Complete Unit 1 Notes Chem

A Level Chemistry
UNIT 1 THE CORE PRINCIPLES OF CHEMISTRY NOTES

Written by Mr Ser e!nt !n" #r L!$ren%e
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Intr&"'%ti&n
This unit includes the following. Development of skills in formulae writing, equation writing and calculating chemical quantities. The study of energetics; definition, measurement and calculation of enthalpy changes; how the study of enthalpy helps chemists understand chemical bonding. The study of atomic structure, introducing a more detailed understanding of electron configuration and using this to account for the arrangement of elements in the Periodic Table. The study of chemical bonding. Organic chemistry; alkanes and alkenes
Assessment
The nit e!amination will be "hour "# minutes. $t will carry %& marks. $t will contain two sections, ' and (. Se%ti&n A is an ob)ective test *multiple choice questions+. Se%ti&n ( short,answer and e!tended answer questions. $t will include questions on analysis and evaluation of practical work. -uality of written communication will also be assessed in this section.
FORMULAE) E*UATIONS AN# MOLES

Im+&rt!nt terms $n order to use formulae and equations it is necessary to understand the meaning of important terms. 'tom The smallest unit of an element that can e!ist .olecule The smallest part of an element or a compound which can e!ist alone under normal conditions. $on 'n atom or group of atoms possessing a negative charge /lement ' substance containing )ust one type of atom. 0ompound ' substance that contains different elements that have been chemically combined /mpirical formulae The simplest ratio showing the different types of atom present in a substance. .olecular formulae The actual numbers of each type of atom in a molecule of the substance.
Am&'nt &, S'bst!n%e

Av! !"r&-s C&nst!nt !n" the M&le $n order to carry out quantitative investigations in chemistry it is necessary to be able to 1count1 atoms. This is done using the mole. ' mole contains a given number *the 'vogadro constant+ of atoms or other particles, and this is measured by mass. $f we take a mole of atoms of a particular element, the mass will be the 2elative 'tomic .ass for that element. The 'vogadro constant is the number of particles in " mole of substance *3.&45 ! "& 45+ The m&le is the amount of a substance that contains the same number of particles as there are atoms in "4.&&g of carbon,"4. This number of atoms is 3.&4 ! "& 45 and is called the Av& !"r& %&nst!nt. 'mount of substance 6 number of particles 'vogadro constant
M&les ,r&m m!ss To find the number of moles of atoms we use the formula7 .oles 6 mass of substance relative atomic mass
$f we take a mole of ionic lattice or molecules of a material, the mass will be the molar mass To find the number of moles of molecules or compounds we can use the formula7 .oles 6 mass molar mass *28., .r+
/!amples ". 0alculate the number of moles in "&g magnesium sulphate *.g9O :.+ Molar mass of MgSO4 = 24 + 32 + (4x 16) = 120 Moles = 10 /120 = 0.083 mol 4. 0alculate the mass of &.&:mol 0opper*$$+nitrate Molar mass of Cu(NO3)2 = 63.5 + (2 x 14) + (6x 16) = 1 8.5 Mass = Moles x !ormula mass = 0.04 x 1 8.5 = .5g
F&rm'l!e "etermin!ti&n
'n em+iri%!l ,&rm'l! is the simplest formula which shows the ratio of each type of atom present in a compound. ' m&le%'l!r ,&rm'l! is a simple multiple of the empirical formula showing how many of each type of atom are present in a compound. The formula of a compound can be calculated from the mass of elements in it. This is done as follows7 9tep "7 8rom the mass of each element find the number of moles. 9tep 47 8rom the number of moles find the simplest ratio. 9tep 57 0onvert the mole ratio to a whole number ratio; this gives the formula. E.!m+le " #$%ro&ar'o( &o(s)s*s of 14.4g &ar'o( a(% 1.2g #$%roge(. Cal&ula*e )*s em+)r)&al formula. C 14.4 / 12 =1.2 mol , 1.2 / 1 =1.2 mol
-a*)o = 1 . 1 So *#e em+)r)&al formula )s C, $f we try to work out the structure of this we can see that this is not the formula of the molecule. To find this formula we need to know the molecular mass. $f the molar mass of this compound is ;%gmol,", what is the molecular formula< C, #as a mass of 13 *#e (um'er of *#ese u()*s )s 8/13 = 6 so *#e formula )s C6,6 ' similar process is used to find formulae from percentage composition. E.!m+le " &ar'o#$%ra*e )s &om+ose% of 40.00/ Car'o(0 6.6 / ,$%roge( a(% 53.33/ Ox$ge(. 1* #as a molar mass of 120gmol21. Cal&ula*e *#e mole&ular formula. C 40.00 / 12 = 3.33 -a*)o 1 , 6.6 / 1 = 6.6 2 O 53.33 / 16 = 3.33 1
3m+)r)&al formula . C,2O mass . 30 so (um'er of u()*s = 120 / 30 = 4 Mole&ular formula = C4,8O4
M&les &, !s
One mole of any gas has appro!imately the same volume as any other gas at a particular temperature and pressure. *This is Av& !"r&-s L!$+. /!ample7 2 C4,10 + 13 O2 8 CO2 + 10 ,2O 4#a* 5olume of ox$ge( )s (ee%e% *o rea&* 6)*# 15 &m3 of 'u*a(e u(%er room &o(%)*)o(s7 !rom *#e e8ua*)o(0 1 mole of 'u*a(e rea&*s 6)*# 6.5 moles of ox$ge(. 9#erefore0 1 5olume of 'u*a(e (ee%s 6.5 5olumes ox$ge(. 9#erefore0 15 &m3 of 'u*a(e (ee%s 15 6.5 = : .5 &m3 ox$ge(. 't room temperature and "'tm this is 4:dm 5 *4:&&&cm5+. *'t &o0 and "'tm this is 44.:dm5+. 9o the number of moles of a gas at room temperature can be found from the formula. .oles 6 =olume *in dm5+ 4: /!ample. Cal&ula*e *#e moles of &ar'o( %)ox)%e )( 480&m 3 of *#e gas. Moles = 480 / 240000 = 0.002
M&les in s&l'ti&n
The concentration of solutions is also e!pressed in terms of moles. 0oncentration 6 .oles =olume *in dm5+
The concentration of a solution can be stated as the mass of solute per cubic decimeter of solution *g>dm5+ or the amount in moles of a solute present in "dm 5 of solution *mol>dm5+. To make a solution of "mol dm,5 concentration, "mol of substance is dissolved and the solution made up to a total volume of "dm5. /!amples 1. Cal&ula*e *#e &o(&e(*ra*)o( of a solu*)o( &o(*a)()(g 2.4g MgSO 4 )( 500&m3 of solu*)o(. Moles = 2.4 / 120 = 0.02mol Co(&e(*ra*)o( = 0.02mol / 0.5%m3 = 0.04mol%m23 2. Cal&ula*e *#e mass of NaO, re8u)re% *o ma;e 100&m 3 of a 0.2 mol %m23 solu*)o(. Moles = Co(&e(*ra*)o( x <olume (%m3) = 0.2 x 0.1 = 0.02mol Mass = Moles x !ormula mass = 0.02 x 40 = 0.8g
P!rts +er milli&n

This is a way of e!pressing very dilute concentrations of substances *usually pollutants+. ?ust as per cent means out of a hundred, so parts per million or ppm means out of a million. sually describes the concentration of something in water or soil. One ppm is equivalent to 1 milli r!m +er 1////// %m0 &, $!ter 1m 2"m03 &r 1 milli r!m +er 4il& r!m s&il 1m 24 35 or the volume of a gas pollutant in air. One ppm is equivalent to 1 %m0 +er 1////// %m0 &, !ir /!ample " 250 &m3 sam+le of r)5er 6a*er 6as fou(% *o &o(*a)( 56 ++m of gol%. Cal&ula*e *#e mass of gol% )( *#e 250&m3 sam+le of r)5er 6a*er. 9#e sam+le &o(*a)(s 56 ++m of gol% = 56 mg +er %m 3 of r)5er 6a*er = 56 mg +er 1000&m3 1 &m3 of 6a*er &o(*a)(s 56 / 1000 mg = 0.056 mg of gol% 25 &m3 of 6a*er &o(*a)(s 0.056 x 25 = 1.4 mg = 1.4 x 10 23 g of gol% /!ample C#ro()& ex+osure *o CO a* &o(&e(*ra*)o(s of 0 ++m or grea*er &auses &ar%)a& %amage. 4oul% $ou 'e a* ser)ous r)s; )f $ou 6ere ex+ose% 380 &m 3 of &ar'o( mo(ox)%e )( a 3500 %m3 room7 380 &m3 )( 3500000 &m3 = 380 &m3 )( 3.5 m)ll)o( &m3 = 380 / 3.5 = 108.6 ppm You are at risk!
Re!%tin 6'!ntities !n" %hemi%!l e6'!ti&ns

Chemi%!l e6'!ti&ns !n" m!ss %!l%'l!ti&ns .ole calculations can be used together with chemical equations to determine the quantity of material formed or used up in a chemical reaction. @hether using masses, volumes of solutions *of known concentration+, or volumes of gases the same general method can be used. Ste+ 17 Ste+ 87 8ind the number of moles of one substance se the mole ratio from the chemical equation to find how many moles of the other substance will be formed > used up. Ste+ 07 8rom the number of moles of this substance calculate the mass > volume > concentration of the desired substance. /!ample "7 Cal&ula*e *#e mass of 1ro((11)sul+#a*e (!eSO 4)0 6#)&# &a( 'e +ro%u&e% from .84g of ,2SO4. 8e A B49O: 8e9O: A B4 Ste+ 1 , Moles of ,2SO4 use% = mass / -!M = .84 / :8 = 0.08 Ste+ 8 9 !rom e8ua*)o( 1 mol ,2SO4 forms 1mol of 1ro((11)sul+#a*e So mole of 1ro((11)sul+#a*e = 0.08 Ste+ 0 : Mass of 1ro((11)sul+#a*e = moles x -!M = 0.08 x 152 = 12.2g (3 s)g.f)g.) /!ample 4. 4#a* mass of alum)()um )s (ee%e% *o rea&* 6)*# .00g of a(#$%rous CuSO4 7 4'l A 50u9O: 'l4*9O:+5 A 50u Ste+ 1 , Moles of CuSO4 use% = mass / -!M = / 15:.5 = 0.043: mol Ste+ 8 9 !rom e8ua*)o(0 3 mol of CuSO4 rea&* 6)*# 2 mol of "l. So 1 mol of CuSO4 rea&*s 6)*# = mol of "l. So 0.043: mol CuSO4 rea&*s 6)*# 0.043: = 0.02:3 mol "l Ste+ 0 : Mass of "l = moles x -!M = 0.023: mol 2 g/mol = 0. :0 g (3 s)g.f)g.) /!ample 57 Cal&ula*e *#e 5olume &ar'o( %)ox)%e gas 6#)&# 6)ll 'e +ro%u&e% from *#e &om'us*)o( of 2.20g of +ro+a(e (C3,8). 05B% A #O4 50O4 A :B4O Ste+ 1 , Moles of +ro+a(e use% = mass / -!M = 2.20 / 44 = 0.05 mol Ste+ 8 9 !rom e8ua*)o( 1mol +ro+a(e forms 3mol &ar'o( %)ox)%e So mole of &ar'o( %)ox)%e = 0.15 mol Ste+ 0 9 <olume of &ar'o( %)ox)%e = moles x 24000 = 0.15 x 240000 = 30600&m 3
Titr!ti&ns
' titration is a method of finding out how much of one material will react with how much of another.
Carryin o!t the titration

". 4. ' pipette,filler is added to the volumetric pipette. 9ome of the solution is drawn into the pipette. The pipette is tilted and rotated so that all the surfaces are rinsed in the solution. 5. The rinsing solution is then discarded. :. The solution is drawn into the pipette until the bottom of the meniscus is on the mark. #. The solution is then released into a clean conical flask. 3. @hen no more solution emerges from the burette, touch the tip of the pipette against the side of the conical flask. 9ome of the liquid will remain in the tip and this should be left as the pipette is calibrated to allow for this. ;. ' suitable indicator should be added to the conical flask %. The flask is placed on a white tile under a burette. C. The flask should be held in the right hand *or writing hand+ and swirled. "&. The burette tap should be controlled by the left hand, first and second fingers behind the tap and the thumb in front of it. 'dd the solution from the burette until the indicator changes colour. Dote the reading on the burette. This is the rough reading. "". Discard the contents of the flask and rinse it with tap water and then distilled water. "4. 2epeat the process, adding the solution from the burette fairly slowly with continual stirring. 's the level in the burette approaches that of the rough reading, the solution is added drop by drop. @hen one drop changes the colour of the indicator, allow the solution to drain down the sides of the burette before taking the reading. "5. 'ccurate burette readings should be recorded to two decimal places, the second decimal place being & or #. ":. 2eadings should continue to be taken in this way until one rough and two accurate readings that are within &." cm5 of each other E concordant readings , are obtained. "#. 0alculations should be based on the mean average of the two concordant readings.
Titr!ti&n %!l%'l!ti&ns
se the same three step method as before. /!ample 1f 23.45 &m3 of 0.2 mol %m23 so%)um #$%rox)%e rea&* 6)*# 25.0&m3 of sul+#ur)& a&)%. !)(% *#e &o(&e(*ra*)o( of *#e a&)%. 4DaOB A B49O: Da49O: A 4B4O Ste+ 1 9 Moles of NaO, = 23.45 / 1000 x 0.2 = 0.0046: mol Ste+ 8 9 Moles of ,2SO4 = 0.0046: / 2 = 0.002345 mol Ste+ 0 9 Co(&e(*ra*)o( of ,2SO4 = 0.002345 / 0.025 = 0.0:38 mol %m23 (3 s)g.f)g.)
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Per%ent! e Yiel"
0hemical reactions are carried out in the laboratory and by industry to make new materials. $n the process of producing new substances, some material is lost. The efficiency of the conversion process is measured using percentage yield or atom economy. F Gield 6 'ctual .ass of material produced ! "&& Theoretical ma!imum mass which could be produced /!ample 1( *#e +re+ara*)o( of &o++er sul+#a*e0 a solu*)o( of sul+#ur)& a&)% &o(*a)()(g 2.00g of *#e +ure a&)%0 )s rea&*e% 6)*# a( ex&ess of &o++er ox)%e. 4.3 g of *#e #$%ra*e% &o++er sul+#a*e0 CuSO4.5,2O 6as +ro%u&e%. Cal&ula*e *#e / $)el%. 0uO A B49O: 0u9O: A B4O Moles of sul+#ur)& a&)% use% =mass / -!M = 2.00 / :8 = 0.05 = 0.0204mol !rom e8ua*)o( 1mol sul+#ur)& a&)% forms 1mol &o++er sul+#a*e So moles of &o++er sul+#a*e forme% = 0.0204mol Molar mass of #$%ra*e% &o++er sul+#a*e = 63.5 + 32 + 64 + :0 = 24:.5 9#eore*)&al max)mum mass 6#)&# &oul% 'e +ro%u&e% = 24:.5 x 0.0204 = 5.0:g / >)el% = "&*ual $)el% / *#eore*)&al x 100 = 4.3 / 5.0: x 100 = 85.9%
At&m E%&n&my
@hereas the percentage yield gives us information about the actual efficiency of a reaction, atom economy e!amines the theoretical potential yield of a reaction, by considering the quantity of starting atoms in all the reactants end up in the desired product. .olar mass of useful product F atom economy6 Total molar mass of starting materials Taking the laboratory preparation of copper*$$+ sulphate from sulphuric acid and copper*$$+ o!ide as an e!ample. 0uO A B49O: 0u9O: A B4O .ass of starting atoms is .ass of desired product is 0uO 6 35.# A "3 6 ;C.# 0u9O: 6 35.# A 54 A 3: 6 "#C.# B49O: 6 4 A 54 A 3: 6 C% Total 6 ";;.# "#C.# F atom economy 6 ";;.# The atom economy for the production of ethanol from ethene and steam is shown below. 04B: A B4O 04B#OB F atom economy 6 :3 > :3 ! "&& 6 "&&F *there are no unwanted products+. ! "&& 6 %C.CF ! "&&
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#eriv!ti&n &, E6'!ti&ns

'n equation can be derived or confirmed by measuring quantities of substances involved in the reaction. /quations can be written to e!plain simple test tube reactions such as displacement and precipitation. /!ample " 1. 4g of ma(ga(ese(1<) ox)%e )s a%%e% *o a( ex&ess of &o(&e(*ra*e% #$%ro&#lor)& a&)% a(% 6arme%. 9#e &#lor)(e g)5e( off 6as a'sor'e% a(% 6e)g#e%. 9#e mass of &#lor)(e g)5e( off 6as 1.42g. "(o*#er +ro%u&* of *#e rea&*)o( 6as +ur)f)e% a(% a(al$se%. 1* 6as fou(% *#a* *#)s sal* &o(*a)(e% 1.10g of ma(ga(ese a(% 1.42g of &#lor)(e. (a) ?e*erm)(e *#e formula of *#e sal*. (') Cal&ula*e *#e (um'er of moles of ma(ga(ese(1<) ox)%e use% )( *#e rea&*)o(. (&) Cal&ula*e *#e (um'er of moles of &#lor)(e a(% sal* +ro%u&e% )( *#e rea&*)o(. (%) 4r)*e a &#em)&al e8ua*)o( for *#e rea&*)o(. (a) M( 1.10 / 55 =0.02 mol -a*)o = 1 Cl 1.42 / 35.5 =0.04 mol . 2
!ormula = M(Cl2
(') (&)
Moles M(O2 = mass / -!M = 1. 4 / 8 = 0.02 mol Moles Cl2 +ro%u&e% = mass / -!M = 1.42 / 1 = 0.02 mol Moles M(Cl2 +ro%u&e% = mass / -!M = 2.52 / 126 = 0.02 mol .nO4 A B0l &.&4 " .n0l4 A 0l4 A &.&4 &.&4 " " <
/quation7 .oles .ole ratio
(alancing for 0l7 .nO 4 A :B0l .n0l4 A 0l4 A < (alancing for B H O7 .nO4 A :B0l .n0l4 A 0l4 A 4B4O /!ample 4 !or *#e follo6)(g rea&*)o(s0 6r)*e &#em)&al a(% )o()& e8ua*)o(s us)(g s*a*e s)g(s. (a) 4#e( %)lu*e ()*r)& a&)% )s a%%e% *o so%)um &ar'o(a*e solu*)o(0 effer5es&e(&e o&&urs a(% *#e gas forme% *ur(s l)me6a*er &lou%$. Da40O5*aq+ A 4BDO5*aq+ 4DaDO5*aq+ A B4O*l+ A 0O4*g+ 0O54,*aq+ A 4BA*aq+ B4O*l+ A 0O4*g+ (') 4#e( )ro( f)l)(gs are a%%e% *o &o++er sul+#a*e solu*)o(0 *#e 'lue solu*)o( *ur(s gree( a(% *#e gre$ sol)% )s re+la&e% '$ a re%2'ro6( sol)%. 0u9O:*aq+ A 8e*s+ 8e9O:*aq+ A 0u*s+ 0u4A *aq+ A 8e*s+ 8e4A*aq+ A 0u*s+ (&) 4#e( s)l5er ()*ra*e solu*)o( )s a%%e% *o so%)um &#roma*e solu*)o(0 a re% ++* forms. Da40rO:*aq+ A 4'gDO5*aq+ 4DaDO5*aq+ A 'g40rO:*s+ 0rO:4,*aq+ A 4'gA 'g40rO:*s+
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ENER;ETICS
'll types of chemical reaction involve changes in energy. @hen energy is emitted it can take a number of forms, but the most common form is as heat energy. Beat energy is called enth!l+y. /nthalpy change is represented by the symbol <H. $n general when bonds break energy has to be supplied and when bonds form energy is given out. @hen heat energy is given out the reaction is described as /IOTB/2.$0 and this happens when more energy is obtained from bonds being formed than is used by bonds being broken. The heat energy given out can cause a temperature increase. @hen the breaking of bonds in a reaction requires more energy than is given out by the formation of new bonds, heat energy is taken in, and the reaction is said to be /DDOTB/2.$0. The heat energy taken in can cause a temperature decrease. The ma)ority of reactions are e!othermic. /nergy changes which take place during a chemical reaction can be represented on an energy *enthalpy+ profile diagram. Ener y +r&,ile "i! r!m ,&r !n e.&thermi% re!%ti&n
() (ntha*py $eactants &' %rod!cts
%ath o+ reaction
(y convention the value of JB for e!othermic reactions is ne !tive and endothermic reactions is +&sitive.
St!n"!r" C&n"iti&ns
Obviously the quantity of energy given out or taken in during a reaction depends on the amount of material involved, so the enthalpy values have to be standardised. The standard enthalpy value ' refers to; molar quantities at 4C%K and " atm pressure *"!"& # Pa+
Enth!l+y Ch!n es nits of &' are k? molE"7 the mol@1 does not refer to one mole of any particular substance, but to
molar quantities in the correct proportions of the equation, and therefore the equation must always be stated *or implied+7 e.g. &.# D4 A ".# B4 DB5 &', 6 E:3.4 k? molE" The enthalpy change here refers to half a mole of nitrogen molecules reacting with ".# moles of hydrogen molecules to form one mole of ammonia. $t follows that for; D4 A 5 B4 4 DB5 we multiply everything by the same factor and &', 6 4 ! E:3.4 6 EC4.: k? molE" 9tate symbols are important. The values for the two reactions below are different.
'2- . / 012- . '2- . / 012- .

'llotropic form can also be important;
'21- . '21-*. C-diam. ' 2 / 1."34mo*-1
C- raph.
9ome important definitions;
(ntha*py chan e
/nthalpy of formation, JB
L f
/nthalpy of combustion, JBLc
/nthalpy of neutralisation, JBLneut /nthalpy of atomisation, JBLat
Definition The enthalpy change that takes place when one mole of substance is formed from its elements in their standard state under standard conditions. e.g. &.# D4 A ".# B4 DB5 The enthalpy change that takes place when one mole of substance is completely burned in o!ygen under standard conditions. e.g. 0%B"% A "4.# O4 % 0O4 A C B4O The enthalpy change that takes place when one mole of water is formed in a neutralisation reaction. e.g. B0l*aq+ A DaOB*aq+ Da0l*aq+ A B4O*l+ The enthalpy change that takes place when one mole of gaseous atoms is formed from the element under standard conditions. e.g. M0l4*g+ 40l*g+
N&te , (y definition, the ' 1 + value for an element in its standard state must be Nero. *$t takes no energy to form an element is its standard state from its constituent element in its standard state+.
E.+eriment!l Me!s'rements &, Enth!l+y

/!perimental measurements of enthalpy change are generally based on knowing that the specific heat capacity of water is :.4?g,"K,". The temperature change of a given mass of water is measured, and the energy change is found from7 Beat energy change 6 mass of water ! :.4 ! temperature change * E = m % T3
OOr to make sure the sign is always correct Beat energy change 6 mass of water ! :.4 ! *9tarting temp E final temp+ P
This is converted to an enthalpy change by dividing the energy change by the number of moles *of the substance not in e!cess+ and adding the appropriate sign; , for e!othermic reactions and A for endothermic reactions. /!ample #&cm5 of ". B0l is placed in a polystyrene cup. #&cm 5 of ". DaOB solution is placed in a beaker. The temperature of each is "%o0. The DaOB solution is then added to the B0l in the cup. The temperature increases to 4:o0. 0alculate the enthalpy change for this reaction. Beat energy change 6 "&& ! :.4 ! *"% E 4:+ 6 ,4#4& ? .oles B0l 6 .oles DaOB 6 #& > "&&& ! " 6 &.&# mol JBL 6 ,4#4& > &.&# 6 ,#&,:&& ? mol," or E #&.: k? mol," *5 sig fig+
The two main ways of investigating enthalpy changes are mi!ing substances in an insulated container, and using a calorimeter in a combustion e!periment. ' typical e!periment to determine an enthalpy change using an insulated container *to .easure the enthalpy of neutralisation of hydrochloric acid and sodium hyrdro!ide+ which takes steps to reduce errors is given below. 5& cm5 is a reasonable volume of liquid to use in an e!panded polystyrene cup. ". sing a measuring cylinder, 5& cm5 of dilute hydrochloric acid is placed into an e!panded polystyrene cup. 4. ' thermometer is placed in the solution and the temp is recorded every min for 5 mins. 5. 5& cm5 sodium hydro!ide solution is measured out. :. 't 5.# minutes the sodium hydro!ide solution is added. #. The mi!ture is stirred continuously. 3. 2eadings continue to be taken every minute up to ten minutes.
' graph of the readings is plotted and the lines e!trapolated as shown in the diagram below.
5emperat!re / oC
5emperat!re chan e +or reaction 67
3.5 mins 5ime / mins

Qikely errors in these e!periments; o 'ssuming the volume *and therefore mass+ of water used in the calculation is the same as the volume of the solution used in the reaction. o 'ssuming that the specific heat capacity of the solution is the same as that of water. ' calorimeter could be used to measure enthalpies of combustion. ' typical process for this is outlined below.
". 4. 5. :. #. 3. ;. %. C. ' measuring cylinder is used to measure out "&&cm5 of water. The water is placed in a calorimeter *basically a metal can+. The liquid to be investigated is placed in a spirit burner. The spirit burner is weighed. The temperature of the water is noted The apparatus is set up as shown below. The liquid is ignited and allowed to heat the water. 'fter a temperature rise of around 4&o0, the flame is e!tinguished. The e!act temperature is noted The burner is weighed to find out how much liquid has been burned.
w a te r
m e th y *a te d s p irit
Typical results Qiquid
/thanal, 04B:O Cal&ula*)o( 3(erg$ = m x C x A = 100 x 4.2 x 8 = 3360 B Moles = 0.1: / 44 = 0.0043 C, = 23360 / 0.0043 = 2 8103:5 B/mol = 2 81 ;B/mol (3 s)g f)g).
.ass of burner at start >g ""#.;%
.ass of burner at end >g ""#.#C
Temperature at start >o0 4"
Temperature at end >o0 4C
Hess>s L!$ !n" Ener y Cy%les

Bess1s Qaw follows from the "st law of thermodynamics *conservation of energy+ and states that; 8or a given chemical change, the overall energy change will always be the same whether the change takes place in one step or a number of steps. *$t is independent of the route taken+. @e can use BessRs law to construct cycles, and then equate the enthalpies from different pathways. 2emember that the direction of the arrow is directly linked to the sign of JB. $f the arrow is reversed, then the sign of JB must be changed *see JB: in the e!ample below+.
)
' 1
8 Consider ) to 8: c*oc3wise 2 antic*oc3wise
'
'3
( 9
' 1
' 4 / ' 3 / ' 2
' 4
E.!m+le 1 The energy level of liquid water at 4#o0 will be the same whether it is formed from burning hydrogen or the decomposition of hydrogen pero!ide. 9uppose we wanted to find the enthalpy of formation of hydrogen pero!ide, JB Lf*B4O4+. 0hemical equation H81 3 ? O81 3 H8O81l3
This reaction does not readily occur, and so we cannot measure its enthalpy directly. Bess1s Qaw can be used to find the value for it using other enthalpy values by constructing a cycle, and then equating the enthalpies from the different routes. @hen " mole hydrogen is burnt in o!ygen to form water, 4%#.C k? mol," of energy are given out. This is the enthalpy of formation of water, JBLf*B4O+.
H81 3 ? @O81 H8O81l3
H8O1l3
<HA, = 98BC5D 4Em&l91
Bydrogen pero!ide decomposes according to the equation7
H8O1l3 ? @O81 3 <HAR = 9DB50 4Em&l91
These changes can be represented in an energy triangle. 'ccording to BessRs law, the energy change to go from SB4*g+ A O4*g+T SB4O4*l+T is the same whether we go direct or via S B4O*l+ A MO4*g+T.
'2- . / 12- . &',+-'21.
&',+-'212.
'212-*. &',$
'21-*. / 012- .
9o using BessRs Qaw; JBLf*B4O4+ 6 JBLf*B4O+ , JBL2 6 ,4%#.C , ,C%.5 6 ,"%;.3 k?mol,"
The dashed arrow shows our indirect route SB4*g+ A O4*g+T to SB4O4*l+T. @hen the dashed arrow points in the same direction as the energy change arrow, the value is added in. @hen the dashed arrow points in the opposite direction as the energy change arrow, the value is subtracted.
E.!m+le 8 : C!l%'l!tin ' 1 + ,r&m enth!l+ies &, %&mb'sti&n 9#e e(*#al+)es of &om'us*)o( of e*#e(e0 #$%roge( a(% &ar'o( are @140:0 @286 a(% @3:4 ;B mol@10 res+e&*)5el$. !)(% *#e e(*#al+$ of forma*)o( of e*#e(e. *i+ F'll %y%le meth&" 0onstruct a triangle with the elements in their standard states *including o!ygen+, ethene A o!ygen, and the combustion products as the three corners. 1 ' + 2C-s. / 2' - . / 31 - .
2 2
C2'4- . / 312- .
2 '1 '1 + -C12. / 2 + -'21. 2 2-3"4. / 2-286. 2C12- . / 2'21-*.
'1 c -C2'4.
2 14#"
sing BessRs Qaw, total enthalpy change from elements to ethene must be the same by either route.
' 1 +
' c *04B:+ '1 6 4 ' 1 + *0O4+ A 4 + *B4O+ E 6 4*E5C:+ A 4*E4%3+ E *E":&C+ 6 A :C k? molE"
1
N.D. "l6a$s )(&lu%e *#e + s)g( )( <, a(s6ers for e(%o*#erm)& rea&*)o(s. E.!m+le 0 : Fin"in enth!l+y &, re!%ti&n ,r&m ' 1 + v!l'es *ii+ FAl ebr!i%G meth&" ' 1 U r *reaction+ must be added to all the enthalpies of formation on the le,t hand side of equation, to be equal to the total enthalpies of formation on the right hand side. @rite out this statement, then the equation, with plenty of space, and write the enthalpies of formation underneath each substance7
' 1 reaction
A sum of ' 1 + *reactants+ 04B:*g+ A 5O4*g+ 5* &+
6 sum of ' 1 + *products+ A 4*E4%3+ 6 A :C k? molE"
6 40O4*g+ A 4B4O*l+ 6 4*E5C:+
E":&C A ' 1 + *ethene+ A 9o
' 1 + *ethene+ 6 4*E5C:+ A 4*E4%3+ E *E":&C+
U The advantage of the algebraic method is that you are less likely to omit enthalpy values, and each value used is directly linked to the formula in the equation above, so that the layout is self,e!planatory.
sing the algebraic method7

' 1 reaction ' 1 reaction
A sum of ' 1 + *reactants+ 4 'l4O5 A 50 A 4*E"33C+ A & 6 1 ' reaction 6 6 1 ' so for " mol 6 reaction
6 sum of ' 1 + *products+ :'l*l+ A 50O4 :*A"&+ A 5*E5C:+ E"":4 E *E555%+ A 4"C3 k? molE" for 4 mol A "&C% k? molE"
E.!m+le H : 'se &, enth!l+ies &, %&mb'sti&n "ire%tly Occasionally, instead of enthalpies of formation, only enthalpies of combustion *or solution+ are given in a question *in /!ample ", two of the enthalpies of combustion were also enthalpies of formation+. These cannot be used in e!actly the same way as enthalpies of formation, and you are less likely to make mistakes if you draw the full cycle out. e.g. 9#e e(*#al+)es of &om'us*)o( of e*#$(e(g) a(% 'e(Ee(e(l) are @12:: a(% @32 3 ;B mol@10 a(% *#e e(*#al+$ of 5a+or)sa*)o( of 'e(Ee(e )s +30;B mol @1.
1 !)(% ' reaction for.
3C2,2(g) C6,6(g)
().e. 3 e*#$(e 'e(Ee(e)
Meth&"7 construct a cycle, including the combustion products. This means adding ;.# o!ygen molecules to both sides.
3 C 2' 2- . / 7.5 12 - .
'
C 6' - . / 7.5 12 - . 6
3-12"". 6 C12 - . / 3 ' 2 1-*.
3273
8rom Bess1 Qaw7
'1 6
5 *E"4CC+ E *E54;5+ 6 E#3: k? molE"
(&n" Enth!l+y
@hen a chemical reaction takes place it involves bond breaking and bond forming. @hen a bond is formed one electron from each atom enters a new electron cloud of lower energy. 's the system moves to a lower energy level, energy is given out. $n order to break the bond this energy has to be put back into the system. The heat energy obtained when a bond is formed, and taken in when it is broken is called the bond enthalpy. $f we considered a molecule such as methane, the energy required to break each of the bonds is not e!actly the same. 9o the total energy required to break up a methane molecule is divided by : to give an !ver! e b&n" enth!l+y. 'verage bond enthalpies can be used to determine !++r&.im!tely the enthalpy change which will take place in a particular reaction.
' 1 re!%ti&n
= s'm &, b&n"s br&4en &n le,t : s'm &, b&n"s m!"e &n ri ht 08: A :B8
0onsider the reaction between fluorine and methane. 0B: A :84 8or each mole (onds broken; 0,B : ! :"4 6 "3:% k? 8,8 : ! "#% 6 354 k? T&t!l ener y 'se" 6 A44%& k?
(onds formed; 0,8 : ! ,:%: 6 ,"C53 k? B,8 : ! ,#34 6 ,44:% k? T&t!l ener y +r&"'%e" 6 ,:"%: k?
Total enthalpy change for the reaction 6 (roken E 8ormed 6 A44%& ,:"%: 6 ,"C&: k?. @e can show this on an energy diagram7
C / 4' / 8;
(ntha*py
/228#
4184 ' 2 -1"#4 34 mo*1 C;4 / 4';
C'4 / 4;2
$n reality the reaction between methane and fluorine does not required four fluorine molecules to collide with a methane molecule at the same instant, but actually takes place as a series of steps *in a process called the re!%ti&n me%h!nism+. (ond energies are useful as a guide to the possible sequence of events. 8or e!ample in the reaction between methane and fluorine, which is the first bond to break 0,B *bond enthalpy :"4+ or 8,8 *bond enthalpy "#%+< 9ince the 8,8 bond requires less energy to break it, this will be the first bond broken. The bond enthalpies relate to the activation enthalpy for a reaction and therefore have an influence on how fast the reaction can go. $f the bond enthalpies are low, then the activation enthalpy will be low and the reaction can take place at a high rate.
- 1" /var/www/apps/conversion/tmp/scratch_6/216168315.doc
Re!%ti&n Me%h!nisms
' reaction mechanism shows which bonds are formed and broken during a reaction and informs chemists how a reaction proceeds. The weaker the bond, the more likely it is to break.
Ty+es &, b&n" bre!4in

(onds can break in two ways. "+ The electrons in the covalent bond return to their original atoms. The species that form have an unpaired electron E they are called ,ree r!"i%!ls.
Cl
Cl
Cl
Cl
This is known as H&m&lyti% ,issi&n *Bomo as the products formed are both free radicals+. 4+ The electrons in the bond both move in the same direction. The process forms i&ns and is called hetr&lyti% ,issi&n.
Cl+ Pr&bin re!%ti&n me%h!nisms
Cl-
(ond enthalpies allow us to postulate what happens during a reaction. e.g. The most likely bond to break in the molecule below *bromoethane+ is the 0,(r bond as it is the weakest.
B 0 B B 0 B B (r
(&n" 0,B 0,0 0,(r
(&n" enth!l+y 14E :"5 5:; 4C&
@hen bromoethane reacts the most likely mechanism for the reaction will involve the breaking of the 0,(r bond to form the carbocationic intermediate *0 4B#A+ and a (r, ion.
B 0 B B 0 B B 0 B B B (r B 0/ B
8r-
0arbocationic intermediate
(&n" enth!l+ies !n" enth!l+ies &, At&mis!ti&n

The enth!l+y &, !t&mis!ti&n of an element is the enthalpy change when one mole of gaseous atoms of an element is formed from an element is its standard state under standard conditions *4C%K and " atm+. e.g. $t is the enthalpy change for the following process7 128Cl81 3 Cl1 3 ; enthalpy change 6 H!I128Cl81 3J = ? 181 4E m&l91 During atomiNation all the bonds in the reactants are broken and no new bonds are formed *as all the products are atoms+. Therefore H! = The s'm &, !ll the b&n"s in the re!%t!nts5 8or 128Cl81 3 Cl1 3 the bonds broken 6 M *0l,0l+ Therefore (ond enthalpy of *0l,0l+ 6 4 ! "4" 6 A 4:4 k? mol," 'nother e!ample H!ICHH1 3J = ?1KHK 4E m&l91 The equation for atomisation of 0B: is; (onds broken 6 : *0,B+ Therefore : *0,B+ 6 "3:3 *0,B+ 6 "3:3 > : 6 :"4 k? mol," CHH1 3 C1 3 ? HH1 3
The bond enthalpy of *0,B+ in 0B: is :"4 k? mol,"
(&rn9H!ber %y%les
Qattice enthalpies cannot be determined directly and are found instead by cycles, called the (&rn9H!ber %y%les, which are similar to the cycles used for determining enthalpy changes using Bess1s law. 9tarting with the elements in their standard states, we first form gaseous atoms *atomisation enthalpies+. @e then remove electron*s+ from the metal *ionisation enthalpy+, and give electron*s+ to the non,metal *electron affinity+. The gaseous ions are now combined to form the crystal *lattice enthalpy+. The alternative route is to form the crystal directly from the elements *enthalpy of formation+.
@e can illustrate the use of a (orn,Baber cycle by calculating the enthalpy of formation of magnesium chloride *in order to compare with the observed value of E3:4 k? mol , " +. $f there is good agreement, it is likely that the compound fits the ionic model well. .g4A*g+ A 4eE A 40l*g+
2 < e*ectron a++inity o+ C* = : +irst >.( / second >.(.
.g4A*g+ A 40lE*g+
.g*g+ A 40l*g+
2 < atomisation o+ C*
.g*g+ A 0l4*g+
atomisation o+ =
*attice entha*py o+ = C*2-s.
.g*s+ A 0l4*g+
entha*py o+ +ormation o+ = C*2
.g0l4*s+
8or the route via atoms, and gaseous ions, the values are as follows7 Pr&%ess7 a+ /lements to atoms b+ metal atom to cation c+ non,metal to anion d+ ions to crystal Therefore7 Enth!l+y 'tomisation of .g 4 V 'tomisation of 0l 8irst ionisation / of .g A second $./. 4 V electron affinity 0l lattice enthalpy of .g0l4 enthalpy of formation L!l'e ,&r M Cl824E m&l : 1 A"#& A4:4 A;53 A":#& E;4% E4:C5 E3:5 k? molE"
Dote; $n *a+ and *c+ allowance is made for t$& 0l atoms, and in *b+ the total energy needed is the s'm of the first two ionisation energies. $n *d+, the lattice enthalpy is defined as the enthalpy change on formation of one mole of crystals from the gaseous ions *see previous section+, and is negative. The (orn,Baber cycle is a conventional BessRs Qaw cycle, following the directions of the arrows, but the vertical heights give a rough idea of the enthalpy content *lower 6 thermodynamically more stable+. 9tudy of this (orn,Baber cycle shows that although the *negative+ electron affinity of the non, metal goes some way towards compensating for the high ionisation energy, it is the large negative value for the lattice energy which makes the whole process favourable. $onic compounds are likely to be formed if one element *the metal+ has low ionisation energy *or energies+, the other *non,metal+ has a reasonably high electron affinity, and if the lattice energy of the compound formed is high.
ATOMIC STRUCTURE AN# PERIO#ICITY

(!si% str'%t're &, the !t&m5
'n atom contains protons, neutrons and electrons. The protons and neutrons are found in the nucleus of the atom while the electrons e!ist in the energy levels around the nucleus. The characteristics of these basic particles are shown in the table PARTICLE Proton /lectron Deutron RELATILE MASS " ">"%:& " RELATILE CHAR;E A" ," Done
The nucleus carries virtually all the mass of the atom and is positively charged. Dumber of protons in the nucleus 6 the atomic number of that atom. The total number of particles in the nucleus is given by the mass number. .ass number 6 Protons A Deutrons Dumber of neutrons in a nucleus 6 .ass number , 'tomic number The atomic and mass numbers can be shown with the symbol of the atom7
=ass n!m@er )tomic n!m@er
$n a neutral atom, there will be no overall charge, so the no. of electrons 6 no. of protons. The chemical nature of the atom is determined by the number of electrons it has and in particular the electron arrangement. 9o the atomic number tells us what type of atom we have. The number of neutrons in a particular type of atom often varies. One e!ample of this is in hydrogen " proton Bydrogen," 1 " proton A " neutron Bydrogen,4 Deuterium 2 " proton A 4 neutrons Bydrogen,5 Tritium 3
The atomic number for all these is " because they are all hydrogen atoms. The mass number is different. 'toms of the same type with different numbers of neutrons are called is&t&+es.
0arbon also has isotopes. 0,"4 is an important isotope in chemical definitions; Rel!tive At&mi% M!ss is the weighted mean of one mole of a normal sample of the element e!pressed on a scale on which one mole of the atoms of the 0,"4 isotope has a mass of e!actly "4 units. 2.'... 'r 6 meanU mass of " atom of the element one,twelfth of the mass of " atom of "40
2elative .olecular .ass and 2elative $sotopic .ass are measured on the same scale. Rel!tive Is&t&+i% M!ss is the mass of one mole of an isotope of the element e!pressed on a scale on which one mole of the atoms of the 0,"4 isotope has a mass of e!actly "4 units. 2.$... 6 mass of " atom of the isotope one,twelfth of the mass of " atom of "40 Rel!tive M&le%'l!r M!ss is the weighted mean of one mole of a normal sample of the substance e!pressed on a scale on which one mole of the atoms of the 0, "4 isotope has a mass of e!actly "4 units. 2..... .r 6 mean mass of " m&le%'le of the substance one,twelfth of the mass of " !t&m of "40 The term rela*)5e mole&ular mass should only be applied to substances which have covalently,bonded molecules e.g. 0l4, 9O4, 0%B"%. 8or ionic materials like Da0l and 0u9O : the term relative formula mass is preferred, though it is calculated in the same way, by adding up the 2.'...s of all the atoms in the formula. -.!.M. can be used for molecular substances, too. The rel!tive ,&rm'l! m!ss of a substance is7 2.8... .r 6 the mean mass of one formula unit of the substance one twelfth of the mass of one atom of "40.
The M!ss S+e%tr&meter

The mass spectrometer is a method of determining relative atomic and molecular masses. The main processes involved are; ". the sample is vaporised, 4. the sample is ionised, 5. the ions are accelerated by an electric field, :. the accelerated ions pass through a magnetic field and are deflected, #. the ions are detected and recorded.
Aaporised samp*e )cce*eratin +ie*d (*ectron !n =a netic +ie*d
$ecorder
)mp*i+ier >on detector
5!@e !nder vac!!m
The vaporised sample is fed into the ionisation chamber. Bere it is bombarded by a stream of electrons which knock electrons out of the molecules in the sample. I*g+ A e, IA*g+ A 4e, These charged ions are then accelerated through an electric field and pass into a magnetic field. The magnetic field deflects the ions according to their mass and charge. 8or a particular setting of electric and magnetic fields only particles of a certain mass reach the detector. Qower masses are deflected too much and higher masses too little. The magnetic field strength is gradually altered changing the mass of particles which will reach the detector. The detector is connected to an amplifier and recorder so the mass of particles can be determined.
The mass spectrum of an element shows the relative isotopic mass and relative abundance of each isotope of the element being tested. $n a mass spectrum the height of each peak 6 the relative abundance. The Rel!tive At&mi% M!ss of an element can be found by finding the sum of the products of the relative abundance of each isotope and its relative isotopic mass and the dividing by the total relative abundance. e.g. 9#e *6o s;e*&#es s#o6 *#e mass s+e&*ra o'*a)(e% from a*oms of *6o %)ffere(* eleme(*s. 1( ea&# &ase %e*erm)(e *#e -.".M. 5#.5B 4".5B hei ht hei ht
-a. *a+
64 66 68 mass/char e ratio mass/char e ratio @e assume the two peaks are due to atoms of two isotopes. .ean r.a.m. 6 ;C A %" 6 ;C.CC 6 %&.& *to 5 s.f.+ -@.
7"
81
*b+ Do scale is given, so we must use a ruler to measure the heights. Qet us assume these are *from left to right+ 5.% cm, 4.: cm, and ".4 cm. Total 6 ;.:cm .ean r.a.m. 6 3: A 33 A 3% 6 3#.5 *to 5 s.f.+ ' very accurate version of the mass spectrometer can be used to "etermine rel!tive is&t&+i% m!sses to a high degree of accuracy7 e.g. "3O 6 "#.CC:"# and ";O 6 "3.CCC"5.
M!ss S+e%tr! &, M&le%'les

The full mass spectrum of chlorine is more complicated than the e!amples shown on page :. This is because chlorine is made up of diatomic molecules *molecules containing two atoms+. Peaks occur at mass numbers 5#, 5;, ;&, ;4 and ;:. The identity of these is as follows. Peak at 9pecies responsible 5# 5# 0lA 5; 5; 0lA 5# ;& 0l4A 5# ;4 0l5;0lA 5; ;: 0l4A Peaks still occur at mass numbers 5# and 5; because molecules break up in the mass spectrometer. /!ample Drom)(e #as *6o )so*o+es of mass : a(% mass 81. Fre%)&* *#e +ea;s $ou 6oul% ex+e&* *o see )( a mass s+e&*rogra+# of 'rom)(e0 Dr 2. Peak 9pecies ;C ;C (rA %" %" (rA "#% ;C (r4A "3& ;C (r%"(rA "34 %" (r4A
@hen molecules are passed through the mass spectrometer, the peak with the highest mass is caused by the ion formed from the whole molecule E this is called the m&le%'l!r i&n or +!rent i&n. The RFM of a compound can be found from the mass value of the molecular ion. .olecules of a particular compound will always break up in the same way and in the same proportion when passed through a mass spectrometer. This means that a given compound will always produce the same pattern in a mass spectrum. This can be used to identify the presence of compounds in analysis. This has been used as follows. $n sport to detect the use of anabolic steroids (y pharmaceutical industries to identify synthesiNed compounds as possible potential drugs In"e+en"ent rese!r%h7 2esearch how the mass spectrometer used in space research.
Ele%tr&ni% Str'%t're &, the !t&m

The electronic structure of an atom that determines its chemical properties. /lectrons can be regarded as having certain energy levels. The lower levels fill before the higher levels are occupied. The simple theory your learnt at $W09/, pictures the atom as having shells, the shell of lowest energy being closest to the nucleus. The ne!t shell can hold up to eight electrons. The third shell also holds up to eight electrons. (onding is e!plained in terms of atoms trying to obtain a stable electrons arrangement by; *i+ transfer from electron rich atoms*metals+ to electron deficient atoms*non,metals+; *ii+ sharing electrons between electron deficient atoms. This model on its own is not sophisticated enough for understanding ' level work fully and does not e!plain how the atoms arrange electrons above a number of twenty. The simple bonding theory which comes from the model cannot e!plain the structure of molecules such as P0l# or 983.
Ele%tr&ni% C&n,i 'r!ti&n

The shells used in the simple view of the atom are divided into s'bshells. 9hell 9ubshells " s 4 s p 5 s p d : s p d f The higher the energy of the shell, the more subshells it contains.
/lectrons inside the atom should be thought of as waves rather than particles. The area occupied by an electron wave is called the &rbit!l. 'n orbital has no edge7 the electron density )ust tails off more and more. Bowever, we can calculate the surface which would contain a given percentage *say, C#F+ of the electron density, and use this to gain an idea of the shape of the orbital *below+.
$t is important to remember that the electron density is not uniform within this shape. The s,orbital is always spherically symmetrical, while the three 4p orbitals each point along one particular a!is, at right angles to the other two. 2emember that when one electron occupies a 4p orbital it occupies both halves; when two electrons occupy it, they b&th occupy both halves. /ach electron in an atom is different from all the other electrons. The s s'bshell s orbitals can contain a ma!imum of two electrons. These have the same energy value, but are said to have opposite spin values.
The + s'bshell There are three p orbitals, each of which can contain a ma!imum of two electrons. The " s'bshell There are five d orbitals, each of which can contain a ma!imum of two electrons.
Ele%tr&n shells
The first shell holds two electrons in an s subshell. 1s The electrons have the same energy value, but are said to have opposite spin values.
The second shell holds eight electrons. These are split into two energy levels; the lower level has two electrons in the 1s1 subshell 8s the higher level has si! electrons in the 1p1 subshell. 8+ The electrons in the 1p1 subshell are found in three different regions of the atom which are called 1!1, 1y1 and 1N1.
Se%&n" shell % electrons
The thrid shell holds eighteen electrons. These are split into three energy levels; the lower level has two electrons in the 1s1 subshell the ne!t highest level has si! electrons in the 1p1 subshell. the highest level has ten electrons in the 1d1 subshell.
0s 0+ 0"
Dote , $n the higher shells there is overlap between the energy levels of the subshells. /.g. The :s subshell is filled before the 5d subshell.
Ele%tr&ni% %&n,i 'r!ti&ns

/lectronic 0onfiguration can be predicted. $f the following rules are followed7 /lectrons go into lower energy levels before higher ones. /lectrons go into lower sub,shells before higher ones. /lectrons occupy orbitals with " electron rather than 4 if possible. /lectrons can only occupy the same orbital if they have opposite spins. The orbital order "s, 4s, 4p, 5s, 5p, :s, 5d, :p
e.g. 'tom 9i K .n We Kr
Do of electrons ": "C 4# 54 53
0onfiguration "s4, 4s4, 4p3, 5s4, 5p4 "s4, 4s4, 4p3, 5s4, 5p3, :s4 "s4, 4s4, 4p3, 5s4, 5p3, :s4, 5d# "s4, 4s4, 4p3, 5s4, 5p3, :s4, 5d"&, :p4 "s4, 4s4, 4p3, 5s4, 5p3, :s4, 5d"&, :p3
'nother way of representing electronic configuration giving greater detail is as Xelectrons in bo!esY DZZ. ;
1s
2s
2p
@hen writing the electron configurations of ions, it is important to take into account the number of electrons lost or gained. 0a4A "s4, 4s4, 4p3, 5s4, 5p3 'n e!actly half full or full d subshell is particularly stable. This gives chromium and copper what is at first sight an une!pected electronic configuration. The e!tra stability of the e!actly half full or full d subshell means that an electron from the :s goes to the 5d to give a half full subshell for chromium and a full subshell for copper. /lement 0hromium, 0r 0opper, 0u $nitially e!pected but wrong "s4, 4s4, 4p3, 5s4, 5p3, :s4, 5d: "s4, 4s4, 4p3, 5s4, 5p3, :s4, 5dC 0orrect electron configuration "s4, 4s4, 4p3, 5s4, 5p3, :s", 5d# "s4, 4s4, 4p3, 5s4, 5p3, :s", 5d"&
C&n,i 'r!ti&ns !n" the Peri&"i% T!ble

s) + !n" "9bl&%4 elements
'll s,block elements have their highest energy electrons in s,orbitals. 'll p,block elements 1s have their highest energy electrons in p,orbitals. 'll d,block elements have their highest energy electrons in d,orbitals.
2s 3s 4s 5s 6s 3d 4d 5d
2p 3p 4p 5p 6p
Evi"en%e ,&r Ele%tr&n shells !n" s'bshells

I&nis!ti&n Ener ies
'n electron is attracted to the positive charge in the nucleus of the atom. $t is possible to remove an electron from an atom. The process of removing an electron form an atom to form a positive ion is called i&nis!ti&n. The energy required to remove one electron from an atom is the first ioniNation energy. The siNe of the ionisation energy is an indication of the strength of attraction between the outer electrons and the nucleus. /nergy changes in chemistry are generally measured as heat energy or enthalpy. The definition of the first ionisation energy is7 The energy required to remove one electron from each atom in one mole of mole of gaseous atoms producing one mole of gaseous ions with one positive charge. or The enthalpy change for the following reaction7 I*g+ IA*g+ A e, /!amples The first ioniNation energy of chlorine 0l*g+ 0lA*g+ A e,
The second ioniNation energy of sodium DaA*g+ Da4A*g+ A e,
S'%%essive i&nis!ti&n ener ies

The graph of successive ionisation energies against number for potassium *'t Do "C+ shows electrons grouped into four energy levels or quantum shells with similar energies.
Co >onisation (ner y
$onisation number To remove the second electron it is necessary to break into a complete shell, so a lot more energy needed. 9imilarly with the tenth electron there is an increase in the energy required for its removal as this has to come from a complete shell. 8rom successive ioniNation energies it is possible to tell which group of the Periodic table an element is in. The table below shows successive ionisation energies for an element. /nergy values are given in k?mol,". "st #;; 4nd "%4& 5rd 4;:& :th ""3&& #th ":%&& 3th "%:&&
Dotice that there is a large increase after the third ionisation energy E so the fourth electron is much more difficult to remove. This means that there are three electrons in the outer shell, so the element is in group 5. E.!m+le ,ere are su&&ess)5e 1.3. 5alues )( ;B mol21 for *6o eleme(*s. element I "&"& "C&& 4C&& #&&& 35&& 810// 4#:&& 4C%&& element G #C& ""#& HDH/ 3:%& %"4& "&;&& "45&& ":3&& "%4&& 4&:&& #;"&&. 1( 6#a* grou+ of *#e +er)o%)& *a'le are G a(% >7 8or I there is a sharp rise between the #th and the 3th values, so I must have five electrons in itRs outer shell. I is a Wroup # element. G shows a )ump between the second and third values, so it is in Wroup 4.
First i&nis!ti&n ener y

The first ionisation energy is energy required to remove one electron from an atom. The factors which affect ionisation energies are7 the n'%le!r %h!r e, the "ist!n%e !$!y ,r&m the n'%le's of the electron, the shiel"in &, the n'%le's by &ther ele%tr&ns. *(eing spherical s subshells are much better at shielding than p subshells+. $f first ionisation energy is plotted for a number of elements the results provide evidence for the e!istence of subshells.
Qithium has the lowest first ionisation energy of the second period. $t is more difficult to remove an electron from (eryllium since the charge on the nucleus has increased (eryllium having a :A nuclear charge, whereas lithium is only 5A. 'lthough (oron also has a higher nuclear charge, it has lower first ionisation energy because the electron is now in the 1p1 subshell, and the inner [sR subshell shields it from the nucleus. The ionisation energy increases again to 0arbon and Ditrogen as the nuclear charge increases. O!ygen has a higher nuclear charge, but the first ionisation energy is lower because the e!tra electron now has to pair up in an orbital *in Ditrogen each p orbital has an electron in it+ so the e!tra electron is repelled and it is easier to remove it. The values increase after o!ygen as the nuclear charge increases. The pattern repeats itself for the ne!t period of the periodic table E 8irst ioniNation energy is a +eri&"i% +r&+erty.
Peri&"i%ity
Periodicity is the regular occurrence of a trend across a period *or down a group+. .any periodic properties can be e!plained in terms of structure and bonding. e.g. /!plaining trends physical properties in period 5 from sodium to argon. Da atomU radius > nm ion radius > nm ion charge A5 structure metal melting point > K boiling point > K relative conductivity first $./ > k? mol," &."#; &.&C% A" E5 metal diamond P:\ 5;" ""35 " #&& .g &.":& &.&3# E4 9% C45 "5C& ".45 ;:& 'l 9i P 9 0l 'r E
&."43 &.""; &.""& &.&#: no ion &.4"4 E" 0l4 C54 4;4& ".C3 #%& E atomic "3%5 435& semi ;C& 5";\ ##5\ & "&"&
&."&: &.&CC
&."%: &."%" E
5C4 ;"% &
";4 45C &
%: %; &
"&&& "43& "#4&
\white P ] red P, a polymer, sublimes at %35
1!3 At&mi% r!"ii7 The radius of an atom depends on whether it is bonded to another one, and on the nature of the bonding *metallic, ionic, covalent+. $f we compare similar types of radius, the general trend is for atoms to get smaller across a period. This is because the nuclear charge is increasing, and the e!tra electrons being added go into the same outer shell. On the whole, electrons in the same shell do not shield one another very efficiently, and the siNe contracts as the effective nuclear charge increases. The alkali metal, in Wroup ", is the largest atom, and the halogen, in group ;, is the smallest. 1b3 I&ni% r!"ii7 $onic radii depend on the charge. Positive ions are always smaller than the neutral atoms, and higher charges make cations smaller still. Degative ions are much larger than neutral atoms, and larger still if the charge is higher. 8rom the table, it is clear that although Da atoms are larger than 0l, Da A ions are much smaller than 0l , ions. 1%3 Meltin +&ints7 These depend on the type of bonding, and the structures of the solids. Wenerally, going across a period metallic bonding at first increases in strength *Da^.g^'l+ as successive atoms have more valence electrons, and then gives way to a giant covalent structure *9i E like diamond+, and then to molecular solids *P :, 9%, 0l4, 'r+. .elting points therefore tend to increase, reaching a ma!imum in the middle, and fall sharply to a minimum on the right *see table+.
=alues for the four molecules reflect the siNe of the molecule, and so the intermolecular forces *i.e. 9% _ P: _ 0l4 _'r+.
1"3 (&ilin +&ints7 These are less dependent on crystal structure, and so give a better idea of the forces between the particles. 'gain we can note the increase in metallic bonding from Da to .g to 'l; the high value for the giant molecule 9i; the remainder are simple molecular structures. 8or these, intermolecular forces again depend on siNe of molecule7 P : ^ 9%; then there is a fall to 0l4 and 'r, since they have weaker dispersion forces and lower boiling points. 1e3 Ele%tri%!l %&n"'%tivity7 'long the series DaE.gE'l the number of outer shell electrons which can be delocalised in metallic bonding increases, and the electrical conductivity increases accordingly. (y 9i, however, the effective nuclear charge is too high to allow electron delocalisation, and 9i is not a metal, although it is a semiconductor because an electron can be torn free relatively easily. The remainder are non,metallic insulators7 their effective nuclear charges are too great to allow electrons to escape under normal conditions. 1,3 I&nis!ti&n ener ies7 The e,,e%tive n'%le!r %h!r e is the charge XseenY by an outer electron, after allowing for the effect of shielding. Thus for sodium *element ""+, which has the configuration ODeP 5s ", ten of the nuclear charges are effectively shielded by the neon shells, and the effective nuclear charge on the outer electron is close to A". The first ionisation energies for the first "5 elements are shown below7 The general trend !%r&ss ! +eri&" in the Periodic Table, from Qi to De, is for the values to increase sharply. This is because, while the nuclear charge is increasing by one each time, the additional electron is being added in the same outer shell, and generally it is not shielded completely by the others. Bowever, there are two XkinksY. $n Wroup 5 boron, 4s 44p", is lower than e!pected. This is because its 4p electron is sufficiently shielded by the 4s 4 pair for the effective nuclear charge to be lower than it was in (e. $n Wroup 3 o!ygen, 4s44p:, is also low. This is attributed to the fact that the fourth p electron has to be spin,paired, and so it is partly repelled by the other electron in the same orbital *also of note is that, once an electron is lost, OA has a half,filled 4p sub,shell, and in general half, filled and completely filled sub,shells are particularly stable+. ' similar pattern is followed in Period 5, with low values in Wroup 5 and Wroup 3. ODote that if se&o(% ionisation energies are plotted, the pattern is again similar, but this time shifted along one element e.g. QiA*"s4+ is high, while (eA*"s44s"+ is low.P The general trend "&$n ! r&'+ is for ionisation energies to fall by a small amount. 'lthough the nuclear charge increases, this is cancelled out by the addition of another closed shell, so the effective nuclear charge on the outer electron is similar, but the electron is further away from the nucleus, since it is being removed from a higher quantum number shell.
(ON#IN;
$n the process of bonding electrons move to a lower energy level to form a more stable structure. This can be done by transferring electron*s+ to another atom or by pairing with an electron from another atom.
C&v!lent b&n"in
Two non, metal atoms can form a stable octet structure by sharing electrons. .any simple covalent compounds obey the &%tet r'le7 the atoms form sufficient covalent bonds to make their outer shells up to eight electrons. /!ample; chlorine
C*
C*
The shared electrons are positioned between the nuclei of each atom, and there is attraction between the positive nucleus of each atom and the shared electrons which holds the atoms together.
NUCLEUS
e e
NUCLEUS
This is called covalent bonding. The two electrons which are shared are called the bonding pair. Mey P&ints &n C&v!lent (&n"in /lectron deficient atoms share a pair of electrons to form stable electronic structures. The shared electron pair is attracted to the nuclei of each atom holding the atoms together strongly. 'toms )oined in this way form molecules. 0ovalent materials may consist of simple molecules, polymers or giant molecules
8urther e!amples
' C*
Bydrogen chloride
' ' C ' '

.ethane
$f two electron pairs are shared between the same atoms, they form a double bond, as in 0O4, O47
1 C 1 1 1
$f three electron pairs are shared between the same atoms, they form a triple bond, as in D47
Dote that non,bonding electrons are paired up as Xlone pairsY.
Physi%!l Pr&+erties &, %&v!lently b&n"e" %&m+&'n"s

0ovalent compounds composed of simple molecules have weak intermolecular forces between the molecules. Qittle energy is needed to overcome these forces, so the melting and boiling points of these substances are low. Wiant molecular substances have strong covalent bonds throughout the structure and so require a large amount of energy to overcome them and these substances have high melting and boiling point. $n general covalent substances do not have free electrons, so they are non,conductors of electricity. Wraphite is e!ceptional as a covalent material in that it does have free electrons and so is a conductor. *Details of diamond and graphite are covered in the X9hapes of .olecules and $onsY section+.
Ele%tr&n "ensity m!+s

/lectron density maps for covalent molecules can be plotted. The electron density map for a molecule such as iodine is shown below.
The even distribution of electron density between the two atoms can be seen in this diagram.
E.+!nsi&n &, the &%tet

'lthough the octet is a particularly stable structure, it is possible for other stable structures to form. 'n atom can increase the number of single electrons it has, and so the number of bonds it can form by `splitting` an electron pair. 9ulphur is an e!ample. @hat would you e!pect the formula of sulphur fluoride to be< Draw a dot and cross diagram of sulphur fluoride. 98 4
$t is possible for an electron pair in sulphur to split. 9plitting an electron pair takes in energy, but the e!tra energy produced by forming e!tra bonds makes it possible.
E
/!ample, 98:
$f an electron pair in sulphur is split, the sulphur can then form four bonds.
; ; E
; ;
This process splitting electron pairs means that an atom in a compound can have more than % electrons, and it is referred to as e!panding the octet.
Other e!amples are 983 and P0l#.
; ; E ; ; ; C* ; C*
C* % C* C*
9ulphur he!afluoride, 983
Phosphorus pentachloride, P0l#
The elements in the second period do not do this because the energy to split the electron pair is too great to be compensated for by the formation of e!tra bonds, but elements below Period 4 form a number of compounds of this type.
#!tive %&v!lent b&n"in

C&&r"in!te b&n"in or "!tive %&v!lent b&n"in is similar to normal covalent bonding in that the bond consists of an electron pair. $t is different in that instead of one electron coming from each atom, both the electrons come from a single atom. 0onsider the structure of boron trifluoride and ammonia;
'
D '
'
8 ;
The boron only has three electron pairs in the outer shell. The nitrogen has a lone pair of electrons. These two molecules form a dative bond by the nitrogen using the lone pair to donate to the vacant site on the boron.
' ' D '

The following structure is formed
; 8 ; ' ; 8 ; ' ' D ' ; 8 ; ; ; ;
'
D '
This can be represented as follows, with the dative bond represented by an arrow;
Other e!amples of the dative bond occur in the formation of the hydro!onium and ammonium ions; H8O ? H? H0O?
+ ' 1 '+ ' ' 1 ' ' ' ' 1 '
NH0 ? H?
NHH?
'+ D ' ' '
' D '
+ ' ' '
' D
'
'
Met!lli% b&n"in
.etals can be visualised as being made up of positive ions surrounded by a cloud of electrons. .etals are electropositive; that is they tend to release their valence electrons and form positive ions. $t is these electrons which make up the electron cloud. The structure is held together by the attraction between these positive ions and the electron cloud or delocalised electrons.
+ +
+ + +
+ + +
+ + +
+ + +
+ + +
+ + +
This structure gives metals their properties. 9ince the bonding electrons are not fi!ed they are said to be "el&%!lise", it means that a small potential difference will cause the electrons to move , making metals good electrical conductors. /lectron movement also assists in the conduction of heat energy, making metals good conductors of heat. The absence of fi!ed bonds allows the ions to move giving the characteristics of malleability and ductility.
F!%t&rs e,,e%tin the stren th &, met!lli% b&n"in 7

". The more valence electrons the stronger the bonding; as there is a higher charge on the cations and there is a higher charge in the electron fields. 4. The smaller the metal ion the stronger the bonding; as the electrons become closer to the centre of the positive charge. The metallic bonding determines physical properties of metals. The more valence electrons there are, the better the conductivity. The stronger the metallic bonding the higher the melting and boiling points.
I&ni% b&n"in
.etal atoms hold their outer *valence+ electrons weakly. Don,metals have a strong pull for the outer electrons. There is a tendency for metal atoms to transfer electrons to non,metal atoms.
NUCLEUS
NUCLEUS
@hen this happens the metal atom forms a positive ion *so metals are termed electropositive+ and the non,metal atom forms a negative ion *non,metals are said to be electronegative+. The ions formed have a stable `octet structure` The strong electrostatic attraction between the cation and the anion lead to a strong ionic bond. This forms a giant structure built up of these oppositely charged ions. The strong electrostatic forces within the giant structure mean that it requires a large amount of energy to break them down. 's a result of this, ionic compounds have high melting and boiling points. The ionic compounds are unable to conduct electricity in solid form, but when dissolved in water or in molten from the ions are free to move and so they conduct.
9odium chloride is an ionic compound. The structure of this compound is shown here.
Mey P&ints &n I&ni% (&n"in 'n electron *or electrons+ is transferred form one atom to another to form stable electronic structures. $n this process positive and negative ions are formed The oppositely charged ions attract have very strong electrostatic forces ' giant structure of ions is formed The compounds have high melting and boiling points The compounds do not conduct as solids, but do when molten or in solution.
Re+resentin i&ni% %&m+&'n"s

$onic substances are giant structures, but the essential electronic structure of an ionic compound can be represented by showing one set of ions. /!ample , 9odium chloride 9imple electronic configuration 9odium7 4, %, " 0hlorine7 4, %, ;
To form stable structures an electron is transferred from sodium to chlorine. 9odium ion7 4, % 0hloride ion7 4, %, %
' diagram to the ionic compound shows )ust the outer shell. + -
Da
/!ample 4 , 0alcium bromide
C*
0alcium7 4, %, %, 4 (romine7 4, %, "%, ;
To form stable structures two electrons are transferred from calcium one each to two bromine atoms. 0alcium ion7 4, %, % (romide ion7 4, %, "%, %
2/
8r
Ca
8r
Ele%tr&n "ensity m!+s

I rays can be deflected off solids to give us information about their structure. I ray diffraction of ionic solids can be presented as an electron density map. 'n electron density map shows lines which represent areas of equal electron density. 'n idealised electron map for an ion pair in an ionic compound is shown to the right. $t is important to remember that the lines do not represent shells. $n practice the situation is more comple! as the cation can distort the electron field of the anion. The electron density map for sodium chloride is shown to the left. The distortion of the ions, particularly the chloride can be seen.
SiNes &, i&ns in ! ;r&'+

Woing down a group of the Periodic Table, the ions formed have the same charge. 's the atoms from which they were formed become larger so do the ions.
SiNes &, is&ele%tr&ni% i&ns

$soelectronic ions are ions that have the same number of electrons. 'tom Dumber of electons 8orms ions by 8ormula of ion Dumber of electrons 9iNe of ion >nm D ; Waining 5 electrons D5, "& &.";" O % Waining 4 electrons O4, "& &.":& 8 C Waining " electron 8, "& &."53 Da "" Qosing " electron DaA "& &.&C# .g "4 Qosing 4 electrons .g4A "& &.&3# 'l "5 Qosing 5 electrons 'l5A "& &.&#&
's the ions all have to same number of electrons, the siNe of the ion is determined by the charge on the nucleus. 's the nuclear charge increases from D to 'l so does the attraction of the electrons to the nucleus and so the ionic siNe decreases.
I&ni% %&m+&'n"s !n" Ener y

/nergy changes take place when ionic compounds are formed. The process of bond breaking is endothermic and the process of bond breaking is e!othermic. The energy changes that take place when an ionic compound forms are shown below. (&n" bre!4in /nergy taking in , to convert the metal lattice into individual metal atoms. /nergy taking in , to convert the non,metal molecules to individual non,metal atoms. I&n ,&rm!ti&n /nergy taking in , to convert the individual metal atoms into individual metal ions. /nergy given out , when the individual non,metal atoms gain an electron to from an anion. (&n" ,&rmin /nergy given out E as the cations and anions come together to form an ionic lattice , the L!tti%e Enth!l+y. This process is shown below for sodium chloride.
Eodi!m ions / ch*orine atoms Energy to ionise sodium Eodi!m atoms / ch*orine atoms Energy to atomise sodium and chlorine Sodium metal + chlorine molecules Energy given as compound forms Sodium chloride
9uch an energy diagram is called a (&rn9H!ber %y%le.
*$t is not necessary to construct a (orn,Baber cycle for nit "+.
Energy given as chloride ions form Eodi!m ions / ch*oride ions
Energy given as the sodium chloride lattice forms
The Qattice /nthalpy can be calculated from this. JBQlat 6 JBf E *JBatSDaT A JBatS0lT A $/SDaT+ E /'*0l+ 8or sodium chloride JBQlat 6 ,:"" E *"&C A "4" A :C:+ E ,53: 6 ,;;"k?mol ," The values obtained from these (orn,Baber cycles have to be found by e!perimental measurement of the various energy values and so are often referred to as e.+eriment!lly "etermine" l!tti%e enth!l+ies5 They represent the actual lattice enthalpy, as opposed to a theoretical lattice enthalpy, which is based on a theoretical model for ionic compounds. 0onsidering (orn,Baber cycles allows us to see why compounds have the formulae they do. Take calcium chloride as an e!ample. 2elevant values "st ioniNation energy of calcium 4 ioniNation energy of calcium 5rd ioniNation energy of calcium /lectron affinity of chlorine Qattice enthalpy of 0a0l Qattice enthalpy of 0a0l4 'tomiNation enthalpy of 0a 'tomiNation enthalpy of 0l
nd
#C&k?mol," ""#& k?mol," :C:& k?mol," ,53: k?mol," ,;4& k?mol," ,445; k?mol," "C5 k?mol," "4" k?mol,"
The enthalpy of formation can be found by rearranging the equation used above. JBQlat 6 JBf E *JBatS0aT A JBatS0lT A $/S0aT+ E /'*0l+ JBf 6 JBQlat A *JBatS0aT A JBatS0lT A $/S0aT+ A /'*0l+ 8or 0a0l 8or 0a0l4 JBf 6 ,;4& A "C5 A "4" A #C& ,53: 6 ,"%& k?mol ," JBf 6 ,445; A "C5 A "4" A #C& A ""#& A 4! ,53: 6 ,;C& k?mol ,"
.ore energy is needed to form 0a4A but this is outweighed by the much larger lattice enthalpy, so the formation 0a0l4 of is energetically more favourable than for 0a0l. The lattice enthalpy of 0a0l5 is greater than for 0a0l4, but the e!tremely large amount of energy needed to form the 0a5A makes the process energetically unfavourable.
F!%t&rs in,l'en%in l!tti%e enth!l+y5

The lattice enthalpy of an ionic compound is affected by the siNe and charge on the ions which make it up. ' decrease in the siNe of any ion increases the lattice enthalpy. This is because small ions can be close together and the smaller distance of separation the larger the attractive force between the ions. 'n increase in charge also increases lattice enthalpy. This is because the force of attraction between ions increases as the charge on the ion increases.
The&reti%!l "etermin!ti&n &, l!tti%e enth!l+y

$t is possible to calculate the lattice enthalpy by visualiNing the ionic lattice as made up of perfectly spherical ions in a lattice. The lattice enthalpy is determined theoretically by calculating all the forces of attraction and repulsion in the lattice. ' simplified version of this is given below7 z+ z BQ/o 6 E constant V i.e. O+r&"'%t &, %h!r esP O Is'm &, r!"iiJ r+ + r Bere, the constant depends on the type of structure *the way in which the ions pack together+. N A and N E are the charge on the cation and anion respectively, and r A and rE are the radii of cation and anion. ' comparison of the lattice energies of Da0l *E;;& k? mol E " + and .g0l4 *E4#&& k? mol E " + shows a much more negative value for the magnesium compound7 not only is N A double for .g4A, but also its ion has a smaller radius *rA+, and this too leads to a larger lattice energy.
C&m+!rin e.+eriment!l !n" the&reti%!l v!l'es ,&r l!tti%e enth!l+y

The lattice energy is the energy change which occurs when well separated gaseous ions are brought together to form a crystal. 's stated above, it is possible to obtain a theoretical value of the lattice energy by considering all the attractions and repulsions between the ions in the lattice. The values obtained by using (orn,Baber cycles are determined by e!periment and reflect the actual value. The table below compares theoretical lattice energies with e!perimental lattice energies. 0ompound .g84 .g$4 /!perimental value > k?mol," ,4C#; ,454; Theoretical value > k?mol," ,4C"5 ,"C:: Difference in values > k?mol," :: 5%5
The compound magnesium fluoride has theoretical values which agree quite well with the e!perimental value, but the magnesium iodide values agree less well. $n general the iodides tend to show a greater difference between these values than fluorides. The e!perimental values show that lithium halides are actually more stable than would be e!pected by regarding them as purely ionic compounds. $n the same way, iodides are in reality more stable than would be e!pected by treating them theoretically as purely ionic compounds. This discrepancy is caused by a covalent character which e!ists in the ionic lattice. The greater the difference between the e!perimental value and the theoretical value, the greater the degree of covalency in the lattice. This covalency is caused by +&l!ris!ti&n.
P&l!ris!ti&n in I&ni% (&n"in

@hen an ionic bond is formed, the metal atom transfers one or more electrons to the non, metal and a cation *A+ and an anion *,+ are formed. $n perfect ionic bonding there is complete separation of charge. $n polarised ionic bonding some of the electron charge on the anion is pulled back towards the cation.
Cation
)nion
+
The cation attracts electrons in the anion
Cation
)nion
The electron field around the anion is distorted
Polarisation occurs to different e!tents according to the ions involved
' highly ionic material
Polarisation
0onsiderable polarisation
The e!tent of the polarisation depends on how much the cation pulls on the electrons; the +&l!risin +&$er, and on how much the anion allows the electrons to be pulled away7 the +&l!ris!bility. Polarising power is increased by higher positive charge and smaller cation. Polarisability is increased by higher negative charge and larger anion.
F!%t&rs $hi%h in%re!se +&l!ris!ti&n in i&ni% %&m+&'n"s

". increased charge on anion or cation, 4. increased siNe of anion, 5. decreased siNe of cation. Qow polarisation low charge *A",,"+ small anion large cation e.g. KA8, Bigh polarisation high charge *A5,,5+ large anion small cation e.g. 'l5A *$,+5
$t is of course incorrect to regard ion pairs in isolation, because they actually e!ist in a lattice. Polarisation of ionic compounds gives the compounds a covalent character. The greater the polarisarion, the greater the covalent character. The e!tent of this polarisation can be found by comparing theoretical and e!perimental lattice enthalpies. @hen such a comparison was carried out with selected compounds in the previous section, it was seen that lithium and iodide compounds demonstrate significant covalent character. Qithium has a high polarising power and iodides have a high polarisability. The more polarised the compound, the greater the difference between the theoretical values and the e!perimental values. 8urther e!ample Qattice enthalpy value based on theoretical Qattice enthalpy value based on compound ionic model e!periment sodium chloride ,;33." k?mol," ,;;3.: k?mol," ,C"3.5 k?mol,"
silver chloride ,;3%.3 k?mol,"
9odium chloride is almost "&&F ionic, hence the good agreement. 9ilver chloride has a poor agreement and so has some covalent nature in its bonding.
INTRO#UCTORY OR;ANIC CHEMISTRY

Intr&"'%ti&n
Organic chemistry is the study of carbon compounds e!cluding carbon mono!ide, carbon dio!ide and carbonates. 0arbon atoms usually form four bonds. They have the unusual property of being able to )oin with other carbon atoms to form chains. This is known as %!ten!ti&n. Organic chemicals occur in series such as alkanes, alkenes, alcohols and halogenoalkanes. These series are known as h&m&l& &'s series. 'll the compounds in a particular homologous series have the same general formula and similar chemical properties.
N&men%l!t're
There are two components to the name of an organic compound. The first part of the name is given based on the number of carbon atoms in the molecule. First +!rt of name Dumber of 0 atoms " 4 5 : # 3 ; % C "& Dame Meth9 Eth9 Pr&+9 ('t9 Pent9 He.9 He+t9 O%t9 N&n9 #e%9
The second part of the name is given according to which homologous series they belong. 'lkanes always have name endings of 9ANE . The part of the molecule that determines which group it is a member of, is called the ,'n%ti&n!l r&'+.
Se%&n" +!rt of name 8unctional group Dame of group 'lkene 0hloro bromo $odo 'lcohol 'ldehyde Dame ending 9ene Chl&r&9 Pl!%e" !t ,r&nt (r&m&9 Pl!%e" !t ,r&nt I&"&9 Pl!%e" !t ,r&nt 9&l See n&te bel&$ 9!l
C C $ C* $ 8r $ > $ 1 ' 1 $ C ' 1 $ C $ 1 $ C 1 '
Ketone
9&ne
0arbo!ylic acid
9&i% !%i"
$f a molecule contains an OB group, it will end with the name Eol. $f it contains another group, such as a carbo!ylic acid, the alcohol is named as hydroy, in front on the name, and the ,oic acid at the end.
R'les ,&r n!min sim+le &r !ni% %&m+&'n"s

*i+ $dentify the longest XstraightY carbonEchain *backbone+. *ii+ Dumber the carbon,chain from the end with the most functional groups attached. *9ome functional groups, like E0OOB, must be the first carbon atom, if possible+. *iii+ Qist the functional groups in alphabetical order, each prefi!ed by the number*s+ of the carbon atom in the backbone to which it is attached. Dashes separate numbers and words. C' 3 C' 3 C' C C' C' 2 2 3 C' C' C' C'C' 3 2 3 2 8r C* 2-methy*pentane 2-@romo-1-ch*oro-2-methy*@!tane *iv+ 9ome groups appear at the e(% of a name. Dumbering here starts from the end of the chain which is nearest to one of these groups7 e.g. 0B50B(r0B*OB+0B5 is 5,bromobutan,4,ol
E.!m+les propan,4,ol 0B50B*OB+0B5
the dash , separates numbers and words.
4,#,dimethylheptane
04B# 0B5 a a 0B50B0B40B40B40B5
",bromo,4,chloroethane
0B40l,0B4(r
(ut,",ene
0B5 , 0B4 , 0B6 0B4
",4,Dibromopropane 0B50B*(r+0B4(r numbers are separated by commas
Ty+es &, ,&rm'l!e

The em+iri%!l ,&rm'l! of a substance shows the simplest ratio of atoms in the compound *e.g. for alkenes, 0B4+, while the m&le%'l!r ,&rm'l! shows the actual numbers of atoms of each element in one molecule *e.g. 0:B% for butene+. The semi9str'%t'r!l ,&rm'l! of a compound shows the order in which the atoms are bonded together in one molecule of the compound7 from it one must be able to work out all the atoms to which each particular atom is bonded *e.g. 0B 50B40B60B4 for but,",ene; 0B50B60B0B5 for but,4,ene+. The str'%t'r!l ,&rm'l! shows both the relative placing of the atoms, and the number of bonds between them7 ' ' ' ' ' 1 C C ' C ' ethanoic acid C 1 ' ' ' cis@!t2ene C C ' '
The s4elet!l ,&rm'l! is a simplified version showing bonds between 0 atoms and any functional groups, but omitting other 0 and B atoms. /ach end of each line in the main skeleton shows a 0 atom, but a bond to a functional group does not end in a 0 *e.g. 0](r becomes ](r, and 0]OB becomes ]OB, while 0]0B5 becomes ] +. /!amples7
8r 1'
butan,4,ol
:,bromo,4,methylpent,4,ene
' ener!l ,&rm'l! is used to represent members of a homologous series. e.g. al;a(es 0nB4nA4 or 0B5*0B4+!0B5 +r)mar$ al&o#ols 0nB4nA"OB or 0B5*0B4+!OB. /ach member of a homologous series differs from the ne!t by one CH8 group7
Usin &, Or !ni% Chemi%!ls

.any organic chemicals and reagents used in their reactions have properties that mean they need to be handled with care. The dangers presented by these chemicals such as flammability, being irritant or being carcinogenic, are called haNards. @hen these materials are handled, the likelihood of the haNards they present being realiNed is called the ris4. $n a practical using haNardous chemicals, the likely dangers and how they can be minimiNed is carried out in a ris4 !ssessment. @ays in which risk can be minimiNed include; @orking on a smaller scale Taking specific precautions or using alternative techniques se an alternative procedure that involves less haNardous substances
Al4!nes !n" Al4enes

The Al4!nes
'lkanes are hy"r&%!rb&ns *i.e. compounds of carbon and hydrogen only+. They are called s!t'r!te" hydrocarbons because they contain no double bonds, and so cannot undergo addition reactions. They have the general formula 7 0nB4nA4
Physi%!l Pr&+erties
The boiling points of the alkanes increase steadily with the number of 0 atoms. This is because the van der @aalsR forces between the molecules increase with the total number of electrons in the molecule. 's the chain length increases, the van der @aalsR attractions increase, and the liquid needs to reach a higher temperature before the molecules can acquire enough energy to separate and go into the vapour state. 's isomers become more highly branched, boiling points usually fall slightly. This is because the branching means that the molecule has less surface area in contact with its neighbours, thus decreasing the van der @aals attractions.
Is&merism
$somerism is when two molecules of the same molecular formula have a different arrangement of atoms *structural formula+. There are two main types of isomerism7 str'%t'r!l is&merism and stere&is&merism. Str'%t'r!l is&mers7 these have different structural formulae. i.e. the atoms are )oined together in a different order. 't the most e!treme, they may have different functional groups7 e.g. 0 4B3O may be ethanol, 0B50B4OB, or it may be metho!ymethane *an ether+, 0B 5O0B5. 'lternatively, they may have similar functional groups, but differ in the position of these in the molecule7 e.g. propan,",ol, 0B50B40B4OB, and propan,4,ol, 0B50B*OB+0B5. Or they may differ only in the hydrocarbon chain *see below+7
0B5 B50 0B4 0B 0B4 OB B50 0B5 0B 0B4 0B4 OB
2methy*@!tan1o*
3methy*@!tan1o*
Stere&is&mers5 These have the same structural formulae, and differ only by the arrangement of the atoms in space. There are two sorts7 cis,trans *or geometrical+, and optical. Optical isomerism will be looked at ne!t year.
Is&mers &, !l4!nes

'lkanes e!hibit structural isomerism. e.g. $somers of pentane
B50 0B4 0B4 0B4 0B5 0B5 B50 0 0B5 0B5 B50 0B5 0B 0B4 0B5
Pentane
methylbutane
Dimethylpropane e.g. $somers of he!ane

B50 0B4 0B4 0B4 0B4 0B5 B50
0B5 0B 0B4 0B4 0B5
Be!ane
4,methylpentane
0B5 B50 0 0B5 0B4 0B5 B50 0B 0B5
0B5 0B 0B5 B50 0B4 0 0B5 0B4 0B5
4,4,dimethylpropane
4,5,dimethylpropane
5,methylpentane
F'els
One of the main uses of alkanes is as fuels. 0rude oil consists of a mi!ture of a large number of hydrocarbon compounds. 0rude oil undergoes ,r!%ti&n!l "istill!ti&n, and the fractions obtained by this process consist of mi!tures of hydrocarbons that boil within particular ranges. The more useful fractions are those with the lower boiling ranges, such as that of gasoline which is used for petrol, but they generally occur in smaller proportions. To convert some of the larger, less useful alkanes into smaller, more useful alkanes the process of %r!%4in is used. 0racking involves passing the alkane vapour through a heated catalyst. The alkane molecules break up to form a smaller alkane molecule and at the same time an alkene, such as ethene, is formed which can then be used to make polymers. ' typical cracking reaction might be7 0"&B44 0%B"% A 04B: The straight chain alkanes do not burn very evenly, and tend to cause X 4n&%4in Y in a car engine. (ranched alkanes burn more smoothly and are much more appropriate for modern high,performance engines. The petrochemical industry carries out the process of re,&rmin to convert straight chain alkanes into branched chain alkanes. Bydrocarbon fuels produce carbon dio!ide when they burn. 0arbon dio!ide is a X reenh&'se !sY. @hen infra red radiation from the sun hits the /arthRs surface, it is absorbed and then re,radiated at a lower frequency. ' greenhouse gas absorbs the re,radiated infra red and converts it to heat energy, so causing a warming of the atmosphere. This means that the production of carbon dio!ide by burning fossil fuels increases the concentration of greenhouse gases in the atmosphere and is considered to cause %lim!te %h!n e. The problem of climate change means that there is a search for alternative fuels which do not place greenhouse gases in the air.
Chemi%!l +r&+erties &, !l4!nes

'lkanes contain carbon,hydrogen bonds, and, from ethane on, carbon,carbon single bonds. These are all non,polar, and the electron density in the ,bonds is hard to distort *not polarisable+, so that alkanes do not react with electrophiles or nucleophiles, or other polar reagents, like acids, alkalis or aqueous o!idising agents. The bonds can only undergo h&m&lyti% b&n" ,issi&n, which occurs when a covalent bond breaks in such a way that each atom takes one electron. This leads to formation of two ,ree r!"i%!ls5 ' ,ree r!"i%!l is an atom, or group of atoms, which have an unpaired electron. $t is normally highly reactive, and written with a dot *which does not show an e!tra electron, simply the unpaired one+. e.g. 0lb or 0B5b. 'lkanes therefore undergo very few reactions7 %&mb'sti&n and %r!%4in are the most important.
Re!%ti&ns &, !l4!nes

1!3 C&mb'sti&n 'lkanes burn in a plentiful supply of air or o!ygen, to give carbon dio!ide and steam7 CHH ? 8O8 CO8 ? 8H8O $f air is restricted, carbon mono!ide is likely to be formed7 CHH ? 1@ O8 CO ? 8H8O The former reaction gives out much heat, and so alkanes are useful fuels. .ethane itself is called natural gas, and is used in the home and in modern gas,turbine power stations. 1b3 H!l& en!ti&n $t is possible for the hydrogen atoms in the alkane to be s'bstit'te" by chlorine or bromine. 'lkanes react with chlorine or bromine, in the presence of light, or on heating, to form halogenoalkanes and the hydrogen halide7 8or e!ample the reaction between methane and chlorine can be represented as follows7
' ' C ' + '
C* C*
' ' C C* + '
' C*
The reaction does not necessarily stop at one substitution, and the reaction between methane and chlorine produces dichloro,, trichloro, and tetrachloro, methane. 0B: A 0l4 0B50l A 0l4 0B50l A B0l 0B40l4 A B0l 0B0l5 A B0l 00l: A B0l
0B40l4 A 0l4 0B0l5 A 0l4
The process of substitution is random, so all possible products result, though if there is e!cess methane the main one will be 0B50l, while a large e!cess of chlorine will give mainly 00l:. The substitution of a hydrogen atom by a chlorine atom actually takes place in a number of stages. Qooking in detail at what happens in each stage of such a reaction is called the re!%ti&n me%h!nism. The halogenation of an alkane takes place by a ,ree r!"i%!l reaction. The reaction between alkanes and these halogens requires an energy source such as ultra violet *u.v.+ light. 0onsidering the reaction between methane and chlorine, looking at the bond enthalpies for the bonds present (ond 0,B 0l,0l /nergy k?>mol :"5 4:4
$t can be seen that the 0l,0l bond requires less energy to break, so this is the bond which is broken by the u.v. light.
C*
C*
C*
C*
This energy is used to split the halogen molecule to form two chlorine atoms; the chlorine atoms have an unpaired electron E such a species is called ,ree r!"i%!l. The chlorine radical reacts with a methane molecule. $t forms a bond. Qooking at the bond enthalpies for the bonds that could be formed; (ond 0,0l B,0l /nergy k?>mol 55C :5"
$t can be seen that the B,0l bond has a higher bond enthalpy, so this is the bond which forms.
' + ' C ' ' ' ' C '
C*
' ' C '
' C*
This forms a methyl radical. The methyl radical then reacts with a chlorine molecule7
C*
C*
' ' C C* '
C*
$n this reaction a chlorine radical is generated; this then reacts with a methane molecule and the process continues.
C'rly !rr&$ me%h!nisms

2eaction mechanisms look at the movement of electrons within and between molecules and ions. The movement of electrons are shown by Xcurly arrowsY, using for a single electron and for an electron pair. The first step in the reaction between methane and chlorine is the formation of the chlorine radical. This is called the initi!ti&n ste+. $t is shown as follows.
C* C*
C*
C*
The chlorine radical then attacks the methane molecule. 0B: A 0l b 0B5b A B0l The methyl radical from this reaction reacts with a chlorine molecule to form chloromethane and a new chlorine radical. 0B5b A 0l4 0B50l A 0l b The chlorine radical starts the cycle again and the process continues. These two reactions are called the +r&+! !ti&n st! e. The propagation stage continues until two radical meet to form a molecule. There are three possibilities for this reaction. 9ince the ends the sequence it is called the termin!ti&n st! e. 0l b A 0l b 0l4 0l b A 0B5b 0B50l 0B5b A 0B5b 04B3 The overall mechanism is called ,ree r!"i%!l s'bstit'ti&n. Dote that in the propagation stage the 0l b at the end can go on to attack another 0B : and so the chain can go on for several thousand reactions from one initiation. The presence of traces of 04B3 in the products shows that 0B5b radicals must have been formed. Of course, the 0l b atoms can remove a hydrogen atom from 0B50l, and so the reaction can go on to 0B40l4, then 0B0l5 and finally 00l:.
The Al4enes
'lkenes are hydrocarbons that contain one double bond. They are 'ns!t'r!te" %&m+&'n"s7 compounds which are able to undergo addition reactions. They have the general formula 7 0nB4n The double bond in alkenes does not consist of two identical bonds. One of the bonds is a normal bond with the electron cloud lying between to two atoms. This is called a sigma, c, bond. The other bond has an electron cloud which is placed above and below the two atoms. This is called the pi, d, bond. The electron clouds in ethene can be represented as shown below.
Is&mers &, !l4enes */,e $somerism+

The geometry of the 060 bond is determined by the d,bond, and means that ethene is a rectangular, flat molecule.
B B 0 B 0 B
The bond angles are at about "4&o, and rotation about the 060 a!is is restricted, since twisting through C&o would mean the p,orbitals would no longer overlap and the d,bond would be broken. The restriction of rotation produces isomers called E9P is&mers *geometric isomers or cis, trans isomers+.
8or /,e isomerism *cis,trans isomerism+ to occur there must be a "&'ble b&n" and t$& "i,,erent r&'+s on e!%h of the double bonded %!rb&n atoms.
B 0 0 2 B 2 B 0 0 2
.
2
/, isomer *trans+
e, isomer *cis+
/,e and cis,trans are different terms for the same type of isomerism. Trans refers to the isomer where the 2 groups are on opposite sides of the 060. 0is refers to the isomer where the 2 groups are on the same side of the 060.
Is&mers &, b't!ne

B50 0 B 0 0B5 B B B50 0 0 B 0B5
B50 0 B50 0
4/ but,4,ene trans but,4,ene
4e but,4,ene cis but,4,ene
4Emethylpropene
The /,e *cis > trans+ isomers will be chemically very similar, though not quite identical, and will have slightly different melting and boiling points. ODote that a third isomer, 4Emethylpropene, which has two methyl groups attached to the same carbon atom, is a str'%t'r!l isomer of these, as is but,",eneP
E9 !n" P9 vs %is9tr!ns n&men%l!t're

The cis trans system breaks down with e!amples like;
0l 0l
The /,e naming system is more useful than the cis,trans system. The naming of the isomer is determined by priorities. /ach atom on the double bond is given a priority determined by its atomic number. The smaller the atomic number the lower the priority E hydrogen in the e!ample above. $f atoms with the lowest priority are on the same side on each end of the 060 the isomer is called the P9is&mer. *e6eusammen *together++. $f atoms with the lowest priority are on the same side on each end of the 060 the isomer is called the E9is&mer. */6/ntgegen *opposite++.
Re!%ti&ns &, !l4enes

The alkenes are more reactive than the alkanes because of the 060 bond. $t is possible for the double bond to break, allowing each carbon to form a new bond, which is often energetically favourable. Balogens, hydrogen halides, hydrogen and potassium manganate*=$$+ will produce !""iti&n re!%ti&ns with alkenes. A""iti&n &, hy"r& en 1hy"r& en!ti&n3 'lkenes react with hydrogen in the presence of a nickel catalyst at"#& o0.
' $ C
' C $ + ' ' $
' C
' C ' $
'
This is important in the hydrogenation of vegetable fats to make margarine. 'n unsaturated vegetable oil is mi!ed with a nickel catalyst at #& o0,and hydrogen gas bubbled through. The saturated product has a higher melting point, and is less easily o!idised *longer shelf life+. A""iti&n &, br&mine 'lkenes will decolorise bromine immediately7
' $ C
' C $ + 8r 8r $
' C 8r
' C 8r $
The decolorisation of bromine water is used as a test for the 060 double bond. This reaction occurs in an inert solvent like volasil. A""iti&n &, %hl&rine
' $ C
' C $ + C* C* $
' C C*
' C C* $
A""iti&n &, Hy"r& en %hl&ri"eQ
' $ C
' C $ + ' C* $
' C ' ' $ + ' 8r $ C '
' C C* ' C 8r $ $
A""iti&n &, Hy"r& en br&mi"eQ
' $ C
' C
U @hen addition of a hydrogen halide takes place, if the alkene is not symmetrical, the hydrogen adds to the carbon that already has the most hydrogen. This is called M!r4&vni4&,,>s r'le
' ' C '
' C
' C ' + ' 8r '
' C '
' C 8r
' C ' '
Re!%ti&n $ith P&t!ssi'm m!n !n!te1LII3 'cidified potassium managanate*=$$+ is decolourised *from purple to colourless+ by an alkene and a "i&l is formed.
' $ C
' C $ + F1G + '21 $
' C 1'
' C 1' $
OOP is a shorthand for the o!idiNing agent potassium manganate*=$$+.
A""iti&n Re!%ti&ns &, Al4enes

The addition reactions have a mechanism which we need to study. $t is the electron rich area in the double bond which causes the initial attack. ' molecule attacking such an area is called an ele%tr&+hile *electron loving+. This reaction results in addition, so this type of reaction is called ele%tr&+hili% !""iti&n. ' definition of the term electrophile is; 'n electrophile is a species attracted to an area of negative charge and is an electron pair acceptor. Me%h!nism ,&r the re!%ti&n &, hy"r& en br&mi"e $ith eth!ne5 Qooking at dot and cross diagram for the reaction. This is n&t the $!y ! me%h!nism is sh&$n5 ". The hydrogen in the hydrogen bromide has a partial positive charge. $t is attracted to the high electron density in the double bond.
' C ' ' 8r
' C ' ' C ' ' C ' ' 8r
4. The hydrogen draws an electron pair out of the double bond and forms a bond to the hydrogen.
5. The bond between the bromine and the hydrogen weakens and breaks, both the electrons going to the bromine.
'
' C ' 8r
' C + '
:. The carbon on the right now has only three of its original four electrons, so it has a positive charge. This intermediate is called a %!rb&%!ti&n i&n. #. The bromine has gained an electron making it a bromide ion with a negative charge.
3. The bromide donates an electron pair to the positively charged carbon forming a bond.
' ' C '
' C ' 8r
The reaction mechanism for this is shown as follows.
' C ' ' 8r
' C ' '
' C '
' C ' 8r
' ' C '
' C ' 8r
The mechanism for the attack of bromine on ethane is almost identical, but as bromine is not a polar molecule it has no partial charge. 's a bromine molecule approaches the ethane, the high electron density in the double bond repels electrons in the nearest bromine so causing an induced partial positive charge.
' C ' 8r 8r
' C ' 8r
' C '
' C+ ' 8r 8r
' C '
' C ' 8r
Asymmetri% A""iti&ns 1M!r4&vni4&,,>s r'le3

The addition of hydrogen bromide to propene could lead to two possible intermediates.
' ' C '
' C
' C ' '
' C '
' C '
' C+ ' '
' C '
' C
' C ' '
' 8r
$f the hydrogen )oins the central carbon the ion on the left will be formed. $f the hydrogen )oins the end carbon the ion on the right will be formed.
The carbocation ion with the charge on the central carbon is formed as the charge is stabilised by the two carbons on each side of it. 9o the mechanism is as follows
' ' C '
' C
' C ' '
' C '
' C
' C ' '
+
8r
' 8r ' ' C ' ' C 8r ' C ' '
M!r4&vni4&,,>s r'le states that; @hen addition of a hydrogen halide takes place, if the alkene is not symmetrical, the hydrogen adds to the carbon that already has the most hydrogen.
Test ,&r !l4enes

The addition reactions are used to test for the presence of a double bond. $f br&mine $!ter is added to an unsaturated compound, an addition reaction occurs fairly rapidly and the bromine water changes from orange to colourless. $n this test the product contains a (r and an OB. This is because the bromine water contains hydro!ide ions from water. The reaction mechanism for the test on ethene shows why this product is formed.
' C ' 8r 8r
' C '
' 8r C '
C + ' 1'
'
' 8r C '
' C ' 1'
OB, from the water takes place in the second step.
A""iti&n P&lymers
'n addition polymer is formed when monomers containing double bonds are polymerised. $n the process of polymerisation the double bond breaks and the molecules )oin to form molecules of thousands or millions of units. Polymer /thene structure of .onomer structure of polymer
Propene
' C ' ' C '
' C ' C'3 C '
' ' C C ' ' n ' C ' ' C ' C'3 C ' n C* C ' n
0hloroethene
' C* C C ' ' ; ; C C ; ;
Tetrafluoroethene
; ; C C ; ; n
In"e+en"ent rese!r%h7 0onsider the uses of energy and resources over the life cycle of a polymer in the conte!t of how renewable resources, recycling and energy recovery can lead to a more sustainable use of materials.

Complete Unit 1 Notes Chem

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A Level Chemistry

UNIT 1 THE CORE PRINCIPLES OF CHEMISTRY NOTES

FORMULAE) E*UATIONS AN# MOLES

Am&'nt &, S'bst!n%e

P!rts +er milli&n

Re!%tin 6'!ntities !n" %hemi%!l e6'!ti&ns

Carryin o!t the titration

#eriv!ti&n &, E6'!ti&ns

/quation7 .oles .ole ratio

() (ntha*py $eactants &' %rod!cts

'2- . / 012- . '2- . / 012- .

'21- . '21-*. C-diam. ' 2 / 1."34mo*-1

/nthalpy of combustion, JBLc

/nthalpy of neutralisation, JBLneut /nthalpy of atomisation, JBLat

E.+eriment!l Me!s'rements &, Enth!l+y

5emperat!re chan e +or reaction 67

3.5 mins 5ime / mins

Typical results Qiquid

.ass of burner at start >g ""#.;%

.ass of burner at end >g ""#.#C

Temperature at start >o0 4"

Temperature at end >o0 4C

Hess>s L!$ !n" Ener y Cy%les

8 Consider ) to 8: c*oc3wise 2 antic*oc3wise

' 4 / ' 3 / ' 2

H81 3 ? @O81 H8O81l3

<HA, = 98BC5D 4Em&l91

Bydrogen pero!ide decomposes according to the equation7

H8O1l3 ? @O81 3 <HAR = 9DB50 4Em&l91

'2- . / 12- . &',+-'21.

2 '1 '1 + -C12. / 2 + -'21. 2 2-3"4. / 2-286. 2C12- . / 2'21-*.

A sum of ' 1 + *reactants+ 04B:*g+ A 5O4*g+ 5* &+

6 sum of ' 1 + *products+ A 4*E4%3+ 6 A :C k? molE"

6 40O4*g+ A 4B4O*l+ 6 4*E5C:+

E":&C A ' 1 + *ethene+ A 9o

' 1 + *ethene+ 6 4*E5C:+ A 4*E4%3+ E *E":&C+

sing the algebraic method7

().e. 3 e*#$(e 'e(Ee(e)

3-12"". 6 C12 - . / 3 ' 2 1-*.

8rom Bess1 Qaw7

5 *E"4CC+ E *E54;5+ 6 E#3: k? molE"

4184 ' 2 -1"#4 34 mo*1 C;4 / 4';

Ty+es &, b&n" bre!4in

Cl+ Pr&bin re!%ti&n me%h!nisms

(&n" 0,B 0,0 0,(r

(&n" enth!l+y 14E :"5 5:; 4C&

(&n" enth!l+ies !n" enth!l+ies &, At&mis!ti&n

The bond enthalpy of *0,B+ in 0B: is :"4 k? mol,"

*attice entha*py o+ = C*2-s.

ATOMIC STRUCTURE AN# PERIO#ICITY

=ass n!m@er )tomic n!m@er

The M!ss S+e%tr&meter

Aaporised samp*e )cce*eratin +ie*d (*ectron !n =a netic +ie*d

)mp*i+ier >on detector

5!@e !nder vac!!m

M!ss S+e%tr! &, M&le%'les

Ele%tr&ni% Str'%t're &, the !t&m

Ele%tr&ni% C&n,i 'r!ti&n

Se%&n" shell % electrons

Ele%tr&ni% %&n,i 'r!ti&ns

Do of electrons ": "C 4# 54 53

C&n,i 'r!ti&ns !n" the Peri&"i% T!ble

'21- . '21-. C-diam. ' 2 / 1."34mo-1

8 Consider ) to 8: coc3wise 2 anticoc3wise

A sum of ' 1 + reactants+ 04B:g+ A 5O4g+ 5 &+

6 sum of ' 1 + products+ A 4E4%3+ 6 A :C k? molE"

6 40O4g+ A 4B4Ol+ 6 4*E5C:+

' 1 + ethene+ 6 4E5C:+ A 4E4%3+ E E":&C+

5 E"4CC+ E E54;5+ 6 E#3: k? molE"

attice enthapy o+ = C*2-s.

Aaporised sampe )cceeratin +ied (ectron !n =a netic +ie*d

The second ioniNation energy of sodium DaAg+ Da4Ag+ A e,