti1ation energy. The higher the 1alue of the acti1ation energy" the lower the number of effecti1e collisions and so the lower the rate of reaction. The acti1ation energy can be shown on the (a!well3/oltJmann distribution graph.

:? :?

&nly molecules with energy e%ual to or higher than the acti1ation energy can react. This is represented by the area under the line to the right of the .cti1ation 5nergy line.

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This means that as the temperature is increased many more molecules can react.

Catalysts
. catalyst is a substance which" when added to a reaction #normally in a small amount$ will increase the rate of reaction. The substance does take part in the reaction" but if it changes it is normally reformed by the end of the reaction" so it can perform its task again. Catalysts are of great economic importance" because many of the chemical reactions used in industry will not take place #or re%uire too much energy$ without a catalyst. 5!amplesA (aking fertilisersA 8e in =aber process #see below$ to make ammonia' Pt for o!idation of ammonia to make nitric acid Petroleum processingA .l2&9 in cracking' Pt in isomerisation' PtR e and PtRIr in reforming (argarine productionA <i in hydrogenation of unsaturated oils. Catalysts do not generally affect the original pathway for a reaction" but pro1ide a different pathway in addition" which re%uires a lower activation energy. /ecause of this" more molecules will ha1e enough energy to react" and so there will be more successful collisions.

/ represents the intermediate formed on interaction of reactant and catalyst.

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This lower energy can be shown on a (a!well3/oltmann distribution cur1e.

5. )ncatalysed reaction

5. Catalysed reaction

.s the acti1ation energy is lowered" more molecules ha1e sufficient energy to react. The lower acti1ation energy also applies to the re1erse reaction" so both forward and re1erse reactions are speeded by the same amount. =ence there is no change in the e%uilibrium yield" although e%uilibrium is attained more rapidly.

Homogeneous and heterogeneous catalysts

Catalysts are di1ided into homogeneous #in the same phase as the reactants" e.g. in solution for li%uid3phase reaction' or all in gas phase$ and heterogeneous #different phase 2 usually a solid catalyst for gas3phase or li%uid3phase reactants$ catalysts. Heterogeneous catalysts such as surface catalysts in1ol1e steps such as' diffusion to surface" adsorption on surface" reaction at surface" deadsorption from surface" diffusion from surface. If two reactant molecules collide they may react if they ha1e enough energy. If they are brought together on the surface of a catalyst the acti1ation energy may be lower so at a gi1en temperature the reaction will be faster.
CH:9&SO>P2&ON
= = = = = < < = = = = < = < =

>:?C2&ON
= <

@:?@SO>P2&ON
= = < = =

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Homogeneous catalysts can form intermediates which contain the catalyst but then decompose to form products. e.g. The reaction' ./>C high acti1ation energy low acti1ation energy low acti1ation energy

Catalysed reaction . > catalyst .3catalyst Intermediate .3catalyst / > C > catalyst

<ote 3 The catalyst may change o!idation state during the reaction.

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CH MICAL I#ILIB2IA
Dynamic ?uilibrium
5%uilibrium in1ol1es reversible reactions which do not go to completion. If we consider a reaction between . and / to form C and 6 which is re1ersible. 7hen . and / are mi!ed" the molecules will form C and 6. =owe1er" as soon as molecules of C and 6 are formed and collide they can also react to become . and /. Such a reaction is written' . > / C > 6 The reaction reaches a point at which the proportion of each chemical becomes constant. This is described as e?uilibrium. If the reactants are mi!ed" their concentrations will fall" rapidly at first" but then more and more slowly" until they settle to their ?e%uilibrium@ 1alues. (eanwhile the amounts of products will increase" until they too achie1e their e%uilibrium amounts. The actual 1alues of these amounts depend on the conditions.

5%uilibrium is when a reaction has a constant concentration of reactants and products. 7hen e%uilibrium is reached" the reaction has not stoppedA instead" the rate at which the forward reaction is proceeding is e!actly balanced by the rate of the re1erse reaction. This is what is meant by ?dynamic@ e%uilibrium P indi1idual molecules are reacting all the time" but the o1erall concentrations of the substances do not change. Summary 3 at e?uilibriumJ the system is closed #no substances can be added or lost$. rate of forward reaction B rate of re1erse reaction. all measurable 1ariables are unchanging #concentration of each substance" pressure" temperature$.

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((ect o( Conditions on the ?uilibrium

The conditions which can be applied to a system are change in concentration" pressure" temperature and the use of a catalyst. In an e%uilibrium there is a constant ratio between the concentration of reactants and products at a particular temperature. Le Chatelier<s %rinci%le states that when a reaction at e%uilibrium is sub0ected to a change in condition #temperature" pressure or concentration$" the e%uilibrium composition R position alters to reduce the effect of the change.

Changing the Concentration

If the e%uilibrium is disturbed by changing the concentration of either reactants or products" the reaction will ?shift@ in order to re3establish the e%uilibrium. Suppose that in a reaction 5 G There is an e%uilibrium ratio of concentration of * A 2. So if the e%uilibrium mi!ture contains * mole of 5" then there will be 2 mole of G. If -.D mole of 5 is added" the e%uilibrium is disturbed and the ratio temporarily becomes *.D A 2 The increased concentration of reactant causes the rate of the forward reaction to increase. This means that product is formed at a faster rate and its concentration increases. The system shifts to the right to re3establish the e%uilibrium. This will continue until an additional -.; mole of 5 has been con1erted to G" and the 1alues become *.2 A 2 .; The ratio of concentration is now back at * A 2" 5%uilibrium has been re3established. In general" if the concentration of reactants is increased" the system can counteract this change by shifting to the right" so reducing the concentration of the reactants again. This process increases the concentration of the products and continues until the ratio returns to its original 1alue again. 6uring this process the reaction has shifted to the right. Increasing the concentration of the products correspondingly mo1es the position to the left. Increasing the concentration o( a reactant causes a shi(t to the right6 Increasing the concentration o( a %roduct causes a shi(t to the le(t .

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Changing the Pressure

.ltering the pressure will effect a gas reaction if there are different numbers of moles of reactant and product in the e%uation. 8or e!ample in a reaction. 2N E

If the pressure of the system is increased" the system reacts to counteract the increase. In the reaction abo1e this means that the reaction will shi(t to the right" reducing the number of gas molecules present and so reducing the pressure.
A ) A A A ) ) A A A A

The pressure of a gi1en 1olume of gas will depend upon how many gas molecules there are in it. .s the pressure is increased" two N molecules form * E molecules" reducing the pressure of the gas.

) ) ) ) A ) A A

In generalA Increasing the %ressure o( a gaseous reaction causes a shi(t towards the side with (ewer gas molecules6 Decreasing the %ressure o( a gaseous reaction causes a shi(t towards the side with the larger number o( gas molecules6

Changing the 8em%erature

.n endothermic reaction is one that takes in heat energy and so causes a temperature decrease.

:n!o%.e miea-%ion

If the temperature of an e%uilibrium reaction is increased" the system tries to counteract this change by reducing the temperature again by carrying out the endothermic reaction. In generalA Increasing the tem%erature o( a reaction causes a shi(t towards the endothermic reaction6 Decreasing the tem%erature o( a reaction causes a shi(t towards the e+othermic reaction6
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Adding a Catalyst
Catalysts do not alter the e%uilibrium constant or the position of e%uilibrium. They do affect the time needed for the system to reach e%uilibrium.

Laboratory e+am%les o( e?uilibrium

The e%uilibrium Cl2#g$ > Pale green ICl#l$ /rown ICl9#s$ yellow

Iodine chloride is placed in a ) tube and chlorine passed o1er it . chlorine

.s chlorine is passed into the system its concentration is increased. The system acts to reduce the chlorine le1el again by shifting to the right.

Iodine chloride /rown li%uid The chlorine supply is then stopped

Iodine chloride Oellow solid

.s the chlorine concentration is decreased. The system acts to increase it again by shifting to the left.

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2.e eB0ili" i0m N2O4 2NO2 CH>D 8 ( 58 EAmol-1

.s the temperature is increasd" the system acts to oppose this change. The cooling endothermic reaction is fa1oured and it shifts to the right.

Hea%

8he Haber Process

$'Gg1 5 )H'Gg1 '$H)Gg1 H : 3K'=Hmol30

emo1ing the of ammonia as soon as it forms will cause the position of e%uilibrium to mo1e to the right and gi1e a bigger yield of ammonia. #This is achie1ed by cooling the mi!ture as the ammonia turns into a li%uid first$. 7hen the pressure is increased the e%uilibrium shifts to the side with least gas molecules. " The reaction shifts from left to right" gi1ing a bigger yield of ammonia. . =aber process plants operate between 2--3;-- atmospheres pressure. 6ecreasing the temperature leads to a higher yield of ammonia because the reaction from left to right is e!othermic and causes the temperature to rise again if ammonia is formed. In the =aber process a moderately high temperature of around +-- oC is used to speed the rate at which e%uilibrium is reached. This temperature is chosen in spite of the fact that a lower temperature gi1es a higher yield. The optimum #best$ conditions for this process which gi1e the greatest yield areA 9+- atmospheres' high pressure increases yield. about ;+-VC ' high temperature cuts yield but increases rate. and the use of a catalyst" iron" to increase the rate.
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!rganic Chemistry 3 Halogenoal=anes and Alcohols

Halogenoal=anes
=alogenoalkanes contain a halogen as the functional group 3=al.

The first part of the name of an halogenoalkane gi1es the position and name of the halogen concerned. The second part of the name is based on the rest on the hydrocarbon structure.
= = C = = C = = C = = C = Cl = = C = = C = = C = = C /r = C = =

*3chlorobutane
= = C = = C = = I C C = =

23/romopentane

= C = =

Cl Cl
2"936ichloroheptane

23Iodo323methylbutane

93/romo393methylhe!ane

8y%es o( Halogenoal=anes
There are three types of halogenoalkane' primary" secondary and tertiary. They are classified according to the number of carbon groups attached to the carbon with the halogen" I" group.

H H C 3 H

H > C 3 H

> > C 3 H
Secondary Two carbon # $ groups attached to the carbon with the I group is a seconary halogenoalkane.

> > C 3 >

Tertiary Three carbon # $ groups attached to the carbon with the I group is a tertiary halogenoalkane

Primary <o or one carbon # $ group attached to the carbon with the I group is a primary halogenoalkane.

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Chemical %ro%erties o( Halogenoal=anes

8luoroalkanes are different from the other halogen deri1ati1es" since the C28 bond is so strong that they are 1ery unreacti1e. (ost of the discussion here will refer to Cl" /r and I. Chloromethane" bromomethane" and chloroethane are gases" while the rest are li%uids which do not mi! with water as they do not ha1e the ability to hydrogen bond.

Pre%aration o( Halogenoal=anes
=alogenoalkanes are generally made by reacting the appropriate alcohol it with a halogenating reagents. =alogenating agents include phosphorus pentachloride" sodium chloride with concentrated sulphuric acid" sodium bromide with concentrated phosphoric acid and phosphorus with iodine. Phosphorus pentachloride reacts 1igorously with alcohols at room temperature. C2=+&= > PCl+ C2=+Cl > =Cl > P&Cl9 Choro3 compounds can also be formed by heating the alcohol under reflu! with sodium chloride and concentrated sulphuric acid. =2S&; > <aCl =Cl > <a=S&; =Cl > C9=7&= C9=7Cl > =2& To form a bromo3 compound" the alcohol is heated under reflu! with sodium bromide and concentrated phosphoric acid. The concentrated phosphoric acid reacts with the sodium bromide to form hydrogen bromide" and the hydrogen bromide carries out the substitution. =9P&; > <a/r =/r > <a=2P&; =/r > C9=7&= C9=7/r > =2& To produce iodo3 compounds" the alcohol is mi!ed with red phoshorus and iodine is added gradually. The mi!ture is then heated under reflu!. P > *WI2 PI9 PI9 > 9C=9C=#&=$C=9 9C=9C=IC=9 > =9P&9 Concentrated sulphuric acid cannot be used to make bromoalkanes or iodoalkanes as the halide ion is o!idiJed to the halogen.

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2eactions o( Halogenoal=anes
=alogenoalkanes commonly undergo nucleo%hilic substitution and elimination reactions. $ucleo%hilic substitution reactions . nucleo%hile is a species #molecule or negati1e ion$ which can donate an electron pair in a chemical reaction. =alogenoalkanes undergo substitution reactions with nucleophiles such as &= 2 and <=9. with %otassium hydro+ide6 ConditionsA =eat under reflu! in a?ueous solution. /oth <a&= or H&= are suitable. C'H,Br 5 $a!H Ga?1 C'H,!H 5 $aBr with %otassium cyanide ConditionsA eflu! solution of halogenoalkane and potassium cyanide in ethanol. C'H,Br 5 >C$ C'H,C$ 5 >Br propanenitrile This adds a carbon atom to the chain and forms a nitrile. with ammonia ConditionsA =eat with concentrated ammonia in a sealed tube. or heat with alcoholic ammonia. C'H,I 5 $H) C'H, $H' 5 HI 5thylamine #an amine$ &ther products includeA #C 2=+$2<= and #C2=+$9< .mines are molecules containing a < functional group. limination reactions If a halogenoalkane is boiled with potassium hydro!ide solution in ethanol rather than water an elimination reaction takes place in which an alkene is formed and hydrogen halide is gi1en off #eliminated$. ConditionsA =eat under reflu! with al=ali and ethanol as sol1ent. )se H&= here. CH)CH'Br CH'CH' 5 HBr

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Identi(ication o( halogenoal=anes 4 2eaction with Silver nitrate solution6

In the presence of water" halogenoalkanes undergo hydrolysis. The halogenoalkanes ha1e a slightly polarised C3=al bond. 7ater acts as a nucleophile towards the carbon atom in this bond. .s a result " the 3&= group substitutes for the halogen" gi1ing an alcohol and a hydrogen halide. The reaction is much slower than with an alkali. I > =2& &= > =I

The hydrogen halide formed will dissol1e in the water forming = > and I3 ions. The ions then react with the sil1er ions in the solution producing a precipitate. The appearance of the precipitate depends upon the halide ion generated in the hydrolysis reaction. .g>#a%$ > I3#a%$ .gI#s$ 8his reaction is used to test (or halogenoal=anes6 =eat sample of halogenoalkane with a%ueous hydro!ide ions. .cidify with dilute a%ueous nitric acid. .dd a few drops of a%ueous sil1er nitrate. . white precipitate soluble in dilute a%ueous ammonia" indicates chloride. . buff precipitate insoluble in dilute a%ueous ammonia but soluble in concentrated a%ueous ammonia" indicates bromide. . yellow precipitate insoluble in concentrated a%ueous ammonia indicates iodide.

2eactivity o( halogenoal=anes
esults of in1estigations show that the rate of hydrolysis of the halogenoalkanes occurs in the orderA 03iodobutane / 03bromobutane / 03chlorobutane The ease of reaction depends on the ease of breaking the C3=al bondA /ond A C3I C3/r C3Cl C38 3* /ond enthalpy terms #kN mol $A >29, >27D >99, >;,; Thus the ease of bond breaking is" C3I / C3Br / C3Cl / C3"6 #This outweighs the effects caused by greater polariJation in the C3=al bond$.

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#ses o( halogenoal=anes
=alogenoalkenes are use as fire retardants and refrigerants as they are unreacti1e and particularly for the fire retardants they are non3combustible . 8reon *2 C82Cl2 is a refrigerant and an e!ample of a chlorofluorcarbon #C8C$. The C38 and C3Cl bonds are 1ery strong. The result is that it does not decompose easily so lasts for the lifetime of a refrigerator. It does not decompose %uickly when discarded but does so in the upper atmosphere. The radicals it forms react with oJone. The loss of oJone leads to an increase in )F radiation reaching the 5arthGs surface and a corresponding increase in skin cancers in humans. (odern refrigerants are hydrofluorocarbons" =8Cs" such C8 9C=28. They do not lead to oJone depletion. PFC used as electrical insulator 3S3C=23C=Cl3Tn3 The C3Cl bond is strong so PFC insulation lasts a long time but when discarded it does not rot #it is not biodegradable$. Teflon" or %olyGtetra(luoroethene1 is essentially poly#ethene$ chains in which all the = atoms ha1e been replaced by fluorinesA 2C822C822C822C822C822C822C822C822C822 etc. It is used to line non3stic= (rying %ans and sauce%ans" and for low3friction bearings. .s the C38 is 1ery strong it is non3biodegradable. 66T is a pesticide used to kill mos%uitos. CCl9 X Cl3CD=+3C3CD=+3Cl X = The strong C3Cl bonds gi1e 66T a long life in the field killing pests. It is howe1er so long li1ed that it persists in the en1ironment and builds up in the food chain threatening creatures at the top of the chain.

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Alcohols
.lcohols contain the 3&= functional group. General formula 2 CnH'n50!H The first part of the name of an alcohol is according to the longest carbon atom se%uence. The second part of the name is 2ol. . number will be included to indicate the position of the alcohol group.
= & & = & =

Pen%anol o pen%an-1-ol 8y%es o( Alcohol

Pen%an-2-ol

3-me%.yl"0%an-2-ol

There are three types of alcohol' primary" secondary and tertiary. They are classified according o the number of carbon groups attached to the carbon with the &= group.

H H H C O H > C O H H H
Primary <o or one carbon # $ group attached to the carbon with the &= group is a primary alcohol.

> > C O H H
Secondary Two carbon # $ groups attached to the carbon with the &= group is a secondary alcohol.

> > C O H >

Tertiary Three carbon # $ groups attached to the carbon with the &= group is a tertiary alcohol.

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Physical %ro%erties o( alcohols

The &= group can take part in hydrogen3bonding" both as a donor #= is sufficiently >$ and as an acceptor #through the two lone pairs on the o!ygen atom$. .s a result alcohols ha1e higher melting and boiling points than hydrocarbons of comparable molar mass. They are also more soluble in water because of =3bondingA ethanol is miscible with water in all proportions. .s the non3polar hydrocarbon chain becomes longer" it becomes harder for water to dissol1e the alcoholA from C ; alcohols are less soluble" and donKt mi! with water.

2eactions o( Alcohols
Combustion .ll alcohols undergo combustion to form carbon dio!ide and water. 8or e!ample the e%uation for the combustion of butanol is as follows' C;=:&= > D&2 ;C&2 > +=2& 2eaction with sodium .ll alcohols react with sodium. 2 &= > 2<a 2 &<a > =2 This e%uation is similar to the reaction of sodium with water" e!cept that an al=o+ide is formed rather a hydro!ide. e.g. 5thanol and sodium 2C2=+&= > 2<a 2 C2=+&<a > =2 Sodium etho!ide

2eaction with %hos%horus %entachloride .ll alcohols react with phosphorus pentachloride. 8his is used as a test (or the 3!H grou%. The presence of the &= group can be shown by adding phosphorus pentachloride to the compound. . reaction takes place forming hydrogen chloride which appears as steamy white fumes. &= > PCl+ Cl > P&Cl9 > =Cl In the reaction with phosphorus pentachloride a chloro group replaces the 3&= group. e.g. Propanol and phosphorus pentachloride C=9C=2C=2&= > PCl+ C=9C=2C=2Cl > P&Cl9 > =Cl 2eaction with other halogenating agents .lkyl bromides can be made from the reaction of an alcohol with =/r. =/r is made in situ from H/r and =2S&; forms bromoalkanes during heating under reflu!. C2=+&= > =/r C2=+/r > =2& .lkyl chlorides can be made by reflu!ing the alcohol with conc. =Cl in the presence of YnCl 2 C2=+&= #l$ > =Cl #g$ C2=+Cl #l$ > =2& #l$ Iodoalkanes can be made in a reaction phosporus triiodide from iodine and red phosporus. 9C2=+&= > PI9 9C2=+I > =9P&9 The relati1e reacti1ities of alcohols in halogenation are tertiary U secondary U primary alcohol.
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!+idation o( alcohols
Primary and secondary alcohols can be o!idised by heating with a mi!ture of dilute sulphuric acid with sodium or potassium dichromate#FII$ solution. .cidified dichromate#FI$ solution is produces a colour change from orange to blue3green when it has undergone o!idation reactions. In writing e%uations for these o!idation reactions S&T is used to represent the o!idising agent. Primary alcohols form an aldehyde" and then on further o!idation" form carbo!ylic acids.

H > C O H H
Primary alcohol

O > C H
.ldehyde

O > C O H

Carbo!ylic acid

Secondary alcohols form ketones" but no further o!idation takes place.

> > C O H H
Secondary alcohol e.g. CH)CHG!H1CH) 5 L!M propan323ol

O > C >
Hetone CH)C!CH) 5 H'! propanone

Tertiary alcohols do not react with o!idiJing agents.

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Partial !+idation to aldehydes

e.g. ethanol to ethanal. C=9C=2&= > S&T C=9C=& > =2& To make the aldehyde" the one reagent is added dropwise to the other and the product is distilled off as it forms. /y distilling the aldehyde off as it forms" it means it will not undergo further o!idation to the acid.

Hea% 8otal !+idation to Carbo+ylic acids

e.g. ethanol to ethanoic acid. The mi!ture of reagents is heated under re(lu+. C=9C=2&= > 2S&T C=9C&2= > =2& Heating under re(lu+ The apparatus shown here is used a large number of organic preparations. The reaction mi!ture is placed in the pear shaped flask. It has a reflu! condenserC fitted. This means that as the reactants are heated and the 1olatile li%uids boil off" they are con1erted back to li%uid in the condenser and return to the flask. C. reflu! condenser ?is not a special type of condenser" it is an ordinary condenser fitted so that reflu! takes place.

Hea%
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&nce the carbo!ylic has been formed" it needs to be separated from the reaction mi!ture and other products. This is done by distillation.

6istillation is used to separate a 1olatile product from a mi!ture of in1olatile substances" or substances that ha1e a boiling point of at least +-oC higher than the component being collected.

Hea%

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2 AC8I!$ M CHA$ISMS
2eaction Classi(ication
The table below re1iews the organic reactions studied for .S chemistry" how they are classified and the reaction mechanisms where re%uired. 2eaction .lkane and halogen .lkene and =2 .lkene and halogen and =/r .lkene and hydrogen halide .lkene and H(n&; .lkene polymeriJation .lcohol with =2S&;#a%$ and H2Cr2&7 .lcohol with halogenating agents =alogenoalkanes and H&=#a%$ =alogenoalkanes and H&=#eth$ =alogenoalkanes and water 2eaction classi(ication Substitution .ddition #reduction$ .ddition .ddition &!idation PolymeriJation &!idation Substitution Substitution 5limination Substitution R =ydrolysis 2eaction mechanism 8ree radical substitution 5lectrophilic addition #/r2$ 5lectrophilic addition #=/r$

<ucleophilic substitution <ucleophilic substitution <ucleophilic substitution

"ree radical reactions . typical e!ample of these is between an alkane and a halogen. e.g. methane and chlorine. They in1ol1e an attack by an atom or group with an unpaired electron called a free radical. In the abo1e reaction ultra1iolet light causes chlorine atoms #free radicals$ to form" Cl. and methyl radicals" C=9. are also in1ol1ed. The dot shows the unpaired electron. lectro%hilic addition reactions . typical e!ample of these is between an alkene and a hydrogen halide. e.g. ethene and hydrogen bromide. They in1ol1e an attack by an ion or group with a positi1e or partial positi1e charge called an electrophile. In the abo1e reaction the electrophile is a hydrogen ion =>. 5lectrophiles attack centres of negati1e charge like the electrons in a double bond. These are addition reactions because the two reactants are added together to gi1e one product. e.g. C'H* 5 Cl' CH'ClCH'Cl $ucleo%hilic substitution reactions . typical e!ample of these is between an alcohol and hydro!ide ions. e.g. ethanol and a%ueous sodium hydro!ide. They in1ol1e an attack by an ion or group with a negati1e or partial negati1e charge called a nucleophile. In the abo1e reaction the hydro!ide ion &= 3 is the nucleophile. . nucleophile attacks a centre of positi1e charge such as the partial positi1e charge on the carbon atom holding a halogen C>3I. It is a substitution reaction because the attacking species replaces the species originally attached to the carbon atom under attack. e.g. CH)CH'Br 5 !H3 CH)CH'!H 5 Br3
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limination reactions . typical e!ample is the formation of an alkene from an alcohol. 5.g. 5thanol reacting to form ethene. They in1ol1e atoms or groups from either side of a single carbon to carbon bond being remo1ed #eliminated$ to form a double bond. e.g. CH)CH'!H C'H* 5 H'! Hydrolysis reactions These all in1ol1e a reaction with water. e.g. CH)CH'Br 5 H'! CH)CH'!H 5 HBr 2eduction reactions These in1ol1e a reaction with hydrogen. . compound gains hydrogen. This can be hydrogen =2 or from a reducing agent like Ei.E=; in ether or a%ueous <a/=;. e.g. CH)CH! 5 'LHM CH)CH'!H !+idation reactions These reactions in1ol1e the loss of hydrogen or the gain of o!ygen. .n o!idising agent like acidified potassium dichromate #FI$ is used. e.g. CH)CH'!H 5 'L!M CH)C!!H 5 H'! Polymerisation reactions These reactions in1ol1e the 0oining of small molecules called monomers to make large molecules called polymers. . large number #n$ of monomer molecules in in1ol1ed and a long polymer molecule is formed. e.g. nC'H* 3GC'H*1n3

Classi(ication o( 2eagents
Chemists aim to de1elop a systematic approach to chemical reactions. In order to do this for organic chemistry it is useful to classify types of compound and how they beha1e. It is also useful to classify reagents so that predictions can be made about the most effecti1e way of carrying out a new reaction. eagents can be classified in 1arious ways including o+idising agents" reducing agents and chlorinating agents.

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Bond Brea=ing and 2eaction Mechanisms

eaction mechanisms were introduced in )nit * as the study of the step by step processes in1ol1ed in a reaction. .ll reaction mechanisms in1ol1e looking at bond breaking. There are two ways in which bond breaking takes place' homolytic and heterolytic. In a homolytic %rocess" the bond breaks so that the atoms on each side of the bond being broken recei1e one of the electrons from the bonding pair.

3 3

The single headed curly arrows represent the mo1ement of one electron. Homolytic (ission in1ol1es the formation of radicals. . radical is an atom or group of atoms with an unpaired electron. In a heterolytic fission process" the bond does not split the electrons e1enly" but both electrons go to one of the atoms on one side of the bond.

The species formed by this process are ions' a cation and an anion. The cation" because of the positi1e charge" will be attracted to a region of negati1e charge. It has a 1acancy for two electrons" so it tends to accept an electron from another atom and form a bond. Such a species is called a nucleo%hile. . carbon atom possessing a positi1e charge is called a carbocation. The anion" because of the negati1e charge" will be attracted to a region of positi1e charge. It has two electrons a1ailable" so it tends to donate an electron to another atom and form a bond. Such a species is called an electro%hile. . carbon atom possessing a negati1e charge is called a carbanion.

De(initions
Three important definitions are gi1en here. "ree radical 3 . free radical an atom or group of atoms with an unpaired electron. $ucleo%hile 3 . nucleophile is a species attracted to a region of positi1e charge and is an electron pair donor. lectro%hile 3 .n electophile is a species attracted to a region of negati1e charge and is an electron pair acceptor.

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Bond ty%e and 2eaction Mechanism

The nature of bond present in a compound will determine what type of mechanism takes place in a reaction. . halogenoalkane" for e!ample" will ha1e a polar bond because of the electrogati1ity of the halogen. This lea1es the carbon bonded to the halogen with a partial positi1e charge. This makes the carbon with the partial positi1e charge susceptible to nucleophilic attack. .lkenes ha1e a double bond which has a high electron density. The high electron density creates a region of higher negati1e charge and so in1ites electrophilic attack.

2eaction Mechanisms
The following reaction mechanisms ha1e been studies in )nit *A The reaction of methane with chlorine 2 Photochemical (ree radical substitution The reaction of bromine and hydrogen bromide with ethene 2 lectro%hilic addition The reaction hydrogen bromide with propene 3 lectro%hilic addition

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Mechanisms in #nit ' Substitution reaction in halogenoal=anes

=alogens are electronegati1e and draw electrons away from the carbon atom lea1ing it with a partial positi1e charge. This is susceptible to attack by a nucleophile. There are two different nucleophilic substitution mechanisms. 7ith primary halogenoalkanes the nucleophile approaches the carbon atom and begins to form a bond. .t the same time to bond with the halogen begins to break" with both electrons in the bonding pair going to the halogen. Eooking at dot and cross diagram for the reaction. This is not the way the mechanism is shown.

H H C
'(

3
'-

*. The halogen in the halogenoalkane is electronati1e so draws the bonding electron pair towards itself and creating a partial positi1e charge on the carbon.

2. The partial positi1e charge on the carbon in1ites attack of nucleophiles such as a hydro!ide ion.

H H C
'(

3
'-

9. The hydro!ide ion donates an electron pair to the carbon and starts to form a bond.

H C H

;. .n intermediate is formed with the C3& bond forming and the C3I bond breaking.

This reaction in1ol1es two species #the halogenoalkane molecule and hydro!ide ion$ in the slow #bond breaking$ step and is designated S$'.

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The mechanism is shown as follows'

H H H HO C H H -

H C 3

HO

H H 3 HO C H 3

7ith tertiary halogeonalkanes" the carbon groups around the carbon with the halogen attached stabilise the ion" so allowing the ion to form. &nce the ion has been formed the hydro!ide ion can 0oin in place of the halogen. The intermediate formed" the carbocation" is planar" so the hydro!ide ion can attack from either side.

> >

> C 3

> +> C > HO

> >

> C OH

If the hydro!ide ion attacked from the opposite side from that shown" the product would be the mirror image of the molecule abo1e. In these reactions" the slow step is the breaking off of the halogen and this in1ol1es only the halogenoalkane" that is one species" and it is designated S$0.

Inde%endent research
esearch the formation of oJone in the upper atmosphere" the free radical reaction mechanisms in1ol1ed in the breakdown of this oJone and the part played by aircraft emission of nitrogen o!ides.
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;reen Chemistry
Green Chemistry refers to the processes in the chemical industry that are being rein1ented to make them more sustainable. The term sustain means to keep going. If we use resources faster than they can be replaced" clearly this is a situation that cannot keep going. Sustainability is about li1ing in a way that preser1es resources and the en1ironment for future generations. The idea of ?green chemistry@ is to obtain all the 1aluable products" but in ways that do not damage the en1ironment. Green chemistry is about making the chemical industry more sustainable. The Chemical industry needs to become greener to' educe waste. 6e1elop more economically 1iable processes. educe their en1ironment impact. Sa1e limited resources.

"ive ways in which the Chemical industry can become ;reener

Change to renewable resources. 8ind alternati1es to 1ery haJardous chemicals. 6isco1er catalysts for reactions with high atom economies" e.g. the de1elopment of methods used to produce ethanoic acid based on catalysts of cobalt" rhodium and iridium (ake more efficient use of energy" e.g. the use of microwa1e energy to heat reactions in the pharmaceutical industry educe waste and pre1ent pollution of the en1ironment.

Changing to renewable sources If renewable resources replace non3renewable materials raw materials will be conser1ed and the process becomes more sustainable. Plants can be used as a source of certain organic compounds instead of oil. These can be e!tracted directly from plants or deri1ed from processing plant material" such as using fermentation to produce ethanol from plant starch and sugars. #se o( alternatives to haDardous chemicals This in1ol1es replacing dangerous chemicals used in a process with less harmful chemicals which can do the same 0ob. It includes changing processes so that less risky reagents are used or less destructi1e intermediates are formed. It also includes using less damaging sol1ents for a process. #se o( more e((icient catalysts Introduction of more efficient catalyst enables lower temperatures and pressures to be used and so sa1es energy. (ore efficient catalysts create fewer bye3products and so reduce waste.
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2eduction o( energy use Changing to processes that use lower pressures and temperatures reduce the energy re%uired to make a gi1en product. )se of e!othermic reactions to pro1ide heat reduces the amount of non3renewable energy used" for e!ample introducing a heat transfer system #using hot products to heat incoming reactants$. )se of microwa1es instead of hotplates allows more efficient heating" as it heats the rele1ant molecules directly. 2eduction in the amount o( waste ecycling materials means that less waste is produced. (aking biodegradable products means that they can be broken down by natural processes and so reduce the materials that need to be treated after use. +am%les Polylactic acid .n e!ample of this is the production of the biodegradable plastic" polylactic acid" PE.. The lactic acid" 23hydro!ypropanoic acid" for this process can be produced by using bacteria to carry out the con1ersion from plant starch and sugars.

H H C H n O H O C H C O H O

H H C H O C H n C ( nH2O

Since lactic acid is a substance produced by li1ing organisms it means that the PE. is biodegradable. 2oundu% . new process for the production of a herbicide called ? oundup@ was de1eloped. The original process re%uired the use of methanol #to!ic$ and hydrogen cyanide #e!tremely to!ic$" but the new process" using a copper catalyst" does not use these materials. The new process utiliJes endothermic reactions" so it is safer and easier to control. The original process produced *;L waste" whereas the new process re3uses the catalyst and recycles any other uncon1erted chemicals" and so has no waste. The new process uses fewer steps and so produces a higher yield. thanoic acid 5thanoic acid can be manufactured from methanol and carbon mono!ideA C=9&= > C& C=9C&2= . new process uses a combination catalyst consisting of iridium with ruthenium compounds. This catalyst produces purer ethanoic acid and so reduces the energy re%uired for the purification.

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Summary The table below summarises which of the new processes fulfills the fi1e main ways of making the chemical industry more sustainable. PE. enewable resources .lternati1e to haJardous chemicals 6e1elopment of new catalyst (ore efficient energy use eduction in waste Oes Oes Oes Oes Oes Oes Oes oundup 5thanoic acid

Main Industrial ((ects on the nvironment

;lobal Climate Change
Products or waste products may enter the atmosphere and absorb Infra red radiation" thus leading to increased global climate change 3 anthro%ogenic climate change e.g. Carbon dio!ide" methane.

Acid 2ain
Products or waste products may enter the atmosphere and dissol1e in clouds to form acid rain" thus leading to change of soil p= and ri1er water p= etc. e.g. Sulphur dio!ide" nitrogen o!ides" carbon dio!ide.

!Done De%letion
Products or waste products may enter the atmosphere and lead to oJone depletion" thus leading to increased le1els of )F radiation reaching the 5arths surface. e.g. C8CKs" products from combustion of plastics and <itrogen o!ides.

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Climate change
&ne of the key concerns of sustainability is pre1enting damage to the en1ironment. The atmosphere is a 1ital part of the 5arthKs en1ironment" and so the effect of peopleKs acti1ities on the atmosphere needs to be understood and monitored. The 5arth recei1es radiation from the sun. This arri1es mainly as 1isible light and ultra3 1iolet radiation. Certain proportions of this radiation are absorbed by the atmosphere or reflected into space. .bout half of it reaches the surface of the 5arth" where it is absorbed and re3radiated" but at a lower energy' in the infra3red fre%uency.

Fi/i"le an! 0l% a ,iole% li#.% + om %.e /0n Some #a/e/ in %.e a%mo/p.e e a"/o " in+ a- e! a!ia%ion

Some li#.% i/ a"/o "e! in %.e a%mo/p.e e an! /ome i/ e+le-%e! in%o /pa-e

Hal+ %.e li#.% ea-.e/ %.e :a %.G/ /0 +a-e $.e e i% i/ a"/o "e! an! e- a!ia%e! in %.e in+ a- e!.
Some gases in the atmosphere absorb infra3red radiation. <itrogen and o!ygen" the main gases in the atmosphere do not absorb infra3red radiation as they are completely non3polar. Gases composed of polar molecules do absorb infra3red radiation. 7hen the molecules absorb infra3red they increase their 1ibration and their kinetic energy" which of course increases to temperature. Such gases are therefore called ?greenhouse gases@ and can be responsible for climate change or global warming. Carbon dio!ide" water 1apour and methane are the main greenhouse gases. The atmosphere naturally contains a certain le1el of carbon dio!ide" but human acti1ity increases these le1els. The effects of human acti1ity are called anthro%ogenic e((ects. Scientists are able to use computer pro0ections to plot the e!pected climate based on there being no anthropogenic carbon dio!ide. 7hen these pro0ections are compared with plots of global temperatures" they show clearly that it is the anthropogenic carbon dio!ide that is responsible for climate change.

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The e!tent to which human acti1ity placed carbon dio!ide into the atmosphere can be measured by use of the ?carbon footprint@. The carbon footprint is the %uantity of carbon dio!ide a certain item or acti1ity places into the air in a complete cycle. The carbon footprint is measured in tones of carbon dio!ide. If any item or process" when input and output of carbon dio!ide is considered" does not add any carbon dio!ide to the atmosphere" it is designated carbon neutral.

Alternative (uels
)se of fossil fuels as energy sources for 1ehicles" power generation plants or domestic heating is one of the key acti1ities which places carbon dio!ide into the atmosphere. If these can be made carbon neutral or ha1e their carbon footprint reduced" it is ad1antageous to the en1ironment. &ne way of reducing the carbon footprint is to use biofuels. The principle of a biofuel is that they are formed by plants that take up carbon dio!ide from the air to make the plant material which is then con1erted into fuel" and when the fuel is burnt" it simply puts back into the air the carbon dio!ide it originally remo1ed" so o1erall it does not add to the carbon dio!ide le1el" and can therefore be described as carbon3neutral. This simple 1iew of biofuels does not howe1er pro1ide the full picture. /ioethanol for e!ample is produced from sugar cane in /raJil and from maiJe in the )S.. The production of ethanol in the )S. uses fertiliJers and pesticides which ha1e taken energy #form oil$ to make. The ethanol then needs to be separated by distillation" a process again which uses energy from oil. /iodiesel is more effecti1e in reducing the carbon footprint because it does not re%uire distillation. =ydrogen is a much better alternati1e fuel as it only produces water when it is burnt. The key point about hydrogen is how it is produced. If it is made by electrolysis using mains electrical supply" it can still ha1e a large carbon footprint if the electrical generation in1ol1es the combustion of fossil fuels. In the same way hydrogen generated by the reaction of methane with steam" the final products being hydrogen and carbon dio!ide" has a significant carbon footprint. =ydrogen produced by electrolysis" where the electrical energy was deri1ed from sunlight would of course be 1ery en1ironmentally friendly.

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8he oDone layer and C"Cs

The atmosphere is composed of se1eral layers. (ost pollutant molecules are broken down before they reach the upper atmosphere. =owe1er it is possible for some particularly stable molecules to enter the upper atmosphere. &ne such type of molecule are the chlorofluorocarbons" C8Cs" which are stable because of the strength of the C38 bond. These were used in aerosols and refrigerants. 7hen they enter the upper atmosphere" the C8Cs can damage the ?oJone layer@. The oJone layer is formed by the energy from the sunKs ultra 1iolet radiation being able to split an o!ygen molecule into two o!ygen atoms. &2 2&Z The o!ygen atom formed can then combine with an o!ygen molecule to form oJone" & 9. &2 > &Z &9 The oJone formed is able to absorb harmful ultra 1iolet radiation from the Sun" so protecting the 5arthKs surface from these rays. 7hen this happens the reaction abo1e is re1ersed. &9 &2 > &Z In the *:,-s it was disco1ered that this protecti1e oJone layer was diminishing during the summer o1er the .ntarctic and that the ?hole@ was increasing in siJe. Chemists tracked the cause down to the C8Cs. The stability of C8Cs means that they are not broken down in the lower atmosphere" but when they reach the upper atmosphere the u1 radiation causes the C3Cl bond to be broken forming ClZ radicals. These radicals then react with oJone as followsA &9 > ClZ &2 > Cl&Z The radical then proceeds to react with the o!ygen atoms present in the stratosphereA &Z > Cl&Z &2 > ClZ This reaction remo1es o!ygen atoms that could otherwise generate more oJone" but it also regenerates the ClZ radical" allowing a series of reaction to take place similar to the propagation stages of the chlorination of methane. It is estimated that one ClZ radical can breakdown a million oJone molecules. .s a result scientists recommended the phasing out of C8Cs. In *:,7 a )nited <ations conference was held in (ontreal to tackle the problem and an agreement was established in which there would be a phased reduction in the use of C8Cs leading to an e1entual ban. This agreement was called the (ontreal Protocol.

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