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Atomic structure
f& Inffoduction
Much of chemistry depends upon Coulomb's Law which states that the electrostatic force of attraction, F, is given by: F*(q..Q)*r, where q- and q- are the charges on the objects (e.g. the nucleus, an electron, ions etc.) and r" is the square of the distance between their centres. This means that the bigger the charge, the bigger the force, and the further the centres are apart, the weaker the force.

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Things learn to

iJ Atomic numbet (4 of an element is the number of protons in the nucleusof its atom. [l wtass number of an isotope is the number of protons plus the number of neutrons in the nucleus. E Isotopes are atoms of the sameelement which have the samenumber of protons but different numbers of neutrons. They have the same atomic number but different massnumbers. E nehtive atomic mass (A) of an element is the average mass (taking into account the abundanceof each isotope)of the atoms of that element relative to llIzth the massof a carbon-LZatom. f

The relative molecular isalso mass called relative the formula mass especially forionic substances.

nehtive isotopic mass is the massof one atom of an isotope relative to lll2th the massof a carbon-L2atom.

f] Rehtive molecular mass (MJ of a substanceis the sum of all the relative atomic masses its constituent atoms. of E Molar mass is the massof one mole of the substance. units are Its gramsper mole (g mol-'), and it is numerically equal to the relative molecularmass.

lonisation energies always are endothermicrelate the and to formation positive ofa ion.

E fst lonisation energy is the amount of energyrequired per mole to remove one electron from each gaseous atom to form a singly
positive ion

E(g)*E.(g)+e-

Zna ionisation energy is the energychangeper mole for the removal of an electron from a singly positive gaseous to form a ion doubly positive ion E.(g)-E'.(g)+e-

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*i lst electron affinity is the energychangeper mole for the addition atom to form a singly negativeion of one electronto a gaseous E(g)+e---E(g) J Znd, electron affinity is the energychangeper mole for the addition ion of an electron to a singly negativegaseous to form a doubly ion negative rG) + e--- E'-(g) iJ s block elementsare thosein which the highestoccupiedenergylevel is an s orbital. They are in Groups I and 2. Similar definitions apply to p block (Groups3 to 7 and 0) and d block (Scto Zn) elements. ^_______-

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!

Thingsto understand

Mass spectra by and is t An element first vapourised then bombarded high-energy

electrons that remove an electron from the element and form a positive ion. This ion is then acceleratedthrough an electric potential, deflected according to its mass and finally detected. O Metals and the noble gasesform singly positively charged ions in the ratio of the abundance of their isotopes. t Non-metals also give molecular ions. For example Br, which has two 'nBr will give three lines at m/e values of and "Br 150o/o), isotopes 15oo/o) 158, 160 and L62 in the ratio I:Z:L These are caused by ('nBr-'nBr;+, ltnBr-ttBr;+ and (ttBr-ttB1;+'

out A common is to miss the error of + charge theformula a species on in for responsiblea line a mass spectrum.

I The relative atomic mass of an element can be calculated from mass spectra data as follows: A, = the sum of (mass of each isotope x percentage of that isotope)/l0O

oxaloLpb Work"ei,
in spectrometer. was Boron analyseda mass the below. using results mass boron of the atomic Calculate relative Peaks mleot at (%) Abundance 18.7 81.3

10.0
11.0

x + A,= x Answer'. ( 10.0 18.7 11.0 81.3 100 = 10.8 )/

Electron strrrcture
O The first shell only has an s orbital. o The second shell has one s and three p orbitals. o The third and subsequent shells have one s, three p and five d orbitals. o Each orbital can hold a maximum of two electrons. o The order of filling orbitals is shown in Figure 1.1 below.

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F ig l. l Theorderof filling of atomic orbitals

Electron structurescan be shown in two ways: o The S,p, d notation. For vanadium (atomic number 23) this is: rs", 2s' zpu, 3s' 3pu3d" 4st. o The electronsin a box notation. For phosphorus (Z = 15) this would be:

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1s 2s 2p, 2p, 2p, 3s 3p, 3p, 3p, and ions

Sizes of atoms

the electrons are lnanatom, outer from of shielded thepull thenucleus nearer to inshells bytheelectrons (the thenucleus inner electrons).

O The atoms becomesmaller going acrossa period from left to right, pulling the electronsin closer, the because nuclear chargeincreases, though the number of shellsis the same. The atoms get btgger going down a group, becausethere are more o shellsof electrons. O A positive ion is smallerthan the neutral atom from which it was made, the because ion has one shell fewer than the atom. the O A negativeion is bigger than the neutral atom, because extra them to spreadout. repulsion between the electronscauses

lst ionisation

enerry

O There is a general increase going from left to right across a period (see Figure 1.2). This is caused mainly by the increased nuclear charge (atomic number) without an increase in the number of inner shielding electrons.
ts I

2400 2200 2000 &' 1800 x 1600 bo (u 1,400 (u 1,200 1000 ( 800 600 400
k cn

Fig 1.2 The first ionisation energies (kl mol-') of the elements up to krypton

20 15 Atomic number

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You should able sketch be to the variation1stionisation of energies withatomic number thefirst20 for elements.

for after Group 2 (this is because, Group 3, it O There are slight decreases is easierto remove an electron from the higher energyp orbital), and for after Group 5 (this is because, Group 6, the repulsion of the two electronsin the p, orbital makesit easierto remove one of them). going down a Group. This is causedby the outer O There is a decrease electron being further from the nucleus.(The extra nuclear chargeis balancedby the sameextra number of inner shielding electrons.) Successive ionisation energies

The sixionisation firs! energies/ kJmol ofanelement are: 1st 786 2nd 1580 3rd 3230 4th 4360 sth 16000 20000 6th There a bigjumpafter fourth, is the is sothe elementinGroup 4.

o The 2nd ionisation energy of an element is alwaysbigger than the first, because secondelectron is removed from a positive ion. the ionisation O When there is a very big jump in the value of successive energies, electron is being removed from a lower shell, e.g.if this an iump happensfrom the 4th to the 5th ionisation energy,four electrons have been removed from the outer shell during the first four ionisations, and so the element is in Group 4. Electron affinity

o The 1st electron affinity valuesare alwaysnegative(exothermic),as a negativeelectron is being brought towards the positive nucleusin a neutral atom. They are the most exothermic for the halogens. o The 2nd electron affinity valuesare alwayspositive (endothermic), because negativeelectron is being addedto a negativeion. a

Checklist
Beforeattempting the questionson this topic, check that you can: iJ pefin e A, , M, , and relative isotopic mass. ,J Calculatethe number of neutrons in an isotope,given the atomic and massnumbers. iJ Calculatethe relative atomic massof an element from massspectra data. [l Oefine first and subsequent ionisation energies. [l mplain the changesin first ionisation energiesfor elementsacrossa Periodand down a Group. f Deducean element'sGroup from successive ionisation energies.

E Work out the electronic structureof the first 36 elements. E Oefine the Lst and 2nd electron affinities.

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your knowledge understanding and Testing

For the following set of questions,cover the margin, write down your answer,then check to seeif you are correct. (You may refer to the Periodic Tableon the inside back cover) (relativeto a proton) of: and charges I Statethe masses a proton (p) a neutron (n) an electron(e). o How many neutrons are there in an atom of ?iXa ? o What is the atomic number of an elementwhich has an atom of mass number 99 and contains56 neutrons? I Write equationswith state symbolsfor: a the 1st ionisation energyof sodium b the 1st ionisation energyof chlorine c the 2nd ionisation energyof magnesium. of O Using the ls, 2s 2p. . notation, give the electronicstructures the
elements: a u C b ,rM8 c ,uF. Explain the difference between relative isotopic mass and relative atomic mass. Illustrate your answer with reference to a specific element. Lithium has naturally occurring isotopes of mass numbers 6 and 7. Explain why its relative atomic mass is 6.9 not 6.5. Magnesium was analysed in a mass spectrometer. Peaks were found at three different mle ratios.

' M a s s ,c h a r g+ 1 1 e 1, Mass charge 0 -1 Mass 1i1860charge , 2 3( p + n-) 1 1 p = 1 2 f i

99(p+n) 56n= 43.

N a ( g*)N a - ( g ) e + C l ( g-)C l - ( g )+ e -Mg'-(g)+eMg-(g)

1s',2s',2p' 1s', 2pu, 2s', 3s'. 1s', 2pu,3s" 3du,4s' 2s', 3pu,

The to answers thenumbered questionsonpage 121. are

mle 24.0 25.0 26.0

(%) Abundance
78.6 10.1 11.3

Calculatethe relative atomic massof magnesium. Gallium has a relativeatomic massof 69.8. Its massspectrumshowstwo peaks atmle of 69.0and 71.0. of Calculatethe percentage each isotope in gallium. of ionisation energies an elementX are given below: The successive Ionisation energy Value/kJmol-' 1st 1060 Znd 3rd 4th 4960 5th 6th 7th Bth

1900 2920

6280 2L ZOO2s 900 30 s00

which group the element X is in. State,giving your reasons, 6 a b Sketchthe variation of 1st ionisation energyagainstatomic number for the first LL elements. Explain why the ionisation energyis lessfor: i the elementof atomic number (4 of 5 than that for elementof Z=4 ii the element of Z -- 8 than that for element of Z = 7

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B.NDTNG AND MAIN GRoup

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iii the element of Z = 11 than that for element of Z = 3. 7 Using the electron in a box notation, give the electronic structure of chlorine (Z = I7). 8 Explain, in terms of electronic structure, why the chemical properties of lithium, sodium and potassium are similar but not identical. 9 a b c Give the equation, with state symbols, that representsthe 1st iii oxygen. ii chlorine, electron affinity of i lithium, Give the equation that representsthe 2nd electron affinity of oxygen. Why is the 2nd electron affinity of oxygen endothermic whereas the 1st electron affinities of lithium, chlorine and oxygen are all exothermic?

and equationsmoles @ Formulae,

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tri

Introduction

The keysto this topic are: I To be able to calculatethe number of moles from data. t To set out calculations clearlv.

Things to learn
iJ The Avogadro Constant is the number of carbon atoms in exactly 12 g of the carbon-I} isotope. Its value is 6.O2 x 10" mol-'.

1 molof NaOH a mass 40g has of 1 molof 0, has mass 32 g. a of

iJ O.re mole of a substance is the amount of that substance that contains particles of that substance.This means that one mole of a 6.O2 x 1023 substance is its relative atomic or molecular mass expressedin grams. t] fne molar mass of a substance is the mass (in grams) of one mole. [J Amount of substance is the number of moles of that substance.

[] fne empirical formula is the simplest whole number ratio of the elements in the compound.

Things to understand
Calculation of empirical formulae from percentage data
It is best calculated using a table.

Element Percentage of element Carbon Hydrogen Oxygen 48.7 8.1 43.2

Percentage divided by A,of element 48.7+12-4.1 + 8.1 1=8.1 43.2+16-2.7

Divide each by lowest

4 . I + 2 . 7= 1 . 5 8 . 1+ 2 . 7= 3 2 . 7+ 2 . 7= 7

ro*MULAE,

EeuATroNS AND MoLEs

The last column gives the empirical formula, but if any value in this column comes to a number ending in .5 or .25, you must multiply all the values by 2 or 4 to get integers. So here the empirical formula is C3H6O,.

Equations
These must balance. The number of atoms of an element on one side of the equation must be the same as the number of atoms of that element on the other side.

Ionic equations There threerules: are (salts, strong of for o Writethe ionsseparately solutions ionic compounds
must lonic equations also balance forcharge.
acids and bases). o Write full 'molecular' formulae for solids and all covalent substances. o Spectator ions must be cancelled and so do not appear in the final equation.

Moles
There are three ways of calculating the amount of substance (in moles): I For a pure substance X The amount rnASS of X (in moles) = mass of X (in grans)/its molar

Workpi, oxaloLpb
g A v o i w r i t i nm o l= 0 . 1 1 . I n s t e a d d the or of state name formula the substance m o e . ga m o u n tf N a= 0 . 1 1 o l . . the of Calculate amount H,0in 1.1g of water = gl18 mol Answer:1.1 g mol-' 0.061 of H,0

t For solutions: The amount of solute = concentration (in mol d--') (in dm') Thereforeconcentration = moles / volume in dm'

x volume

in in Asyolumedm-= volume formula the can cm-/1000, following beused: = m o l e sM x W 1 0 0 0 = moles orconcentration x1000lV where istheconcentration M and in t/isthe volumecm-.

Workd,oxiloLpb
mol in of the of Calculate amount NaOH 22.2cm3 0.100 dm-'solution = Answer:0.100 x 0.0222 2.22x10-'molof Na0H

O For gases: Amount volume. of gas (in moles) = volume

(in dm')/molar

at The molar volurne of a gas is 24 dm3mol-r,measured room temperature and pressure (RTP).

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Work^ei, oxiloL\-lx'
in at the of Calculate amount H,(g) 3.2dm" RTP. = 0.13 of Answer'. 3.2124 mol H,(g)

Calculation

of number

of particles

from the number of moles. The number of particlescan be calculated = constant. r The number of molecules molesx Avogadro's constantx the number of o The number of ions = molesx Avogadro's those ions in the formula.

Workpi,oxilo7-h,
molecules g ofC0,. in3.3 the of dioxide Calculatenumber carbon = 0.075 mol Amount C0,= 3.3144 Answer: of = 0.075 x x Numbermolecules x 6.02 10"= 4.5 10" of g ions the of Calculatenumber sodium in5.5 of Na,CO, = 0.0519 =5.51106 mol Answer: Amount NarCO, of 10" x 6.02 NumberNa- = 0.0519 x 10"x2 =6.2x of ions Calculations based on reactions

Thesecan only be done if a correctlybalancedequation is used. Reocting moss questions Firstwrite a balancedequation for the reaction. Then follow the route: Step1
Ma s sA -

Step2
Mol es A -Mol es

Step3
B + Mass B

For Steps1 and 3 usethe relationship: mass amount of A or B (in moles) = mass/molar For Step2 use the stoichiometric ratio from the equation: moles of B = moles of A x ratio B/A

oxilo7-h' Work^ei,,
to with g hydroxide requiredreact 1.23 ofsilicon the Calculatemass sodium of
In Step thestoichiometric is 2, ratio 211 there 2Na0H molecules as are foreach 1Si0, moleculethe in equation. dioxide. Answer.

+ Equation: + 2Na0H---lNa,Si0,H,0 SiO, = 0.0205 mol mol 1 of Step amount SiO,= 1.23160 = = mol mol 2 of Step amount NaOH 0.0205 x 211 0.0410 = 1.64 g x 3 of Step mass NaOH= 0.041040

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u LAE, EeuATroNs

AN D M.LES

Titrotions (this will only be exomined ot AS in Unit test 38) The route is much the same: SteP1 Step2
Step 3 ^ answer

concentration and + v o l u m e o fA

MolesA+MolesB+aboutB

For Steps1 and 3 usethe relationship: amount (in moles) = M x V/1000 For Step2 usethe stoichiometricratio from the equation: moles of B = moles of A x ratio B/A

oxalo7.b Work^ei,
ratio In Step thestoichiometric is 2 there 1H2S0o is molecule 112as in forevery 2Na0H molecules theequation. 0.212 hydroxideconcentration moldm-' of of 25.0 cm'ofa solution sodium the acid. of wasneutralised23.4cm'ofa solution sulphuric Calculate by acid of the concentration sulphuric solution. + 2Na0H+ H,SO. ---) Na,SOo 2Hr0 Answer. Equation: = 5.3 = 1 amount Na0H 0.212x25.011000 x 10-'mol of Step =o 5 . 3x 1 0 - x 1 l 2 = 2 . 6 5 1 0 - ' m o l x 3 2 a m o u n tf H 2 S 0 0 Step = 2.65 10-'mol/0.0234 x dm3 of H2S0o Step 3 concentration = 0 . 1 1 3 o ld m - ' m
Concentrotion of solutions This is either: amount of solute (in molqs) volume of solution in dm'' or: mass of solute (in grams) volume of solution in dm'' units: mol dm-"

units: g dm-'

Gos volume colculotions 1 For reactions where a gas is produced from solids or solutions, follow:

Step1 Massof A*Moles

Step2 of A+Moles

Step3 Volumeof gasB of gasB +

Step 1 use the relationship: moles = mass/molar mass Step 2 use the stoichiometric ratio from the equation: moles of A = moles of B x ratio of B/A Step 3 use the relationship: volume of gas B = moles of B x molar volume

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Workpj,oxu,u?h,
i-,',-.,;r:,,'' L

ratio lnStep the 2 stoichiometricis is molecule for ll2asthere 1C0, molecules inthe 2NaHCO, every equation.

gas measured atroom dioxide evolved, the of Calculatevolume carbon is heated. hydrogen carbonate when temperaturepressure, 7.8g ofsodium and and of mol-' thetemperaturepressure at is volume a gas 24dms of The molar theexperiment. + HrO 2NaHC0, NarCO, + COr(g) Answen Equation: =7.8184 = 0.0929 mol mol 1 amount NaHCO' of Step = mol mol of 2 amount C0,= 0.09286 x 112 0.0464 Step mol-' mol volume C0,= 0.0464 x 24 dms = 1.1dm' of 3 Step

For calculations involving gasesonly, a short cut can be used. The volumes of the two gasesare in the same ratio as their stoichiometry in the equation.

i ,Workti, oxilov-l"o ry
o Youmust in all show thesteps your calculations o Don't down two or three to cut figures themiddle in significant of a calculation o Check to calculationensure every the thatyouhave entered data correctly
L$.:i*'q'ffr'' r:

15.6 to completely cm'ofethane? is volume oxygenneededburn of What + 2C,Hu(g)70,(g) 4C0,(g) 6Hr0(l) + Equation: Answen ofoxvqen Calculation:volume oas= 7 = 3.5 gas 2 volume ethane of = g?s x cm' volume oxygen = 3.5 15.6 54.6 of

Significant

figures

your answerto the samenumber of significant You should alwaysexpress figuresas statedin the question or as there are in the data. If you cannot work this out in an exam, give your answerto 3 significant figures (or 2 decimal placesfor pH calculations),and you are Do unlikely to be penalised. not round up numbersin the middle of a calculation. Any intermediate answersshould be given to at least 1 more significant figure than your final answer.

Checklist
Beforeattempting questionson this topic, check that you can: iJ Calculatethe empirical formula of a substance from the o/o composition. t-J Write balancedionic equations. from its mass,of a [i Culc.rlatethe number of moles of a pure substance from the volume and concentration of its solution, and of a gas solute from its volume. i] Catculatereacting masses and reactinggasvolumes. L] Use titration data to calculatethe volume or the concentration of one solution.

a"RMULAE,

EeuATroNs

AND MoLEs

11

your knowledge understanding and Testing

For the first set of questions, cover the margin, write down your ans\\-er, then check to see if you are correct. r The table below contains data which will help you.

Substance Nitrates
Chlorides

Solubility
All soluble

All solubleexceptfor AgCl and PbCI,

All soluble

Sodiumcompounds Hydroxides

All insolubleexceptfor Group 1 and barium hydroxides

Write ionic equations for the reactions of solutions of:

-+ a Pb"(aq) 2Cl-(aq) PbCl,(s) + b Mg'-(aq)20H-(aq)-'Mg(0H),(s) + c Cl-(aq)Ag'(aq) -- AgCl(s) + d H-(aq) 0H-(aq) --' H,0(l) t

a b c d

lead nitrate and potassium chloride magnesium chloride and sodium hydroxide sodium chloride and silver nitrate sodium hydroxide and hydrochloric acid.

Calculate the amount (in moles) of: a b c d Na in I.23 g of sodium metal NaCl in 4.56 g of solid sodium chloride Cl, in 789 cm'' of chlorine gas at room temperature and pressure NaCl in 32.1 cm'' of a 0.111 mol dm-' solution of sodium chloride.

= mol a 1.23123 0.0535 = 0.0779 mol b 4.56/58.5 = 0.0329 mol G 0.789124 = 11 x mol d 0.1 x 0.0321 3.56 10-3 = 0.205d = 205 m' cm' 0.045610.222 (1 8)x 6.02 10"= 3.34 10" .00n x x (1.00/106) x 1d'x 2 =1.14 x1ff x 6.02
g a 4.44g10.250 = 17.8 dm-' dm' =0 . 1 1 1 o l m E 4.4414 0 Therefore mol/0.250 0.111 dmg = 0.444 dm-' mol

I Calculate the volume of a 0.222 mol dm-'' solution of sodium hydroxide, which contains 0.0456 mol of NaOH. t Calculate the number of water molecules in 1.00 g of HrO. o Calculate the number of sodium ions in 1.00 g of NarCO,,. ) 4.44 g of solid sodium hydroxide was dissolved in water and the solution made up to 250 cmS.Calculate the concentration in a b g dm-' mol dm-'.

The to answersthenumbered questionsonpages are 121-122.

1.a b

carbon and 17.24o/o An organic compound contains 82.760/o hydrogenby mass.Calculateits empiricalformula. It was found to have a relativemolecularmassof 58. Calculateits
molecular formula.

Balance the equations: a b NH.+O,-NO Fe'.(aq) + HrO -- Fe'.(aq) + Sn'.(aq) + Snn.(aq)

What mass of sodium hydroxide is needed to react with 2.34 g of phosphoric(V) acid, H3PO*,to form the salt Na,POnand water? What volume of 0.107 mol dm' potassium hydroxide, KOH, solution is needed to neutralise 12.5 cmt of aO.O747mol dm-' solution of sulphuric acid? What volume, measured at room temperature and pressure,of hydrogen sulphide gas, HrS, is required to react with 25 cm" of a 0.55 mol dm-'

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BoNDtNG AND MAtN GRoup cHEMtsrRy "t*ucruRE,

solution of bismuth nitrate, Bi(NO3)r?The molar volume of a gas is 24 dmt mol-' under these conditions. They react according to the equation: 3HrS(g) + 2Bi(NO3).(aq)'BirSr(s) + 6HNO,(aq). 6 What volume of hydrogen gas is produced by the reaction of 33 dm'of methane gas when it is reacted with steam according to the equation: CHn(g) + H,O(g)--' CO(g) + 3H,(g) ?

ing re Structu andbond

ffil try
Introduction
You should be able to distinguish between:
o Chemical bonds Ionic Covalent

Metallic

ions between separate which are divided into two tyPes: polar covalent where the bonding pair of electrons is nearerto one atom pure covalent where the bonding pair of electrons is sharedequally bonding causedby electronsdelocalised throughout the solid.

O Intermolecular forces(between covalent molecules) between 6- H in one molecule and 6 F, O or Hydrogen bonds
N in another molecule

Dispersionforces

between all molecules. Their strength depends upon the number of electrons in the molecule. between 6- atoms in one molecule and 6 atoms in another molecule.

Dipole/dipole forces -

Things to learn
E en ionic bond is the electrostatic attraction that occurs between an atom that has lost one or several electrons - the cation - and one that _ has gained one or several electrons the anion. c-I e covalent bond occurs when two atoms share a pair of electrons. It results from the overlap of an orbital containing one electron belonging to one atom with an orbital that contains one electron that belongs to the other atom. The overlap can be head on, which results in a o bond or, side by side, which results in a n bond (see Figure 1.3). A double bond is a o and a n bond, with two pairs of electrons being shared. tr n dative covalent bond is a covalent bond formed when one of the _ overlapping orbitals contained two electrons and the other none. U n metallic bond is the force of attraction between the sea of delocalised electrons and the positive ions which are arranged in a _ regular lattice. of an element is a measure of the attraction its iJ the electronegativity atom has for a pair of electrons in a covalent bond.

o-bond

n-bond

Fig l . 3 o a n d n b o n d s .

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AND B.NDTNG J n hydrogen bond is an intermolecular force that exists between a 6oxygen or hydrogen atom in one molecule and a 6- fluorine, nitrogen atom in another molecule. "J van der Waals forces are between covalent molecules and are caused by dipole/dipole and induced dipole/induced dipole (dispersion) forces.

In hydrated cations, as such molecules thewater [Mg(HrO)r]'', ion to arebonded themagnesium by Each bonds. oxygen dative covalent pair with atom bonds itslone into in empty andp orbitals theMg' s ion.

Things to understand
Ionic bonding
o An ionic bond is likely if there is a large difference (greater than about 1.5) in the electronegativities of the two atoms.

will lonic substances bewater required to if solubletheenergy the separate ionsin thelattice (lattice for is energy) compensated nature bytheexothermic of This hydration. is theenergy when water released theverypolar to molecules attracted the+ and are - ions.

o Cations with a small radius and/or high charge have a large charge density, and so are very polarising. Anions with a large radius and/or high charge are very polarisable. If either the cation is very polarising or the anion is very polarisable, the outer electrons in the anion will be pulled towards the cation and the bond will have some covalent character. I Ionic bonding gives rise to an ionic lattice, which is a regular threedimensional arrangement of ions. * An ionic bond is, on average,the same strength as a covalent bond.

Covalent bonding
Covalent substances are either: i ii iii iv giant atomic, such as diamond, graphite and quartz (SiOr) simple molecular, such as I, and many organic substances hydrogen-bonded molecular, such as ice, and ethanol non-crystalline, such as polymers like poly(ethene).

Polar covalent bonds may result in polar molecules, but for linear molecules of formula AB, planar molecules of formula AB, tetrahedral molecules of formula AB, and octahedral molecules of formula ABu, the polarities of the bonds cancel out, and the molecule is not polar.

Intermolecular

forces

In HCI there nohydrogen bonds, are for thedispersion forces count about 80%of thetotal forces, intermolecular with for dipole/dipole accountingthe remaining 20%.

o The strongestintermolecular force is hydrogen bonding. In molecules with many electrons,such as l, the next strongestare induced dipole/induced dipole forces(sometimescalled dispersionforces)and, in the most cases, weakestare permanent dipole/permanent dipole (or dipole/dipole)forces. o The strength of dispersionforcesdependsmainly upon the number of is in electrons the molecule.This is why I, with 106 electrons a solid, is whereas with 34 electrons a gas. Cl, of as o This explainsthe trend in boiling temperatures the noble gases, the dispersionforcesare lessin helium than in neon than in argon etc. of Likewisethe boiling temperatures the Group 4 hydrides increasein the Group from CHnto PbH4. of o The boiling temperatures the hydridesof Groups5, 6 and 7 (see there is hydrogenbonding Figure1. 4) can alsobe explained.Because betweenHF moleculesbut not betweenthe other hydrides in the group, After the drop to HCl, there is a HF has the highestboiling temperature. from HCI to HI (in spite of steadyupward trend in boiling temperatures the forces)because dispersionforces in a decrease the dipole/dipole increase.

II

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B.NDTNGAND MA'N GRoup cHEMrsrRy

400 350 300 250 K ZOO 150 100 50 0 NHs

400 350 300

2so
K 200 150 100 50 0 sbH3 Hzo

400 3s0 300 250 K 200 150 100 50 0 HzS HrSe Group 6
H2Te HF HCI HBT Group 7 HI

PH: AsH3 Group 5

Fig 1.4 Boilingtemperatures of Groups 6 and 7 hydrides 5,

f If the number of electronsin two different substances about equal is and neither has hydrogen bonds, then dipole/dipole forcescausea differencein boiling temperature.This is the casebetweenbutane (34 electrons, non-polar,boiling temperature 0.5 'C) and propanone (32 electrons, but polar, so boiling temperature 56.2'C). + Effect of heat (melting)

When a solid is heated from room temperatureuntil it melts: O The particles(ions, moleculesor atoms) vibrate more. o As the temperaturerisesthe vibrations increaseuntil they becomeso great that the forcesbetweenthe particlesare overcome,and the regular arrangementin the lattice breaksup. The substance then a liquid. is O In an ionic solid, such as NaCl, the vibrating particlesare ions which are held by strong forcesof attraction, and so the ionic solid has a high melting temperature. o In a simple molecular solid, such as iodine (Ir) or ice, the vibrating particlesare moleculeswhich are held by weak van der Waalsor hydrogen bonding forcesof attraction, and so the solid has a low melting temperature. o In a giant atomic solid, such as diamond, the vibrating particlesare atoms which are held by strong covalent bonds, and so the solid has a very high melting temperature.

Donotsay theparticles to that start vibrate, they vibrating at as are even very temperatures. low

Thestronger force the between particles, more the energy needed to separate andhence higher them the themelting temperature.

Shapes of molecules O Theseare explained by the electron pair repulsion theory which states: i The electron pairs arrangethemselvesas far apart from each other as possible order to minimise repulsion. in ii The repulsion betweenlone pairs is greaterthan that betweena lone pair and a bond pair, which is greaterthan that between two bond pairs. o The number of o bond pairsof electrons and lone pairsin the molecule should be counted. o Any r bond pairs should be ignored when working out the shapeof a molecule.

o lt isthebonds the not atoms that repel, o Don't forget count number to the pairs. of lone

srRucruRE AND BoNDTNG

2 bond pairs linear

h:r
Lg0'

o The total number of pairs of electronsindicatesthe arrangement the electrons. 2 = linear 3 = trianSularplanar 4 = tetrahedral 5 = trigonal bipyramid 6 = octahedral But the shape will differ if any of the pairsare lone pairs (see Figure1.5). 4pairs:3bond+1lone: molecularshapeis pyramidal,e.g.NHr, or PCl, 2bond + 2lone: e.g. molecularshapeis bent or V-shaped, HrO 6pairs:5bond+1lone: pyramid. molecularshapeis a square-based 4bond+2lone: molecularshapeis squareplanar. Shapes of ions

of

bond pairs triangular planar

?
\120'

tA{v

I tos't,"
\

bond pairs tetrahedral

o4f\
.^(/

bond pairs + 1 lone pair pyramidal

o4/b-rc
Ot <I07"

bond pairs + 2lone pairs V-shaped

6w <lo5'

;>-"
noo ^

o ?
pairs s bond Trigonal bipyramid Il 120"\lre o/l

bond pairs octahedral

i

Negativejons have gained 1 electron for each negativecharge. Thus SO;- has 4 o bonds (and 2 n bonds)and no lone pairsaround the sulphur,and so the ion is tetrahedral. CO.'- has 3 o bonds (and 1 z bond) and no lone pairsaround the carbon, and so it is triangularplanar. NO; has one single covalent, one dative covalent and one double covalent bond (i.e. 3 o and 1 z) and no lone pairsaround the nitrogen and so is alsotriangularplanar. Positiveions have lost 1 electronfor eachpositivecharge. Thus NHn.has 4 o bonds and no lone pairsaround the nitrogen, and so is tetrahedral
-H )J//l
^,.'-

90"and 180'

-?'f'-

Checklist

Fig 1.5 Shapesof molecules ond ions

Before attempting the questions on this topic, check that you understand: lJ the nature of ionic, covalent and dative covalent bonds LJ tfre effect of difference in electronegativity on type of bonding iJ that polar bonds may not give rise to polar molecules J the effect of size and charge of ions on the type of bonding J intermolecular forces such as hydrogen bonding and van der Waals ,J the different structures of solids and their properties J the trends in boiling temperatures caused by intermolecular forces ,J the nature of hydration of ions iJ the changes in motion and arrangement of particles on change of state J a metallic bond J the shapes of molecules and ions.

ll "t*ucruRE,

B.NDTNG AND MA'N GRoup

cHEMrsrRy

your knowledge understanding Testing and

For the first set of questions, cover the margin, write your answers, then check to see if you are correct. O State which types of bond are present in a double bond as in O=C=O. I State the value of the charge on the ions of the following elements:

Al3*, Mgz*, F, N*, o',Na*, a Al" b Al" G AI3-

Al, Mg, Na, R N, O. o State which of the cations above: a b c has the smallest radius has the largest charge density is the most polarising.

O State which of the anions above is the most polarisable. O Which ion has the largest radius: Li'or Na- or K-? o Which of these three ions, Li*, Na* or K*, has: a b the largest surface charge density the largest polarising power?

Which is the most electronegative element in each list: a C,O,N,F b Cl, Br, I?

aCa bNa

Which is the least electronegative element of: a Be, Mg, Ca Na, Mg, A1? b a Which is the molecule in each group with the most polar bond: a b c d HE, HCl, HBr HF, HrO, NH3 HrO, HrS, HrSe Alcl' sicln, PClr?

a b c d

hydrogen fluoride hydrogen fluoride water aluminium chloride

o List all of the following molecules that are polar:

H2

HCI
ICI

HrO H,S

NH,

CHn CFn

HCl, Hro,NH3, HrS l0l,

CO,

BH,

o Rearrange the noble gasesin order of decreasing

boiling temperature:

Xe>Kr>Ar>Ne>He

Ar, He, Kr, Ne and Xe o State which of the following has the lowest boiling temperature: HE HCl, HBr, or HI o Which of the following form hydrogen bonds between their molecules? HF cH3F HCI cHCl3

HrO, NH3, , HF CH30 H , H 3 N H , C

H,O cH3oH

NH, cH3NH2

CO,
cH2-cH2

CHn

poly(ethene)

1 Draw a diagram of two p orbitals overlapping which produce:

The answers thenumbered to questions on pages are 122-123.

a b

aobond anbond

2 For each pair, state which is the more covalent substance and give a reason: a b AlF. or AlCl3 BeCl, or MgClr.

@sr*.rcruRE

AND BoNDTNG Intermolecular forces can be divided into three types: a b c hydrogen bond dispersion (induced dipole/induced dipole) permanent dipole/permanent dipole.

For all the following substancesstate all the types of intermolecular forces a, b andlor c that are present: i HF ii 12 iii HBr iv PH, v Ar

4 Solid structures can be divided into six types: a metallic, b giant atomic (network covalent), c ionic, d hydrogen bonded molecular, e simple molecular, f polymeric. For each of the solids listed below, state the structural type in the solid. iodine silica (sand), SiO, ice, HrO(s)

copper

dry ice, COr(s) calcium oxide, CaO

poly(ethene)

graphite

sulphur
lithium fluoride. LiF

coppersulphate,CuSOosucrose

Explain the processesof melting and boiling in terms of the arrangement and motion of the particles. State, for each of the following pairs, which has the stronger forces between particles and hence has the higher boiling temperature, and explain why in terms of the types of force present:

a b c d e

NH, or PH, HCI or HBr CH3COCH..(propanone) or CnH,o@utane) Pnor Su NaCl or CCln

In order to work out the shape of a molecule or ion, you should first evaluate the number of o bond pairs of electrons and the number of lone (unbonded) pairs of electrons around the central atom. Construct a table similar to that shown below, and use it to deduce the shapes of the following species. XeFn,NHr*, PCl6SiH4,BFr, BeCl2,PCI3,SFu, Molecule/ ion NH,

Number of Number of o bond pairs lone pairs 3 1

Total number of electron pairs 4

Shape

pyramidal

Explain why solid sodium metal conducts electricity whereassolid sodium chloride doesnot.

tt*ucruRE,

B.NDTNG AND MArN GRoup

qHEMIsrRy

Periodic I Table The ffi Introduction try

of r The melting and boiling temperatures the elementsdepend on the type and strength of the bond or intermolecular force betweenparticles. a There are trends in physical and chemical propertiesacrossa Period and down a Group. For instance 1 Elementsshow decreasing metallic characteracrossa Period. 2 Elementsshow increasing metallic characterdown a Group.

Things to learn and understand

Electronic structure
O The elementsin the PeriodicTableare arrangedin order of atomic number, so each element has one more proton and hence one more electron than the previous element. o Elementsin the samegroup have the samenumber of electronsin their outer shells.Theseare called the valenceelectrons. o Elementsin the samePeriod have the samenumber of shellscontaining electronsso their outer or valenceelectronsare in the sameshell. o The order in which electronsfill the orbital types is: Figure1.1 on page3) 1s; 2s,2p; 3s, 3p; 4s,3d,4p; 5s,4d, 5p; 6s (see (and boiling) Melting (Na to Ar) elements temperatures of the Period 3

There twoexceptions the with are first40 elements. Becausethe of extra stability a half filled full of or setof d orbitals, is chromium [Ar] 4s',3du, copper [Ar]4s',3d'o and is

O The melting temperaturedependsupon the strength of the forces during melting (or boiling). betweenparticlesthat separate Theseparticlesmay be: i metal ions in a seaof electronsin metals ii covalently bonded atoms in a giant atomic structure iii moleculeswith intermolecular forcesbetweenthem in simple molecular solids. you should first o To understandthe trends in melting temperatures, decidewhat type of bonding or force is betweenthe particles. o If the solid is metallic: the greaterthe chargedensity of the ion in the lattice, the strongerthe force holding the lattice together and so the higher the melting temperature. o If the solid is a giant atomic lattice: the covalent bonds throughout the lattice are strong and so the solid has a very high melting temperature. the o If the solid is a simple molecular substance: melting (or boiling) temperaturedependsupon the strength of dispersion (induced dipole/induced dipole) force betweenthe molecules. o In Period3, sodium, magnesiumand aluminium are metallic, silicon forms a giant atomic lattice, and phosphorus,Pn,sulphur, S' chlorine, Cl, and argon, Ar, all form simple molecular solids.

The more inthe electrons molecule, the the stronger dispersion force the andthehigher melting boiling or temperature.

t"E

PERroDrcTaeLE I

Electrical

conductivity

Solids conduct electricity by the flow of delocalised electrons. Thus metals conduct electricity. Graphite also conducts, but only in the plane of the layers. This is due to the n-electrons that are delocalised above and below the lavers.

^.H
H

flK ' l/H

Checklist

Beforeattemptingthe questionson this topic, checkthat you can: i-i Write the electronic structure for elementsnumbers 1 to 36. lJ Explain the variation of melting and boiling temperatures the for elementsin Period3. iJ Explain the change in electricalconductivity of the elementsin Period3. of lJ Explain the variation in ionisation energies the elementsin Period3.
)H j-lJ)/l -

T)()
H

your knowledge understanding and Testing

to The answers thenumbered questions onpage 123. are

L What, in terms of electronic structure,are the featuresthat the following have in common: a membersof the samegroup , .8. Group 2, b membersof the sameperiod,e.g.Periodpotassiumto krypton? 2 Statethe type of solid structureof the elementslisted. Give your answeras one of: metallic, giant atomic, ionic, hydrogen bonded molecular,simple molecular,polymeric: a hydrogen e chlorine b sodium f argon.
c silicon

d sulphur

of 3 Explain the differencein melting temperatures the following elements: Element

Melting temperature/O6 Na

Mg 650

Si

Pn

s8

CI,

98

1 4 1 0 44

1 1 3 -101

4 The ionisation energies of sodium and magnesium are listed below:

Element
Sodium Magnesium

lst ionisation energy/kJmol-' 2nd ionisation energy/kJmol-' 494 736 4560 1450

(or Explain the meaning of: i nuclearcharge,ii screening shielding) by inner electrons. Usethe conceptsexplainedin (a) to explain why: i The 2nd ionisation energyof sodium is very much more than its 1st ionisation energy.ii The lst ionisation energyof sodium is lessthan the 1st ionisation energyof magnesium.

II

tt*ucruRE,

B.NDTNGAND MArN GRoup cHEMrsrRy

Introductionoxidation to and red uction

Introduction
o Redoxreactionsare those which involve a transfer of electrons o RememberOIL RIG (Oxidation Is Loss,Reduction fs Gain of electrons)

4A 'W

Thingsto learn

E Oxiaation occurswhen a substance losesone or more electrons. There is an increasein the oxidation number of the element involved. [l nn oxidising agent is a substance that oxidisesanother substance and so is itself reduced.The half equation involving an oxidising agent has electronson the left-hand side,i.e. it takes electronsfrom the substance being oxidised. l] neduction occurswhen a substance gains one or more electrons. There is a decrease the oxidation number of the element involved. in

orl Rtc

|J A reducing agent is a substance that reducesanother substance and so is itself oxidised.The half equation involving a reducing agent has electronson the right-hand side,i.e. it gives electronsto the substance being reduced.
J,,+

- ^ f"/ ,- |

!---.-.-l'

Things to understand
number

Oxidation

Inanoverall equation,total the increase inoxidation number one of (increase element x number of atoms that of element) equal must thetotal decrease inoxidation number another of element.

I The oxidation number is the chargeon an atom of the element in a compound calculatedassumingthat all the atoms in the compound are simple monatomic ions. The more electronegative element is given an oxidation number of -1 per bond. O There are some rules used for calculatingoxidation numbers.They should be applied in the following order: 1 The oxidation number of an uncombined element is zero. 2 3 4 A simple monatomic ion has an oxidation number equal to its charge. The oxidation number of Group 1 metals is always+1, and of Group 2 metals is +2. Fluorine alwayshas an oxidation number of -1, hydrogen (except in metallic hydrides) of +1, and oxygen (exceptin FrO and peroxides)of -2.

The sum of the oxidation numbers in a molecule addsup to 0, and those in a polyatomic ion (such as SOr*)add up to the chargeon the ion. O When an element is oxidised, its oxidation number increases.

lNTRoDUcrroN

To oxrDATroN AND REDUcrroN

21

oxal44f-{x, Work^ei,
in Cl-, and number chlorineClr, MgCl, Cl0r-. of the Calculateoxidation (uncombined rule element: 1) Answers:.in = 0 Cl, (monatomicrule ion: 2) inCl- = -1 = (Mg 2+; +ZCl 0;therefore Clis-1: each is (+2) = inMgCl,-1 rules and 5) 3 ( C+ 3 x ( - 2 = - 1 : r u l e s 4 a n d 5 ) l ) i n C l 0= 1 5 ; Half equations
These are written: either as reduction with electrons on the left side of the half equation, e.g. Cl, (g) + 2e ^- zCl- (aq) here chlorine is being reduced and so is acting as an oxidising agent. or as oxidation with electrons on the right side of the equation, e.g. Fe'- (aq) -.-Fe'- (aq) + ehere iron(ll) ions are being oxidised, and thus are acting as a reducing agent. .- Many oxidising agents only work in acid solution. Their half equations have H. ions on the left hand side and HrO on the right. This is likely with oxdising agents containing oxygen (such as MnOr-), e.g. MnO.,-(aq)+ 8H.(aq) + 5e- + Mn'.(aq) + 4HrO(l) r If a redox system is in alkaline solution, OH- may need to be on one side and HrO on the other, + e.g. Cr'.(aq) + BOH-(aq) * CrOn2- 4H,O(l)+ 3e-

Remember anoxidising that agent (loses reduced electrons), becomes a agent and reducing becomes oxidised. must for Half equations balance and atoms forcharge. . For both of example, sides theCr"' add equation upto -5.

Overall redox equations

t Overall redox equations are obtained by adding half equations together. I One half equation must be written as a reduction (electrons on the left) and the other as an oxidation (electrons on the right).

lf thequestion fortheoverall asks for of equation thereaction A withB, A make thatboth andB appear sure ontheleft-hand of thefinal side overall equation.

o When they are added the electrons must cancel. To achieve this it may be necessaryto multiply one or both half equations by integers, e.g. for the overall equation for the oxidation of Fe'. ions by MnOnlons add to5x MnOf(aq) + BH-(aq) + 5e- + Mn'-(aq) + 4H,O(l) Fe' -(aq)+ Fe" (aq)+ e-

+ MnOo-(aq) + 8H-(aq) + SFe2-(aq) Mn'z-(aq)+ 4HrO(l) + 5Fe3-(aq)

II

=t*ucruRE,

BONDING

AND

MAIN

GROUP

CHEMISTRY

Checklist
Beforeattempting the questionson this topic, check that you can: [] Define oxidation and reduction. lJ oefine oxidising agent and reducing agent. E Calc.tlateoxidation numbers in neutral moleculesand in ions. fl Write ionic half equations. I-l Combine half equationsand so deducean overall redox equation.

your knowledge understanding Testing and

For the first set of questions, cover the margin, write your answer, then check to see if you are correct. O In the following equations, state which oxidised: a 2Cen.(aq) + 2l- (aq) + zce'* (aq) b H. (aq) + OH- (aq) + H,O (l) + Zn'- (aq) c Zn (s) + 2H. (aq) d zFe'* (aq) + 2Hg" (aq) + 2Fe'. (aq) substance,if any, has been + I, (aq) + H, (g) + Hgr2. (aq)

a b c d

iodide ions none zinc iron(ll) ions

+4 -2 +6 +6 -1 +6 Z!1t at+2 2 ar+3; and

o Calculate the oxidation number of the elements in bold in the following:

so2, H2s,
CtOn'-, HrO", CtrOr'-, H2SO4,
FerOn

average 2i)

The answersthenumbered 1 Construct ionic half equationsfor: to questions onpages are 123-124. a Sn'* ions being oxidised to Snn* ions in aqueoussolution
b c Fe'*ions being reducedto Fe2* ions in aqueoussolution. Now write the balancedequation for the reaction between Fe3* and Sn'* ions in aqueoussolution.

2 Construct ionic half equationsfor: a hydrogen peroxide being reducedto water in acid solution b sulphur being reducedto hydrogen sulphide in acid solution c Now write the balancedequation for the reaction between hydrogen peroxide and hydrogen sulphide in acid solution.

3 Construct ionic half equationsfor: a PbOr(s) being reducedto PbSOr(s) the presence HrSOn(aq) in of b PbSO.(s) being reducedto Pb(s)in the presence water of c Now write the balancedequation for the reaction between PbO, and lead in the presence dilute sulphuric acid. of

eRouP I AND GRoup 2

p G 2 @ G r o u1 a n d r o u p
fntroduction J fne properties elementsand their compoundschangesteadilydown of a Group. J fnis meansthat the answerto a questionabout which is the most/least reactive, easiest/hardest decompose, to most/leastsoluble,etc. will be an element,or a compound of that element,either at the top or at the bottom of the Group. J Down a Group the elements becomeincreasingly metallic in character. Thus: o their oxidesbecomestrongerbases O they form positive ions more readily O they form covalentbonds lessreadily.
-H Gt'\ tlz'l

t/''Ea' Physical properties of the elements

I Group1: All aresolidmetals; their meltingtemperatures hardness and

decrease down the group; all conduct electricity. o Group 2: AII are solid metals; their melting temperatures and hardness decrease down the group (except magnesium which has a lower melting temperature than calcium); all conduct electricity; their melting temperatures are higher than the Group 1 element in the same period.

Flame colours of their compounds

O Group 1: lithium sodium potassium calcium strontium barium
carmine red yellow

O Group 2:

lilac brick red crimson red green.

,A l*
light out

o These colours are caused because: I Heat causesthe compound to vaporise and produce some atoms of the metal with electrons in a higher orbital than the ground state (e.g. in the 4th shell rather than the normal 3rd shell for sodium). 2 The electron falls back to its normal shell and as it does so, energy in the form of visible light is emitted. The light that is emitted is of a characteristic frequency, and hence colour, dependent on the energy level difference between the two shells (seeFigure 1.6).

3rd

Fig 1,6 Emission a spectrol of line

Ionisation

energies

o The value of the lst ionisation energy for Group 1 and of the lst and 2nd ionisation energies for Group 2 decreases down the group. This is

STRUCTURE,

BONDING

AND

MAIN

GROUP

CHEMISTRY

because the atoms get larger,the outer electronsare further from the as nucleusand so are held on lessfirmly. The increasein nuclear chargeis for compensated by an increasein the shielding by the inner electrons. Reactions The vigour thereaction of increases the down group. of the elements with oxygen

O Group 1: All burn. 4Li * O, - zLizO Lithium forms an oxide: peroxide: 2Na + Or - NarO, Sodium forms a Potassiumand the others form a superoxide: K + O, - KO, o Group 2: AII burn to form ionic oxides of formula MO, except that in oxygen barium forms a peroxide (BaOr). excess ZCa+ Or'ZCaO Reaction of the elements with chlorine

o Group 1: All react vigorously to form ionic chlorides of formula MCl. Thesedissolvein water to produce hydrated ions, e.g. NaCl(s)- Na*(aq) + Cl (aq) I Group 2: All react vigorously to produce ionic chlorides of formula MCl, exceptthat BeCl,is covalent when anhydrous.All Group 2 chlorides are soluble in water producing hydrated ions of formula Beryllium chloride givesan acidic solution because of [M(H,O).]2-. deprotonation: + +H,O + [Be(H,O)'(OH)]. H,O* [Be(H,O)u]'* Reaction of the elements with water

Therate reaction increases of down thegroup.

o Group 1: All react vigorously with cold water to give an alkaline solution of metal hydroxide and hydrogen gas,e.g. + 2Na(s)+ 2H,O(l) -- 2NaOH(aq) H,(g) t Group 2: Beryllium doesnot react but magnesiumburns in steamto produce an oxide and hydrogen: Mg+HrO-MgO+H, the others react rapidly with cold water to form an alkaline suspension of metal hydroxide and hydrogen gas: Ca + zH,O - Ca(OH)r+H,

Reactions

of Group

2 oxides

with

water

O BeO is amphoteric and doesnot reactwith water. O MgO is basicand reactsslowly with water to form a hydroxide. a All the others react rapidly and exothermically to form alkaline suspensions the hydroxide, which have a pH of about 13. of CaO + H,O-- Ca(OH), Solubilities of Gro$p 2 sulphates and hydroxides

their solubilities decrease down the group. BeSOo MgSOo and O Sulphates: is and are are soluble;CaSOo slightly soluble,SrSOo BaSOo insoluble. o Hydroxides:their solubilities increase down the group. Be(OH),and Mg(OH), are insoluble,Ca(OH),and Sr(OH),are slightly soluble,and Ba(OH),is fairly soluble. O Addition of aqueoussodium hydroxide to solutions of Group 2 salts producesa white precipitateof metal hydroxide. (Barium producesa faint precipitate): M'.(aq) + 2OH-(a9) M(OH)'(s)

eRouP I ANo Gnoup 2 O Addition of aqueous sulphate ions to a solution of Sr'* or Ba'* ions produces a white precipitate of metal sulphate: Ba'.(aq) + SOn'-(aq) BaSOn(s)

Thermal

stability

of nitrates

and carbonates

The compound is more to be likely decomposed onheating cation if the polarises anion. the Thus (cation Groupcompounds 2+) 2 decompose readily Group more than (cation 1+). 1 compounds only Compounds ofmetals higher a in group (smaller radius) ionic decompose easily more than compounds of metals inthe lower Group.

o Thermal stability increases down both groups: o Group 2 nitrates all decompose give a metal oxide, brown fumes of to nitrogen dioxide, and oxygen: 2Ca(NOr)r- 2CaO+ 4NO, + O, O Group 1 nitrates, except lithium nitrate, decompose give a metal to nitrite and oxygen: 2NaNO,-- 2NaNO,r O, but 4LiNO,,-- ZLirO+ 4NO, + O, o Group 2 carbonates decompose (exceptbarium carbonate all which is stableto heat) to give a metal oxide and carbondioxide: CaCO',-CaO+CO, t Group 1 carbonates stableto heat exceptfor lithium carbonate: are Li?CO,-Li'O+CO.
H 9
-

'
^a/ H

f__- Checklist
^-'-

Beforeattempting the questionson this topic, check that you know: tJ ttre physical propertiesof the Group 1 and Group 2 elements r-l ttre flame colours causedby their compounds iJ the trends in ionisation energies within a group iJ ttre reactionsof the elementswith oxygen, chlorine and water J the reactionsof their oxides with water ,J the oxidation statesof the elementsin Group 1 and in Group 2 ,J the trends in solubilities of Group 2 sulphatesand hydroxides .J tfre reasonfor the trend in thermat stability of Group 1 and Group 2 nitrates and carbonates.

your knowledge understanding Testing and

For the first set of questions,cover the margin, write your answer,then check to seeif you are correct. Lithium o Which Group 1 metal has the highest melting temperature? o What is the oxidation number of: i potassiumin KrCrrO,and ii calcium in CaCOr? o Barium compounds normally are poisonous,but barium sulphateis given to people in order to outline their gut in radiography (X-ray imaging).Why is barium sulphatenot poisonous?

K is +1,Cais +2

It is extremely insoluble.

II

B.NDING AND MAIN GRoup cHEMtsrRy "t*ucruRE,

to The answers thenumbered questions onpage 124. are

You are given sotid samplesof three chlorides.One is lithium chloride, one is potassiumchloride and the other is barium chloride. Describethe teststhat you would do to find out which was which. 2 Explain why sodium compounds give a yellow colour in a flame. 3 Exptain why the Lst ionisation energyof sodium is larger than the Lst ionisation energy of potassium. 4 Write balancedequationsfor the reactionsof: calcium with oxygen a b c d calcium with water potassiumwith water magnesiumwith steam.

Explain why the addition of dilute sodium hydroxide to a solution of magnesiumchloride producesa white precipitate,but little or no precipitatewhen dilute sodium hydroxide is added to a solution of barium chloride. 6 Stateand explain which Group 2 element forms the leastthermally stablecarbonate. Write balancedequationsfor the thermal decomposition of the say following, but if there is no reaction at laboratory temperatures, so: lithium nitrate, sodium nitrate and magnesiumnitrate a b sodium carbonate,magnesiumcarbonateand barium carbonate.

cRouP 7 (caLoRrNE To rooiNre)

7 Group (chlorine toiodine)

<ta
iAl y-v Introduction
Group 7 chancteristics are that: r The halogensare oxidising agentswith their strength decreasing down the group. 1 Chlorine is the strongest oxidising agent and iodine is the weakest. 2 Chloride ions are the weakestreducing agents,and so are the hardest to oxidise, whereasiodide ions are the strongestreducing agents,and so are the easiest oxidise. to I They form halide ions, such as Cl-, and oxoanions, such as ClO,-. o Solutionsof the hydrogen halides are strong acids.

ffi Lry

Thingsto learnand understand

Disproportionation
This occurswhen an element is simultaneouslyoxidised and reduced.It follows that there must be at leasttwo atoms of that element, with the sarne oxidation number, on the left of the equation, and that the element must be able to exist in at least three different oxidation states. Chlorine disproportionatesin alkali: Cl, + zOH- - Cl- + OCI- + H,O (0) (-1) (+1)

Physical properties (at room temperature)

o Chlorine is a greenishgas. O Bromine a brown liquid. o Iodine is a dark grey lustrous solid which givesa violet vapour on heating. o A solution of iodine in aqueouspotassiumiodide is red/brown, and in non-oxygen-containingorganic solventsit is violet. Tests for the elements (only examined at AS in Unit

Test 3B)
o First observe the colour of the halogen or its solution. O Chlorine rapidly bleaches damp litmus paper. It will displace bromine from a solution of potassium bromide (then test for bromine by adding a suitable organic solvent such as hexane, which will show the brown bromine colour). o Bromine is brown and will (slowly) bleach litmus. It will displace iodine from a solution of potassium iodide (then test for iodine with starch or hexane as below). o Iodine turns a solution of starch blue-black, and it forms a violet solution when dissolved in suitable organic solvents such as hexane.

II "t*ucruRE,

B.NDTNG ^ND MAIN GRoup

cHEMIsrRy

Halides but o All hydrogen halides are covalent gases, are soluble in water because ions. Their solutions are strongly acidic: they reactwith water to form HCI + HrO + H,O*(aq) + Cl-(aq) Hydrogen fluoride is a weak acid and is only partially ionised. All metal halides are soluble in water, except for silver and lead halides. o Test for halides (only examined at AS in Unit Test 38)

To a solution of the halide add dilute nitric acid to prevent carbonates from interfering with the test. Then add silver nitrate solution followed by ammonia solution.
Bromide Chloride cream precipitate Addition of Ag-(aq) white precipitate Addition of precipitate dissolves no change dilute NH, Iodide yellow precipitate no change

Addition of concentrated NH, precipitate dissolves precipitatedissolvesno change

Addition halide

of concentrated

sulphuric

acid

to the solid

o Chloridesproduce steamyacid fumes of HCl. O Bromidesproduce steamyacid fumes of HBr with some brown bromine and someSO,gas. a Iodides give clouds of violet iodine vapour. This is due to the fact that HBr is just powerful enough as a reducing agent to reducesome of the concentratedsulphuric acid to sulphur dioxide and itself be oxidisedto bromine. The HI initially produced is a very powerful reducing agent. It reducesthe concentratedsulphuric acid and is itself oxidised to iodine. Oxidation numbers

o Chlorine is 0 in Clr. o Chlorine is -1 in chlorides. o Chlorine is +1 in CIO- ions. O Chlorine is +5 in CIO; ions. Redox is Chlorinea stronger oxidising than which is agent bromine, than stronger iodine. o Chlorine is a powerful oxidising agent and is reducedto the -1 state. o The half equationis: Clr(aq)+ 2e-.. 2Cl-(aq) and is similar for the other halogens. o Chlorine disproportionatesin alkali at room temperature: Cl,(aq) + 2OH-(a9)- Cl-(aq)+ OCI-(aq)+ H,O(l) (+1) (0) (-1) o Chlorate(I) compounds disproportionatewhen heated: 3OCf+2CI-+ClOr3x(+1) Zx(-L) (+s) from seawater bubbling in chlorine gaswhich by o Bromine is extracted the Bf ions. oxidises

e Rou P 7 (cHLoRtNE To toDtNE)

ffi l4),

Checklist

Before attempting questionson this topic, check that you can recall:

iJ the physical propertiesof the elements lJ ttre testsfor the elementsand for the halides iJ ttre reactionsof concentratedsulphuric acid with the halides iJ examples -1, 0, +1 and +5 oxidation states chlorine and the of of disproportionationof chlorine and chlorate(I)ions I ttre relativestrengthsof the halogens oxidising agents. as

<ffi
tH'

your knowledge understanding and ,rftn Testing

For the first set of questions, cover the margin, write your answer, then check to see if you are correct. Name the halogen that is a liquid at room temperature. ,r Describe the test for iodine. * Which of Cl, Br, and I, is the strongest oxidising agent? O Which of HCl, HBr and HI is the strongest reducing agent?

t Why is hydrogen chloride gas very soluble in water? The answers thenumbered to questions on pages are 124-125. 2 It is thought that a sample of solid sodium carbonate has been
contaminated by some sodium chloride. How would you test for the presence of chloride ions in this sample? Explain why hydrogen chloride gas is produced but chlorine is not when concentrated sulphuric acid is added to solid sodium chloride, whereas iodine and almost no hydrogen iodide is produced when concentrated sulphuric acid is added to solid sodium iodide. Define disproportionation and give an example of a disproportionation reaction of chlorine or a chlorine compound.

tt*,rcruRE,

B o N D T N GA N D M A r N G R o u p c H E M r s r R y

Practlce Test: Unit L

Time allowed Lhr All questionsare taken from parts of previous EdexcelAdvancedGCE questions. The answers on pagesIZ5-t26. are
La

Complete and balancethe following equations. i Ca+O, t1I ii NarO + HrO + tlI iii NarO + HCI + l2l b Stateand explain the trend in thermal stability of of the carbonates the Group 2 elementsas the of group is descended. t3l (Totat 7 marks) [May 2002 Unit Test1 question2]

2 a Statethe structure of, and the type of bonding in, the following substances. Draw labelled diagrams to illustrate your answers. i Graphite t4I ii Sodium chloride t3I b Explain why both graphite and sodium chloride have high melting temperatures. t3l c i Explain why graphite is able to conduct electricity in the solid state. r2l ii Explain why sodium chloride conducts electricity in the liquid state. tlI (Totat 13 marks) lMay 2002 Unit TestL question6l 3a i ii Define the terms atomic number and mass number t2l Identify the particle that contains 35 protons, 44 neutrons and 34 electrons. tlI Bromine consistsof two isotopesof massnumbers 79 and 81. A sampleof bromine gas,Br, was examined in a massspectrometer. The massspectrumshowing the molecular ions is given below.
100
Relative intensity

158

160

162

b i Explain how the moleculesin the sampleare ionised. ii Statehow the resulting ions are accelerated. iii Identify the species responsiblefor the peak at mle = 160.

t2l tll tl] (Total 7 marks) llanuary 2001 CH1 questionL & lune 2001 Unit TestL question3l

Hydrogen forms compounds with most non-metallic elementsand with some metals. Calculatethe empirical formula of the compound used in the manufactureof artificial rubber,which has the following composition by mass: hydrogen tI.Lo/o carbon 88.9o/o t3l b The boiling temperatures hydrogen chloride and hydrogen iodide are: of -85'C -35 "C hydrogen chloride Hydrogen iodide Explain why hydrogen iodide has a higher boiling temperaturethan hydrogen chloride l2l c Draw and explain the shapesof:
i ii the PH. molecule the AIH; ion.

I2l I2l

Pnlctrce

Calculate the number of molecules in 8.0 cm' of gaseousphosphine, PH. at room temperature and pressure. (The molar volume of a gas at room temperature and pressure should be taken as 2.4 x lOn cm' mol-t. The Avogadro constant is 6.0 x 10" mol-'.) t2l (Total L1 marks) ffanuary 2001 CH1 question 2]

5 a Hydrogen sulphide is produced when concentrated sulphuric acid is added to solid sodium iodide, but
sulphur dioxide is produced when concentrated sulphuric acid is added to solid sodium bromide. i Complete the following table:

Compound
Sulphuric acid

Formula
HzSO' H,S SO,

Oxidation stateof sulphur in the compound

Hydrogen sulphide
Sulphur dioxide

i ii

Write an ionic half-equation to show the oxidation of chloride ions, Cl-, to chlorine, Cl,. tU Write an ionic half-equation to show the reduction of chlorate(l) ions, OCf, to chloride ions, in acidic solution. I2l iii Bleach is a solution of chlorate(l) ions and chloride ions. Combine the two ionic half-equations above to produce an equation which shows the effect of adding acid to bleach. tll (Total 9 marks) [May 2002 Unit Test 1 question 7l

ii Use youranswers a parti to suggest to whichof the ions,iodide bromide, the greater or has reducing power. t2l

tsl

6 a Complete the following for the element sulphur

= Number of electrons in the 1st shell = Number of electrons in the 2nd shell = Number of electrons in the 3rd shell t1l Write one equation in each caseto represent the change occurring when the following quantities are

measured. i The first electron affinity of sulphur ii The first ionisation of sulphur.
c

r2l
tll

The graph below shows the logarithm of the successiveionisation energies of sulphur plotted against the number of the electron removed. Account for the form of the graph in terms of the electronic structure of sulphur.
6.00

$ s.so H s.oo ! +.so

4.oo

A 3.so I E.oo 3oz.so

2.00
o 2 4 6 8 1 0 1 2 1 4 1 6 1 8 Number of electron removed

One of the chlorides of sulphur is sulphur dichloride, SClr. It is a liquid at room temperature; the electronegativity of S is 2.5 and that of chlorine is 3.0 i Draw a dot and cross diagram to show the bonding in SClr. r2l ii The shape of the molecule is bent (V-shaped).Explain why the molecule has this shape. r2l iii State, with reasons,whether SCl, is a polar molecule overall. r2l (Total L3 marks) 4l fJanuary2002 CHl question 2 & May 2002 Unit Test 1 question

t3I

2 OfAA"niL,
J,VVI

l,/Va-/ a.tA VL'771 /

y, e*Ufrzo*irr
, Jvvl.v))

Mkr

u e4 ar4d, uilib r i/,u,t

I [nergetics
Introduction
o Statesymbolsshould alwaysbe used in equationsin this topic. O In definitions in this topic, there are three points to note: 1 the chemical changethat is taking place 2 the conditions (reactantor product). 3 the amount of substance o It alwayshelps to add an equation with statesymbolsas an example, because this may gain marks lost by omission in the word definition. for O It is assumed simplicity that the value of LH is an indicator of the direction of a chemical reaction. The more exothermic the reaction, the more likely it is to take place,but other factors,such as activation energy (seepage 44), alsodetermine whether the reaction happens.

Things to learn
J Standardconditions are: at of O gases a pressure L atmosphere o a statedtemperature(usually 298 K) o solutions, if any,at a concentration of 1.00 mol dm-' in o substances their most stablestates,e.g. carbon as graphite not diamond. [-l Standardenthalpy of formation, AI{'is the enthalpy change,under standardconditions, when one mole of a compound is formed from its elements in their standardstates,e.g. AFII'for ethanol is the enthalpy changefor the reaction: + 2C(graphite) 3H,(g)+'/,Or(g) - C,H.OH(l) [f Standardenthalpy of combustion, AF/,'is the enthalpy change,under is standardconditions, when one mole of a substance completely burned in oxyger, .g.AI1.'for ethanol is the enthalpy changefor the reaction: C,H'OH(I) + 3O,(g)- ZCO,(g)+ 3H,O0) AI/:.,, of an acid is the enthalpy E Standard enthalpy of neutralisation change,under standardconditions, when the acid is neutralisedby of baseand one mole of water is produced,e.g.A.Fif;",, sulphuric acid, by sodium hydroxide solution, is the enthalpy changefor the reaction: '/,HrSOn(aq) + NaOH(aq)-'l,Na,SO,(aq)+ H'O(l)

It follows thisdefinition from that the enthalpy offormation ofan in state, element,itsstandard is zero.

give You should always anequation for and asanexample this other enthalpy definitions.

EneRGETrcs r

for hydrochloric acid the enthalpy changeis for the reaction: HCI(aq)+ NaOH(a9)- NaCl(aq)+ H,O(l) for any strong acid being neutralisedby any strong base,the enthalpy changeis for the reaction: H-(aq)+ OH-(aq)- H,O(l) Aff" = -57 kJ mol-' E Aoerage bond enthalpy. This is the average quantity of energy required to break one mole of covalent bonds in a gaseous species (at one atmospherepressure). is always endothermic, e.g. the It C-H bond enthalpy in a gaseous compound is the enthalpy changefor the reaction: C-H(in compoundxs) - C(8) + H(g) E nn exothermic reaction gets hot, so that heat is then given out to the surroundings.For all exothermic reactions A^tIis negative (see Figure2.1).This meansthat chemicalenergyis being convertedinto _ thermal (heat) energy. [J An endothermic reactiongetscold, so that heat is then taken in from the surroundings.For all endothernic reactions AII is positive (seeFigure2.2).

t -

*..ctants

I
I
Products

I
Enthalpy Products

Enthalpy

Route 1

Fig 2.1 Enthalpy diagromfor an exothermic reoction

Fig 2.2 Enthalpy diogramfor on endothermic reoction

E Hess's Law. The enthalpy changefor a given reaction is independent of the route by which the reactionis achieved(seeFigure2.3). Thus the enthalpy changeproceedingdirectly from reactantsto products is the sameas the sum of the enthalpy changesof all the reactionswhen the change is carriedout in two or more steps. NI = A.FI, NIr+ AJI., +

Route 2 Fig 2.3 A reaction cycle

ffi Lry

Thingsto understand
A^tI, data

Calculation of A.ff*.ooo from You can usethe expression:

Afl"uoio,,= the sum of Aflo,rnation products of

- the sum of AI{o,-u,ionof reactants

O Rememberthat if you have two moles of a substance, you must double the value of its AId. O The enthalpy of formation of an element (in its standardstate)is zero.

H "RGANrc

cHEMrsrRy,

ENERGETT.', KrNETrcs AND EeurLIBRruM

Workri, oxiloq-lr'
the Calculate standard for enthalpy change thereaction: -4NH,(g)50,(g) 4N0(9) 6H,0(g) + + given following the AHelkJ mol-': = = = NH,(g) -46.2, N0(g) +90.4, H,0(g) -242. - Sum = AnSwer. AHf,o", SUITI of produCtS Aff AH,F reactants of -5x (0)= -906kJ mol-' = 4 x(+90.a) 6 x (-242)-4x (-46.2) +

Calculation

of LII, from
LH,

A^f["data

To do this you use the alternative route:

LH2= LH" because represents aH, thereverse combustion. of lf anequationreversed, sign is the of itslH must changed. be

Elemen

1 mol of substance

LH'\

/o,.

/ combustionproductsof the elements

where AH, = the sum of the enthalpies of combustion of the elements taking into account the number of moles of each element, = and A^H, - the enthalpy of combustion of I mol of the substance. = Thereforer Aflo,-u,,on LH, + A,H,

Workz,oL oxiloLf./*,
given the Calculate standard enthalpy formation propan-1-ol, of of C2H'CH,0H, thefollowing aH+,..ou*onmol-1 : /kJ = -2010, = -394,H,(g) -286 = propan-1-ol(l) C(graphite) Answer. 3C(s) 4H,(g) 10,(g) C,H'CH,OH(|) + +

(sraphite) 3x AH. m"fi1c,HscH,0H) \+ " I + 3C0,(g) 4H,0(l)'

=4H",of elementsaH", of compound AH*, = 3 x (-394) 4 x(-286)- (-2010) -316 kJmol-' = +

Themass thisexpression in is the (usually totalmass thesystem of water) themass thereactants. not of

Calculation of AII values frorn laboratory examined at AS in unit test 38)

I Calculation of heat change from temperature change:

data (only

heat produced = rl?SS x specific heat capacity x rise in temperature I Then heat produced per mole = heat produced in experiment the number of moles reacted o Then enthalpy change, AFI, is minus the heat produced per mole (for an exothermic reaction A/{is a negative number). O For an endothermic reaction, calculate the heat lost per mole. This equals A,H,a positive number.

-t

rl

eNERGErrcs I

Work^ei, exiloLf.b
g produced A 0.120 sample ethanol burnt theheat was of and warmed g 250 'C 'C.The from ofwater 17.30 to 20.72 specific capacitywater 4.18 heat is of
J gto0-t. A{omustion Calculate of ethanol. = produced250g x 4.18J gj o6-t Answer. x3.42'C = 3574 Heat J. = g146 mol-' 2.61 10-'mol g Amount ethanol = 0.120 of x = produced ffi010 3574 per Heat x x mol J12.61 10-3 = 1370 10'J mol-'.
= -1370 kJ mol-t A4omuustion

Calculation Calculation

of A^tI values from average bond enthalpies

O Draw the structural formulae for all the reactants and all the products. il Decide what bonds are broken in the reaction and calculate the energy

requiredto breakthe bonds (endothermic). Decidewhat bonds are made in the reactionand calculate the energy released making the bonds (exothermic). by Add the positivebond breakingenthalpy to the negative bond making enthalpy.

Workpi,oxiloLplr,
Calculate enthalpy thereaction: the of
H H + H_ H H
H

t l --__________+ C - C - H H_
H

Given following the average enthalpies/kJ bond mol-': C-Cis +348, is +612, is +436, C-His +412. C=C H-H and (endo) Answer. break C=C +612 H-H +436

2 x C-H -824 -1172 +1048 = +1048 1172 -124kJ mol-' = A4,,,rion

(exo) make -348 c-c

Checklist
Before attempting questions on this topic, check that you: i Kno* the standard conditions for enthalpy changes.

J Kno* the signs of A,Hfor exothermic and endothermic reactions. J Can define the standard enthalpies of formation, combustion and neutralisation. l-l Understand an energy level diagram. J Can define and use Hess'sLaw. li Know how to calculate values of A/{from laboratory data. iJ Can use bond enthalpies to calculate enthalpies of reaction.

El

o * o A N r c c H E M I s r R y , E N E R G E T T c sK r N E T r c s A N D E e u r L r B R r u M ,

try
The answersthenumbered to questions onpages are 126-127.

ffi
Testing your knowledge understanding and
1 Statethe conditions usedwhen measuringstandard enthalpy changes. 2 Give equations,with statesymbols,which representthe following enthalpy changes: i the enthalpy of formation of ethanoic acid, CH,COOHQ) ii iii the enthalpy of combustion of ethanoic acid the enthalpy of neutralisation of an aqueoussolution of ethanoic acid with aqueoussodium hydroxide.

Draw an enthalpy level diagram for the following sequence reactions: of I'N,(g)+ O,(g) -.' NO(g) +'t,O, A,H= +90.3 kJ mol-' NO(g)+'1,O.(g)' NO,(g) A,H= -57.L kJ mol-' and hence calculatethe enthalpy changefor the reaction: '/,Nr(g) or(g) * Nor(g) + 4 Given that the standardenthalpiesof formation of NOr(g) and NrOn(g) are +33.9 kJ mol-' and +9.7 kJ mol-' respectively, calculatethe enthalpy changefor the reaction: 2NO,(g)- N,O,(g) 5 The standardenthalpy of combustion of lauric acid, CH3(CHr),'COOH(s), which is found in someanimal fats,is -7377 kI mol-'. The standardenthalpiesof combustion of C(s) and Hr(g) are -394 kJ mol-' and-286 kJ mol-1. Calculatethe standardenthalpy of formation of lauric acid. 6 100 cm' of L.00 mol dm-'HCI was addedto 100 cm'of 1.00 mol dm-' NaOH in a polystyrenecup, both solutions being initially at 2L.IO'C. On mixing the temperaturerose to 27.9OoC.Determine the enthalpy of neutralisation and statewhether the reaction is exothermic or endothermic. You may assumethat the polystyrenecup has a negligible heat capacity,the solution has a density of L.00 g cm-t and that the final solution has a specificheat capacityof 4.18 J g-' oC-'. 7 Calculatethe enthalpy changefor the reaction: CrH,(g)+ HrO(g)- CHTCHTOH(g) given the following averagebond enthalpies in kJ mol-': C-C +348; C=C +612; C-H +41,2; H-O +463; C-O +360.

oRGANrc cHEMrsrRY I

I chemistry 0rganic
da

LN
Introduction
i.J Organiccompoundsconsistof a chain of one or more carbonatoms Table2.1).The functional group and contain functional groups(see For givesthe compound certainchemicalproperties. instancethe C=C (exceptin benzenerings) reactsin a similar way in all group compounds.Thus knowledgeof the chemistryof ethene,H,C=CH, you to predict the reactions all compoundscontaining the of enables C=C group.
* Acid chloride _C
,aO

Substance

Alcohol I - C-OH I

Aldehvde
H.tC:o R/

Ketone

Acid ..O

Ester
arO

* Amide
,ro \NHZ

Nitrile

Amine

Group

R tc:o . R'/

_C

\oH

R_C

to-R'

tcl

_C

_C =N

-C-NHz I

group. groups.*These only be met at A2. R is o carbon-contoining will Toble 2.1 Functionol E you must learn the equationsand conditions for the reactionsin the specification.

tfa

LN

Things learn to

you When write formulae, structural that: check atom four carbon has bonds oevery has and oevery oxygen twobonds hydrogen every and halogen oevery have one only bond.

o Homologous series: a seriesof compoundswith the samefunctional group, the samegeneralformula, and where one member differs from the next by CHr. r Emplrical formula: showsthe simplestwhole number ratio of the atoms presentin one molecule. I Molecular formula: showsthe actual number of atoms presentin one molecule, e.g. propane is CrHr. o Structural formula: shows each atom in the molecule separatelyand how it is bonded. A more condensedway is to show the groupings around each carbon atom, e.g. propane can be written as CHTCH,CH3 and propan-2-ol as CH'CH(OH)CH3. fl Isomers: two or more compounds with the samemolecular formula. f Homolytic fission: when a bond breakswith one electron going to each atom (forming radicals). ff Heterolytic fission: when a bond breakswith the two electrons going to one atom. E Substitution: a reaction in which an atom or group of atoms in one molecule is replacedby another atom or group of atoms. [l laaition: a reaction in which two moleculesreact together to form a single product.

E "RGANrc

cHEMrsrRy,

ENERGETT.', KrNETrcs AND EeurLrBRruM

U nnmination: a reaction in which the elementsof a simple molecule such as HBr, HrO etc. are removed from the organic molecule and not replacedby any other atom or group of atoms. [l nyArolysis: a reaction in which water (often catalysedby aqueousacid or aqueousalkali) splits an organic molecule into two compounds. f Free radical: a species which has a single unpaired electron, e.g. Cl' f Nucleophile: a specieswhich seeksout positive centres,and must have a lone pair of electronswhich it donatesto form a new covalent bond.

[l nlectrophile: a species which seeksout negative centres,and acceptsa lone pair of electronsto form a new covalent bond.

Things to understand
Isomerism

There three are isomers structural of O Structural isomers may have: formula CrHu0: i different carbon chains (straight or branched) o propan-1-ol CH3CH,CH,OH tt the functional group in different placesin the carbon chain r propan-2-ol CH'CH(0H)CH3 iii different functional groups. I methoxyethane CH3OCH,CH3
cHa cH, \ / C-C / \ H H cHs \ C/ H H / C \ O Geometric lsomerism I Geometricisomerismoccurswhen there is a C=C in the molecule, and both carbon atoms have two different atoms or groups attached. ii Geometricisomersare not easilyinterconvertedbecause the of difficulty of rotating about the n bond. Alkanes (e.9. methane, CHJ

cis

trans

O Alkanes burn in excessoxygen to form carbon dioxide and water: CHn+ 2Or-' CO, + zHzO O Alkanes react with chlorine (or bromine) in the presenceof UV light in a stepwisesubstitution reaction: CHn+ Clr- CH3CI+ HCI CH3CI+Clr-CHrClr+HCl

CHs Ftg 2.4 Geometric isomers of but-2-ene

Nkenes

(e.g. propene,

CIITCH=CH,)

The decolourisation ofa brown solutionbrominea test a of is for group a molecule. C=C in

O Alkenes add hydrogen: CH3CH=CH, H, - CH:CHTCH' + conditions: passgases over a heatednickel catalyst O Alkenesadd bromine (or chlorine): CH3CH=CH, Br, - CHTCHBTCHTBT + conditions: at room temperaturewith the halogen dissolvedin hexane. O Alkenes add hydrogen halides, e.g. HI + CH3CH=CH, HI' CH3CHICH3 gases room temperature. conditions: mix at

With unsymmetrical the alkenes, goes hydrogen to thecarbon that already more has hydrogen atoms directly bonded it.This to is Markovnikov's rule.

oRGANrc cHEMrsrRY I

t l C-C
H

Fig 2.5 Poly(ethene)

Ftg 2.6 Poly(propene)

lLII

O Alkenesare oxidised by potassiummanganate(Vll)solution: CH,CH=CH,+ [O] + HrO - CH'CH(OH)CHTOH

conditions: at room temperature,when mixed with sodium hydroxide solution it producesa brown precipitate. o Alkenescan be polymerised. Etheneforms poly(ethene)(Figure2.5) and propene forms poly(propene)(Figure2.6): n-CHr-Qlf, + -(CH r-CHr)-, (about 2000 atm) conditions either: a very high pressure and a temperatureof about 250 "C or: a catalystof titanium(Iv) chloride and triethyl aluminium at 50 oCand pressure about L0 atm. of

Halogenoalkanes

(e.9. 2-iodopropane,

CHTCHICH,)

o They substitute with aqueous sodium (or potassium) hydroxide to give an alcohol: + CH3CHICH, NaOH - CH.CH(OH)CH. NaI + conditions:boil under reflux with aqueous sodium hydroxide. o They eliminate with ethanolic potassium hydroxide to give an alkene: CH3CHICH, KOH - CH,CH-CH'+ KI + H,O + conditions: boil under reflux with a concentratedsolution of potassium propene over water. hydroxide in ethanol, and collect the gaseous o They substitute with potassium cyanide: + CH3CHICH. KCN' CH,CH(CN)CH, KI + conditions: boil under reflux with a solution of potassiumcyanide in a mixture of water and ethanol. O With ammonia they form amines: + CH3CHICH, 2NH, - CH,CH(NHr)CH, NH'I + conditions: heat excess a concentratedsolution of ammonia of in ethanol with the halogenoalkane a sealedtube. in o The test for halogeno compounds: 1 Warm the substance with aqueoussodium hydroxide. 2 Add dilute nitric acid until the solution is just acidic. 3 Add silver nitrate solution. Result: t white precipitate,soluble in dilute ammonia indicateschlorocompound O cream precipitate,soluble in concentratedammonia indicatesbromocompound o yellow precipitate,insoluble in concentratedammonia indicatesiodocompound. AIcohols Primary (1') alcohols contain the CHrOH group. Secondary(2') alcohols have two C atoms attachedto the CHOH group. Tertiary (3') alcohols have three C atoms attachedto the COH group (see Figare2.7).

The ofallthese rate reactions increases to C-Br C-|, C-Cl to the because bond enthalpy and hence bond the strength decreases C-Cl C-Brto C-|.The to weaker the the the bond lower activation energy hence faster reaction. and the the

H -C-OH

H 1 0

-cl l -c-c-oH

t
-C-

l
0

-c-c-oH

t- c - l
I
3o

Ftg 2.7 1", 2" and 3" alcohols

}RGANrc

cHEMrsrRy,

ENERGETI.',

KtNETtcs AND EeutLtBRtuM

reaction with aqueous orange potassium o Oxidation KrCrrO, acidified with dilute sulphuric acid. dichromate(Vl), a 1' alcohols are oxidised via an aldehyde to a carboxylic acid. The solution turns green ([Cr(HrO)u]'. ions formed). CH,CH,OH + [O] - CH,CHO + H,O then CH3CHO + [O] - CH,COOH conditions: to stop at the aldehyde: add potassium dichromate(Vl) in dilute sulphuric acid to the hot alcohol and allow the aldehyde to distil off. to prepare the acid: boil the alcohol with excess acidified oxidising agent under reflux. b

ln equationsorganic in chemistry, as agent anoxidising canbewritten agent a [0] and reducing asIH],but theequation stillbalance. must
c

2" alcohols are oxidised to a ketone. The solution turns green. + CH3CH(OH)CH3 [O] 'CH.COCH, + H,O conditions: boil the alcohol and the acidified oxidising agent under reflux. 3'alcohols are not oxidised and so do not turn the solution green. of an alcohol to an alkene: CTH'OH-HrC=CHr+HrO

works all for Note thisreaction that and of alcohols, isomers thealkene maybeproduced.

o Dehydration

conditions: add excess concentrated sulphuric acid (or concentrated phosphoric acid) to the alcohol and heat to 170'C. o Ilalogenation 1. Io,2" and 3'alcohols react with: Phosphorus pentachloride, PCI' to form a chloroalkane: CTH.OH + PCl, - CrHrCl + HCI + POCI, conditions: at room temperature and the alcohol must be dry.

is for This a test an0Hgroup. acidic are off Steamy fumes given phosphorus pentachloride is when to dry substance. added the organic

Solid sodium bromide and 50o/osulphuric acid to give a bromoalkane: NaBr + HrSOn-- HBr + NaHSO, then HBr + CTH'OH - CrHrBr + HrO conditions: add the sulphuric acid mixed with the alcohol to solid sodium bromide at room temperature. Phosphorus and iodine to give the iodoalkane: 2P + 3lr- 2Pl, then 3CrHrOH + PI, -- 3CrHrI + H.PO, conditions: add the alcohol to a mixture of moist red phosphorus and iodine at room temperature. A summary of reactions is shown in Figure 2.8.

oRcnrurc cHEMrsrRY I

41,
CH2BTCHTBT

zCOz+3HrO o2 Spark

cH2oHCH2OH KMnOn NaOH(aq)

conc H2SO4

cH3cooH
Boil under reflux KtCtrOrlHrSOn(aq)

Brz

at 100'C

at l7O"C

Crz W

NaOH

cH3cH2cl NH, in ethanol

cH3cH2cN
Fig 2.8 Summory of orgonic reoctions

cH3cH2NHz

Bonding and reactivity

Bond strength is the dominant factor that determines reactivity. a A n-bond between two carbon atoms is weaker than a o bond between two carbon atoms. Thus alkenes are more reactive than alkanes and react by addition, whereas alkanes react by substitution. A C-I bond is weaker than a C-Cl bond, and so iodoalkanes are rapidly hydrolysed by aqueous sodium hydroxide, unlike chloroalkanes which react very slowly.

Quantitative
percent is less yield The than 100% because competing of reactions and handling losses.

organic

chemistry

unThis involves calculation of empirical formulae from percent data (see page 6). w This involves calculation of percentage yield. First calculate the theoretical yield from the equation (seepage B), yield = actual yield in grams x 10oo/o then the o/o theoretical yield in grams

Applied

organic

chemistry

* Liquid versus gaseous fuels. You should consider the following points: L 2 3 the the the a b c 4 5 easewith which gaseousfuels can be piped into the home easier handling of liquid fuels at a filling station for cars extent and type of pollution produced: the quantity of carbon dioxide and any other greenhouse gases produced per kilojoule of energy the emission of oxides of nitrogen and sulphur, and the way in which these can be limited the emission of particulates

the energy produced per unit mass of fuel for aeroplanes the extent to which the world's supply of fossil fuels is limited.

E "RGANrc

cHEMrsrRy,

ENERGETT.', KrNETrcs AND EeurLrBRruM

a Polymers. You should realisethat simple polyalkenesare resistantto of breaking down under environmental conditions. This is because the strength of the C-C and the C-H bonds. * Organic halogen compounds. There are three main usesof these: 1 As polymers. PVC is used as a waterproofing material, as an electricalinsulator and as a stableand maintenancefree material for window frames.When burnt it producesharmful fumes of is hydrogenchloride.PTFE usedas a non-stickcoatingfor saucepans etc. Thesepolymers are very stableowing to the strength of and C-C bonds. carbon-halogen Complicatedchlorine compounds,such as 2,4-D and As herbicides. They are stableand so weedkillers. 2,4,5-Tare usedas selective persistin the environment. but they Chlorofluorocarbons(CFCs)make excellent refrigerants, are so stablein air and water that they diffuseto the stratosphere where they are broken down by light energyand form chlorine the radicals. Thesecatalyse destructionof ozone.New substances which contain hydrogenaswell as chlorine, have been developed fluorine and carbon,and theseare lessstableand are broken down by atmospheric oxidation.

DDT a chlorine-containing is pesticide it haseradicated and malaria some from countries, its but has overuse ledto thedestruction of lt inert wildlife.is a very chemical (owing thestrength theC-Cl to of in bond) so persists an and in organism, stored fatty being tissue.

Checklist
Before attempting the questions on this topic, check that you: tJ Can name simple organic molecules. tf Can write structural formulae of structural and geometric isomers. lJ Know the reactions of alkanes with air and halogens. Ll Know the reactions of alkenes with hydrogen, halogens, hydrogen halides, potassium manganate(Vll) and in polymerisation. [J Kno* the reactions of halogenoalkanes with potassium hydroxide (both aqueous and ethanolic), potassium cyanide and ammonia. [f Kno* the oxidation, dehydration and halogenation reactions of alcohols. 'J Can relate reactivity to bond strength and polarity and to the stability of intermediates. if Can calculate the empirical formula of a compound. iJ Understand the advantages and disadvantages of the use of organic compounds.

your knowledge understanding Testing and

For the first set of questions,cover the margin, write your answer,then check to seeif you are correct. o Which of the following compounds are membersof the same homologousseries: but-l-ene CHTCHTCH=CH, ethene CrHn, cyclopropaneCrHu, cyclohexene CuH,o? CH'=CHCH=CH', but-1,3-diene
Name CH3CHTCH(CH3)CHCICHTOH

-ene ethene but-1 and

-ol 2-chlo ro-3-methylpentan-1

oRGANrc cHEMrsrRy I O What product is obtained if a large excess of chlorine is mixed with methane and exposed to diffused light?

tetrachloromethane, CClo c2H4o

O A compound X contained 54.5olocarbon, 36.40/o oxygen and9.Io/o hydrogen by mass. Calculate its empirical formula.

The answersthenumbered to questions onpages are 127-128.

1 Write the structural formulae of: a b a b c a b a b a b a b c d 1,l-dibromo-I,2-dichloro-2,3-difluoropropane 1-chlorobutan-2-ol. C3H8O(alcohols only) CrH,, CoH, (no cyclic compounds). free radical homolytic fission. an electrophile heterolytic fission. ethane + chlorine ethane + oxygen. hydrogen bromine * hydrogen iodide

2 Write out the structural formulae of the isomers of:

3 Define:

4 Define:

5 Write equations and give conditions for the reaction of:

6 Write equations and give conditions for the reaction of propene with:

potassium manganate(Vll) solution * For reactions marked *, state what you would see. 7 Write equations and name the products obtained when 2-iodopropane is: a b c shaken with aqueous dilute sodium hydroxide heated under reflux with a concentrated solution of potassium hydroxide in ethanol heated in a sealed tube with a concentrated solution of ammonia in ethanol.

8 Write the equation and give the conditions for the reaction of propan-Z-ol with sulphuric acid. 9 Write the structural formula of the organic product formed, if any, give its name and say what you would see when: a b c propan-l-ol is heated under reflux with dilute sulphuric acid and excessaqueous potassium dichromate(Vl) 2-methylpropan-2-ol is heated under reflux with dilute sulphuric acid and aqueous potassium dichromate(Vl) phosphorus pentachloride is added to propan-2-ol.

1O Why does bromine react rapidly with ethene at room temperature but only slowly with ethane?

ORCAI\|IC CHEMtSTRy,

ENERGETTCS,

KINETICS

AND

EQUILIBRIUM

L1 Why does L-bromopropanereact more slowly than l-iodopropane with water? with excess bromine, 15.4 g reacted CuH,o, 12 When 5.67 g of cyclohexene, and was of CuH,oBrz obtained. Calculatethe theoretical yield of CuH,oBr, yield of the reaction. percentage hence the 13 Explain why compounds such as CClrF,are harmful to the environment.

Kinetics I
o The rate of a reaction is determinedby: collide 1 the rate at which the molecules that possess enough kinetic 2 the fraction of the colliding molecules energy 'to get over the activation energybarrier' on 3 the orientation of the molecules collision.

Things to learn
[] ^Lctivation energy is the minimum energythat the reactant moleculesmust have when thev collide in order for them to form product molecules. [l Factors which control the rate of a reaction are: 1. the concentration of a reactant in a solution if 2 the pressure, the reactantsare gases 3 4 5 6 the temperature of the presence a catalyst the surfaceareaof any solids light for photochemical reactions.

Things to understand
Collision theory

in also Anincreasetemperature in of an causes increase therate but collision, thisis unimportant in with compared theincreasethe with fraction molecules the of energy. necessary activation

o The effect of an increasein concentration of a solution, or the of increasein pressure a gas,is to increasethe frequency of collision of the molecules,and hence the rate of reaction. O The effect of heating a gasor a solution is to make the moleculesor ions: kinetic energy 1 move fasterand so have a greateraverage the 2 which increases fraction of colliding moleculeswith a combined energygreaterthan or equal to the activation energy collisions. 3 which resultsin a greaterproportion of successful o The effect of heating can be shown by the Maxwell-Boltzmann distribution (seeFigure2.9) of molecular energiesat two temperaturesT, and T, where T, is > 7,.

KrNErrcs I

ttt q,)

Note thepeak moved the that has to right f,, and thetotal for that areas the under curves thesame, are but thearea to under curve theright the the of E equals fractionthe of molecules energyE^, with 2 which is greater Trthan I,. for for

(u

(J fr .

Fig 2.9 Moxwell-Boltzmann distribution

(t)

(u
I q)

(J

Catalysts work by providing an alternativeroute with a lower a Thus, at a given temperature, greaterproportion of activationenergy. will possess lower activation energyby this the colliding molecules following the route with the catalyst,and so the reaction will be faster. This is shown on a Maxwell-Boltzmann diagram (seeFigure2.lO). The enthalpy profile diagramsfor an uncatalysedand a catalysed reactionare shown in Figure2.I1.
Energy E^^. E
Ldt d

Fig 2.lO Effect a catalyst of

Do not say that a catalystlowers the activation energy. Note that the A.Elvalues the samefor both paths. are

:------- Transi ti on Intermediate

rrl

profilediagrams Fig 2.1| Energy

Uncatalysed

Thermodynamic

stability

o This is when the enthalpy level of the products is much higher than the enthalpy level of the reactants. on o Thus the substances the left-hand side of a very endothermic reaction are said to be thermodynamically stablerelative to those on the right. on o The substances the left-hand side of a very exotherrnic reaction are said to be thermodynamically unstablerelative to those on the right. Whether a reaction will then take place dependsupon its kinetic stability.

Kinetic

stability

If a reaction has such a high value of activation energy that no molecules possesssufficient energy on collision to react, the system is said to be kinetically stable. An example is a mixture of petrol and air, which is

E "RGANrc

cHEMrsrRy,

ENERGETT.', KrNETrcs AND EeuILrBRruM

thermodynamically unstablebut kinetically stable.No reaction occurs unlessthe mixture is ignited.

Checklist
Beforeattemptingthe questionson this topic, checkthat you: iJ Can recall the factorswhich effect the rate of reaction. J Can explain theserate changes terms of collision theory. in [i Can draw the Maxwell-Boltzmann distribution of molecular energiesat two different temperatures. ,J Can use this to explain the effect of a change of temperatureand the addition of catalyst. J Understandthe conceptsof thermodynamic and kinetic stability.

your knowledge understanding Testing and

For the following questions, cover the margin, write your answer, then check to see if you are correct. O For a reaction involving gases,state three factors that control the rate of the reaction. O For a reaction carried out in solution, state three factors that control the rate of the reaction.

Pressure, temperature, and catalyst

The surlace of thesolid area

e For the reaction of a solid with a gas or with a solution, state one other factor that controls the rate of reaction. o Give an example of a solid catalyst used in a gas phase reaction. L Define

(Haber),V,Ou (Contact), Fe or or Ni or Pt(addition hydrogen C=C) of to

The answers thenumbered to questions on page are 128.

activation energy

ii catalyst. 2 Explain, in terms of collision theory, why changes in temperature and in pressure and the addition of a catalyst alter the rate of a gas phase reaction. 3 Draw the Maxwell-Boltzmann i distribution of energy curve for a gas: at room temperature (mark this T,) and

ii at 50 "C (mark this [). Now mark in a typical value for the activation energy of a reaction that

proceeds steadilyat room temperature. Explain, in terms of activation energy,why animal products such as meat and milk stay fresherwhen refrigerated. Draw energyprofile diagramsof: i an exothermic reaction occurring in a single step ii the samereaction in the presence a suitablecatalyst of iii iv a reaction where the reactantsare thermodynamically stable a reaction where the reactantsare both thermodynamically and kineticallyunstable.

G H E M T c A LE e u r L r B R r A I

Chemical I equilibria
<ffi

Introduction

Many reactionsdo not go to completion because reaction is reversible. the As the rate of a reactionis dependenton the concentrationof the reactants,the reaction will proceedup to the point at which the rate of the forward reaction equalsthe rate of the reverse reaction, when there is no further changein concentrations. The systemis then saidto be at equilibrium.

to ffi Things learnandunderstand Lry

Dynalnic equilibrium
O At equilibrium, the rate of the forward reaction equals the rate of the reverse reaction. O Both products and reactants are constantly being made and used up, but their concentrations do not change. O This can be demonstrated by using isotopes. For the reaction: CH3COOH(I) + C,HsOH(l)+CH,COOC,H,(I) + H,O(l) Mix the four substances in their equllibrium concentrations, but have the water made from the isotope tto. After some time the "O isotope will be found (by means of a mass spectrometer) in both the ethanoic acid and the water, but the concentrations of the four substances will not have changed.

Effect of changes in conditions equilibrium

on position

of

principle that LeChatelier's states governing when of thefactors one thepositionequilibrium of is the changed, position alter will in such way if to restore a as the original conditions.

Donotsay'the with smaller side a volume',a gas always its as will fill container.

O Le Chatelier'sprinciple may help you to predict the direction of the changein the position of equilibrium, but it doesnot explain it. O Temperature. An increase in temperaturewill move the position of equilibrium in the endothermic direction. Likewisea decrease in temperaturewill move the equilibrium in the exothermic direction: N,(g) + 3H,(g) =. 2NH,(g) LH - -92.4 kJ mol-' As this reaction is exothermic left to right, an increasein temperature will causeless ammonia to be made, thus lowering the yield. O Pressure. This appliesonly to reactionsinvolving gases. increasein An pressure will drive the equilibrium to the side with fewer gasmolecules. Thus, for the reaction above,an increasein pressure will result in more ammonia in the equilibrium mixture, i.e. an increased yield. This is because there are only two gasmoleculeson the right of the equation and four on the left. O Concentration. This appliesto equilibrium reactionsin solution. If a substance physically or chemically removed from an equilibrium is system,the equilibrium will shift to make more of that substance:

'RGANrc cHEMrsrRy, ENERGETT.',KrNETrcs AND EeurLrBRruM

2CrOn'z-(aq) 2H.(aq) + Cr,O,'-(aq) + HrO(l) + Addition of alkali will remove the H'ions, causingthe equilibrium to move to the left. O Catalyst. This has no effect on the position of equilibrium. What it doesis to increase the rate of reaching equilibrium, thus a catalyst rate at a lower allows a reaction to be carried out at a reasonable temperature.

Optimum industrial
Temperoture

conditions

for Many industrial reactions,such as the Haber process manufacturing ammonia, are reversibleand exothermic. For such reactions: o If a high temperatureis used,the yield at equilibrium is small, but the rate of reaction is fast. r If a low temperatureis used,the theoretical yield is higher, but the rate of reactionis slow. O In systemssuch as this, a catalystis used to allow the reaction to proceedrapidly at a temperatureat which the yield is reasonablygood. This is often called a compromisetemperature,balancing yield with from the products and rate. Any unreactedgases then separated are recycledback through the catalystchamber. Pressure

processes involve Allindustrial that passing throughbed gases a of catalyst work must above pressure 1 atmosphere inorder to force gases the through system. the

are O High pressures extremely expensive,and are only used if the yield at lower pressures too small to be economic. is that usevery high pressures o Two examplesof manufacturing processes are the Haber processand the polymerisation of ethene.

Checklist
Beforeattempting the questionson this topic, check that you: J Understandthat equilibria are dynamic. J Can deducethe effect of changesin temperature,pressure and concentration on the position of equilibrium. lJ Can predict the economic conditions for an industrial process.

ffi
The answers thenumbered to questions onpage are 129.
i ii

your Testing knowledge understanding and

Considerthe reversiblereaction at equilibrium: A(g) + B(g) Which statementsare/is true about this system? There is no further changein the amounts of A or B. No reactionsoccur, now that it has reachedequilibrium. iii The rate of formation of B is equal to the rate of formation of A. Considerthe equilibrium reaction: NrOn(B)+ 2NO,(g) NI = +58.1 kJ mol-' Stateand explain the effect on the position of equilibrium of:

INDU'TRTAL IN.RGANTc cHEMI'TRY

i ii iii

the decreasing temperature halving the volume of the container

adding a catalyst. Ethanoic acid and ethanol react reversibly: + + + CHTCOOH CTHTOH CH.COOCTH, HrO NI = 0 kJ mol-'

Explain the effect of adding an alkali. What will happen to the position of equilibrium if the ii from 25 "C to 35 'C? temperatureis increased White insoluble lead(Il) chloride reactsreversiblywith aqueouschloride solution: ions to form a colourless PbCl,(s) + 2Cl-(aq) + PbCl,'(aq) i Stateand explain what you would seewhen concentratedhydrochloric acid is addedto the equilibrium mixture. In the manufactureof sulphuricacid, the critical reactionis: 2SO,(g)+ O,(g) -- 2SO,(g) Nf = -196 kJ mol-' Why are conditions of The reactionis very slow at room temperature. 725 K and a catalystof vanadium(V)oxide used?

chemistry inorganic Industrial @

ffi Inffoduction
Industrial chemistsalwaysneed to keep manufacturing costsdown. They do this by: L making the reaction as fast as possible 2 ensuring a high yield as 3 keepingthe temperatureand pressure low as possible.

ffi Lry

Thingsto learnand understand

process for the manufacture of ammonia

The Haber

N,(g) + 3H,(g) + 2NH,(g) NI=-92.4 kJ mol-' this reaction, left to right, is exothermic and the number of gas O Because the moleculesdecreases, yield and kinetics are affectedaccordingto the table below: Reaction conditions in Increase temperature Increasein pressure
Addition of catalyst Effect on yield Effect on rate

Decrease

Increase
None

lncrease Very slight increase

Very large increase

O Thus the following conditions are found to be the most economic: 400 "C. A higher temperature would reduce the yield, Temperafire: and a lower one would make the reaction uneconomically slow.

E "RGANrc

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ENERGETT.', KrNETrcs AND EeurLrBRruM

Pressure:

Uses ammonia: of I manufacture acid ofnitric t manufacture offertilisers as such ammonium and nitrate urea o manufacture ofpolyamides such asnylon.

200 atm. The yield at 1 atm is too low, and so a high pressure is necessary even though it is very expensive. Catalyst: Iron.This allows the reaction to proceed at a fast, and hence economic, rate at a moderate temperature. Yieldper cycle: 15o/o. The gasesfrom the catalyst chamber are cooled in order to liquefy the ammonia, and then the unreacted nitrogen and hydrogen are recycled, giving a final conversion of nearly lOoo/o.

The oxidation

of ammonia

to nitric

acid

This happensin three stages: 1 The ammonia and air are passed over a platinum/rhodium catalystat 900 "c: 4NH.(g) + 5O,(g)+ 4NO(g) + 6H,O(g) 2 On cooling, the nitrogen(Il) oxide reactswith more air: aNO(g) + 2O,(g)-* 4NO,(g) 3 The nitrogen(IV) oxide and air are then absorbedinto water: 4NO,(g) + O,(g) + 2H,O(l) + 4HNO,(aq)

The contact acid

process

for the manufacture

of sulphuric

O This takesplace in three stages: 1 The combustion of sulphur: S(l)+O,(g)-SO,(8) 2 The reversibleoxidation of the sulphur dioxide: SOr(g) +'lrOr(g)+ So,(g) 3 Absorption by the water in 98o/o sulphuric acid. I The conditions for stagetwo, which is exothermic and has fewer gas moleculeson the right, are: Temperature: 425 "C. A higher temperaturewould reducethe yield, and a lower one would make the reaction uneconomically slow. Pressure: 2 atm. This is enough to force the gases through the plant. A higher pressure not necessary is because the yield is high under theseconditions. Catalyst: Vanadium(v) oxide. YieId: per 960/o cycle. The gases from the catalystchamber are passed into the absorbercontaining the 980/o sulphuric acid, and all the SO,is removed.The gases then go back through another bed of catalyst,giving a final conversionof 99.8o/o.

Uses sulphuric of acid: I themanufacture offertilisers such ammonium as sulphate r themanufacture of phosphate fertiliser r themanufacture and ofpaints detergents.

Manufacture

of aluminium

O Aluminium is too reactive for its oxide to be reduced by carbon monoxide or other cheap reducing agents, so the expensive method of electrolysis of a molten ionic compound has to be used. o The ore contains aluminium oxide (amphoteric) with large impurities of iron oxide (basic) and silicon dioxide (weakly acidic). The ore is treated with a hot 10olosolution of sodium hydroxide, which reacts with the amphoteric aluminium oxide to form a solution of sodium aluminate. Iron oxide does not react as it is a base, and silicon dioxide does not

INDUSTRIAL

INORGANIC

CHEMISTRY

isprotected from Aluminium which by of corroding its layer oxide lt is reforms it isscratched. when less than These also dense iron. properties it ideal a material make as foraeroplane and wings fuselage it for thoughis and drink (even cans than lt more expensive iron). isalso conductorelectricity, of anexcellent power in so and is used overhead three cables because ofthese properties. Astheelectrolytic of method it is manufacture expensive, isvery economically to recycle sensible aluminium objects.

of react because its giant atomic structure.Thesesolids are filtered off, and carbon dioxide is blown through the solution precipitating aluminium hydroxide. This is obtained by filtration and heatedto produce pure aluminium oxide. o The purified aluminium oxide is dissolvedin molten cryollte, NarAlFu, at 900'C. O The solution is electrolysed using carbon anodesdipping into a steel cell lined with carbon, which is the cathode. a At the cathode, aluminium ions are reduced: Al'*+3e--Al(l) O The molten aluminium sinks to the bottom of the cell and is siphoned off. o At the carbon anode, oxygen ions are oxidised and reactwith the anode: 2O'- + C(s)-' CO'(g) + 4eof o Because the expenseof this method of manufacture,it is economic to recyclealuminium drink cans. The production of chlorine

is used for: Chlorine i water sterilisation ii themanufacture oforganic such chlorine compounds, asthe plastic and herbicide PVC the 2,4-D iii themanufacture of HCl.

o This is done by the electrolysisof an aqueoussolution of sodium chloride (brine). At the titanium anode (+): NaCl contains Cl- ions and theseare oxidised to Clr: -Cl,(g) +2{ zCl-(aq) chlorine gasis produced. o At the steel cathode (-): water is ionised in an equilibrium reaction: H,O[) + H-(aq)+ OH- (aq) Na* ions are very hard to reduce, and so H* ions are preferentially reduced: 2Hr(aq)+2e--Hr(g). The removal of the H- ions drives the water equilibrium to the right, producing OH ions. The overall equation for the reaction at the cathode is: zHrO + 2e- - ZOtf(aq) + Hr(g) Thus sodium hydroxide and hydrogen are produced. The anode and cathode compartments are separatedby an ion-exchange membranewhich allows Na. ions to passthrough but keepsthe chlorine separatedfrom the hydroxide ions that are produced at the cathode. Manufacture of sodium chlorate(I)

is used: chlorate(l) Sodium i asa domestic bleach ii asa disinfectant.

If the electrolysisof sodium chloride solution is carried out with the solution being stirred, sodium chlorate(I) and hydrogen are obtained. The when in contact with chlorine produced at the anode disproportionates the alkali from the cathode: Cl,(aq) + 2OH-(aQ) OCI-(aq)+ Cl-(aq)+ H,O(l)

OnceNIc

cHEMISTRY,

ENERGETICS,

KINETICS

AND

EQUILIBRIUM

Checklist
Before attempting questions on this topic, check that you: ."j Know the conditions for the manufacture of ammonia. *i Know the conditions for the manufacture of nitric acid. .-- Know the conditions for the manufacture of sulphuric acid. .-; Can iustify the conditions in terms of the economics and the chemistry of these processes. ; Know some of the uses of ammonia, nitric acid and sulphuric acid. -.,1 Know the conditions and electrode reactions used in the manufacture of aluminium. J Can recall the details of the production of chlorine and sodium chlorate(l) and their uses.
o-

lH

t-----!

your knowledge understanding and ,i.:. Testing

For the following questions, cover the margin, write your answer, then check to see if you are correct. o State the conditions used in the manufacture of ammonia. O State two uses of ammonia. o State the conditions used for the oxidation of ammonia in the manufacture of nitric acid. O State the conditions used for the oxidation of sulphur dioxide in the Contact process. O State two uses of sulphuric acid.

rrl

'C, A temperature to 450 a of350 pressure 200to 250atmandan of iron catalyst Tomake fertllisers, to make and (or nylon nitric acid) A temperature of900'C a and plati um/rhodm catalyst n iu A temperature400to 450'C, of a vanadium(V) catalyst a oxide and pressure2 atm of (or Tomake fertilisers, paints and detergents) It isamphoteric.

o What property of aluminium oxide is the basis of its purification from bauxite? f What is the essential condition used in the manufacture of aluminium?

Al'Cathode + 3e- Al A n o d e :2 0 ' - + C - C O z + 4 e The to answers thenumbered questionsonpage are 129.

O Write the equations for the reactions at the cathode and at the anode in the manufacture of aluminium.

Explain the economic reasonsfor the choice of the conditions used in the Haberprocess. why is the gasmixture cooled after it has left the In the Haber process catalystchamber? Write the equationsfor the reactionsat the anode and at the cathode in the manufactureof chlorine.

PRAGTIcE:

Practice Test: Unit 2

Time allowed Lhr All questionsare taken from parts of previous EdexcelAdvancedGCE questions. The answers on pagesI29-I3O. are Explain the term are CH.CH=CHCH3, in the samehomologousseries. La Propene, C.Hu,and but-2-ene, homologous series. t3l length of the polymer chain of poly(propene) b Draw a representative r2l c i Draw the geometricisomersof but-2-ene. r2l ii Explain how geometricisomerismarises. t1I (Total 8 marks) llune 2001 Unit Test2 question2 & May 2002 Utrit Test2 qtestion 5l The rate of any chemical reaction is increasedif the temperatureis increased. Draw a diagram to representthe Maxwell-Boltzmann distribution of molecular energiesat a temperatureT, and at a higher temperatureTr. t3l Useyour diagram and the idea of activation energyto explain why the rate of a chemical reaction increases with increasingtemperature. t4l (Total 7 marks) 3) llune 2001 Unit Test2 questiott Considerthe following reaction scheme: step 1
CrHu

a b

propene
KMnOn in alkali

I I
I
*

CrHrBr(maior product) S I NaOH aqueous I

t c3H8o
P cH3cocH3

*.0 3 (oxidation)

a i ii b i ii

Give the reagentand the conditions neededfor step 1. Give the structural formula of S. Give the structural formula of P. Statethe type of reaction in: step 1 the conversionof S to P. c i Give the reagentand the conditions neededfor step 2. ii Give the reagentand the conditions neededfor step 3. d Give the structural formula of compound Q.

r2l

tu
tlI

r2l r2l r2l

t3l tlI
(Total 14 marks) IMay 2002 Unit Test2 question4l

4a b c

State Hess's Law. change of combustion. Define the term standard enthalpy The equation for the combustion of ethanol in air is CrHsOH[) + 3O,(g) - 2CO,(E) + 3H,O0)

I2l t3I

El

o*.ANIc

cHEMrsrRy, ENERGETT.',KrNETrcsAND EeurLrBRruM

And the structural representationof this is:

t H-C t
H

C-OH

l l

H + 3O:O

2O-C:O

+ 3H-O

-H

Calculatethe enthalpy changefor this reaction using the average bond enthalpy valuesgiven below.

t3I
Bond C-H Averagebond energy/kJmol-' + 4L2 + 360 + 496 Bond C-C Averagebond energy/kJmol-' + 348 + 463 + 743

c-o
Ot:O

o-H

c:o

tt Draw and label an enthalpy level diagram to representthis reaction.

I2l
Gotaf 1O marks) 200L Unit Test2 question5f lJune

5 a The reaction in the Haber Process that is used to produce ammonia is: N,(g) + 3Hr(g) : 2NH,(B) N:I=-92k1mol-' i What temperatureis used in the Haber Process? tl] ii Justify the use of this temperature. t3I lii Name the catalystused in the Haber process. tll iv How does a catalyst enable a reaction to occur more quickly? t2l b Another industrial process the one which recoverschlorine from HCl, which often is a by-product in is organic preparations NI = -115 kJ mol-'

rhisisahomog.-X.:l13)oi'*!?.il,u1*11i1f,1;"3,?:1t'

Statethe meaning of the terms i homogeneous ii dynanic equillbrium Stateand explain the effect on the position of equilibrium of the reaction in b of: I decreasing temperature. the ti decreasing volume of the reaction vessel the

tlI l2l l2l

(Total 14 marks) lMay 2002 question3 Unit Test2 & lanuary 2001 question4 Module Test2l Aluminium metal is manufactured by a processin which purified bauxite, dissolved in molten cryolite, is electrolysed 800'C. Graphite electrodes at and a current of about 120 000 amperesare used. Give the ionic equation for the reaction taking place at the anode. tlI Give the ionic equation for the reaction taking place at the cathode. tlI Statewhich of thesereactionsis an oxidation process. tll Explain why the anodesneed to be replaced frequently. tzl Explain why an electrolyte of pure molten bauxite is not used. r2l Gotaf 7 marks) lJune2001 Unit Test2 question7f [Paper total 6O marks]

r2l

a b c d e

Mtry s ASlaborator/
I Laboratory chemistry
o The specificationfor thesetestsincludes all of Units L and 2. O Unit Test38 will contain many of the calculationsfor AS level, and so Topic t.2 (pages6 to 12) must be thoroughly revised.

ffi 'Lb

of Unit Test3A: Assessment practical skiltsI

iJ tfris is either internally assessed a practicalexam. or iJ Notesand textbooksare allowedin the tests. J the practicalexam will contain somequantitativework, probablya titration or an enthalpy changeexperiment. J You should know the following gastests: o H, I O, o CO, o NH3 O Cl, a NO2 I SO, burns with a squeakypop relights a glowing spill turns lime water milky turns red litmus blue bleachesdamp litmus; turns KBr solution brown brown gaswhich turns starch/iodidepaper blue-black turns acidified potassiumdichromate(Vl) solution green.

E you should know the testsfor the following ions: o COr'o HCO3o SOn'Add acid. Testfor COr. Add to almost boiling water.Testfor COr. are Giveswhite precipitatewhen dil HCI and BaClr(aq) added to the solution. above. Solution is acidic to litmus, then test as for SOn2Add dil acid to solid and warm. Testfor SOr.

Ion Li' Na'

Flame colour camine red

yellow
lilac

o HSO4o SO32o Halide ion: To solution add dil HNO3then AgNOr(aq).White precipitate soluble in dil ammonia indicateschloride; cream precipitateinsoluble in dil but soluble in conc ammonia indicatesbromide; pale yellow precipitate insoluble in conc ammonia indicatesiodide. Heat solid. All nitrates give off Or. All but sodium and a NO3potassiumnitrates also give off NOr. Alternatively add aluminium powder and sodium hydroxide solution. Nitrates give off ammonia gas. a NHn. o Mg'.

K'
Ca'*

Sr'* Ba"*

brick red crimson red pale green

Add dil NaOH and warm. Testfor ammonia. Giveswhite precipitatewhen dil ammonia is added to a solution. O You must know how to carry out a flame test and the colours obtained.

LABoRATORY

CH EM ISTRY

ffi

I chemistry 38: []nit Test Laboratory

J this is a written paper,taken by alt candidates. a J tt is designedto assess candidate'sability (relatedto the topics in Units 1 and 2) to:
I ll

evaluate information generated from experiments describe and plan techniques used in the laboratory.

C=C group

Decolourises brown bromine in hexane

J Tests o You should know the testslisted in Unit 3A above. o You should also know the testsfor alkenes,the OH group and the halogenin halogenoalkanes. o You should be able to deducethe identity of a compound from the of resultsof a series tests. J Techniques techniquesusedin: You should be able to describe o titrations and enthalpy changemeasurements O simple organic proceduressuch as distillation and heating under reflux. [l Phnning You should be able to: O Plan a seriesof teststo determine the identity of an inorganic or organic compound. O Describehow to make up a solution of known concentration for titrations. O Plan an experiment to determine the enthalpy of a reaction such as the combustion of a liquid, or the neutralisation of an acid. of o Plan an experiment to follow the progress a reaction in which there is a changein physical state,such as the production of a gas. [l calculations You should be able to calculate: o empirical formulae O reacting masses o resultsfrom titration data o enthalpy changesfrom experimentaldata. iJ Evaluation You should be able to criticise: o an experimental plan or apparatus o the resultsof an experiment in terms of significant figures,accuracy or experimentalerror etc.

C-OH group

Steamyfumes with PCl.

Organic halides Warm with sodium hydroxide solution. Acidify with dilute nitric acid and then test as for ionic halides as on page 55

[J sarety
specificsafetyprecautionswhen a substance You should be able to suggest is flammable, toxic or irritating.

Practice Test: Unit 38

Time allowed t hr All questions, except5, are taken from partsof previousEdexcel AdvancedGCEquestions. The answers on pagesl3O-I32. are 1 Complete the table below. Gas Hydrogen Oxygen
Carbon dioxide Sulphur dioxide Potassiumdichromate(VI ) solution acidified with dilute sulphuric acid. Solution turns from orange to .

Reagents test or Burning splint Glowing splint

for Observation expected a positiveresult

Moist blue litmus paper

Turns red and is then bleached white

t6I
(Total 6 marks) 2002 Unit Test 38 question 2l llune In a series of experiments to investigate the factors that control the rate of a reaction, aqueous hydrochloric acid was added to calcium carbonate in a conical flask placed on an electronic balance. The loss in mass of the flask and its contents was recorded for 15 minutes. CaCO,(s) + 2HCl(aq) CaCl,(aq) + H,O(l) + CO,(g) Four experiments were carried out. . Experiments L, 3 and 4 were carried out at room temperature (20"C). o The same mass of calcium carbonate (a large excess)was used in each experiment. o The pieces of calcium carbonate were the same size in experiments 1, 2 and 4.

Experiment
1

Calcium carbonate
Small pieces Small pieces One large piece Small pieces

Hvdrochloric acid

z
3
4

50.0cm' 1.00mol dm-' 50.0 cm' 1.00 mol dm-' heatedto 80 "C 50.0 cm' 1.00mol dm-' 50.0cm'2.00 mol dm

a The resultsof experiment I give the curve shown on the graph below.
Massloss/g

1.50 1.00 0.50

15

Time/min

El

to"oRAroRY

c H E Mr s r R Y I

i Explainwhy there is a lossin massas the reactionproceeds. t2l Explain the shapeof the curve drawn for experiment 1. ii t2l Draw curveson the graph aboveto representthe resultsyou would expect for experiments2, 3 and 4. tsl i Calculatethe massof calcium carbonatethat exactly reactswith 50.0 cm3of 1.00 mol dm-' aqueoushydrochloric acid. (Molar massof CaCOr= 100 g mol-') t3l a Basedon your answerto c part (i), suggest suitablemassof calcium carbonateto use in the ii experiments.Explain your answer. t2l (Total 1.2 marks) 2] [anuary 2002 Unit Test38 question A student was required to determine the enthalpy change for the reaction betweeniron and copper sulphatesolution. The student produced the following account of their experiment. Then 50 cm'of 0.5 mol dm-'aqueous A pieceof iron,massabout3 g, was placedin a glassbeaker. The and addedto the beaker. cylinder usinga measuring was measured solution coppersulphate and everyminuteafterwards immediately beforethe addition was measured temperature the mixture of untilno furtherchangetook place Fe+CuSOo Timing Temperature/'C Before addition 16 1 min 27 + FeSOo Cu 3 mins 26 4 mins 24 5 mins 22

2 mins 29

two improvementsyou would make to this experiment. Give a reasonfor each of the Suggest improvements suggested. t4l oC occurred b In an improved version of the same experiment a maximum temperaturerise of I5.2 iron with 50.0 cmt of 0.500 mol dm-' aqueouscopper sulphate solution. when reacting excess solutionsas 4.181 g-' deg', i Using this data and taking the specificheat capacityof all aqueous calculatethe heat change. ii Calculatethe number of moles of copper sulphate used. iii Calculatethe enthalpy changefor this reaction in kJ mol-' r2l (Total 8 marks) [une 2002 Unit Test38 question4]

tu

A student carried out an experiment to find the percentage of calcium carbonate, CaCO, in a sample of limestone following his own plan. The student's account of the experiment, results and calculations of the mean titre are given below. Account = I Massof pieceof limestone 5.24 g to acid was usedto transfer cm'of 2.00 mol dm-'aqeoushydrochloric (an excess) a 50 ll A pipette pieceof limestone was placedin the beakerand left untiltherewas no more The 100 cm' beaker. effervescence. Equation Ill lV + CaCO.(s) 2HOl(aq)+ CaOl'(aq) CO'(g)+ H,O(l)

flask.A smallamountof the in The acidicsolution the beakerwas filteredinto a250 cm3volumetric madeup flaskwas carefully in The solution the volumetric in remained the filterpaper. solidimpurity water. to 250 cm'with distilled The solution flasks. to of 25.0 cm3portions the acidicsolution conical was usedto tranfer A pipette sodiumhydroxide. was then titrated with 0.100mol dm-'aqueous HCI(aq) NaOH(aq)+ + tttaQl(aq) H,O(l)

uNrr TEsrBB

Results 1 (final) Burettereading Burettereading(at start) Titre/cm3 Meantitre= 14.90 0.00 14.90 1 4 . 9 0 + 1 5 . 3 5 + 1 4= 8 5 . 15.033 cm' 2 15.40 0.05 15.35 3 30.25 15.40 14.85

that The accuracyof the student'smethod was judged to be poor by his teacher.The teachersuggested the procedurein II could be improved, and that the titres used to calculatethe mean were incorrectly
chosen. i Suggest,with a reason, one improvement to the student's procedure in II. ii Recalculate a value of the mean making clear which titres you choose.

I2l

b i
ii
lll

Using your answerto a part (ii), calculatethe amount in moles of sodium hydroxide in the mean titre. tlI
Hence state the amount in moles of hydrochloric acid in a 25.0 cm' portion of the acidic solution

r2l

transferredin IV.
lv v vt

tll
moles of hydrochloric acid remaining after the reaction in II. of hydrochloric acid transferred to the beaker in II. moles of hydrochloric acid used in the reaction. moles of calcium carbonate and the mass of calcium carbonate tll tU tl] in

Hence calculate the amount in Calculate the amount in moles Hence calculate the amount in Hence calculate the amount in

= the sampleof limestonelM, (CaCOr) 100) I2l vii Hence calculatethe percentage calcium carbonateby massin the sampleof limestone. of tU The burette used in the titrations had an uncertainty for each reading of +0.05 cm'. i Which of the following should be regardedas the actual value of the titre in titration 3? A between 14.80 and 14.90cm': B between L4.825and 14.875cm3: C between 14.75 and 14.95cm'. tlI ii Suggest one reasonwhy a student may obtain volumes outside the uncertainty of the burette when carrying out a titration. tll (Total L4 marks) 2001 Unit Test38 question 4] fJune Propan-Z-ol(molar mass60 g mol-1 and boiling temperature82 "C) can be preparedby the reaction between 6.15 g of 2-bromopropane(molar mass I23 g mol-' and boiling temperature59 "C) and excess aqueous2.0 mol dm-' sodium hydroxide. This reaction is slow at room temperature. Describethe procedure,identifying the apparatusthat you would use,to preparea pure sampleof propan-2-olfrom 6.15 g of 2-bromopropane. tsl b Calculatethe minimum volume of sodium hydroxide solution that must be taken to ensurecomplete reaction of the 2-brompropane. r2l yield would be an excellent result. Calculatethe massof pure Your teachersuggested that an 80o/o propan-Z-olthat you would need to prepareto obtain this yield. r2l Suggest one reasonwhy your yield will be below 1,00o/o. (Total 1O marks)

tu

4 ?erinry, qMttatun'
e4 rrn, Win rulib arud, nAl

lroryMny
E n e r g e tlilc s
(H \ - H.l Introduction .a- t
C ' I

Law to reactionsinvolving ions. J This topic extendsthe useof Hess's iJ yon must be able to construct a Born Haber cycle. f] Lattice energyis crucial to the understandingof ionic bonding, because of it is this release energythat makesthe formation of an ionic thermodynamically favourable. substance fl Oefinitions of enthalpy changesmust include: i the chemical changetaking place ii the conditions (reactantor product) iii the amount of substance iv an example of an equation with statesymbols,as this may gain marks lost through omission in your word definition.

Things to learn
is a,H^tor chlorine theenthalpy for: change %Cl,(g) Cl(g) AHn,o the Na-ion is the enthalpy for for: change Na-(aq) Na-(g) itQ--+ + is Af{.n sodium for chloride the for: change enthalpy -+ Na-(g) Cl-(g) NaCl(s) ,J fne sign of the value of AIltells you the direction of the movement of heat energy: o positive (endothermic) for heat flowing into the system o negative (exothermic)for heat flowing out of the system. is [J nntnalpy of atomisation, A.f,Iu, the enthalpy change for the production of one mole of atoms in the gas phase from the element in its standardstate.It is alwaysendothermic. is ;J nntnApy of hydration, A.f,foru, the enthalpy changewhen one water. It is alwaysexothermic. mole of gaseous ions is added to excess [i fattice energy, LII""', is the energy change when one mole of gaseous ions. It is always ionic solid is made from its separate exothermic.

<ffi

LH

Thingsto understand
cycle

Born-Haber

o This relates the enthalpy of formation of an ionic solid to the enthalpies of atomisation of the elements concerned, the ionisation

t E N e R G E r r c sl
energies for the formation of the cation, the electron affinity for the formation of the anion and the lattice energy of the ionic substance. O This can either be drawn as a Hess's Law cycle, or as an enthalpy level diagram (seeFigures 4.1 and 4.2).

4,ti
zcr(g)
+ C l z (g )-M g C l r(s )

Mg'.(g) + 2cl(g)

t osn
|

+ I vg2.(g) ctr(gt
Mg-(g) + Clr(g)

ll * * . l1
I N I f I

Nrz
Mg(S) + Clz(g)
NIl

+ zCf (g)

Mg(s) + Clr(g)

MgC l r{s)

leveldiagram Fig 4.2 Enthalpy

AH, of MgCl, = NI^ of Mg (AH,) + lst ionisation energy of Mg (NIr) + 2nd ionisation energv of Mg (aH,) + 2 x A , F / " o C l ( A H r ) + 2 x e l e c t r o n a f f i n i t y o f C l ( A H r ) + A / { , , , , o fM g C l r ( A F l r ) = A H , + A , H . + A H , + l H , + l H . + - \ H " f

Any one value can be calculated when all the others are known.

Lattice enerry
lf a bond partially is covalent, the (from lattice experimental energy (more Born Haber) bebigger will than exothermic) thevalue from ionic calculated a purely model. Thegreater difference the between theexperimental theoretical and the the values, greater extent of This if covalency. willhappenthe (small cation verypolarising is or highly charged) theanion very or is polarisable (large). page See 13.
O Lattice energy is always exothermic. o Its value depends upon the strength of the force of attraction (sometimes called the ionic bond) between the ions. O The strength of this force depends upon the value of the charges and the sum of the radii of the ions: i the larger the charge on either or both of the ions, the larger (more exothermic) the lattice energy ii the larger the sum of the ionic radii, the smaller (lessexothermic) the lattice energy.

o Theoretical values of lattice energy can be calculated assuming that the ionic. substance is 100o/o Voriotion of lottice energies in o Group O Group 2 sulphates. As the radius of the cation increases down the Group, the lattice energy decreases.But because the radius of the sulphate ion is much larger than the radii of any of the Group 2 cations, the sun of the radii of the cation and the anion alters only slightly, and so the lattice energy only decreasesslightly. As the radius of the cation increases down the O Group 2 hydroxides. Group, the lattice energy decreases.But because the anion is small, and matches the size of the cation (the ionic radii of Ba'* and OH- are about and so the lattice the same), the surn of the radii alters significantly, energy decreasesby a large amount.

El

rrRroDrcrry, quANTrrATrvE EeurLrBRrA AND FUNcTtoNAL GRoup cHEMIsTRy

Enthalpy

of hydration

when must use not aHhyd You to lt refers to a referring compound. change ions. enthalpy separate The + Cl-(aq) + ?Q forNaCl(s) + Na+(aq) the ofsolution. iscalled enthalpy

o Enthalpy of hydration is alwaysexothermic. O For a cation it is the result of the force of attraction betweenthe ion and the 6 oxygen in the water. O For an anion it is the result of the force attraction between the ion and the 6- hydrogen in the water. I The value of enthalpy of hydration will depend upon the value of the chargeon the ion and its radius: i the larger the charge,the larger (more exothermic) the enthalpy of hydration, ii the larger the ionic radius,the smaller (lessexothermic) the enthalpy of hydration. Vorlotion of entholpies of hydrotion in o Group The value will becomelessexothermic as the radius of the cation increases down the Group. Solubility The direction of a chemical reaction is partially determined by the value of that the solubilities,it is assumed the enthalpy change.When discussing more exothermic the enthalpy of solution, the more soluble the substance is likely to be. The enthalpy of solution can be estimatedfrom a considerationof lattice energiesand enthalpiesof hydration of the two law diagram. ions as can be seenfrom a Hess's

M-(g) that and Note bothlattice hydration numbers, so are enthalpiesnegative -Aff.n positive is
MX(s)+ aq

rG)

l l*'a l
(aq)

x-(aq)

t l*u t

A H,"rn= - (lattice energy) + (hydration enthalpy of each cation + hydration enthalpy of each anion)

o Solubility of Group 2 sulphates i The enthalpy of hydration becomesmuch less as the cations becomebigger. the ii Because radius of the sulphateion is much bigger than the radius of any of the cations,the lattice energyonly decreases slightly - seeabove. iii (i) and (ii) together mean that the enthalpy of solution becomes the considerablyless exothermic and causes solubility of the sulphatesto decrease down lhe Group. r Solubtlity of Group 2 hydroxides i The enthalpy of hydration becomesless as the cations become bigger. the ii Because radius of the hydroxide ion is a similar sizeto that of the cations,the lattice energydecreases considerably. iii (i) and (ii) together mean that the enthalpy of solution becomes the considerablymore exothermic and causes solubility of the hydroxides to increase down the Group.

r ENeRGETTcs l

Checklist
Beforeattempting questionson this topic, check that you: :J Can define enthalpy of atomisation. iJ Can define enthalpy of hydration. ;J Can define lattice energy. iJ Can construct a Born-Haber cycle. IJ Cun use a Born-Haber cycle to calculatelattice energy or electron affinity. [] U.tdetstandwhy the value of AF/**from Born-Haber might be more exothermic than the theoretical value. [,] Can stateand explain the changein solubilities of the Group 2 sulphatesand hydroxides.

# -x Lvve GT

For the following questions, cover the margin, write your answer, then check to see if vou are correct. I In each of the following state which compound has the larger (more exothermic) lattice energy: a MgCO. or BaCO, b NarCO. or MgCO, c NaF or NaCl. I Arrange the following ions in order of decreasing (less exothermic) enthalpy of hydration: Na*, Mg'*, Bat* and Alt* o State the formula of the most soluble Group 2 hydroxide.

a MgCO, b MgCO, C NAF Al*>Mg'.rBa'*>Na*

Ba(0H),

to The answersthenumbered questionsonpage 132. are

The following data, in kJ mol-', should be used in this question. Enthalpies of atomisation: calcium +193; chlorine +LZL. Ionisation energies for calcium: 1st +590; 2nd +1150 Electron affinity for Cl(g): -364 Lattice energies:for CaClr(s) -2237; for CaCl(s) -650 (estimated). a Construct a Born-Haber cycle for: i the formation of CaCl(s) ii the formation of CaClr(s). Calculate the standard enthalpy of formation of: i CaClr(s) ii CaCl(s) iii hence calculate the enthalpy of the reaction: 2CaCl(s) * Ca(s) + CaCl'(s) and comment on the fact that CaCl(s) does not exist. Comment on the values of the lattice energies, in kJ mol-', given below: NaF

MgI,

Experimental Theoretical -912 -918 -t944 -2327

EI

euANTrrATrvE EeurLrBR'A AND FUN.TT'NAL GRoup cHEMIsrRy "r*roDrcrry,

Table Periodic ll The

'& Inffoduction
;J you will need to look again at Topic 1.4. iJ fne elementsbecomemore metallic down a Group. This meansthat their compounds,such as their chlorides,becomemore ionic and their oxidesbecomemore basic. f fn. elementsbecomeless metallic from left to right acrossa Period. This meansthat their chloridesbecomemore covalent and their oxides becomemore acidic.

[-] There are many formulae and equationsthat must be learnt in this Topic. [l fne propertiesof elementsand their compounds change steadilyfrom the top to the bottom of a Group and from left to right acrossa Period.

Things to learn and understand

Variation of properties across Period 3
A table is given below showing the formulae of the products of the reactions of the elements with oxygen, chlorine and water: Na
Mg

AI
Al2o3

Si

P
PnO,o

CI
No reaction

Ar
No reaction

Oxygen

Na,O or N a rO,(t)

Mgo
MgCl,

sio,
sicl4
No reaction

SO,
SrCl, No reaction

Chlorine NaCl Water

NaOH +
H2

Alcl, (')

PCI, (t) PCl,

No reaction

No reaction HCI + HOCI

No reaction

MgO + No
H,tn'

reaction

(" (') oxygen sodium peroxideis formed, ''' aluminium chloride is covalent, with excess Notes: with excess (n) chlorine, with steam. [l uetA hydroxides and oxides alkaline: NaOH(s) + aq - Na-(aq) + OH-(aq) t NaOH o Mg(OH), basic: Mg(OH),(s) + 2H.(aQ) - Mg'.(aq) + ZH,OQ) basic: MgO(s) + 2H-(aq) -- Mg'*(aq) + H,O(l) o MgO amphoteric: Al(OH),(s) + 3H.(aQ)- Al'.(aq) + 3H,O(l) a AI(OH), Al(OH),(s) + 3OH-(a9) - Al(OH).3-(aq) amphoteric: AlrO.(s) + 6H.(aQ) - 2Al'.(aq) + 3HrO(l) o Al2O3 Al,O,(s) + 6OH-(aq) + 3H,O(l) '2Al(OH)6'-(aq) [] Non-metal o SiO, O P4O6 o P4O10 oxides weakly acidic: SiOr(s) + 2NaOH(l) - NarSiO'(l) + HrO(g) + weakly acidic: PnOu 6HrO ' 4H'PO, + 4H-(aq) + 4HrPOrstrongly acidic: PnO,o+6HrO -' 4HrPOn- 4H'(aq) + 4HrPOn-

Thehydroxides less and become basic more as charge acidic thesurface increases. of density thecation

is dioxide such weak that a acid Silicon molten hydroxiderequired. is sodium The form oxides thenon-metals of increasingly acids the as strong number oxygen of atoms theacid in increases.

THE PERroDrc rABLE rl

I SO, t SO,, + weakly acidic: SO, + HrO --*H2SO3 H.(aq) + HSO.-strongly acidic: SO. + HrO -- HzSOn H'(a9) + HSO,-

iJ cntorides
o NaCl ionic solid, dissolves in water: NaCl(s) f ?q--+Na-(aq) + Cl-(aq) o MgCl, ionic solid, dissolves in water: MgCl,(s) + ?q--+ Mg'.(aq) + 2Ct-(aq) Hydrated AlCl, ionic solid, deprotonated by water: I -[AI(H,O)"]'.(aq) + H,O [A1(H,O),(OH)]'.(ag)+ H,O-(aq) r Anhydrous AlCl, covalent solid, reacts with water: AlCl,(s) + 3H,O(l) -'Al(OH),(s) + 3HC|(aq) w SiCl.,covalent liquid, reacts with water: Sicl,(l) + 2H'O(l) -- SiO,(s)+ aHCl(aq) *r PCll covalent liquid, reacts with water: P C l ,(l )+ 3H .O(l )-- H ,P O,(aq)+ 3H C l (aq) , PCl. covalent solid, reacts with water: PCl.(s)+ 4HrO(l) - H,PO.,(aq) SHCl(aq) +

lonic chlorides in to dissolve water formhydrated ions. These hydrated may ions if the deprotonate, surface charge density themetal is high. of ion (of Covalent chlorides Period 3) react water formHCI with to and either oxide theoxoacid. the or

Variation

of properties

down Group 4

The trend metallic in character is caused thedecreaseionisation by in energy theradius theatom as of increases, making energetically it for favourable theformation ionic of bonds.

-l The metallic character increases down the Group: carbon and silicon are non-metallic (not malleable; only graphite conducts electricity) germanium is semi-metallic (semi-conductor). tin and lead are metallic (malleable and electrical conductors). iJ fne +2 oxidation state becomes more stable relative to the +4 state. Lead(IV) is oxidising and is itself reduced to lead(Il), whereas tin(Il) is reducing and is itself oxidised to tin(IV). This is illustrated by: o lead(IV) oxide oxidises concentrated hydrochloric acid to chlorine: PbO, + 4HCl - PbClz + Cl, + HrO o tin(Il) ions are oxidised to tin(IV) ions by chlorine:

Sn'*+ Cl, -- Sn'.+ zcr

lJ Tetrachlorides. Both CCl, and SiCln are covalent and are tetrahedral molecules owing to the repulsion of the four bond pairs of electrons. SiCl4is rapidly hydrolysed by water. A lone pair of electrons from the oxygen in the water forms a dative bond into an empty 3d orbital in the silicon atom. The energy released is enough to overcome the activation energy barrier involved in the breaking of the Si-Cl bond. Carbon's bonding electrons are in the 2nd shell and there are no 2d orbitals. The empty orbitals in the 3rd shell are of too high an energy to be used in bonding, and equally important is that carbon is such a small atom that water molecules are prevented from reaching it by the four much larger chlorine atoms arranged tetrahedrally around it. if .q.ciaity of the oxides. This decreasesdown the Group: o Carbon dioxide is weakly acidic, and reacts with metal oxides and alkalis: CO,(g) + 2OH-(a9) - CO,'-(aq) + H,O(l) O Silicon dioxide is very weakly acidic, and reacts with molten sodium hydroxide: SiO,(s) + 2NaOH(l) - Na,SiO.(l) + H'O(g) O Lead oxides (and hydroxide) are amphoteric, and react with aqueous acids and alkalis, but lead(Il) oxide is the strongest base of the Group 4 oxides: PbO(s) + 2H-(aq) -- Pb'.(a9) + H,O(l) PbO(s) + 2OH-(aq) + H,O - Pb(OH)*'-(aq)

EI

trRroDrcrry,

A euANTrrATrvE EeuTLTBRIA ND FUN.TI.NAL GRoup cHEMIsTRy

Before attempting the questions on this topic, check that, for the Period 3 elements, you: i Can write equations for the reactions of the elements with oxygen and with chlorine.

J Can write equations for the reaction of the elements with water. J Can state and explain the acid/base nature of the metal hydroxides. J Can state and explain the acid/base nature of the non-metal oxides. J Know the formula of their chlorides and their reactions with water, and can relate the reactions to their bonding. Before attempting the questions on this topic, check that, for the Group 4 elements, you: iJ Kno* why the elements become more metallic down the Group. [J Kno* that the +2 oxidation state becomes more stable down the Group. l-f Know why SiCln is rapidly hydrolysed by water, whereas CCln is unreactive with water. E Can write equations to show the acid/base character of the oxides of carbon, silicon and lead. -.________.-]fl, O,t17i and your knowledge understanding Testing

a. t'For the following questions,cover the margin, write your answer,then check to seeif you are correct. o Statethe formulaeof lead(Il)oxide and lead(IV)oxide. o Statethe formula of the most basic Group 4 oxide. 1 a

PbO Pb0, and Pb0

Write equations for the changescausedby the addition of water to:

to The answersthenumbered questions onpages are 132-1 33.

i sodium chloride ii silicon tetrachloride iii phosphorus pentachloride. b Relate these reactions to the bonding in the chlorides. Explain why silicon tetrachloride, SiCln, reacts rapidly with water, C but tetrachloromethane, CCln, does not react even when heated with oC. water to 100 Write two ionic equations to show that aluminium hydroxide is 2 amphoteric. Write ionic equations for the reactions, if any, of: 3 aqueous acid with: magnesium hydroxide i lead monoxide ii iii sulphur dioxide aqueous alkali with: i magnesium hydroxide ii lead monoxide iii sulphur dioxide. 4 a Write an equation to show lead(IV) oxide acting as oxidising agent. b Write an equation to show aqueous tin(Il) ions acting as a reducing agent.

c H E M T c A LE e u r L r B R t u M l l

ll equilibria Chemical
ffi Lry Introduction
[l Concentration, in the context of equilibrium, is alwaysmeasuredin A mol dm-', and the concentration of a substance is written as [A]. E fne common errors in this topic are to use moles not concentrations and initial valuesnot equilibrium valueswhen substitutedin for expressions K.. iJ Calculations K must be set out clearly,showing eachstep. of are equilibrium is one in which all the substances in J A homogeneous equilibrium there are two in phase,whereas a heterogeneous the same or more phases.

Thingsto learn and understand

The equilibrium constant K"

The equilibrium constant, measuredin terms of concentrations,is found from the chemical equation. o For a reactiont *A + nB+ rC + yD where ffi, fl, x and y arc the stoichiometric numbers in the equation: K. = [C]'"q[D]/"q

to value ( isspecifica of The - and used reaction to theequation - and that to represent reaction can the by only altered changing be temperature.

[A]'"0[B]'", All the concentrationsare equilibrium values. doesnot appearin the equilibrium a solid substance O In a heterogeneous expressionfor K.. o K. is only equal to the quotient [C]' [D]'

tAr tBr
when the systemis at equilibrium. O If the quotient doesnot equal K., the systemis not in equilibrium and equilibrium when there will be no further will react until it reaches concentrations. changein any of the o K. has units. For the reaction: Nr+3Hr+2NH. K. = [NHJr"o Nrl"o [HJ'"' the units of K. are (mot d--')' (mol dm*) (mot d--')' 1
= mol-2 dm6

EI "t*toDlctry'

euANTITATtvE

EeurLrBRrA AND FUN.TT.NAL

GRoup

cHEMrsrRy

Colculotion of K, This must be done using equilibrium concentration values,not initial concentration values.The calculation is done in 5 steps: i Draw up a table and fill in the initial number of moles, the change for each substance and the equilibrium number of moles of each substance. ii convert equilibrium moles to concentration in mol dm-r. iii Statethe expressionfor K.. iv Substituteequilibrium concentrationsinto the expressionfor K.. v work out the units for K. and add them to your answer.

WorkpoL oxiloLf.b
Animportant reaction theblast in furnace theformation carbon is of monoxide from carbon carbon and dioxide. reactionanexamplea This is of heterogeneous m. equilibriu when mol carbon 1.0 of dioxide heated excess was with carbon a to temperature 'c ina vessel volume dm', g5% thecarbon of700 of 20 of dioxide reactedform fo carbon monoxide. calculate K,tor C(s) +CO,(g) +2C0(g) Answer. Units Initial amount 1.0 0 mol -0.95 Change +0.95 2 x mol Equilibrium amount 1.0-0.95=0.05 1.9 mol Equilibrium concentration = 0.051200.0025 1.9120 = 0.095 moldm-' (mol = K = t!91,*= (0.095), dm-s), 3.6mot dm-3
C0,(g)

o C(s) does appear theK. not in expression becauseis a solid. it o The amount C0 made twice of is theamount C0,reacted. of

co(s)

reo;i; ffi

Partial pressure
o The partial pressure a gasA, po,in a mixture is the pressure of that the gaswould exert if it alone filled the container.It is calculatedfrom the expression: partial pressure a gas= mole fraction of that gasx total pressure of
where the mole fraction = the number of moles of that gas

the total number of moles of gas o The total pressure, is equal to the sum of the partial pressures each P, of gasin the mixture. The equilibrium constant K"

The equilibrium constant, measuredin terms of partial pressure, only appliesto reactionsinvolving gases. solids or liquids do not appearin the expressionfor K". For a reaction: mA($ =*xB(g) + ZC(g) where m, x and y arethe stoichiometric numbers in the equation:

K, = (p).-t_(pJ *_
(Po)^ "n

r .HEMT.AL EeurLrBRruMl
are All partial pressures equilibrium values. So for the reaction: CO,(g)+ C(s)+2CO(g) = 160 p(CO)'"' and its units are atm2=atm

in is it Ascarbona solid is ignored theexpression.

P(co,)*
Colculotionsinvolving K,

atm

o The calculation of Kofrom equilibrium data is done in a similar way to those involving K.: i Draw up a table and fill in the initial number of moles,the change the for eachsubstance, equilibrium number of moles of each and the total number of molesat equilibrium. substance ll Convert equilibrium molesto mole fraction. iii Multiply the mole fraction of eachby the total pressure. for K'. lv Statethe expression for into the expression Ko. equilibrium concentrations Y Substitute vl Work out the units for K' and add them to your answer.

oh

oxal,u?12

placed avessel heated 175"C. to When and in mol 0.080 of PCluwas was that it reached,wasfound thetotalpressure 2.0atm had equilibrium been K,tor had Calculate thereaction: of andthat40o/o thePClu dissociated. + + PCl,(g) PCl,(g)Cl,(g) at 60% As Answen 40%haddissociated, wasleft.Thus equilibrium: = was and mol x 0.60 0.080 0.048 of PClu present therefore = had mol 0.080 0.048 0.032 of PClu reacted. PCI. PCI,

cr,

Total

0 0 0.080 -0.032 +0.032 +0.032 Change/mol x amount 0.60 0.080 Equilibrium = 0.048 0.032 0.112 0.032 /mol 0.032t0.1120.032t0.112 0.04810.112 Molfraction =0296 =0286 = 0.429 x pressure x2 0.286 2 0.286 0 . 4 2x 2 9 Partial = 0.571 = 0.571 = 0.857 /atm lnitial amounVmol = p(Cl,),.0.571 x 0.571 = 0.38 atm atm atm l( = p(PCl,),'

Variation

of K with

conditions

the when Konly equals quotient the This is the only factor that alters the value of K. o Temperature. lf the is system atequilibrium. i If a reaction is exothermic left to right, an increase in temperature quotient greater K,the is than will lower the value of K. This means that the position of will to reaction move theleftuntil_ equilibrium will shift to the left (the endothermic direction). lf is thetwoareequal. thequotient ii If a reaction is endothermic left to right, an increase in temperature will less thanK thereaction move will increase the value of K. This means that the position of the to theright until twoareequal. equilibrium will shift to the right. alter Temperature changes thevalue AH= of K(unless 0).Concentration O Catalyst. This neither alters the value of K nor the position of changes thevalue alter andpressure equitibrium. It speeds up the forward and the reverse reactions equally. of thequotient.
Thus it causes equilibrium to be reached more quickly.

H "aRroDrcrry,

euANTrrATrvE

EeurLrBRrA AND FUN.TT.NAL

GRoup

cHEMrsrRy

O Concentration. A changein the concentration of one of the in substances the equilibrium mixture will not alter the value of K, but it will alter the value of the quotient. Thereforethe reaction will no longer be at equilibrium. It will reactuntil the value of the quotient once again equalsK. If the concentration of a reactanton the left hand the sideof the equation is increased, position of equilibrium will move to the right. doesnot alter K. If there are more gas o Pressure. A changein pressure moleculeson one side than the other, the value of the quotient will be Thereforethe reaction will no longer be alteredby a change in pressure. at equilibrium, and will react until the value of the quotient once again equalsK. If there are more gasmoleculeson the right of the equation is the position of equilibrium will move to and the pressure increased, is the left. For example,if the pressure increasedon the equilibrium + NrOn(B) 2NOr(g),the position of equilibrium will shift to the left as there are fewer gasmoleculeson the left side of the equation.

Checklist
Beforeattempting questionson this topic, check that you: [i Can define the partial pressure a gas. of [l Can deducethe expressionfor K. and its units given the equation. E Can deducethe expressionfor Koand its units given the equation. E Can calculatethe value of K. given suitabledata. |J Ca.r calculatethe value of K, given suitabledata. fl Kt o* not to include valuesfor solids and liquids in the expression for Ko. I] Knot" that only temperaturecan alter the value of K, and how it will affect the position of equilibrium.

your knowledge understanding and Testing

For the following questions,cover the margin, write your answer,then check to seeif you are correct.

= = x kN P(N,) 0.781 104 81.2 m-' = 0.210104 =21.8 m-' x kN P(0,) = = x P(Ar) 0.009 104 0.9kNm-'
8 K= [S0J' = mofl dmg

nitrogen 2I.Oo/o of o Dry air at a pressure 104 kN m-'contains 78.Io/o of argon by moles. Calculatethe partial pressures oxygen and 0.9o/o eachgas. O Write the expressionfor K., stating its units, for the following reactions: ^ 2SO,(g)+ O,(B)+ 2SO,(g) b zHcl(g) +'1,o,(g)+ H,o(g) + cl,(g)

tsortoJ
b K= [H,0][Cl,] = mofz dmil2

lHctit ro,r
d 6=p(CH,0H) atm-' p(CO)p(H,))' x

O Write the expressionfor Ko,stating its units, for the following reactions: a CO($ + 2H,(g)+ CH,OH(g) b + Fe,O,(s) CO(g)+ 2FeO(s) CO,(g) +

b K,= 499)no.units p(c0)

L When a 0.0200 mol sampleof sulphur trioxide was introduced into a mol of sulphur trioxide vessel volume I.52 dm3at 1000'C, 0.01,42 of was found to be presentafter equilibrium had been reached.

ACID-BASE

EQUILIBRIA

The to answers thenumbered questions onpage 133. are

Calculatethe value of K for the reaction: + + 2SO,(g) 2SO,(g) O,(g) 2 I.O mol of nitrogen(Il) oxide, NO, and 1.0 mol of oxygen were mixed in a container and heated to 450 "C. At equilibrium the number of moles in of oxygen was found to be 0.70 mol. The total pressure the vesselwas 4.0 atm. Calculatethe value of K, for the reaction: 2NO(S)+ O,(g) -- 2NO,(g) 3 This questionconcernsthe equilibrium reaction: + 2SO,(g) O,(g)-- 2SO.(g) AH = -796 kJ mol-l K. = 3 x 10*mol-t dm3at 450'c a 2 mol of sulphur dioxide, I mol of oxygen and 2 mol of sulphur of trioxide were mixed in a vessel volume l0 dmt at 450 "C in the are presence a catalyst.Statewhether thesesubstances initially in of equilibrium. If not, explain which way the systemwould react. Stateand explain the effect on the value of K. and on the position of equilibrium of: i ii iii adding more catalyst. decreasing temperature the the decreasing pressure

equilibria (g Acid-base
<ffi

Introduction

o It is essentialthat you can write the expressionfor K" of a weak acid. O Make surethat you know how to use your calculatorto evaluate logarithms, and how to turn pH and pK" valuesinto [H-] and K" values. I This meansusing the lg key for log,oand 10'key for inverselog,o. o Give pH valuesto 2 decimal places. O Buffer solutions do not have a constant pH.They resistchangesin pH. O You may use H-, H-(aq)or HrO- as the formula of the hydrogen ion.

d-a LN

Things learn to

[| A Brsnsted-Lowry acid is a substancethat donates an H- ion (a proton) to another species. tr n monobasic (monoprotic) acid contains, per molecule, one hydrogen atom which can be donated as an H" ion. A dibasic acid contains two. tr e Bronsted-Lowry another species. base is a substancethat acceptsan H* ion from

E K. = [H-(aq)][OH-(ag)]= 1.0 x 1O" mol' dm* at 25 "C. f A neutral solution is one where [H-(aq)]= [OH-(aq)]. f = dmt). pH = -log,o[H.(aq)],'or more accurately -log,o([HrO.(aq)]/mot

EI

euANTrrATrvE EeurLrBR'A AND FUN.TT.NAL GRoup cHEMIsrRy "r*roDrcrry,

E pOH = -log,olOH-(aq)1. E pH + pOH - !4 at Z|'C. tr e strong acid is totally ionised in aqueoussolution, and a weak acid is only partially ionised in aqueoussolution. f f K, for a weak acid, HA, = tHl tAl / tHAl. PK. = -log'o K".

tr e buffer solution is a solution of known pH which has the ability to resistchanging pH when small amounts of acid or baseare added.

Gffi
t--------!

to 1ru, Things understand

Coniugate f acid,/base pairs Theseare linked by an H- ion: Acid - H' - its coniugatebase: (coniugatebase) CH3COOH(acid)- H* + CHTCOOBase + H* - its coniugate acid: NH, (base) + H* + NHn*(coniugateacid) E When sulphuric acid is added to water, it acts as an acid and the water acts as a base: + HrO* HrSOn+HrOacid base coniugateacid of HrO HSO*conjugatebaseof HrSOn

J Uydtogen chloride gasacts as an acid when addedto ammonia gas:

HCI+NHrbase acid

+ NHn' conjugate acid of NH.

coniugate base of HCI

pH scale lf theacidity a solution increases, f Waterpartiallyionises of increasesthepHdecreases. but [H-] HrO+ H'(aq) + OH-(aq)
As the [HrO] is very large and so is effectivelyconstant, its value can be incorporated into the K for the reaction: K* = tH-] tOH-]= L.0 x LO'nmol' dm* at 25'C pH + pOH = \4at25"C or f So at 25 "C: o A neutral solution is one where [H-] = [OH-], and the pH = 7. oAnacidicsolutionisonewhere[H]>[oHl,andthepH< oAnalkalinesolutioniswhere[H]<[oHl,andthepH> For alkali 2 0H performula, with an the[0H-]is 2 x the[alkali]. mol ThepHof a 0.109 dm-'solution is of Ba(OH), = = pOH -log,o(20.109) 0.66 x = pH Therefore = 14- 0.66 13.34 Remember acids that have pH< 7 a andalkalis pH> 7. a E pH of strong acids and bases I For a strong monobasicacid: pH - -log,o[acid] Thereforethe pH of a O.321mol dm-' solution of HCI = -log,o(0.321)- O.49 O For a strong alkali with one OH- ion in the formula: pOH = -log,o[alkali]and ' pH =L4- pOH

The ionisation dibasic 2nd ofa acid isweak. [H-] such H2S04 as So for mol isnot 0.321 dm-'H,Soo 0.642 mol moldm-', is only0.356 dm-' but

AcrD-BAsEEeurLrBRrA
Therefore the pH of a 0.109 mol dm-' solution of NaOH is calculated: pOH = -log,o(0.109) = 0.96 fherefore pH = 14 - 0.96 = 13.04 pH of weok ocids o Weak acids are partially ionised. A general equation for this is: HA(aq)+H-(aq)+A-(aq) o The acid produces eqrral amounts of H- and A-, so that: lH'(aq)l = [A-(aq)] O This enables either the pH of a weak acid solution or the value of K. of a weak acid to be calculated.

Worktl'oxarorylt,
has mol of the Calculate pHof a 0.123 dm'solution anacidHAwhich K. = 4.56 10'moldm{: x HA(aq)+H'(aq)+A(aq) = Answer: ( = [H-(aq)] (a_q)]U'(aQl: [A IHA(aq)l [HA(aq)] = lH'(aq)l 7'j( JHA(aq)l) = =/+.SO10*x 0.123) 2.37 10-'mol x dm-3 x -log,o(2.37x10-') = 2.63 pH =

Titration

curves

o These are drawn either for the addition of base to 25 cm' of a 0.1 mol dm-' solution of acid until the base is in excess,or for addition of acid to a base (seeFigure 4.3). a If the acid and base are of the same concentration, the end point is at 25 cm'. t There are several pH values to remember.

(12.5 At halfwayto theendpoint is cm'if theendpoint at 25cm3), thecurve a weak anda for acid will horizontal strong base bealmost the at a pHof about Thisis when 5. = is and solution buffered [HA] [A]. = wayPH,FK. PH Thus thehalf at fortheweak acid.

Starting pH Strong acid/strongbase Weak acid/strongbase Strong acid/weakbase

Strong acid/

End point pH 7 9 5
13 1L 9 7 5 3

Vertical pH range 3 . 5t o 1 0 . 5 7 to 10.5 3.5 to 7

Final pH

1 3 1

13 13 11

1 3 Weak acid/ 11 9 7 5 3

Fig 4.3 Titrationcurves

0 2 5 0 2 s 0 2 5 Volumeof alkali/cm3 Volume of alkali/ cm3 Volume of alkali/ cm3

-|l

5il

PenroDrcrTy,

euANTtTATtvE

EeurLrBR|A

AND FUNGTToNAL GRoup

cHEMTSTRY

Indicators
O For use in a titration, an indicator must change colour within the pH of the vertical part of the titration curve. Vertical range of pH Suitable indicator

Strongacid and base 3.5 to 10.5 Weak acid/strongbase 7 to 10.5 Strong acid/weakbase 3.5 to 7

Methyl orange or phenolphthalein Phenolphthalein Methyl orange

Buffer solutions
conjugatepair, e.g.a weak acid and its salt o Theseconsistof an acid/base such as CH.COOH/CHTCOONa, a weakbaseand its salt, e.g. or
NH3/NH4CI. o To be able to resist pH changes, the concentration of both its conjugate base must be similar. the acid and

I Consider a buffer of ethanoic acid and sodium ethanoate. The salt is ftrlly ionised: CH3COONa(aq)- CH'COO-(aq) + Na-(aq) ionised: The weak acid is partially CH3COOH(aq) + H'(aq) + CH,COO-(aq) The CHTCOO- ions from the salt suppress most of the ionisation of the acid, and so both [CH.COOH(aq)] and [CH,COO-(aq)] are large. If H' ions are added to the solution, almost all of them are removed by reaction with the large reservoir of CH.COO- ions from the salt: H-(aq) + CH,COO-(aq) - CHsCOOH(aq) If OH- ions are added, almost all of them are removed by reaction with the large reservoir of CHTCOOH molecules of the weak acid: OH-(aq) + CH,COOH --' CH,COO-(aq) + H,O(l) Calculotion of the pH of o buffer solution Consider a buffer made from a weak acid, HA, and its salt NaA. The acid is partially ionised: HA(aq)+H.(aq)+A(aq) Thus K^ = [H-(aq)] [A (aq)]

IHA(aq)l the The saltis totally ionised, and suppresses ionisationof the acid,
Therefore[A-(aq)]= [salt] and [HA(ag)]= [weakacid] lf theconcentrations weak of the acid itssaltare same, and the then: = [H-(aq)] K^, and pH= pK,. = Thus 16. [H-(aq)] [salt] tweakacldf

= or [H-(aq)] K. trygg&gql
[salt] = -loglH.(aq)l pH

AcrD-BA'E Eeur.-rBR'A

Workpi,oxiloLf.h'
Calculate pH0f 500cm3 a solution the of containing 0.121m01 ethanoic of acid and0.100 of sodium mol ethanoate. pK^tor ethanoic = 4.76 acid gK, = 4.76, Answer. Therefore = inverse /( log(-p0 = 1.74x 10-u dm-' mol = 0.121+ = 0.242 dm-3 acid] 0.500 mol [weak = 0.100 0.500 = 0.200 dm-3. + mol [salt] = = 1.74 10u x0.242=2j0x 10-u dm-' x mol [H-(aq)](. [weakacid]

Isalt] = 4.68 pH = -log,o[H-(aq)] Enthalpy of neutralisation

0.200

= When a strong acid is neutralised by a solution of a strong base,A.FI,,",,, -57 kJ mol-', becausethe reaction for strong acids n'ith strong basesis: H -(aq)+ OH -(aq)= H ,O(l l The value for the neutralisation of a weak acid is less becauseenergv has to be used to ionise the molecule to form H- ions.
a -

IJ)'I

i //,-r.--t---)a H

Before attempting the questions on this topic, check that you: lJ Can identify acid/base coniugate pairs. *l Can define pH and K-. u.J Can define K" and pK" for weak acids. U Understand what is meant by the terms strong and weak as applied to acids and bases. iJ Can calculate the pH of solutions of strong acids, strong basesand weak acids. iJ Can recall the titration curves for the neutralisation of strong and weak acids. tl Can use the curve to calculate the value of K" for a weak acid. if Understand the reasons for the choice of indicator in an acid/base titrations [J Can define a buffer solution, explain its mode of action and calculate its pH.

j.ld
L/.-

t,XE),Testing your knowledge understanding and

| ,-

For the following questions, cover the margin, write your answer, then check to see if you are correct.

AcidH,S0o: conjugate HSO.- o Identify the acid/base conjugate pairs in the reaction: its base Base CH,COOH: itsconjugate acid HrSOn + CH,,COOH + CH.COOH2- + HSO,-

cH,c00H,-

a 0.96 b 13.04 c 13.34

O Calculate the pH of: a 0 .1 1 mol dm* H C I b 0.1 1 mol dm-' LiOH c 0.11 mol dm-' Ba(OH),

EI

euANTrrATrvE EeurLrBRrA AND FUNcTtoNAL GRoup cHEMtsrRy "a*roDrcrry,

pK. = 4.87. to The answersthenumbered L Calculate the pH of O.22 mol dm-' C2H'COOH which has questionsonpages 133-134. 2 25 cm' of a weak acid HX of concentration 0.10 mol dm-t was titrated are at with 0.10 mol dm-' sodium hydroxide solution, and the pH measured set out below: intervals. The results are
Volume NaOH/cm3

10

T2

20

23

24

25

26

30

pH
a b 3 a b

4 . 5 4 . 8 4.9 5 . 5 6 . 5 7 . 0 9 . 0 12.o 1 2 . 5
Draw the titration curve and use it to calculate pK, for the acid HX. Suggest a suitable indicator for the titration. Define a buffer solution and give the name of two substances that act as a buffer when in solution. Explain how this buffer would resist changes in pH, if small amounts of H- or OH- ions were added.

4 Calculate the pH of a solution made by adding 4.4 g of sodium ethanoate, CHTCOONa,to 100 cmt of a0.44 mol dm-'solution of ethanoic acid. K" for ethanoic acid = I.74 x 10-smol dm-'.

ll chemistry @ 0rganic
..H

"
(H

',"'"\

fhings to learn and understand

Isomerism iJ Structural. Therearethreetypes:

a Carbon chain. Here the isomers have different arrangements of carbon atoms in a molecule, e.g. butane, CH.CH TCHTCH,and methyl propane, CH.CH(CHr)CH.. b Positional. Here a functional group is on one of two or more different places in a given carbon chain, and propan-Z-oI, CH.CH(OH)CH.. e.g. propan-l-ol, CHTCHTCHTOH, c Functional group. Here the isomers have different functional groups, e.g. ethanoic acid, CH3COOH and methyl methanoate, HCOOCH.. :J Stereoisomerism. There are two types: a Geometric. This is caused by having two different Sroups on each carbon atom of a >C=C< group (see Figure 4.4).

The isomers not two are interconvertible atordinary temperatures there no because is rotation a double bond. about

H,C \ / H

CH, C-C / \ H

H:C \ / H

H C-C / \ CH.

cis-but-2-ene

trans-but-Z-ene

of Fig . cisond transisomers but-2-ene

oRcANtc cHEMtsrRY tl

I
Optical. Optical isomers are defined as isomers of which one is the non-superimposable mirror image of the other.

grouPs four Having different atom carbon will to attachedone atom this. carbon is cause This centre. a calledchital

Thus lactic acid (2-hydroxypropanoicacid), cH3cH(oH)cooH' existsas two optical isomers.Thesemust be drawn three dimensionally so as to show that one is the mirror image of the other (seeFigure4.5).
COOH COOH

mixture thetwoisomers of A 50/50 no on willhave effect Plane polarised This ofmixture light. type mixture is and a iscalledracemic when the often result chiral by are substancesproduceda reaction. chemical

HO

,t\

\\ CH, H

Hsc /l
H

. F-.oH

of Fig 4.5 Opticol isomers loctic ocid One isomer will rotate the plane of polarisation of plane polarised monochromatic light clockwise and the other will rotate it anticlockwise.

Further reactions
Grignord reagenfs such as C,HuMgl.They are usedto Thesehave the formula R-Mg-halogen they are nucleophiles and increasethe carbon chain length, because contain a 6-carbonatom which will attacka 6'carbon atom in other compounds. Preparation + Halogenoalkane magnesium Conditions: dry ether solvent (flammable,thereforeno flames),under reflux with a trace of iodine as catalyst:e.g. C2H'I+Mg-CrHrMgI Reactions O + aldehydesto produce (after hydrolysis with dilute hydrochloric acid) a secondary alcohol: C,H,MgI + CH,CHO- CH:CH(OH)C'H' butan-2-ol O + ketones to produce (after hydrolysis) a tertiary alcohol: C,H,MgI + CH.COCH,- CH3C(CH3)(OH)CrH' 2-methyl butan-2-ol O + solid carbon dioxide (dry ice) to form (after hydrolysis)a carboxylic acid: -'CTHTCOOH CrHrMgI+ COr(s) propanoic acid O Grignard reagentsreactwith water to form alkanes: CrHrMgI+HrO-CrHu which is why they must be preparedand used in dry conditions. Corboxylic ocids Thesehave the functional grouP:

producesPrimarY a Methanal alcohol.

o
-C /

o-H

EI

"a*roDrcrry,

euANTrrATrvE EeurLrBR'A AND FUN.TT.NAL GRoup cHEMIsrRy

Preparation They can be made by the oxidation of a primary alcohol. The alcohol is potassium heatedunder reflux with dilute sulphuric acid and excess dichromate(Vl). Reactions O + alcohols to produce esters: + + + CH3COOH CTHTOH CH3COOCTH, HrO ethyl ethanoate conditions: heat under reflux with a few drops of concentrated sulphuric acid. o + lithium tetrahydridoaluminate(Ill) to produce a primary alcohol: + CH3COOH a[H] 'CH'CH,OH + H,O ethanol dissolvein dry ether, followed by hydrolysis with H.(aq). conditions: o + phosphoruspentachlorideto produce an acid chloride: CH'COOH + PCI' - CH'COCI+ HCI + POCI, ethanoyl chloride conditions: dry; observation:steamyfumes given off. Esters Thesehave the generalformula RCOORwhere R and R are atkyl or aryl groups,and which may or may not be different.

Test a carboxylic When for acid. to added aqueous sodium (orsodium hydrogencarbonate it gives C0,, carbonate), a gas, which lime turns water milky.

o
R-C / \ oR'

This The isa catalyst. reaction acid has low it is a yield because a reversible reaction.

Reactions ethyl ethanoate of o Hydrolysis with aqueousacid to produce the organic acid and the alcohol: + + CH3COOCTH, HrO + CHTCOOH CTHTOH ethanoic acid conditions: heat under reflux with dilute sulphuric acid. o Hydrolysiswith aqueousalkali to produce the salt of the acid and the alcohol: + + CH3COOCTH,NaOH - CHTCOONa CTHTOH sodium ethanoate conditions: heat under reflux with aqueoussodium hydroxide. (oldehydesond ketones) Corbonyl compo,unds Thesecontain the C=O functional group. Aldehydeshave the general formula RCHO,and ketonesthe generalformula RCORwhere R and R are alkyl or aryl groups, and may or may not be different.

yield Thisreaction a high has it becauseis notreversible.

o
R-C / \ R-C / \

H Aldehyde

R' Ketone

oRGANrc cHEMrsrRY rl
Reactionsin common a Addition of hydrocyanic acid, HCN, to produce a hydroxynitrile: CH,CHO + HCN - CH,CH(OH)CN 2 -hy dr oxypr o p an en i t ri I e conditions: there must be both HCN and CIS present, e.g. HCN + a trace of KOH, or KCN(s) + some dilute sulphuric acid. o Reduction with lithium tetrahydridoaluminate(Ill) to produce an alcohol: C H 3C H O+ 2[H ] -C H TC H TOH CH'COCH, + 2[H] - CH.CH(OH)CH3 conditions: dissolve in dry ether, followed by hydrolysis with H-(aq). Or reduction with sodium tetrahydridoborate(Ill), also to produce an alcohol: CH3CHO + 2[H] 'CHTCH,OH CH3COCH. + 2[H] - CH,CH(OH)CH, conditions: aqueous solution, followed by hydrolysis with H-(aq). a Reaction with Z,4-dinitrophenylhydrazine (2,4-DNP) to give an orange/red precipitate:

The formation orange red ofan or precipitate 2,4-DNP a testfor is with i.e. for carbonyl compounds, both aldehydes ketones. and

NOt

NO,

2,4.DNP mirror The formation thesilver of is withammoniacal nitrate the silver testwhich distinguishes aldehydes, give result, from which a positive which have reaction. no ketones, Aldehydes also are oxidised by potassium l) or manganate(Vl potassium dichromate(Vl). acidified to Theonly aldehydedothisis ethanal, CH3CH0. reactionof aldehydes Specific Aldehydesare oxidised to carboxylic acidsby a solution of silver nitrate in dilute ammonia. On warming the silver ions are reducedto a mirror of metallic silver. Aldehydesare also oxidised by warming with Fehling'ssolution, which is reducedfrom a blue solution to a red precipitateof copper(I) oxide: C H . C H O + [ O ]- C H ' C O O H Iodoform reoction o This is a reaction which producesa pale yellow precipitate of iodoform, CHI3,when an organic compound is addedto a mixture of iodine and dilute sodium hydroxide (or a mixture of KI and NaOCI). t The group responsiblefor this reaction is the CH'C=O group, and the reaction involves breaking the C-C bond betweenthe CH, group and the C=O group. + produces CTHTCOONaCHI.(s) CHTCOCTH, group will give this precipitate. a All ketonescontaining the CH.C=O O This reaction is also undergoneby alcohols containing the CH.CH(OH) group. They are oxidised under the reaction conditions to the CH.C=O group, which then reactsto give iodoform. Acid chlortdes Thesehave the generalformula RCOCI,and the functional group is:

This reactionoften in is used questions. organic'problem' The yellow precipitate produced pale on hydroxide and additionsodium of iodinethe is clue. organic The this that compound produces precipitateeither a carbonyl will be group witha CH,C=Q or analcohol group. witha CH.CH(0H) lt is nota general forketones. test

o
-C / CI

e.g.ethanoyl chloride,CH.COCI,and propanoyl chloride,CrHrCOCl.

El

e u A N T r r A T r v E E e u T L I B R I AA N D F U N c T t o N A L G R o u p c H E M I s r R y ".RroDrcrTy, Reactions of ethanoyl chloride O + water to produce the carboxylic acid, ethanoic acid: CHTCOCI + HrO - CHTCOOH + HCI(g) observation: steamy fumes of HCl. o + alcohols to produce an ester: CH3COCI + CTHTOH CHTCOOCTH'+ HCI observation: characteristic smell of the ester, ethyl ethanoate. o + ammonia to produce the amide, ethanamide: CHTCOCI + 2NH. - CHTCONH, + NH4CI I + primary amines to produce a substituted amide: CHTCOCI + CrHrNH, - CH3CONH(CrH') + HCI

Nitrogen

compounds

Primory omines
o They contain the -NH, group, e.g. ethylamine C2HrNHz. O They are soluble in water (if the carbon chain is fairly short) because they form hydrogen bonds with water molecules. o They are weak bases. of Reactions ethylamine O + acids,to form an ionic salt that is soluble in water: + C2H'NH2 H.(aq) + CrHrNHr.(aq) | + acid chlorides,to form a substitutedamide: -'CH'CONHC2H, + HCI + C2H'NH2 CHTCOCI Nitriles They contain the C=N group, e.g. propanenitrile C,H'CN. anenitrile Re ationsof prop O Hydrolysis either with acid: + CTH'CN+ H* + zHrO - CTHTCOOH NHn* conditions: heat under reflux with dilute sulphuric acid or with alkali' + NH, crHscN + oH- + Hro'crHrcooconditions: heat under reflux with dilute sodium hydroxide O Reductionby lithium tetrahydridoaluminate(Ill): C'H'CN + a[H] - C2H'CHNH, conditions: dry ether, followed by addition of dilute acid Amldes They contain the CONH, group, .8. ethanamide CHTCONHT.

from can The amine beregenerated alkali. thesaltbyadding strong a

by Nitriles bepreparedthe can with reactiona halogenoalkane of KCN aqueous in ethanol. by be Hydroxynitriles prepared can to theadditionHCN carbonyl of inthe ofbase. compounds presence

o
cHg-Q / \ NH,

Reactions ethanamide of O Dehydration with phosphorus(V)oxide: CH3CONH,-HzO-CH'CN warm and distil off the ethanenitrile. conditions:

oRGANrc cHEMrsrRY rl
o Hofmann degradation reaction: CHTCONH, + Br, + 2NaOH - CHTNHT+ COr+ 2NaBr + ZH'O conditions: add liquid bromine to the amide at room temperature, and then add concentrated aqueous sodium hydroxide solution and warm. The amine distils off. Amino ocids These contain an NH, and a COOH group (usually bonded to the same carbon atom). They react both as acids and bases. They are water-soluble ionic solids because they form a zwitterion. NHTCH.COOH + NH,.CHTCOOReactions o With acids: NHTCHsCOOH+ H'(aq) - NH,'CH.COOH(aq)

Amides beprepared acid can from + ammonia. chlorides Amides beconverted an can into amine with same either the number (reduction) ofcarbon atoms orwith less one (Hofmann degradation).

Amino acids beprepared can from them chloroacidsheating in a by tube sealed withanethanolic solution ammonia. of

t With bases: NH'CH'COOH + OH-(aq) - NH.CH.COO-(aq) + H.O Figure 4.6 summarises the reactions of organic substances.

CO2.-----------C2H'COOH HCHO ---------------- C2H5CH2OH

Grignard CrHrMgBr

CH3CHO -------+ CH3COCH3 + HzO-CrHu C2H5OH -

C2H'CH(OH)CH3 C2H'C(CH,)zOH

Acid chlorides

H2O-CH3COOH C2H'OH ---) CH3COOCzHs NH3-CH3CONH2 CH3NH2+ CH3CONHCH3

cH3cocl
CH3COOCTHs CH3CH2OH CH3COCI

Acids cH3cooH

LiAlHnPCl, -----_+

Amines c2HsNH2

H * -C 2H sN H ; CH3COCICH:CONHC,H'

Esters lCH"COOC"H. I J '

HOH- ___---_-+ H C N -> C (OH )C N

CH3COOH+ CTHTOH CH3COO- + CTHTOH

Amides I CH.CONH, I L

t-

P+Oto-

CH3CN

Aldehydes and ketones >C=O

Brr(r)lNaoH-+CH3NH2

2,4-DNP .-+ lHl Ag'lNH3---+

red precipitate >CH(OH) CH3COO-+ silver mirror Nitriles CH3CN H*---+CH3COOH OH --C H 3C OOLiAlHa--+ CH3CH2NH,

Aldehydes only lCH.CHO I

Fehling's --------------CH3COO- + red precipitate

Fig 4.6 Summary organicreactions of

EI

tr*roDrcrry,

euANTrrATrvE EeurLrBR'A AND FUN.TToNALGRoup cHEMtsrRy

Checklist
Before attempting questions on this topic, check that you: i Can recognise stereoisomerism (geometric and optical) in organic compounds.

iJ Know the effect of an optical isomer on plane polarised light. iJ Understand the nature of a racemic mixture. li Can recall the preparation and reactions of Grignard reagents, .J Can recall the reactions of carboxylic acids. lJ Can recall the reactions of esters. 'J Can recall the reactions of carbonyl compounds (aldehydes and ketones). iJ Can recall the reactions of ethanoyl chloride. iJ Can recall the reactions of amines with acids and with acid chlorides. J Can recall the hydrolysis and the reduction of nitriles.

and with BrrlNaOH. J Can recall the reactions of amides with PnO,o iJ Know that amino acids are both acids and bases.

ffi
a CH,CH,CH(0H)CH3 b cH,cH,c(0H)(cH3)cH3
c CHT CHT O H

your and Testing knowledge understanding

For the following questions, cover the margin, write your answer, then check to see if you are correct. * Write the formulae of the products of the reaction of CH,MgI with: a propanal b c butan-2-one methanal.

reflux dilute with Heat under hydroxide, add then sodium dilute sulphuric acid. lithium b Add Il) indry tetrahydridoaluminate(l followed dilute by ether, sulphuric acid. a water b methanol c ammonia
a b ClCH3CH2NH'cH,c0NHcH2cH3

o State the names of the reagents and give the conditions for the following conversions: a C,H'COOCH, to C,H'COOH + CH,OH in a high yield b C2H'COOH to CHTCH,CH,OH.

O State the names of the reagents needed to convert ethanoyl chloride to: a ethanoic acid b c methyl ethanoate ethanamide.

o State the structural formulae of the product obtained by reacting: a ethylamine with dilute hydrochloric acid b ethvlamine with ethanovl chloride.

O
a

oRGANrccHEMrsrRYrl
O State the conditions for the conversion of: a ethanenitrile, CHTCN, to ethanoic acid, CH3COOH b c ethanenitrile, CH3CN, to ethylamine, CzHsNHz propanamide, CTHTCONH2, ethylamine, C2HsNHz. to

Heat reflux NaOH(aq) with under thenacidify. followed b AddLiAlH4 dryether, in bydilute alkali. withliquid c Warm bromine and concentrated aqueous sodium hydroxide.

it forms Because the,ryitterion -NHrCHS00-

O Explain why aminoethanoic acid is a solid that is soluble in water.

The to answers thenumbered questionsonpage 134. are

L Draw the stereoisomers of: a CH,CH=C(CI)CH, b cH.cH(oH)F. 2 Outline how you would prepare2-methylpropanoicacid from 2-iodopropane. 3 Describethe teststhat you could do to distinguish between: a ethanoic acid and ethanoyl chloride b propanal and propanone.

EI

euANTrrATrvE EeurLrBRrA AND FUNcTtoNAL GRoup cHEMI'TRY "r*roDrcrry,

Practice Test: Unit 4

Time allowed 1. hr 3O min All questionsare taken from parts of previous EdexcelAdvancedGCE papers The answersare on pages134-136. 1 a Draw a Born-Haber cycle for the formation of magnesium chlodde, Mgcl, and use the values below to [5] calculate the lattice energy of magnesium chlodde. AIflkJ mol-'
lst electron affiniW of chlorine

-364 +736 +1450 +LZL +150 -642

1st ionisation energyof magnesium 2nd ionisation energyof magnesium

Enthalpy of atomisation of chlorine

Enthalpy of atomisationof magnesium

Enthalpy of formation of MgClr(s) b Use the following to answer the questions in this section.

AfflkJ mol-' Enthalpyof hydration of Sr'. Enthalpy of hydration of Ba'. Enthalpy of hydration of OHLattice energy of Sr(OH)'(s)
Lattice energy of Ba(OH)r(s)
I ll lll

-1480 -1360 -460

-r894
-L768

Explain why the lattice energyof strontium hydroxide is different from that of barium hydroxide.[2] l2l fxplain why the hydration *tfrutpy of a cation is exothermic. valuesto explain why barium hydroxide is more Use the lattice .n.igy and hydration enthalpy t4l soluble in water than strontium hydroxide. (Total 13 marks) 4l 2001 CH 3 question lJanuary

2 a i ii

tll that has an unbranched chain Give the structural formula of a nitrile, CnHrN, primary amines can be made by reducing nitriles. Suggest reagentthat could be used for this a tlI purpose. the nitrile given in a part i. tU iii Draw the structural formula of the amine producedby reducing a nucleophile? tlI i What feature of an amine molecule makesit both a baseand as a base tll ii Give, by writing an equation, an example of an amine acting reactswith both amines and alcohols Ethanoyl chloride, CHTCOCI, i Give the full structural formula of the compound producedwhen ethanoyl chloride reactswith tll ethylamine, CrHrNHr. tU ii Name the type of the compound producedin c part i. of iii Stateone of ihe advantages reacting ethanoyl chloride with ethanol to make an esterrather than tU reacting ethanoic acid with ethanol. tll iv Write the full structural formula of the estermade in c part iii (Total 9 marks) 5ffanuary2002 Unit Test4 question modified]

PRACTICE

Compound X is a secondaryalcohol which has a molecular formula of CnH,oO. X exhibits optical isomerism. l2l a Draw the structural formulae of the two optical isomersof X. which would enableits preparationvia a reaction involving a reagentsand conditions b Suggest Grignard reagent.(You are not expectedto describehow you would preparea Grignard reagent) t3I c Compound Y is obtained by oxidising the secondaryalcohol X with potassiumdichromate(Vl) acidified with dilute sulphuric acid. t1l i Draw the structural formula of Y. t1I ii To which classof compoundsdoesY belong? the iii Describe testsyou would do on Y, and the resultsyou would expect,to show that your t4I classificationis correct. of iv Both X and Y give a yellow precipitatewhen treatedwith iodine in the presence sodium l2l hydroxide solution. Write the structuralformulaeof the organicproductsof this reaction. (Total 13 marks) 1CH lJwte2OO1 I questiotr modiftefl At about 1000oC,when aluminium chloridevapour is heatedwith solid aluminium, the following equilibrium is set up: AlCl.(g)+ 2Al(s)-'3AlCl(g)
a Give the expression for the equilibrium constant, Kr, for this reaction.

b At a particular temperature,a mixture of the above systemat equilibrium was found to contain 0.67 g the value of the of of AlCl, and 0.63 g of AlCl vapoursat an equilibrium pressure 2.0 atm. Calculate statingits units. Ko,at this temperature, t4l equilibrium constant, to the right as the temperatureis raised.Statewhat this suggests c The position of equilibrium moves tll about the enthalpy changefor the forward reaction. on d State,with reasoning,the effect of an increasein the pressure the systemon the value of the t3I equilibrium constant and on the position of the equilibrium. to how this reversiblereaction could be used in a process recyclealuminium by extracting it e Suggest r2l from impure aluminium. (Total LL marks) 3l 2001 CH3 question lJune S a i ii b i
ii c

IU

Write an equation for the reaction betweenmagnesiumoxide and dilute sulphuric acid, including r2l the statesymbols. r2l Describewhat you would seeduring this reaction.
Write an equation for the reaction between phosphorus(V) oxide and aqueous sodium hydroxide

solution.
With the aid of two equations, show how aluminium hydroxide exhibits amphoteric behaviour.

r2l
t3I

With reference to the reactions in a and b, describe the variation in the metallic character of the tzl elements across Period 3 of the Periodic Table (sodium to argon)

characterof Indium(III) oxide, InrOr. Indium is the fourth with reasoning,the acid-base Suggest, I2l element down Group 3 of the PeriodicTable. (Total L3 marks) 4l llune 2002 Unit Test4 question

EI

quANTrrATrvE EeurLrBR'A AND FUN.TT.NAL GRoup cHEMrsrRy "a*roDlcrry,

6a b i ii c

In the context of Brdnsted-Lowryacid-basebehaviour,explain the terms: acid weak acid dilute acid. Define pH

t3l tll

d
I ll

Calculate the concentration, in mol dm-t, of a solution of chloric(I) acid, HOCI, which has a pH of 4.23. Chloric acid is a weak acid with K^=3.72 x 10* mol dm-t. t4I Sketch, on a grid of pH (y-axis) versus volume of alkali added / cm' (x-axis), the titration curve for the titration of 25 cm' of the chloric(I) acid solution in b part ii with 50 cm' of a solution of sodium hydroxide of equal concentration. tsI

The concentration of hydrogen ions in a 0.100 mol dm-' solution of sulphuric acid is 0.105 mol
dm-t.

Write equationsto show the two successive ionisations of sulphuric acid, H2SO,, water. in tzl Suggest why the concentration of hydrogen ions is not 0.20 mol dm-'in 0.100 mol dm-' sulphuric
acid.

(Total L6 marks) 4 2l llanuary2001 CH2 question & lanuary 2002 CH2 question

t1I

t44"etal,r, 5 Tt'a*actn k(/

qMrtatttv MiLr ar4d, orgaJ,ur,Mtty

@ R edox l i bri a equi
t-fi
i rtl.--1 H

Inftoduction

t You must revise Topic 1.5 (lntroduction to oxidation and reduction). * The sign of E' indicates the direction of spontaneous reaction. t A useful mnemonic is OIL RIG. When a substance is Oxidised It Loses one or more electrons, and if Reduced It Gains one or more electrons. o A half equation always contains electrons. o Half equation data are usually given as reduction potentials, i.e. with the electrons on the left-hand side. o An oxidising agent becomes reduced when it reacts.

Thingsto learn and understand

The standard z(g) +_ atm hydrogen electrode This consistsof hydrogen gasat 1 atm pressure bubbling over a platinum electrode immersedin a 1 mol dm-' solution of H'ions, at a temperature of 25 "C. By definition the potential of a standardhydrogen electrodeis zero(see Figure5.1). Standard electrode potential, E'

H*(aq) 1 mol dm-3 Fig 5.1 A stondord hydrogen electrode

f This is the electricpotential (EMF)of a cell composed the standard of electrodeconnectedto a standardhydrogen electrode,measuredwhen the concentrations all the ions are 1 mol dm-3, of the temperature is 25 "C and any gases at 1 atm pressure. are O for a metal the standardelectrodepotential is when the metal is immersedin a solution of its ions at a concentrationof 1 mol dm-t. For the reaction: Zn'.(aq)+2e-- Zn(s) it is for a zinc electrodeimmersedin a 1 mol dm-' solution of Zn2' ions at 25 "C. o for a non-metal the standardelectrode potential is when the non(or metal at 1 atm pressure a solution of it at a concentrationof 1 mol dm*) is in contactwith a platinum electrode immersedin a

EI

t*oNsrrroN

M E T A L = , e u A N T r r A T r v E K r N E T r c s A N D A , , p ' - tE D . R G A N t c c H E MI s r R y

solution of the non-metal's ions at a concentration of 1 mol dm-' at 25 "C. For the reaction: 'lrcl,(g)+e +Cl-(aq) being bubbled over a it is for chlorine gas,at 1 atm pressure, platinum electrodedipping into a 1 mol dm-'solution of Cl- ions at 25 "C. o for a redox system of two ions of an element the standard electrodepotential is when a platinum electrodeis immersedin a solution containing all the ions in the half equation at a concentration of 1 mol dm-t. For the reaction: Fet.(aq)+e+Fe'.(aq) it is for a platinum electrodeimmersedin a solution which is 1 mol dm-t in both Fet*and Fe'*ions at 25 "C. O The equationsare alwaysgiven as reduction potentials, i.e. with the electronson the left. on O Comparing substances the left of two half equations,the one with the larger positive value of E'is the more powerful oxidising agent (it is the most easily reduced). on o Comparing substances the right of two half equations,the one with the smaller positive (or more negative) value of E'is the more powerful reducing agent. Calculation of -8..".,"" (E""o)

'lr}l,+ e-+ Cl- = +1.36 V E+ 'lr}f,+ e-+ Bi E+= + 1.07 V is > As+1.36 +1.07, chlorinea agent stronger oxidising than bromine.

=. + V Sno* 2e- Sn'-E* = +0.15 F e t * + e - + F e f* = + 0 . 7 7 V ' < As+0.15 +0.77, ions a Sn" are ions. reducing thanFe'better agent

The value can be deducedin one of three ways: L From a cell diagram:
E "tt = Eright-hand electrode Et"rt-n"na electrode

works out to be a negativevalue, |ou have written the cell If E""u diagram backwards,and so the reaction will go right to left. 2 From an overall equation: write both half reactionsas reduction potentials, i.e. with electronson the left. E,"".tio. calculatedas: is
= E,"u.tio, (E of half equation of the reactant being reduced) - (E of half equation of reactant being oxidised.

Thus for the reaction: Zn(s)+ Cu'*(aq)+Znz*(aq)+ Cu(s) The half equationsare: + Cu2.(aq) 2e--- Cu(s) Zn'.(aq) + 2e-=. Zn(s) E' = +0.34 V E' = -0.76 V In the reaction the Cu2*ions are being reduced(electrongain), and the zinc atoms are being oxidised (electronloss): = Et,""*.n +0'34 - (-O'76)= +1'10 V

3 From half equations: To do this one of the half equationshas to be reversed(seeWorked altersthe sign of its Eo. examplebelow). This process

.:r,i"{FF.;

REDox EeurLrBRrA

ri;. E rag'

oxiloLph, Work^eoL
is When redox equation half a its reversed, signmust changed. be Thenumber electrons theleftof on must hand of onehalf equation side the equal number theright-hand on half of side theother equation. is When redox equation half a is multiplied, E+value not its altered. that Always ensure thereactants in thatarespecifiedthequestion (here areiron(ll) they and ions) manganate(Vll) are0nthelefthand ofthefinal side overall equation. and of equation thevalue E*,,.o.n the the data Use following to deduce overall potassium and manganate(Vll)iron(ll) ions. acidified forthereaction between -V + + + i MnOi(aq) 8H-(aq)5e- Mn"(aq) 4H,0(aq) Es = +1.52 V f = +0.77 ii Fe&(aq)e-+ Fe'-(aq) +

Answer. (i): (ii) add it by and Reverse equation multiply 5.Then ittoequation V) V + 5Fe'-(aq) f =-(+0.77 = -0.77 + 5e5Fe'-(aq)
.52V + + 5e+ Mn0i(aq)8H-(aq) + Mn"(aq)4H,0(l) E+= +1 -- Mn"(aq)4H,O(l) + Sre'-(aqi + (aq) + 5Fe'-(aq) MnO, + AH;1aq; = V f,*t, = 4J7 + 1'52 +0'75 Stoichiometry of an overall equation

The total increasein oxidation number of one element must equal the total decreasein another.

the Inthereaction above, oxidation decreases Spontaneous change number themanganese of by5 from+7lo +2,andastheiron O Electrode potential data can be used to predict the feasibility of a must 5 be increases1,there by MnOo- in the ion iron(ll) to each ions chemical reaction. A reaction is feasible (thermodynamically unstable) if overall equation. E.",,is positive.
o However the rate of the reaction may be so slow that the reaction is not observed (kinetically stable). Non-stondord cells O Non-standard conditions may result in a reaction taking place even if the standard electrode potential is negative. I The reaction: ZCu'.(aq) + 4l-(aq) + 2CuI(s) + I,(aq) should not work becauseE' (assuming all speciesare soluble) = -9.39 y. However copper(I) iodide is precipitated and this makes [Cu'(aq)] very much less than 1 mol dm-'. The equilibrium is driven to the right by becomes positive and the the removal of Cu. (aq) ions, so that E,"u.tio. place. reaction takes

Potassium manganate(Vll) reducing agents

titrations

- estimation

of

o Acidified potassium manganate(Vll) will quantitatively oxidise many reducing agents. r The procedure is to pipette a known volume of the reducing agent into a conical flask and add an excessof dilute sulphuric acid. O The potassium manganate(Vlf solution of known concentration is put in the burette and run in until there is a faint pink colour. f This shows that there is a minute excessof the manganate(Vll) ions. o If the stoichiometry of the reaction is known, the concentration of the reducing agent can be calculated. No indicator is needed as the manganate(vll) ions are very intensely coloured.

TRANSITTON

METALS,

QUANTTTATTVE KTNETICS AND

APPLTED ORGANIC

CHEMISTRY

Work^ei' exa*np-lo
The ratio iron(ll) to of ions manganate(Vll)in theequation is 5:1andsothenumber moles of is of Fe'- 5 times number the of moles manganate(Vl of l).

was and against sulphate acidified, titrated 25.0 cm'ofa solutioniron(ll) of cm3 required mol manganate(Vll) solution.23.4were 0.0222 dm-'potassium pink the ofthe sulphate to give faint colour. Calculateconcentration iron(ll) a solution. for is: Answer: equation thereaction The - Mn'*(aq) + 4H,0(l)+ SFe3.(aq) MnOi(aq) + 8H.(aq) + SFe'.(aq) = 5.195 =0.0222x23.411000 x 1Q mol Amount manganate(Vll) of = = 5.195 10*x 5/_t 2.597 10-' x x mol Amount ironlill of suldnaie _? = =2.597 10 + 0.02500.104 dm x mol sulphate Concentration of iron(ll)
Iodine/thiosulphate agents titrations - estimation of oxidising

is o The procedure to add a 25.0 cm' sampleof an oxidising agentto potassiumiodide solution (often in the presence dilute of excess sulphuricacid). iodine, which can then be titrated against The oxidising agentliberates standardsodium thiosulphatesolution. When the iodine has fadedto a pale strawcolour, starchindicator is added,and the addition of sodium thiosulphate continueduntil the blue colour disappears. with thiosulphateions accordingto the equation: r Iodine reacts -' I' + 2S.O,1- 2I- + S*On'-

Work^ei, oxil44f-lt,
peroxide, was H,0,, added anexcess to 25.0 of cm'of solutionhydrogen a of potassium solution, theliberated required cm' iodine 23.8 iodide and acidified the mol thiosulphate solution. Calculateconcentration of of0.106 dm-'sodium peroxide thehydrogen solution. peroxide for ions is: Answen equation theoxidation The ofiodide byhydrogen Hr0r+2H.+21--lr+2Hr0 = 0.106 x Amountsodium thiosulphate x 23.8/1000 =2.523 10-'mol of = 1.261 10-' produced = 2.523 10-' 112 x x x mol Amount iodine of = 1.261 10-3 = peroxide 1.261 10-3x x 1/1 x mol Amount hydrogen of = 1.261 10-3 0.0250 = 0.0505 dm-3 + x mol of H,0, Concentration Disproportionation
A disproportionation reaction can be predicted by using electrode potentials. Use the data to work out E.",,for the proposed disproportionation reaction. If it is positive, the reaction will occur.

The ofiodine thiosulphate ratio to ions 1:2, the is so moles iodine of moles are'lrthe ofthiosulphate.

Reoox EeurLrBRrA

ttWrkpj, oxiloLPb
to and inaqueous solutioncopper ions Will copper(l) disproportionate ions? copper(ll) V + e-+ Cu-(aq) Cu(s) Es= +0.52 V + eCu'-(aq) + Cu'(aq)Eo= +0.15 This the and it Reverse second the equation add tothefirst. gives Answen equation: = V + Cu*(aq)Cu(s) E*o,, +0.52 (+0.15)+0.37 + 20u-(aq) ions copper(l) is and the F,,,, Because is positive, reactionfeasible, soaqueous willdisproportionate.
Corrosion (rusting)

oz(g)

This is an electrolytic process.When iron is stressedor pitted, some areas become anodic and some cathodic. In the presence of water and oxygen the following reactions take place (seeFigure 5.2). a At the anodic areasiron atoms become oxidised and lose 2 electrons: Fe(s) -* Fe'*(aq) + 2eo The electrons travel through the metal and reduce oxygen : 'lrOr(aq) + 2e- + HrO --' 2OH-(ag) o The Fe'. and the OH- ions meet and iron(Il) hydroxide is precipitated: Fe'.(aq) + 2OH-(a9) - Fe(OH)'(s)

Fig 5.2 Rusting steel a Stainless is ironcontaining proportionchromium, which high of forms protective of Cr,0, layer a the over whole surface themetal. of lf thesurface scratched, is a new protective of Cr,O, formed. layer is

I Finally oxygen oxidises the iron(Il) hydroxide to iron(lll) oxide (rust): + 2Fe(OH)r1s; +'/,O,(aq) - Fe,O.(s) 2H,O(l) Prevention of corroslon This can be done by: O placing a physical barrier between the steel and the environment. Such barriers are paint, tin or chromium plating. o adding a sacrificial metal. This can be done by coating with zinc (galvanising), or by attaching blocks of magnesium at intervals.

Storage

cells

Thesestore electricalenergyas chemical energy.The reactionsmust be fully reversibleand the chemicalsproduced in the redox reactionsmust be insoluble. The leod ocid bottery When electricity is drawn from the cell (dischargitg), the following reactionstake place. At the anode (oxidation) which is negative: 'PbSO,(s) + 2e- Eu = +0.36V Pb(s)+ SO,'-(aq) for the Thereactions charging cell place take aretheopposite, only and if a potential V is applied, >2.05 with theanode to being connectedthe terminal thecharging negative of s0urce. At the cathode (reduction) which is positive: + + PbO,(s) +2e- + SO,z-(aq) 4H.(aQ) PbSO.(s) 2H,O(t) V Eu= +1.69
The overall discharging reaction is: Pb(s) + PbO,(s) +ZSOn'-(aq)+ 4H.(a9) -ZPbSOn(s) + 2H,O(l) E' = +1.69 + (+0.36) = +2.05 V

l.

92

Ei

t*oNsrrroN

METAL', quANTrrATrvE

KTNETIcs AND AppLtED oRGANtc cHEMISTR'

o .rH I -; Checklist .,-H

(H

Beforeattemptingthe questionson this topic, checkthat you can: iJ Define standardelectrode potential. -J Describethe construction of a standardhydrogen electrode. iJ Write half equationsand usethem to deduceoverallequations. ,J Predictthe feasibilityof redox and disproportionationreactions. J Deduceoxidation numbersand usethem to balanceredox equations. rJ Recallthe principlesof manganate(Vll) and thiosulphatetitrations. ii Recallthe corrosionof iron and its prevention. 'J Understandthe chemistry of the tead/acidbattery.

and your knowledge understanding Testing

For the following set of questions, cover the margin before you answer, then check to see if you are correct. I Write the equation representing the reaction that takes place in a standard hydrogen electrode. f What are the conditions, other than temperature, for this electrode? * What are the oxidation numbers of manganese in MnOn- and in Mn'.? and in SOn'-? What are the oxidation numbers of sulphur in SO-,2.r, What is the ratio of SOr'- to MnOn- in the reaction between them? O Why is it not necessaryto have an indicator present in potassium manganate (VII) titrations? L a Write ionic half equations for the reduction of: E' = +1.33 V i CrrOrt to Crt* in acidic solution Eu = +0.15 V ii Snn*to Snr* E'= +1.19 V iii Iodate(V) ions, (IOr) to I, in acidic solution V E'= +0.54 iv I, to Ivalues and hence Write overall ionic equations, calculate E,"u.,,o, comment on the feasibility of the reactions between:

'/, H,(g) H-(aq) e-. + + are State symbols essential.

H,(g)at1 atmpressure, =1mol dm-' [H-(aq)]

+7 and+2 numbers of 5:2Sothatoxidation by change 10 both

ions are the Because manganate(Vll) intensely coloured. to The answersthenumbered questionsonpages 136-137. are

potassium dichromate(Vl) and tin(Il) chloride in acid solution i potassium iodate(V) and potassium iodide in acid solution. ii 2 1.32 g of mild steel filings was reacted with excessdilute sulphuric acid, and the resulting solution made up to a volume of 25O cm'. 25.0 cm' samples of this were titrated against 0.0200 mol dm-' potassium manganate(Vll) solution. The mean titre was 23.5 cm'. Calculate the percentage of iron in the steel. 3 Write the half equations for the redox reactions involved in the corrosion of iron.

T n a r u s r r r o N M E T A Lc H E M r s r R Y

ITf;t,ir @ Transition i ;;';rnistrY

Introduction
'..J You should know the colour of the aqua complex ions and of the hydroxides of the d block elements scandium to zinc. iJ you must be able to link the reactions in this topic to the theory of redox equilibria, Topic 5.1.
,tH g-ro
H

, &-- Things to learn

which the highest occupied energy " d block elements are those in levelisadorbital. element c A transition partly filled d shell. *' Electron structure is one that has at least one of its ions with a

is nor Neither scandium zinc a they metal transition although arein have their because ions thed block, 4so structure 3do, theelectronic [Ar] 4so and[Ar],3d'0, respectively.

of the atoms

of Note thenumber d electrons that that left except Cr increases to right, 4s' structures, and have electron Cu is have the whereas others 4s'.This is when stabilitygained the because is full d shell half orfull.

3d 4s

Sc Ti 1 2 2

V 3 2

Cr Mn J 5 1 2

Fe

6 2

Co 7

Ni

8 2

Cu 10
I

Zn 10 2

of the ions. The element first loses its 4s Electron structure electrons when forming an ion. Thus the electron structures of iron and its ions are: Fe Fe'* Fet* [Ar], 3d6, 4s2 [Ar], 3d6, 4so [Ar], 3ds, 4sn

Things to understand
Properties of transition metals Complex ion formotion o Bonding in complex ions. The simplestview is that the ligands form dative covalent bonds by donating a lone pair of electronsinto empty orbitalsof the transition metal ion. Thesecould be empty 3d, 4s, 4p or in of 4d orbitalsin the ion (e.g.seethe arrangement electrons boxesin Figure5.3). 3d
| | Fig 5.3 Electronarrongement in the hexo-aquoiron(ll)ion | | t l /

4s

4p

\E
\

Fl--T'f
,rrurro electrons: ,i* puir,/

Fe2* electron

TRANSTTTON

METALS,

QUANTTTATTVE KTNET|CS AND

APPLTED ORGANTC CHEMISTRY

Typical ligands are:

neutral molecules: HrO (aqua), NH. (ammine) anions: F- (fluoro), Cf (chloro), (CN)- (cyano). o Shapesof complex ions (seepages 14-15). If the complex ion has 6 pairs of electrons donated by ligands, the complex will be octahedral. This is so that the electron pairs in the ligands will be as far apart from each other as possible. Coloured complex ions a If the ion has partially filled d orbitals, it will be coloured. Sc'* and Ti'* have d0 structures, and Cu. and Zn'* have dto and so are not coloured. o d orbitals point in different directions in space, and so interact to different extents with the electrons in the ligands.

isturquoise blue, [Cu(H,O)r]'. isdeep and [Cu(NH.)*(H,0),1'. blue, isyellow. [CuCl.]'-

O This causes a splitting of the d orbitals into two of higher energy and three of lower energy. I When white light is shone into the substance, a d electron is moved from the lower energy to the higher energy level. o The frequency of the light that causesthis iump is in the visible range, so that colour at this frequency is removed from the white light. t The colour depends on the size of the energy gap which varies with the metal ion and with the type of ligand. Vorioble oxidotion stote

4+ Hydrated cations charge or of the more notexist do because sum istoo energies ofalltheionisation large becompensated the to forby hydration energy. forms and and Copper Cu. Cu'*, Cr'.. chromium and Cf.

o Successiveionisation energies increase steadily until all the 4s and the 3d electrons have been removed, after which there is a large jump in the value. o Formation of cations. The increase between successiveionisation energies is compensated for by a similar increase in hydration energies. Thus cations in different oxidation states are energetically favourable for all transition metals. O Formation of covalent bonds. Transition metals can make available a variable number of d electrons for covalent bonding. The energy required for the promotion of an electron from a 3d to a higher energy orbital is compensated for by the bond energy released. o Formation of oxoions. In ions such as MnOi, VOr-, VOi and VO2-,the oxygen is covalently bonded to the transition metal which uses a varying number of d electrons. O Manganese exists: in in in in the the the the +2 +4 +6 +7 state as Mnt* state as MnO, state as MnOn'state as MnOn-.

Catalytic octlvity Tlansition metals and their compounds are often good catalysts. O Vanadium(V) oxide is used in the oxidation of SO, to SO, in the contact process for the manufacture of sulphuric acid. o Iron is used in the Haber process for the manufacture of ammonia. O Nickel is used in the addition of hydrogen to alkenes (hardening of vegetable oils).

TneNsrTroN

METAL cHEMIsTRY

Reactions

of transition

metal

compounds

Reoctionswith sodium hydroxide ond ommonio solutions The table givesa summary of thesereactions.
lon
a

Colour Green Palepink Palegreen Brown/yellow Green Paleblue None

Addition of NaOH(aq)

NaOH(aq) Excess Green solution Ppt remains Ppt remains Ppt remains Ppt remains Ppt remains solution Colourless

Addition of NH.(aq)

ExcessNHr(aq)

Cr'* Mn'* Fe'* Fe'* Ni'* Cu'* Zn'*

Green ppt Sandypptb Dirty green ppt' Foxy red ppt Green ppt Blue pptd White ppt

Greenppt Sandyppto Dirty green ppt' Foxy red ppt Greenppt Paleblue ppt White ppt

Ppt remains Ppt remains Ppt remains Ppt remains Blue soln Deepblue soln soln Colourless

" The correct formula for the ions should be the hexa-aquaion, except for zinc, which forms a tetraqua ion. o The precipitate of Mn(OH), goesbrown as it is oxidised by air. ' The precipitate of Fe(OH),goesbrown on the surfaceas it is oxidised by the oxvgen in the air. o The precipitate of Cu(OH). goesblack as it loseswater to form CuO. Deprotonotion r The aqua ions in solution are partially deprotonated by water. The greater the surface charge density of the ion the greater the extent of this reaction, e.g. hexa-aqua iron(III) ions: [Fe(H,O)u]'.(aq) + H,O + [Fe(H,O),(OH)]'.(aq) + H.O.(aq) This means that solutions of iron(III) ions are acidic (pH < 7).

hydroxides'redissolve' O When an alkali such as sodium hydroxide is added, the equilibrium is Amphoteric alkali, e.g. in excess strong driven to the right, the ion is considerably deprotonated to form a + Cr(0H),(s)30H-(aq) [Cr(OH)u]'neutral molecule which loses water to form a precipitate of the metal (aq) hydroxide: -+ andZn(0H),(s)20H-(aq) lFe(H,O),1'.(aq)+ 3OH-(aq) - Fe(OH),(s)+ 6H,O [Zn(0H),]"(aq).
If aqueous ammonia is added, the same precipitate is formed: +3NH,(aq) * Fe(OH).(s)+ 3NHn.(aq) + 3H,O [Fe(H,O)u]'.(aq) Ligond exchonge

for: is used a test as This reaction with ammonia a nickel(ll): aqueous ions give nickel(ll) first a green precipitate then which forms a with blue solution excess ammonia. ions a blue b copper(ll) give pale precipitate forms deep which a with blue solution excess and ammonia precipitate ions a c zinc give white solution which forms colourless a with excess ammonia.

O When aqueous ammonia is added to aqua complexes of d block elements such as those of nickel, copper and zinc, ligand exchange takes place and a solution of the ammine complex is formed. reaction: First the hydroxide is precipitated in a deprotonation -Cu(OH),(s) + 2NH..(aq) + 4H,O [Cu(H,O)J'.(aq) + 2NH,(a9) The hydroxide then ligand exchanges to form an ammine complex with excessammonia: Cu(OH),(s) + 4NH,(aq) +ZH,O -- [Cu(NH.)*(H,O)J'. + 2OH-(aq) The final result is that the NH, ligand has taken the place of four HrO ligands. O Addition of cyanide ions to iron(Il) ions produces a solution of hexacyanoferrate (I I) : [Fe(H,O).]'.(aq)+ 6CN-(ag) - [Fe(CN)']*(aq) + 6H,O o A test for iron(III) ions is to add a solution of potassium thiocyanate,KCNS. Iron(II! ions give a blood red solution: + [Fe(H,O),]'.(aq) + SCN-(ag)t tFe(SCNXH,O).1'.(aq) H,O

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M E T A L S ,e u A N T r r A T r v E K r N E T r c s A N D A p p ' r E D . R G A N r c c H E M r s r R y Vanadium o Vanadium chemistry compounds exist in four oxidation states:

+5: VOr-(aq) which is colourless, but in acid solution reacts to form a yellow solution of VOr.(aq) ions: VO;+2H* + VOr*+HrO +4: VO'.(aq), which is blue. +3: V'.(aq) which is green and is mildly reducing. +2: V'.(aq) which is lavender and is strongly reducing. o Reduction by zinc.lf zinc and dilute hydrochloric acid are added to a solution of sodium vanadate, NaVO' the colour changes in distinct sequence,as it is steadily reduced from the +5 to the +2 state: start: then: then: then: finally: yellow caused by VO'.(aq)ions (+5 state) green caused by a mixture of yellow VOr.(aq) and blue VO'z.(aq) blue caused by VO'z.(aq)ions (+4 state) green caused by V't(aq) ions (+3 state) lavender caused by V'.(aq) ions (+2 state)

t Redox reactions Vanadium compounds can be oxidised or reduced by suitable reagents. For a redox reaction to work, the E'.",, value must be positive. A list of Evalues for the half reactions of vanadium in its various oxidation states and for some oxidising and reducing agents is given below. These values show, for instance, that vanadium(V) will be reduced only to vanadium (IV) by Fe'* ions, whereas Snt* ions will reduce it first to vanadium (lV) and then to vanadium (lll).

+5 V O r * + 2 H *+ e + V O ' . + H r O Fe'* +e --Fe'* 'lrclr+e- +clvo'* +2H*+e-+vt*+Hro Snn* +2e- +Sn2*

Fet* +e +Fet*

VO,*

+5

E = + 1 . 0V Y E' = +O.77 E'= +1.36 V Eu = +0.34V V E'= +0.15 Eu = +O.77 Y E' = -0.26 V E' = -0.76V Eu = 0.00 V

A
Fet*

CT, VO,' +4

+4 Sn'*

AFe'*
V,* +3

V
+3 ' I znlH. I

+V'* Vt* +e Z r' t' * + 2 e - + Z n H* + e- +'lrH,

4. H'
v'*
+2

+2 8t..,, for the reduction of: Y VOr*by Fe'. = +1.0- (+0.77) - +O.23 = VO'* by Sn'*= +0.34- (+0.15) +0.19V v'. by Zn - -0.26 - (4.7 6) = +0.50V
-H '?\i l//H H

Et

V'* by H.

for the oxidation of: ",, -

= o.o (-0.26)

- +0.26Y = +0.43V = +0.36V

V3*by Fe3* = +O.77- (+0.3a) VO'* by Cl, = +1.36 - (+1.0)

t Checklist

Beforeattempting the questionson this topic, checkthat you: E Can define d block and transition elements. [,] Cun write the electronicstructureof the d block elementsand their ions.

T R r N s r r r o N M E T A Lc H E M r s r R Y rJ Can recall the characteristic properties of the transition elements. J Understand the nature of the bonding in complex ions, the shape of the ions and their colour. lJ Can recall the action of aqueous sodium hydroxide and ammonia on solutions of their aqua ions. J Understand deprotonation and ligand exchange reactions. rJ Can recall the oxidation states of vanadium, and the colours of its ions. J Know reactions to interconvert the oxidation states of vanadium. Can recall examples of vanadium, iron and nickel and their compounds as catalysts.
IH

and ," .Testingyour knowledge understanding o (

-

v is [Ar], 4s'. v'- is 1Ar1, 3d', 3d' turquoise-blue, ICu(H,0),]'H,),(H,0),1'. blue dark [Cu(N (ligand ion)and to Dative covalent (within water the molecule) covalent

For the following set of questions, cover the margin of the page before vou answer, then check to see if you are correct. r' Write down the electronic structure of a vanadium atom and a \''- ion. State the formula and colour of the aqua complex of copper(ll). * State the formula and colour of the ammine complex of copper(ll). o Name the types of bonding in the aqua complex of iron(Il). o What is the shape of the iron(Il) aqua complex ion? o State the type of reaction that occurs when aqueous sodium hydroxide is added to a solution of the aqua complex of copper(Il).

Ligand exchange yellow. V0'-,blug. +5,V0r*, +4, green. +2,\f*,lavgndgr. +3,V'*,

o State the type of reaction that occurs when excess aqueous ammonia is added to a solution of the aqua complex of copper(Il). o What are the oxidation states of vanadium? Give the formula and the colour of the cation for each oxidation state. o Give an example of the use of iron as an industrial catalyst. o Give an industrial use of a vanadium compound as a catalyst.

process in to lron theHaber manufacture ammonia Vanadium(V) intheContact oxide process manufacture to sulphuric acid

The answersthenumbered 1 to questionsonpages are 137-138. 2

Explain why the [Cu(H,O)u)'. ion is coloured. Give the equations for the reactions caused by small additions of sodium hydroxide solution, followed by excessto: a a solution of the b a solution of the c a solution of the Give the equations ammonia solution, aqua complex of chromium(Ill) aqua complex of iron(Il) aqua complex of zinc(Il). for the reactions caused by small additions of followed by excessto:

a a solution of the aqua complex of iron(III) b a solution of the aqua complex of copper(Il). Write the half equations for the following changes in oxidation state: a vanadium(V) to vanadium(Il) b vanadium(V) to vanadium (IV) c vanadium(Ill) to vanadium(IV)

lrl

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METALS, euANTrTATrvE KrNETrcs AND Appl-lED oRGANlc cHEMISTRY

lll chemistry @ Organic

ffiI lry Thingsto learnand understand
The structure of benzene and reactions of aromatic compounds
o The benzenering doesnot consist of alternatedouble and single bonds. o All the bond lengths are the sameand the molecule is planar. t There is an overlap of p orbitals aboveand below the plane of the molecule, forming a continuous or delocalised n system. o This givesstability to the benzenestructurewhich is why it undergoes substitution rather than addition reactions. either by: o Benzenecan be represented

Reactions

of benzene

Benzenereactsmainly by electrophilic substitution: O Nitration. Benzenereactswith a mixture of concentratednitric and sulphuric acidsto form nitrobenzene: + CuHu HNO, - CuHrNO.,+HrO of Bromination. Benzenereactswith liquid bromine in the presence a I anhydrous iron(III) bromide (made in situ from iron and catalystof liquid bromine) or of anhydrous aluminium bromide: + CuHu Brr(l)'CuHrBr + HBr will react with halogenoalkanes or o Friedel-Crafts reaction. Benzene of with acid chlorides in the presence a catalystof anhydrous aluminium chloride: + + CuHu CrHrCl + CuHrCrH, HCI ethylbenzene + + CuHu CHTCOCI C'HTCOCH, HCI phenylethanone (a ketone) Reactions chain of compounds with a carbon-containing side

and ethyl benzene o Compounds such as methyl benzeneC6H'CH3 C6HsC2Hs be oxidised, and the product will contain a COO-group can of on the benzenering, regardless the number of carbon atoms in the chain. On acidification benzoic acid is produced: + + CuHsCzHs6[0] + OH-- C'HTCOO- CO, + 3HrO conditions: heat under reflux with potassiummanganate(Vll)and aqueoussodium hydroxide.

oncerurc cHEMrsrRY lll

Phenol
OH

is Phenola weaker than acid carbonic and it willnot acid, so hydrogen liberate from C0, sodium carbonate, carboxylic unlike acids which will.

Although it forms some hydrogen bonds with water, it is only partially soluble and forms two layerswhen addedto water at room temperature. o + alkali. Phenol is a weak acid and it forms a colourlesssolution with aqueoussodium hydroxide: + + C6HsOH(l) OH-(a9)- CuH'O-(aq) H,O(l) of O + bromine water. The presence the OH group makessubstitution No into the benzenering much easier. catalystis required:
OH

A
|!|J

nr--r\',,nr
+ (aq)+3Brr(aq) V
Br

OH

(s)+3HBr(aq)

observation: when brown bromine water is added, a white precipitate is rapidly formed. I + acid chlorides. Phenol reacts as an alcohol, and an ester is formed: C6H'OH + CHTCOCI' CHTCOOC'H, + HCI

Phenylamine Phenylaminehas a NH, group attachedto the benzenering. Preporotion Nitrobenzeneis reducedby tin and concentratedhydrochloric acid when heatedunder reflux. Then sodium hydroxide is addedto liberate the phenylamine, which is removed by steamdistillation. Reoctions O + acid + C6H'NH2 H.(aq) - CuHTNH'.(aq) o + nitrous acid +2H* +NOr--CuHrNr.+ZH.O C6H'NH2 conditions: add dilute hydrochloric acid to phenylamine and cool the 'C. Sodium nitrite solution is then added,keepingthe solution to 5 temperafure closeto 5 "C and above0'C.

ions The solution diazonium can of react phenol. with A yellow precipitate compound is ofdiazo obtained.

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METAL', euANTrrATrvE KrNETrcs AND App'tED .RGANIc cHEMtsrRy

Mechanisms the A curly arrow (fJ ) represents movement of a pair of electrons,either the from a bond or from a lone pair. A half-headedarrow (f\) represents movement of a single electron.

Ensure thecurly that arrow starts with or froma bond anatom a lone pair electrons. of points Ensure thearrow that forming either a towards atom an negative or a new ion covalent bond.

Homolytic,

free radical substitution

on Reoction befrnreen olkone ond chlorlne or bromine O An exampleis shown of reaction betweenmethane and chlorine. in O There are three stages this type of reaction: homolytic fission of chlorine: 1 Initiation: light energycauses 2g,1' Clr2 Propagation: each propagation step involves a radical reacting with a molecule to produce a new radical: CHn+ Cl'- CHr' + HCl CHr' + Cl, - CH.CI + Cl' etc. then 3 Termirtation: involves two radicalsioining with no radicalsbeing produced,.S. CHr'+CHr'tCrHu free radical addition

Homolytic,

way ethene Another of polymerising titanium tetrachloride isbyusing triethyl, this and aluminium but is mechanism. not homolytic a

Polymertsotlon of ethene The conditions are a very high pressure(1000 atm) and a trace of oxygen. The conditions produce radicals,R', which attack an ethene molecule: R' + H,C=CH,- R-CH2-CH'' then Heterolytic,
R-CHr-CH 2' * H2C=CH, -- R-CH'-CHr-CH,-CHr' etc

electrophilic

addition

Reoctlonsof olkenes wlth hologens or hydrogen holldes The reaction takes place in two steps: 1 The electrophileacceptsthe n electronsto form a new bond with one of the carbon atoms and at the sametime the Br-Br bond breaks. 2 The intermediate carbocationthen bonds with a Bf ion.

With addition a hydrogen the of halide anunsymmetrical to alkene, thehydrogen adds the atom to has which carbon already more to bonded hydrogen directly atoms it. This because secondary is the carbocation, e.o. -

Br- Br \ H,C CH,

t t -C-C-C- l

lT'fl]
L"r. - C*HrJ electrophilic substitution

Br
H2C-

Br
CHz

l @ l than is more stable a primary one.

t t l e,o. t t O - -C-C-O l

Heterolytic,

Nltratlon of benzene 1 Sulphuric acid is a strongeracid than nitric and so protonatesit: + HrSOn HNO, - HrNOr'+ HSO; then the cation loseswater:
H2NO3*tHrO+NOr*

o R c a r u t c c H E Mr s r n v i l l

2 3 Similar mechanisms for occur bromination, thecatalyst where reacts bromine provide with to the electrophile andin theFriedelBr-, Crafts reaction where catalyst the reacts thehalogen with compound to provide electrophiles as such CH3C'0 C,Hu-. or

The Nor. ion is the electrophile and attacks the benzene ring. The HSon- ion pulls off a H. and reforms H2son (the catalystf

The lossof H. resultsin the reforming of the benzene ring and the gain in stability associated with the ring. Heterolytic, nucleophilic substitution

Reoction between hologenoolkonr ond hydroxide or cyonide ions ' Thereare two mechanisms depending the type of halogenoalkane. on with primary (1")halogenoalkanes, S*2 mechanism dominant. an is ' Reaction proceeds a transition statewhen the lone pair of electrons via on the nucleophileattacksthe halogenoalkane. Inthetransition thenew0-C state, bond forms theC-Brbond as breaks. transition hasa The state charge -1. of

-l9H, 'Q ------+ l l - .ur l Ho:' Ho-c. .:-g s' lno- I l---------+ t{' t

,cH, :Bi

H l

| /\ t*u.rr?rro., | tu*'

l "

o with tertiary (3") halogenoalkanes gl the This happensin two steps: 1

mechanism is dominant.

The halogenoalkane ionisesin the relativelyslow,and hencerate determining step,to form an intermediate carbocation.
CHt

Anyoptical activity maintained is in a Sr2reaction. lf themechanism is Sr1, reactant a which anoptical is isomer wilt produceracemic a mixture, the as carbocation beattacked can from either side.

I r-r cHr-C-Br
CH,

CH,

CHr-a"

I
+ :Br-

I
CHt

This then rapidly forms a bond with the nucleophile, oH-.

CH,

CH?-

C* t

tr\

CHt

OH-

I
CHg

CHe-C

I-OH

I
CHt

Heterolytic, The ionis a catalyst, the CNand conditions besuch there must that is a significant amount bothHCN of molecules CN- present, and ions i.e. a mixture HCN KCN. of and

nucleophilic

addition

Reaction between o corbonyl compound and hydrogen cyonide o Although the reaction is the addition of HCN, the first step is the nucleophilic attack by the cN- ion on the 6+ carbon atom in the carbonyl group.

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METAL=, euANTrrATrvE

KrNETrcs AND App'rED

.RGANIc

cHEMrsrRy

O The negatively charged oxygen in the anion then removes an H* from an HCN molecule. This produces another CN- ion, which reacts with another carbonyl group and so on.

aot
R-C

A -o t

*'/

-+

r-\ H \
cN-

I R_C_H I CN

u-cN
+

o-H
R-C-H

I I CN

+ CN-

o The conditions for this reaction are either HCN and a trace of baseor KCN and a small amount of dilute sulphuric acid. (Figure5.5) (Figure5.4) and mechanisms Reactions aromaticsubstances of are summarisedschematically.
conc HNO3 ----------+ conc H2SO4 C6H'NO2

OH-(aq)-CoHsg Phenol c6l{soH Brr(aq)-->

CuHrBr.OH --------------> cH3cooc6Fls

Brt Fe catalyst

CuHrBr

cH3cocl c2Hscl AlClrcatalyst

cH3cocl
AlCl3catalyst

c6Hscocl{3

Phenylamine [c6HsNH2 |

rf(aq) --------------> c6IlNHJ HNO2at 5oC

CoI{sNz-

Fig 5.4 Summary reactions oromaticsubstances of of

Substitution Freeradical: Nucleophilic: alkanes halogenoalkanes + + + Electrophilic: benzene + + + + Cb OH-(aq) CNHNq Brr(l) RCI RCOCI Electrophilic: alkenes + + ClrlBr, HCI/HBr/ HI Freeradical: Nucleophilic: Addition polymerisation of alkenes + carbonyl compounds HCN

Fig 5,5 Summory mechonisms of

ffiChecklist
Beforeattempting the questionson this topic, check that you: [J Understandthe structure of benzeneand why it reactsby substitution rather than by addition.

oRclrurc cHEMrsrRY lll

with nitric acid,bromine and U Can recallthe reactionsof benzene halogencompounds. r.J Can recallthe product of oxidising sidechains. U Can recall the reactionsof phenol with alkali, bromine and acid chlorides. i.l Can recall the preparation of phenylamine and its reaction with nitrous acid and the coupling of the product with phenol. iJ Understandthe mechanismsof free radical substitution and addition. tJ Understandthe mechanismsof electrophilic substitution and addition. if Understandthe mechanisms nucleophilic substitutionand addition. of
-H |I.;g'

"4.
a cuHuc00Nab CuHuOc c,Huc00cuHu

and your knowledge understanding Testing

For the following set of questions, cover the margin before you answer, then check to see if you are correct. * State the structural formulae of the organic product obtained by the reaction of: a propylbenzene with alkaline potassium manganate(Vll) b phenol with sodium hydroxide solution c phenol with propanoyl chloride.

go water would Thebrown bromine precipitate and white a colourless would form.
with reflux tinand Heat under hydrochloric cool acid, concentrated sodium then aqueous add and hydroxide.

o What would you observe if bromine water were added to aqueous phenol? O State the conditions for the conversion of nitrobenzene to phenylamine.

to The answersthenumbered questionsonpage 138. are

a b

Describe the mechanism for the reaction of bromine with benzene. Why does benzene undergo a substitution reaction with bromine rather than an addition reaction?

In the reaction between propanone and hydrogen cyanide no reaction occurs unless a small amount of a base such as sodium hydroxide is added. Explain these observations. When benzenediazonium chloride is prepared, the reaction is carried out at about 5 "C. a b Why are these conditions chosen? What is the formula of the product obtained by the reaction of the benzene diazonium chloride solution with phenol in alkaline solution?

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METAL', euANTrTATrvE KrNETrcs AND AppLIED .RGANrc cHEMIsrRy

ll kinetics Chemical
ffi b Introduction
You must also reviseTopic 2.3 in Chapter 2, page44 and especiallyhow the changesin the Maxwell-Boltzmann distribution of energywith increasein temperatureaffect the rate of reaction.

da
LN
The units k are: of zero-order reaction: I fora mol dm-'s-' reaction: s-' t fora first-order reaction: I fora second-order mol-t s' dmt
f

Thingsto learn
fne rate equation for the reaction:

xM + /N - products,is: - k tMlj [N]bwhere a and b areintegersand are Rateof reaction determined. experimentally i The rate constant, & is the constant of proportionality in the rate equation: I Its value dependson the activation energyof the reaction and the temperature. with a large activation energywill have small valuesof k. o Reactions E fne order with respect to one substance is the power to which is the concentration of that substance raisedin the rate equation. In the example abovethe partial order of the chemical M is a. E fne order of reaction is the sum of the partial orders.In the example above,the order of the reaction is a + b. f fne activation enert[y, Eo,is the total kinetic energy that the moleculesmust have on collision in order for them to be able to react.

reaction Thehalf-life a first-order of is constant.

E naff-life, tr,r, is the time taken for the concentration to fall from any value to half that value. selected

ffi iry

Things understand to
of rate equation from initial rates

Determination

Considerthe reaction: A+B+e+products The initial ratesof reaction with different concentrationsof A, B and C are found, and by taking the experimentstwo at a time, the order with respect can be found. to each substance Look for two experimentswhere the concentration of only one substance the varies.If doubling that concentration causes rate to double, the order is with respectto that substance 1.

C H E M T . A LK r N E T r c st l

Experiment 1 2 3 4

tAl

tBl
1 1 2 2

tcl
1 1 1 2

Relative rate

z
1 1

z
4 4

o From experimentsl- and 2: [A] doublesand rate doubles.Therefore order with respectto A = 1 o From experimentsL and 3: [B] doublesand rate x 4. Thereforeorder with respectto B = 2 o From experiments3 and 4: [C] doublesand rate unaltered.Therefore order with respectto C = 0 = and the reactionis 3rd order. I Rateof reactiorr k [A]' [B]' [C]0, Experimental techniques for following a reaction

graph, Note forthefirst-order that thehalf-life remains constant throughout reaction, the whereas for thesecond-order half-life the increasestheconcentration falls. as

100

* * *

Zeroorder Lstorder Znd order

and start the clock. At intervals 1 Titration method. Mix the chemicals withdraw a sample,add it to iced water to slow the reaction.Then in titrate one of the substances the reaction.This method can be usedif an acid, an alkali or iodine is a reactantor a product. 2 Colorimetricmethod. This can be usedwhen either a reactantor a product is coloured(iodine or potassiummanganate(Vll) examples). are The colorimeter must first be calibratedusing solutions of the coloured substance known concentrations.Then the reactantsare mixed and of the clock started.The intensity of the colour is measuredas a function is of time. The concentration of the coloured substance proportional to the amount of light absorbed. 3 Gasvolume method. If a gasis producedin the reaction, its volume can be measuredat intervals of time. The gascan be collectedin a horizontal gassyringe or by bubbling it into an inverted measuring cylinder filled with water.

Graphs of results
If the concentration of a reactant is plotted against time, three shapes of graph are likely depending on the order of the reaction.

E60
0,)

H 4 0
-l

20

Mechanisms A suggested mechanism must be consistentwith the order of reaction. The partial order of any species which occursin the mechanismafter the rate determining step will be zero.The rate-determiningstep is the slowest step,e.g. Nor(g) + Co(g) -' No(g) + Cor(g) has the rate expression: Rate=kD{O,l'[CO]" A suggested mechanism is: o Step1 (slow): NOr+ NO, -- NOr + NO o Step2 (fast): NOr+CO-NOr+CO, As the CO entersthe mechanismaftter the rate determining step,the mechanism is consistentwith the fact that the reaction is zero order with respectto CO.

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METALS, euANTrrATrvE

KrNETrcs AND AppLtED .RGANtc

cHEMIsrRy

Energy profile

diagrams

The first diagram is for a reaction that takes place in a single step, and the second diagram is for this reaction with a catalyst (seeFigure 5.6). :-------- Transition Intermediate
bo tr q.)

>. bo
rtl

Catalysed Fig 5.6 Energyprofile diagroms

An example of a reaction with a transition state is the S*2 reaction of bromoethane with hydroxide ions. An example of a catalysed reaction forming an intermediate is Fez*ions as a catalyst in: + SrOrz-(aq) 2l-(aq) - 2SO n'-(a9) + Ir(aq) In this mechanism the catalyst first reduces the SrO.'- ions: ZFe'.(aq) + SrOr'-(a9) - 2Fe'.(aq) + 2SO.,'-(aq) ions: then the Fe"*ions are reduced back to Fe2* 2Fe3.(aq) Zl-(aq)'- ZFe'*(aq)+ Ir(aq) +
H c , g

*4-

Checklist

Beforeattemptingthe questionson this topic, checkthat you: J Can define rate constant,order of reactionand half-life. iJ Can deducerate equationsfrom initial rate data. iJ U.tderstandthe concept of activation energy and its relation to the rate constant. E Understandthat information about mechanismscan be deducedfrom the partial ordersof the reactants. iJ Can recall the energyprofiles of reactionswith and without catalysts. ff Ca.r suggest suitablemethods for following reactions. f Can deducethe order of a reaction from concentration/time graphs.

c n e M r c A L K r N E T r c st l

your knowledge understanding and Testing

For the following set of questions, cover the margin before you answer, then check to see if you are correct. O The following results were obtained from a study of the reaction: NO,(g) + CO(g) -' NO(8) + CO,(g)

1 and a From experiments 2, order withrespect N0,= | to 1 and b From experiments 3, order withrespect C0 = 0 to is c 0rder reaction 2 + 0 = 2 of d Rate=k[N0,]'

Experiment

NO,l/mol dm-"

lCol/mol dm-'

Relative rate

1 2 3

o.o2
0.04

0.o2 0.o2
0.04

o.o2

1 4 1

a b c d

What is the order with respect to NOr? What is the order with respectto CO? What is the order of reaction? Statethe rate expression.

o Reaction A has a high value of E., and reaction B has a lower E. r'alue. Which reaction has the larger rate constant? a Which is the faster reaction? b o A reaction takes place in 3 steps. The E^lkI mol-' for each step are:

2 the E,, Step asit has largest value = 100to 6.25 4 half-livee, therefore = time 4x25= 100 minutes

step 1: 32,

step 2: 51,

step 3: 20

Which step determines the rate? O The decomposition of NrO, is first order. At 200 "C the reaction has a half-life of 25 minutes. Calculate how long it will take for the of concentration of NrO, to fall to 6.250/o its original value. L The rate of the second order reaction: 2HI(g) -- H,(g) + I,(8) is 2.0 x 10' mol dm-' s-' when [HI] = 0.050 mol dm-' at 785 K. Calculate the value of the rate constant, giving its units. 'C, the rate of the reaction: Describe how you would follow, at 60 + CH'OH(aq) - CH,COOCH.(|) + H,O(l). CH3COOH(aq) The decomposition of 3-oxobutanoic acid, CH3COCHTCOOH,was studied: CHTCOCHTCOOH- CH.COCH. + CO, The results, at 40'C, are tabulated below.

The to answers thenumbered questionsonpage are 138.

Time/min 0 26 52 78

[3-oxobutanoic acid]/mol dm-'

t.6 0.8 0.4

o.2

Deduce the order of the reaction.

T I

I
El t*oNsrrroN M E T A L ' , e u A N T r r A T r v E K r N E T r c s A N D A p p ' r E D . R G A N t c c H E Mt s r R y

lV chemistry Organic
Introduction
in on I Questions this topic will form part of the synopticassessment Unit Test5. I This Topic brings together all the organic chemistry that has been coveredin earliertopics,so you will need to reviseTopics2.2, 4.5 and 5.3.

Thingsto learn and understand

Organic analysis You should know the testsfor: s Alkenes Add bromine in hexane. Test: colourless. Observation:The brown bromine becomes o llalogenoalkanes Heat under reflux with sodium hydroxide solution, then Test: acidify with dilute nitric acid. Add silver nitrate solution. Observation: Chlorides give a white precipitatethat is soluble in dilute ammonia. Bromidesgive a creamprecipitatethat is insolublein in ammonia. dilute ammonia but dissolves concentrated give a yellow precipitatethat is insoluble in Iodides concentratedammonia. O OH group (in alcohols and acids) To the dry compound add phosphoruspentachloride. Test: Observation: Steamyfumes of hydrogen chloride produced. I Alcohols Test: Warm with dilute sulphuric acid and potassium dichromate(Vl)solution. Observation: Primary (1') and secondary (2')alcohols reducethe

;"""::? .m:r are i11i#1HT,::'{:il $::i,?i as,hey

not oxidised. To distinguish between 1oand 2o rcpeatthe experiment, but distil the product into ammoniacal silver nitrate solution: which give a silver 1' alcohols are oxidised to aldehydes, mirror. which do not react. 2'alcohols are oxidisedto ketones, I Carbonyl, C=O group (aldehydeor ketone) Add a solution of 2,4-dinitrophenylhydrazine. Test: Observation:A red or orangeprecipitateis seen.

oRclluc

cHEMrsrRY lv To distinguish between aldehydes and ketones: Warm with ammoniacal silver nitrate solution. Test: Observation: Aldehydes give a silver mirror, ketones have no reaction. O Iodoform Test: reaction Gentlv warm with a solution of sodium hydroxide and iodine. A pale yellow precipitate of CHI, Observation: This test works with carbonyl compounds containing the CH,C=O and alcohols containing the CH'CH(OH) groups. acids, COOH group I Carboxylic Add to a solution of sodium hydrogen carbonate. Test:

whichturn lime watermilky. Bubbles gas, of Observation: Interpretation of data

The must purified by solid be inorder a recrystallisation to have melting sharp accurate and temperature.

When identifying that species cause lines thespectrum, give in always a formula theionandits for structural + charge.

You should be able to deducestructuralformulaeof organicmolecules given data obtainedfrom: r Chemical methods Carry out testsas aboveto determine the functional groups in the Make a solid the melting point of the substance. molecule.Measure derivative (such as the 2,4-DNPderivative from carbonyl compounds), Checkthe melting its purify it, and measure melting temperature. temperaturevalueswith a data bank to identify the substance. o Mass spectra (seeFigure5.7) o Observethe fragmentsobtained and look for the value of the molecular ion (M)+, if any. probably had a o Seeif there is a peak at (M-15)+.If so the substance CH, group which is lost forming the (M-15)+ peak. probably had a CO group. I If there is a peak at (M-28)+,the substance Other fragmentswill help to identify the structure. 100 b 8 0
(tt

9 6 0

.E 40 &, 20
10 Fig 5.7 Massspectrum ethonol of
15

20

25 30 m/z

3 5 40

45

peaks given 0-HandN-H are The by to usually owing hydrogen broad bonding.

O Infrared spectra (seeFigure5.8) and o Theseare used to identify functional groups in the substance, also to comparethe spectrumof the unknown with a data bank of spectra('finger printing'). to O Peaks look for are at: given bY C=O 1650to 1750 cm-' given by O-H 2500 to 3500 cm-' given by N-H 3300 to 3500 cm-' given by C-O 1000 to 1300 cm-'

El

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METAL', euANTrrATrvE

KrNETrcs AND AppLrED .RGANrc

cHEMrsrRy

100

s
O U

g s o
(a (t) Lr t-

Fig 5.8 lnfrored spectrum ethonol of

1000 2000 1s00 Wavenumbercm-r /

O NMR spectra o The phenomenon of nuclear magnetic resonance occurs when nuclei 'H such as are placed in a strong magnetic field and then absorb applied radio frequency radiation. t The nuclei of hydrogen atoms in different chemical environments within a molecule will show up separately in a NMR spectrum. The values of their chemical shift, 6, are different. o The hydrogen nuclei in a CHr group will have a different chemical shift from those in a CH, or in an OH group. The value of d of the peak due to the hydrogen in OH (or in NH) depends upon the solvent. * In low resolution NMR, each group will show as a single peak, and the area under the peak is proportional to the number of hydrogen atoms in the same environment. Thus ethanol, CH.CHTOH will have three peaks of relative intensities 3:2:1 and methyl propane CH.CH(CH3)CH3,will have two peaks with relative intensities of 9:1. NMR spin coupling is observed. This is caused O In high resolution by the interference of the magnetic fields of neighbouring hydrogen nuclei. If an adiacent carbon atom has hydrogen atoms bonded to it, they will cause the peaks to split as follows:

The chemical is thedifference shift the between absorption frequencies nuclei the in of thehydrogen compound those the and in reference compound.

1 neighbouringH atom 2 neighbouringH atoms n neighbouring H atoms

peaksplits into 2lines (a doublet) peaksplits into 3 lines (a triplet) peaksplitsinto (n + 1) lines.

Thus ethanol gives three peaks (see Figure 5.9): 1 peak due to the OH hydrogen, which is a single line (as it is hydrogen bonded) 1 peak due to the CH, hydrogens, which is split into four lines by the three H atoms on the neighbouring CH, group. 1 peak due to the CH, hydrogens, which is split into three lines by the two H atoms on the neighbouring CHr group.

Fig 5.9 High resolution NMR spectrum of ethonol

oRclrurc cHerarsrnYIV a Visible and fIV spectra o z bonds will absorblight energyas an electron is promoted from a bonding to an anti-bonding n orbital. O The energygap is in the near UV or visible range,and the group causingthis is calleda chromophore. O If the n bonded electronsare linked to a conjugatedsystem(alternate double and single carbon-carbonbonds), the absorption will shift to may be coloured.The colour a lower frequency,and the substance observedwill be the complementarycolour of that absorbed.

Organic synthesis
Reogents ond conditions for the preporatlon oJ substonce B from A If the number of carbon atoms in the chain is: o increased by one, consider: with KCN a halogenoalkane b carbonyl with HCN c the Grignard reagentCHrMgBr d a Grignard reagentaddedto CO, or methanal o increased by more than one, consider: a a Grignard reagentwith more than one carbon atom b Friedel-Craftsreaction for aromatic substances o decreased by one, consider: a the Hofmann degradation b the iodoform reaction. Practical techniques

that A common is to think error KCN HCN react will with or to You alcohols formRCN. must ROH firstconvert to R-halogen. questionsorganic Many on in require, synthesis somewhere the of thesequence,conversion to a thestarting substance compound ora carbonyl halogenoalkane.

for Recrystallisationsuitable isonly purifying solids.

is When specific precaution a safety the of for, asked donotgive use glasses, coats as lab etc. safety is The examples. answerprobably 'nonaked (ether or flames solvent)' 'carry the ina out experimentfume inwhich thespecific case cupboard', must hazard astoxicity be such stated.
Liquid
(u
l-r

O Recrystallisation. Dissolvethe solid in a minim m of hot solvent. Filter the hot solution through a preheated funnel using fluted filter paper.Allow to cool. Filter under reduced pnsssurle (Buchnerfunnel), wash with a little cold solvent and allow to dry. The solid should have a sharpmelting temperature. when either the reactanthas a low o Heating under reflux is necessary boiling temperatureor the reaction is slow at room temperature. r Safety precaution. You must use a fume cupboardwhen a reactantor product is toxic, irritant or is carcinogenic. a o Fractional distillation. This is used to separate mixture of two into pure samples, but liquids. Thesemixtures can usually be separated if the boiling points are too close,a good separationwill be difficult. 'C If a liquid of composition X is heated,it will boil at Tr to give a vapour and reboiled,it will of compositionY (seeFigure5.10).If this is condensed 'C giving a vapour of composition Z. Eventually boil at a temperatureof T, pure B will distill off the top and pure A will be left in the flask. Applied organic chemistry

E T 1 H
C,.'

tr 17 .a)

loOo/o X A

Z TOOo/o B

Fig 5.lO Boiling positiondiag m ro temperoture com /

o Targeting pharrnaceutical compounds. Those which are ionic or have severalgroups that can form hydrogen bonds with water, will tend to be retained in aqueous(non-fatty) tissue.Compounds with long hydrocarbon chains and with few hydrogen bonding groupswill be retained in fatty tissue.The latter will be storedin the body, whereas water-solublecompounds will be excreted. o Nitrogenous fertilisers are of three types: such as those containing NO; and NHn.ions 1 quick release, such as urea, NHTCONH, 2 slow release, 3 nafural, such as slurry, compost and manure. The first two are water-solubleand can be leachedout. The last is bulky and contains little nitrogen.

El

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METAL', euANTrrATrvE KrNETrcsAND AppLrED .RGANtc cHEMIsrRy

o Esters, oils and fats. Simple estersare used in food flavourings, perfumesand as solventsfor glues,varnishesand spray paints. Animal fats are estersof propan-t,2,3-triol and saturated acids such as stearic sodium When hydrolysedby boiling with aqueous acid C,'H3'COOH. hydroxide, they produce soapwhich is the sodium salt of the organic acid. Vegetable oils are liquids which are estersof propan-I,Z,3-triol and unsaturated acids. Margarineis made from polyunsaturatedvegetableoils by partial hydrogenation (addition of hydrogen) so that only a few double bonds remain.

Polymers soften a usually over rather range temperatures than of have sharp melting temperature. a The main reason this that for is the polymer a mixture molecules is of of different lengths. chain

O Polymers are of two distinct chemical types: 1 Addition. The monomers contain one or more C=C groups. Polymerisationis the addition causedby breaking the n bonds, and the polymer and the monomer have the sameempirical formula. and Examplesare poly(ethene),poly(tetrafluoroethene)(PTFE) poly(propene). 2 Condensation. Both the monomers have two functional groups, one at each end. Polymerisationinvolves the loss of a simple molecule (usually HrO or HCI) as each link forms. Examplesare nylon, a polyamide (seeFigure5.11),and terylene,a polyester.
/H C l

cr

o
Fig 5.ll A polyamide

i- (.n,)--( \ r- \ /

lil

\ i/ /
H

N \- (cH,)u-\ /" \ /
a diamine

ts \' lol

l-(

- )..n,),- (.", ii i T- i
O H a polyamide H

a diacid chloride

Synthetic polymers are not easilybiodegradedand can causean environmental problem of disposal.One answeris for them to be recycled.

da
\/'/J-I t-------!

rX,=r Checklist
V

Beforeattempting the questionson this topic, check that you: c.J Can recallthe testsfor C=C, C-Hal, COH, C=O, CHO and COOH groups. iJ Can deducethe functional gtoupspresentfrom resultsof chemicaltests. t.l Can interpret mass,IR, NMR and UV spectra. *J Can deducepathways for the synthesisof organic molecules. *J Rppreciatehow the structure of a pharmaceuticalaffectsits solubility. i-l Can distinguish between types of polymer and understand polymerisation.

your knowledge understanding and Testing

The to answersthenumbered I How would you distinguish between: questionsonpages 138-139. are
a pentan-3-one and pentanal

oRGANrccHEMrsrRYrv
b c 2-bromopropaneand2-chloropropane methylpropan-2-ol, methylpropan-l-ol and butan-2-ol? X The massspectrumof a substance of molecular formula C.HrO had peaksat mass/charge valuesof tZO, 105, and TT.Identify the peaksand suggest structural formula for X. a I72O and 1150cm-'. The IR spectrumof aspirin showedpeaksat32OO, Use the data on page L09 to identify the groupswhich causethese peaks. Low-resolutionNMR spectraof two aromatic isomerswith molecular formula C.H,owere obtained. Isomer Y had three peaksof relative areas 5:2:3, and isomer Zhad two peaksof relative areas6:4. Suggest structural formulae for Y and Z.

El

t*oNsrrroN

M E T A L ' , e u A N T r r A T r v E K r N E T r c s A N D A p p ' r E D . R G A N r c c H E Mr s r R y

Practice Test: Unlt 5

Time allowed thr 3O min All questionsare taken from parts of previous EdexcelAdvancedGCE papers The answersare on pagesI39-14L. with aqueous 1, a The kinetics of the hydrolysis of the halogenoalkane(where R is an alkyl group) RCHTCI sodium hydroxide was studied at 50 "C. The following resultswere obtained: Experiment 1 2 3

lRCHrcll 0.0s0
0.15 0.10

loH-l
0.10 0.10

Initial rate/mol dm-' s-' 4.0 x 10"

1.2 x I0-3 1.6 x 1O3

o.20

RCHrCl,and with respectto the Deducethe order of reaction with respectto the halogenoalkane, for hydroxide ion, OH-, giving reasons your answers. t4l ii Hencewrite the rate equation for the reaction. tU iii Calculatethe value of the rate constant with its units for this reaction. tzl iv Using your answerto part ii, write the mechanism for this reaction. t3I (Total LO marks) 2001CH6question 1l lJanuary i by Benzene, reactswith ethanoyl chloride, CH3COCI, an electrophilic substitution reaction in the CuHu, presence aluminium chloride as catalyst. of a Identify the electrophileinvolved in this reaction and write the equation to show its formation. l2l b Draw the mechanism for the electrophilic substitution of benzeneby ethanoyl chloride. t3l a c Suggest reaction scheme,stating reagentsand conditions, to convert the product of the reaction in OH b into

-c I-COOH CuH, I

tsI

Ethanoyl chloride can be used to prepareesterst:* as 3-methylbutyl ethanoate, (CH,)TCHCHTCHTOOCCH3, is a bee alarm pheromone that signalsdanger to a honey bee. If this which compound is warmed with aqueoussodium hydroxide, a slow reaction takesplace to produce sodium ethanoateand 3-methylbutan-1-ol.The reaction is first order with respectto both 3-methylbutyl ethanoateand the aqueoushydroxide ion. Explain the term first orderand give experimental details showing how this information could be obtained. t8I (Totat L8 marks) 2001 CH6 questions & 4 2 lJune

PRACTIC E

Study the reaction scheme beloq and then answer the questions that follow.

step 1 --+CrHrMgB CrHrBr oH- (aq)

CTH'OH

+D --+ step2
-----+C2H4O

KrCrrOr/HrSOn

C4H,'O E

for and conditions necessary step 1 a Give the reagents b Compound D reactswith ammoniacal silver nitrate solution to give a silver mirror. i Give suitablereagentsfor the conversionof B to D.

l2l

ii
iii

mainly to D and did not react that B wasconverted shouldbe takento ensure What precautions tll turther?
Give the name or the structural formula of the organic compound formed when D reacts with

tzl

tll ammoniacal silver nitrate solution. tzl c Give the structural formula of compound E (C4Hr,O). d Compound F reactswith 2,4-dinitrophenythydrazinesolution but has no effect upon ammoniacal silver nitrate solution. F will also undergo the iodoform reaction. i Explain the significanceof the resultsof the test with ammoniacal silver nitrate and 2,4r2l dinitrophenyl hydrazine concerning the functional group in F. ii What structural featurein F is identified by the iodoform reaction?Give the formula of the products of the reaction. t3t r2l iii Give the structural formula of F. e The massspectrumof F showedmajor peaksat mle valuesof 72,43 and 29. ldentify the species t3l responsiblefor thesepeaks. (Total 18 marks) 1] [anuary 2002 CH4 question
4 a Describe how you would measure the standard electrode (reduction) potential of the Fe'.(aq)/ Fe'.(aq)

tsl system. oc. at electrodeis connectedto a standardgold electrode,Au'-(aq)/Au(s), 25 b A standardFe3.(aq)/Fe'.(aq) The gold electrodeacts as the cathode and the electronsflow, in the external circuit, from the electrodeto the gold electrode. Fe3.(aq)/Fe'.(aq) i Write the half equationsfor the reactionsthat take place at each electrodewhen an electric current l2l is drawn from the cell. tll ii Hencewrite the overall ionic equation for the reaction that takesplace. iii The potential of this cell is +O.73V and the standardelectrodepotential for a Fe3.(aq)/Fe'.(aq) tzl electrodeis +0.77 V. Calculatethe standardelectrodepotential of the gold electrode. (Total LO marks) 3] ffanuary2001 CH3 question

El

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METAL=,euANTrrATrvE KrNETrcs AND App.rED .RGANrc cHEMIsrRy

Iron and chromium are very important industrial metals. a Complete the boxesbelow to show the electronic configurations of: 3d Fe: Cr:
Cr't:

4s

tA4 tArl
lArl

E E t_l

E E t_l

t_l E E E E E

E E E

E t_l E

t3l

b Chromite, FeCrOn FeO.CrO' is a mixed oxide of iron and chromium that is used in the manufacture or of stainlesssteel. It can be reducedby heating with carbon to produce iron, chromium and carbon monoxide. Write an equation to representthe reduction of chromite. I2l dilute sulphuric c The mixture of metalsthat resultsfrom the reduction in b was reactedwith excess acid to give a solution of iron(Il) sulphateand chromium(Ill) sulphate. Sodium hydroxide solution was addedto the mixture until in excess. The mixture was then filtered to give a precipitate Q, containing all the iron, and a filtrate R, containing all the chromium. i What is the formula of the iron-containing ion in the aqueousiron(Il) sulphate solution? tU ii Write an ionic equation for the reaction between sodium hydroxide solution and this ion. State
iii iv v what type of reaction is taking place. tsI State the colour of the precipitate Q. tll Give the formula of the chromium-containing ion in R. l2l State what you would see if solution R was slowly acidified with dilute sulphuric acid until there was no further change. r2l

Electrodereaction

trlv
-0.41 +L.33

Electrodereaction
'lrEr+ + e F tlrclr+e-+Cl'lrBtr+ e- + Br

Elv
+2.87 +1.36 +1.07 +0.54

Crt*+e-+Crt*

'lrcrror'- + 7H* + 3e-+ Cr3*+ 3tlrHro

'lrrr+ e- + I-

Use the standardelectrode(reduction) potentials of the chromium ions and the halogensshown below to answerthe questionsthat follow. potential. i Define the term standardelectrode tzl ii List those halogenswhich will oxidise chromium(Il) to chromium(Ilf . tlI iii List those halogenswhich will oxidise chromium(Il) to chromium(Ill) but not to chromium(Vl).[1] iv Chromium(Il) in aqueoussolution is sky blue whereasaqueouschromium(Il! solution is dark green. Describehow you would show that your prediction in d part ii actually worked in practice.

r2l

(Totat L9 marks) llanuary 2002 CHl question3 & lune 2001 CH3 question5l

6A

h,borator/

Ma'y
Laboratory II chemistry
O The specification (syllabus) for the tests on this module includes all the AS and A2 material. o The Unit Test 68 is a synoptic paper, taken by all candidates, and will also assess the candidate's quality of written communication. .. '- , 4 = 1 Unit Test6A: Assessment practical ,Ki of .t# skills II

E ftris is either internally assessed a practical exam. or f Notes and books may be used in the tests.

E ffre practical exam will be broadly qualitative in its approach. [l You should be able to: observeand interpret details of the chemistry of the elementsand compounds listed in Units 4 and 5. ii recognizethe resultsof experimentsto identify functional groups in organic compounds. iii carry out the techniquesdescribedin Topic 5.5 and those used in volumetric analysis,kinetics and equilibria. iv presentand interpret quantitative and qualitative results. v deviseand plan simple experimentsbasedon the chemistry and techniquesas above. i

K+a
All candidates will do this paper

The Unit

Test question

(exam)

paper

I Section A will consist of a compulsory question and will assess a candidate'sability to interpret data from laboratory situations. O Section B will consist of three questionsand the candidatemust answertwo of the three questions. I Thesequestionswill require candidatesto make connectionsbetween different areasof chemistry,for exampleby applying knowledgeand understandingof principles to situations in contexts new to them.

Ei

oorrANcED LAB.RAT.RY cHEMrsrRY

t Questions will be set on any of the topics in the AS and A2 specification. o The questions will require much less factual recall than those in earlier unit tests. Much more emphasis will be placed upon application of knowledge. o Questions will test a candidate's ability to analyse information from several different areas of the specification. 'deduce'will occur more often in questions o The words 'suggest' and 'state' or 'recall'. than

Tackling

the paper

* Spendsometime looking through SectionB and decidewhich questions you are going to attempt. Readall of the questionbeforereiectingit. You may be able to answerall but the first part and so still scoregood marks.If you are getting nowherein a question,abandonit and try you another, but do not cross out what you have written, because might scoremore for it than for the other question.The examinerwill count your better mark. o Do not be put off by unusualcompoundsor situations.In these questionsyou are not expectedto know the answer,but to be able to work it out, using your knowledgeand understandingof similar compoundsor situations. topics.This is O Synopticquestionswill contain materialfrom several by using the links that exist betweendifferent branchesof done chemistry. O Eachquestion should have a thread or link connecting the different parts.Identificationof this thread will help you to focuson the relevant chemistry.So do not treat eachpart of a questionin isolation from the other partsof it. o For examplein the questionsin the Unit Test6B on pageslI9 and LZO. o Question2 is basedon organicand inorganicnitrogen compounds, and pK",polymers,amine preparation, with questionson fertilisers, K,, ammonium nitrate linked to thermodynamicand kinetic for stability. where the carbonchain is increased o Question3 is a reactionscheme leadingto a carboxylicacid,then a pH and buffer questionabout that acid. O Question4 is about the chemistryof iron, linking bonding, transition pairs,testsfor Fe'. and redox Bronsted-Lowry mental properties, titrations. To do well in this paperyou must revisethe entire specification O (syllabus) Topic I.2. Do not becomeput off by this load and especially of as many of the Topicsin A2 are extensions those in AS.For example: o Topic 4.1 with 2.1 - Energetics o Topic 4.2 with I.4, 1.6 and I.7 - The PeriodicTable o Topic 4.3 and 4.4 with 2.4 and 2.5 - Equilibrium o Topic4.5, 5.3 and 5.5 with 2.2 - Organicchemistry O Topic5.1 with 1.5 - Redox O Topic 5.4 with 2.3 - Kinetics equationsand moles) Topics1.1 (Atomic stmcture),I.2 (Formulae, This leaves and bonding) all of which are fundamentalto chemistryand and 1.3 (Structure much of thesetopicswill,have beenrevisedby your teacherduring the A2 year.

PRAcrrcE TEsr: Utqrr 6E} (SYNoPTtc)

Practice Test: Unlt 6B (Synoptic)

Time allowed All questionsare taken from previous EdexcelAdvancedGCE questions. The answers on pagesI4I-I42. are L hour 3O min

SectionA
1 as A fertiliser is known to contain ammonium sulphate, (NHn)rSOn, the only ammonium salt. This question concerns methods for the determination of the ammonium and sulphate ions. a A sample weighing 3.80 g was dissolved in water and the volume made up to 250 cm'. To 25.0 cm' portions of this solution about 5 cm' (an excess)of aqueous methanal was added. The following reaction took place: 4NHn.(aq) + 6HCHO(aq) ---; CuH',N*(aq) + 4H.(aq) + 6HrO(l) The liberated acid was titrated directly with 0.100 mol dm-'' aqueous sodium hydroxide. The average volume required was 28.0 cm'. Calculate the percentage of ammonium sulphate in the fertiliser. ts] b In a second determination of the ammonium ion content, the same mass of fertiliser (i.e. 3.80 g) was treated with excesssodium hydroxide and heated. The ammonia liberated was passedinto a known excess of hydrochloric acid. The unreacted hydrochloric acid was then titrated with standard aqueous sodium hydroxide. The calculation of the percentage composition of the fertiliser gave a value that was 5ololower than the value obtained by the method in a. Suggest reasons for this error other than those arising from the measurement of volumes. tzl c To determine the sulphate ion concentration of the fertiliser, aqueous barium chloride was added in excess to the fertiliser solution. The precipitate produced was filtered off and dried by strong heating.

i ii

Give the ionic equation, with statesymbols,for the precipitation reaction. why the aqueousbarium chloride was added in excess. Suggest

r2l
tll

d Many carbonates are also insoluble, and can be precipitated, dried and weighed in experiments similar to c. However the strong heating needed to drive off all the water can cause a problem in determining the mass of the carbonate precipitated. Suggestwhat this problem is, and, choosing a suitable example, write an equation for a reaction that might occur when the precipitate is heated. t4I

(Total 14 marks) 1] 2002 Urtit Test68 question [June

B Section
Answer TIIVO questions only 2 a The covalentcompound urea,(NHr)rC= O, is commonly usedas a fertiliserin most of the European in Union, whereas the UK the most popular fertiliseris ionic ammonium nitrate, NH4NO'.Apart from of two advantages using urea as a fertiliser comparedwith using its nitrogen content suggest ammonium nitrate. I2l mol dm-'' The constantK^ = 5.62 x 10-to b The ammonium ion in water has an acid dissociation conjugateacid of urea has K" = O.66mol dm-'. Usethis data to explain which of ammonia or urea is the strongerbase. t2l c Someorganic nitrogen compounds are usedto manufacturepolyamidesby condensation polyrnerisation polyamide. and polymerisation.With the aid of diagrams,define the terms condensation

t4l
d Ethanamide,CH3CONH, can be convertedto methylamine, CHrNHr. i Statethe reagentsand conditions for carrying out this conversion. the ii Suggest formula of the likely product if urea were used instead of ethanamide in this conversron. e Ammonium nitrate can explode when heated strongly. NI = -23 kJ mol-' NHnNO.(s)- N,O(g) + ZH,O(g) t3l

tu

ADVANCED

LABORATORY

CH EM ISTRY

With moderateheating the ammonium nitrate volatilisesreversibly NI = +L77 kJ mol-' NHnNO,(s) + NH,(g) + HNO.(g) i ii Statewhy the expressionfor Ko for the reversiblechangedoesnot include ammonium nitrate. tl] to and Explain the conceptsof thermodynamic kineticstabilitywith reference thesetwo reactions. (Total 18 marks) 4l 2001CH6question lJune The principal sourceof the odour in sweatis the organic acid IIA, CTHnOz.Itwill decolourisebromine water immediately, and it showsgeometricisomerism. of a IIA can be made by the following sequence reactions: cH3cHzcHrcH(cH3)cHroH 2-methylpentan-L-ol

tsI

I Y
cH3cH2cHrcH(cH3)cHo

HCI(aq)

conc. HzSOn

cH(oH)cN cH.cH,cH,cH(cH3)

cTHrno3 D

+ heat

CrHrzOz

HA

i Give the reagentsand conditions for the oxidation of 2-methylpentan-1-olto B. t3l ii Statethe conditions and write the mechanism for the reaction of HCN with B to give C. t4l iii Give the equation for the hydrolysis of C to D, and hence draw the structural formula of D. t2l iv Draw the structure of HA. t2l constantK" = 4.50 x 1Osmol dm-', and is a monobasic(monoprotic)acid which b HA has a dissociation accordingto the equation: dissociates HA(aq) + H,OQ) + HrO.(aq)+ A(aq) i Write the expressionfor K" and calculatethe pH of a solution of HA of concentration 0.0100 mol dm-'. t3l ii The pH of skin is almost constant. Explain how in principle, this could be achievedby using HA and one of its salts.(Given its smell, it is perhapsfortunate that skin doesnot use this compound as a pH regulator) I4l (Total L8 marks) 2002 CH6 question 3] fJanuary Iron(III) chloride existsin two forms, the covalent anhydrous chloride and the ionic hydrated chloride. a Explain why anhydrous iron(III) chloride is covalent whereassodium chloride is ionic. t4I b Hydrated iron(III) chloride is soluble in water and its solution is acidic. conjugate i Write an ionic equation to show why its solution is acidic and identify the acid-base pairs in this reaction. t3I to ii Describewhat you would seewhen a solution of sodium hydroxide is addeduntil in excess a solution of iron(III) chloride. Write an ionic equation for this reaction and identify the type of reaction. t4l which react to form a blood iii A test for Fe'*ions is to add a solution of thiocyanate ions, SCN-(aq), ion, What is the bonding betweenthe SCN-ion and the Fe3. red ion of formula [FeSCN(H'O)J'.. and what is the causeof the colour of the ion? t3l In c Iron also forms the intensely red coloured anion, FeOn'-. acidic solution this is a powerful oxidising ions. agent, and is itself reducedto Fe3* in Calculatethe oxidation number of iron in FeOn'.Suggest, outline, how you could determine the ions. concentration of a solution of FeOo't4l (Total 1"8marks) ffanuary2001 CH6 question6l

ANSwERS

Arcr,tters
U n i1 t
Tonic1.1 Atomic structure
^ v r 7 v L . 1

t The relative isotopic mass is the mass of a single isotope of an element (relative to 1172th the mass of a carbon 12 atom), whereas the relative atomic mass is the averagemass taking into account the isotopes of the element. The relative isotopic m as s es t he tw o c h l o ri n e i s o to p e sa re 3 5 and 37, of b ut t he r elat iv e a to m i c m a s s o f c h l o ri n e i s 35.5 tli 2 There are many more atoms than "Li atoms in natural lithium, so the averageis closer to 7. 3 A, of magnesium = ( 2 4 . Ox 7 8 . 6 + 2 5 . Ox 7 O . I + 2 6 . Ox 7 7 . 3 )= 2 4 . 3 100 4 Let the o/o "ncabe x, of and so the o/o "Ga = (100 _ x) of 69. 8 = [6 9 .0 x+ 7 1 .0 (1 0 0- x )J 100 Therefore6980 = 69x + 7100 - 77x Therefore2x = l2O and x = 60.0 of Gallium contains 6O.Oo/o the ""Gaisotope. 5 Gr oup 5. T here i s a b i g i u m p b e tw e e n th e 5th and 6th ionisation energies.Therefore the 6th electron i s being r em ove d fro m a l o w e r s h e l l (n e a re rto the nucleus) than the first five electrons.

iii Although the element with Z = 11 has 8 more protons, it also has 8 more shielding electrons,but as the 3s electron is further from the nucleus than a 2s electron, so lessenergy is required to remove it. The el ectron i n a box notati on for chl ori ne is:

muruuunnun
1s 2s 2p,2p,2p,3s 3 p . *3 p , , 3 p ,

8 All have one electron in their outer shells, but K is bigger (larger atomic radius) than Na, which is bigger than Li. Therefore the outer electron is held on less firmly (the extra nuclear charge is balanced by the same extra number of shielding electrons) and so is the easiestto remove from potassium and the hardest to remove from Li. This makes potassium the most reactive. 9 a i
ll

iii

Li (g) + e --+Li- (S) cl (g) + e -+ Cl- (g) o (g) + e --+o- (g)

6 a
>\ bo t-<

zsoo
2000 1500
b c

si i N ote thespeci es thel efthand de s a gaseous that on o a t a t o m n d h eo n eo nt h er i g h it s a n e g a t i vi e n . O- (S) + e- - O- (g) For the 1st electron affinity, the (negative) electron is brought closer to the positive nucleus in a neutral atom, and so energy is released.For the 2nd electron affinity, the negative electron is brought towards a negative ion, and so repulsion has to be overcome, which requires energy.

+) .A

1000 500

v)

| 2 t^ti*tt ":-l.r*

e 10 11

b i

ll

A 2p electron, which is in a higher energy level, is being removed. So less energy is required to remove it compared to that required to remove a 2s electron. There are two electrons in the 2p, orbital which repel one another, so less energy is required to remove one of the pair than if there had only been one electron in that orbital.

Topic7.2Formulae, equations and moles

o/o +6.9O 1 C 82.76 + L2 = 6.9O 17.24+1=17.24 2.5 H Therefore the empirical formula is CrH. b Mass of CrH, is 29, but M, - 58, Therefore the molecular formula is C.,H,u 2 a 4NHr+5Or-4NO+6HrO b 2Fet.(aq)+ Sn'.(aq)-- ZFe"(aq) + Sn'.(aq) 1 a

122 ANsweRs

copper sio,
H ie l o n i c q u a t i oms sa l s o a l a n cn c h a r g e .e r e e nu t b sides 8+. are both
+ Equation: HrPOn+ 3NaOH - Na.,.POn 3HrO A m ount of H. P O , = 2 .3 4 1 9 8= 0 .0 2 3 8 8 m o l A m ount of NaO H = 0 .0 2 3 8 8 x 3 /1 = 0 .0 7 L 6 3 mol M a s so f N a O H = 0 . 0 7 L 6 3x 4 O = 2 . 8 7 g Equation: 2KOH + HrSOn= KrS9n+ ZHrO = Amount of HrSOn 0.0125 dm'.x 0.0747 mol dm-' = 9 . 3 3 8x 1 0 - ' m o l A m ount of K O H = 9 .3 3 8 x 1 0 a x 2 l l = 1 .8 6 8 x 1 0 r mo l Volume of KOH solution = mol/conc = 1 .9 6 9 x 1 0 -,m g l O.l O 7 m o l d m -' = 0 . 0 1 7 5d m ' = 1 7 . 5c m ' 5 Am ount of B i( N O,), = 0 .0 2 5 d m' x 0 .5 5 mo l dm-' = 0 . 0 L 3 8m o l = 0.0L38 x 312 Amount of HrS = 0 .0 2 0 6 mo l = rlol x molar volume Volume of HrS gas = 0 .O2 0 6x 2 4 = 0 .5 0 d m' 6 Ratio mol of H,(g):mol of CH.(g) = 3:1 Volume of Hr(g):volume of CHr(g) = 3:L Volume of Hr(g) = 3 x 33 = 99 dm' solid CO, CaO poly(ethene) graphite sulphur CuSOn sucrose LiF

a metallic b giant atomic e simple molecular c ionic f polymeric b giant atomic e simple molecular c ionic d H-bonded molecular c ionic

Melting: on heating, the molecules or ions vibrate more until the intermolecular forces (in molecular) or ion/ion forces (in ionic) substancesare overcome and the lattice breaks down.

to start vibrate. or that Donotsay themoleculesions

Boiling: on heating the average kinetic energy ot Those with a large enough the molecules increases. kinetic energy and hence speed escape,not only from the surface but also from the body of the liquid, forming bubbles. a b NH.. There are stronger intermolecular forces in NH. as it forms H bonds and PH. does not. HBr. It has more electrons in its molecule, and so it has stronger dispersion forces (which outweigh the difference in dipole/dipole forces). Propanone. Both have about the same strength of dispersion forces becausethey have about the same number of electrons,but propanone is polar and so has dipole/dipole forces as well. 58.It has about twice as many electrons as Pn, and so has stronger dispersion forces. NaCl. It has ion/ion forces that are very much stronger than the weak intermolecular dispersion forces between CCln molecules.

and bonding Topic7.3Structure

d

o-bond 2 a AlCl, becauseeither there is less difference in electronegativity between Al and Cl than between Al and F is or A13. very polarising and the bigger Cl- ion is more polarisable than the smaller F- ion. BeCl, becauseeither there is less difference in electronegativity between Be and Cl than between Mg and Cl or Be'* is smaller than Mg'. and so is more polarising. a Hydrogen bon d Yes No No No No b Dispersion Yes Yes Yes Yes Yes c Dipole /dipole Yes No Yes Yes No

Number of o bond pairs siHn BF. BeCl, PCl3 SFu XeFn NHn' PClu4 3

Total Number of lone number of pairs electron pairs 0 0 4 3 2 4 6 6 4 6

Shape

HF r2 HBr P H, Ar
4 iodine ice

2 3 6 4
4 6

0 1 0 2 0 0

Tetrahedral Triangular planar Linear Pyramidal Octahedral Square planar Tetrahedral Octahedral

e simple molecular d H bonded molecular

8 In Na (s) there are loosely held delocalised electrons that can move through the lattice. In

ANswERs NaCl(s) the electrons are localised on the ions, not loosely held and the ions are fixed in their positions in the lattice and so are not free to move.
4 a i
ll

123

Topic7.4 ThePeriodic TableI

b i 1 a b
2 a b c d e f

They all have the same number of electrons in their outer shell. For Group 2 this number is 2. This period is Period 4, and so all the members have electrons in four shells. H, is simple molecular Na is metallic Si is giant atomic S*is simple molecular Cl, is simple molecular Ar is simple molecular (argon is monatomic).
ll

T h e n s w e r ' h y d r o g e n eo r' ' i o n i c 'a n n o tp p lty a bond d a o elements.

Sodium and magnesium are metals. Magnesium is 2+ and has a smaller ionic radius. therefore it will have stronger metallic bonds and a higher melting temperature. Silicon forms a giant atomic structure with each silicon atom ioined covalently to four other silicon atoms. These strong covalent bonds have to be broken. This requires a huge amount of energy and so the melting temperature is very high.

Nuclear charge is equal to the number of protons in the nucleus. Screeningor shielding occurs when an outer electron is insulated from the pull of the positive nucleus by electrons in inner shells. The 1st ionisation energy of sodium is for the removal of the 3s el ectron. S odium has a nucl ear chargeof + 11, but the 3s e lect r on is shi el dedby the 10 el ectronsi n the 1st and 2nd shel l s.The secondel ectron that is removed comes from the Znd shell (it is a 2p el ectron).Thi s el ectron i s shi el dedf r om t he nucl eus onl v bv el ectronsw hi ch ar e in a l ow er shel l , rvhi ch i n thi s casei s by t he t wo 1s el ectronsand so i t i s hel d much m or e strongl v bv the nucl eus.It i s al so n ear ert o t h e n u c l e u s ,r v h i c h m a k e si t e v e n h a r d e r t o remoV e. S o d i u m h a s a n u c l e a rc h a r g eo f + 1 1 a n d i t s 3 s e l e c t r o ni s s h i e l d e db v t h e i n n e r 1 s t a n d 2nd shellelectrons\lagnesiumhasa . n u c l e a rc h a r g eo f + 1 2 ( o n e n l o r e t h a n sodi um), but i ts 3s el ectron i s shi eldedby the same i nner el ectrons.Thus i ts 3s electrons are pulled more strongly to the nucleus and are harder to remove.

I t i s b e c a u s et h i se x t r a u l t h a t m a 0 n e s i u m of o l a i tr a a t o ms s m a l l eh a n s o d i u mt o m . a

n C a r b o in ,t h ef o r m f d i a m o nh a s s i m i l a rt r u c t u r e , o d, a s b u ta st h es m a l l e r r b oa t o mo r m s t r 0 n g e r n d s ca n f bo t h a n i l i c o n ,i a m o n d ' s l t i ntg m p e r a t us e v e n s d me e i re higher.

White phosphorus, sulphur and chlorine all form simple molecular solids. The melting temperatures depend upon the strengths of their intermolecular forceswhich are dispersion (induced dipole/induced dipole) forces.The strength of this force depends upon the number of electrons in the molecule.

Topic7.5 Introductionto oxidationand reduction

1 a Sn"(aq) -- Sn'.(aq)+ 2e

E l e c t r o n s e0 n r i g h tb e c a u sS n ' .i s o x i d i s e d : ar e 2e i s n e e d eb e c a u s e i d a t i o n m b ec h a n g e sy 2 . d ox nu r b b c F e ' - 1 a q+ e --'Fe"-(aq) ) -+ S n ' - ( a q ) 2Fe''.(aq) Snn.(aq) 2Fe'.(aq) +

T h es i m p l e s t a yi n w h i c h o w o r kt h i so u t i s t o a d d w t t o g e t h e r ea t o m i c u m b e ro f a l lt h ea t o m s n t h e th n s i mo l e c l e . u Pnhas 4 x 15 = 60, S*has 8 x 16 = 128 and Cl, has 2 x I 7 = 34 electrons per molecule. Thus sulphur has the strongest intermolecular forces and the highest melting temperature and chlorine has the weakestintermolecular forces and the lowest melting temperature. 2 a

E q u a t i ob h a st o b e d o u b l e d ,o t h a tt h ee l e c t r o n s n s w 2 c a n c e l h e n t i m e s i s a d d e do a . b t HrOr(aq)+ 2H.(aq) + 2e- -. 2HrO(l)

H . 0 ,i s r e d u c e d , e l e c t r o n s e0 n t h el e f t . so ar

124 ANswERs
b S(s)+ zH'(aq) + 2e---'H,S(aq) is yellow becausethe energy difference between the 4th shelt and the 3s orbital is equivalent to the yellow line in the spectrum. The sodium atom is smaller than the potassium atom, becausesodium has three shells of electrons and potassium has four. Thus sodium's outer s electron is held on more firmly, and more energy is required to remove it.

and S is on 2e-are needed theleftbecause reduced its g f 0 nu o x i d a t i o n m b e ro e sr o m t o - 2 .

c H,O,(aq) + H,S (aq) - zH,O(l) + S(s)

they must 0ntheleftbecause are be H,S Both andH,0, to and b is equation reversed added a; thereactants; c o t n o t eh a t h eH -i o n s a n c e lu t .
+ + PbOr(s)+ 2H,SOo(ag) 2e- - PbSOo(s) 2H,O(l) + SOo'-(aq)

has thatpotassium in of This thecase spite thefact is p i a h b th s e i g hm o r e r o t o n s a n o d i u m ,e c a u ste l s o a s t tn an t e ns e i g hm o r e l e c t r 0 b e t w e eh en u c l e u s d h eo u t e r t s ed ch n e l e c t r os ot h ee x t r a u c l e a r a r gie b a l a n c b yt h e n, e x t r ah i e l d i n g . s

2C a + O, - ZC aO (or C a * ' l rO, -- C aO) Ca + zH,O - Ca(OH), + H, 2K + ZH.O -- 2KOH + Hz Mg(s) + H,O(g) - MgO(s) + H,(g)

3 a

4 a b c d

and is needed theleftasPbO, reduced its on 2e-are f o + nu c o x i d a t i o n m b e rh a n g ers m 4t o + 2 .

b + PbSOo(s) 2e--- Pb(s) + SOo'-(aq)

The white precipitate is the insoluble magnesium hydroxide. Barium hydroxide is soluble and so is not precipitated. Beryllium, as BeCO. is the least thermally stable of the Group 2 carbonates.It decomposesvery easily on heating becausethe Be'* ion is very polarising. The other Group 2 ions are less polarising because they are larger. 7 a 4LiNO3 -- ZLizO + 4NO, + O, 2N aN O. - 2N aN Or* O, 2Mg(NO,),- 2MgO + 4NO, + O, NarCO. --' no reaction MgCO,-MgO+CO, no BaCO, --+ reaction

and , e 2e-ar eneeded th e l e ftb e c a u sP b S0 i s re d u c ed on r r c t h eo x i d a t i on u m b eo f l e a d h a n g efs o m+ 2 t o 0 . n

+ PbOr(s)+ Pb(s) + 2H,SOo(ag) 2PbSOo(s) 2H,O(t)

Topic7.7 Group7
ii to Pb equationhas bereversed Because is a reactant, place that is to then added i. This thereaction takes and batterv. from lead-acid a is when current drawn
Covalent HCI ionises when added to water, and the hydration energy given out by the ions bonding with the water molecules is greater than the energy required to break the covalent H-Cl bonds: HCI(g) + H,O(l) -- H,O.(aq) + Cl-(aq) First a solution has to be made. The sample can be dissolved either in water or in dilute nitric acid. (If water is chosen, dilute nitric acid must then be added to destroy the carbonate).To this slightly acidic solution, add silver nitrate solution. If there is chloride present, there will be a white precipitate that will dissolve in dilute aqueous ammonia. is HrSOn a stronger acid than HCI (or HI), and so it will protonate the Cl- ions in the sodium chloride producing HCI gas. HCI is not a strong enough reducing agent to reduce sulphuric acid, and so no further reaction will take place. With sodium

Topic7.6 Group1 and Group2

L Dip a hot platinum (or nichrome) wire in clean concentrated HCI and then into the solid. Place in a hot bunsen flame. The substance that turns the flame carmine red is LiCl, the one which turns the flame lilac is KCI and the one that turns the flame apple green is BaClr. 2 The heat of the flame vaporisesthe sodium chloride, producing some Na and Cl atoms. Electrons are promoted into the 4th shell in some of the sodium atoms. These electrons then fall back to the ground state, which is the 3s orbital, and energy is given out in the form of light. The flame

ANsweRs 125
iodide, HI is produced by the protonation of the iodide ions, but the HI is a very strong reducing agent, and so it will reduce the sulphuric acid and itself become oxidised to iodine. 4 Disproportionation is a reaction in which an element is simultaneously oxidised and reduced. Chlorine disproportionates when added to alkali: Cl, + ?OH- - Cl- + CIO- + H,O ( 0) (-1 ) (+ 1 ) Also, chlorate(I) disproportionates when heated: 3ClO- -- ZCl- + ClO,, (+1) (-1) (+5) b Graphite has covalent bonds between atoms that have to be broken [1]; sodi um chl ori d e has forcesbetw een the i ons [1 ] . I n bot h el ectrostati c these forcesare strong and so a l ot of e ner gy is = [ 31 neededto break them [1] el c i Graphi te has del ocal i sed ectronsabove and bel ow the pl ane of he.ragons [1], which can
flow (which are mobilet [1]
ll ll

Answersto Practice TestUnit 1

The allocation of marks follows Edexcelmark sc hem es . The marks that you will need for each grade are approximately: A 7Oo/o B 6lo/o C 52o/o D 44o/o E 360/o L ai = [1] Z C a +O r - Z C a O = [1] NarO + HrO ---+ 2NaOH Na,O + ZHCI ---; 2NaCl + H,O = l2l Species[.], balancing [.] b The thermal stability increasesdown the group [f.] as the cation size increases[1] and so the carbonate ion is distorted (or polarised) less tll _ t3l ii iii

= f2l

The l atti ce i s broken don' n i n the l iquid and so the i ons are free to nl ove

=[u

t m s io l a S t r u c t u r ee a n g r a na t o m i c . n i c a t t i c e , a s i m p l o r h ,d r o g e b o n d em o l e c u lo rra e n d i l a t t i co f m e t arl o n s n a s e ao f e l e c t r o n s . e , 'r c A s u b s t a n c e, l lc o n d u ce l e c t r i c iitfyi t h a s t d e l o c a l r se l d c t r o nh r o u g h otu tes t r u c t u r e ee ts h rch t o r i o n s ' , ' . , ha r ef r e e o m o v e .

3 a i

A tomi c number i s the number of prot ons in the nucl eus [1] Mass number i s the t ot al ( or sum of the) number of protons and neut r ons

b Donotattempt answer type question to this in of terms size of match.

2 a i Graphite has a giant atomic (or giant covalent) structure [1]. The bonding between atoms is covalent [U. Your diagram must show several interlinked = [4] hexagons [1] in layers tU

ii b i

= [1] High energy electrons bombard the Br, molecules [1] and knock out an electron [1] = [2] ll They are accelerated charged plates (or by = [1] acrossan electric field) -" B r-' ' B r. = [U iii
,.gt-

tu

= l2l

has than a ii Astheparticle 1 fewer electrons p r o t o nis , i l lb ea p o s i t i v o n . tw ie a i i i I na m a s s p e c t r o m e t e rse l e m e n t s mo t p r o d u c o n s o n t a i n io n e t o mb u t ie c ng a , d i a t o mece m e ns u c h sN , ,0 , a n d h e il ts a t h a l o g e g is e o l e c u lia r s u c h sB 1 2 n vm on s a w h i c h a y o n t a i n od i f f e r ein to t o p e s . m c tw s
4 a Divide each o/o their A, values [L] and then divide by by the smallest [1] * H L 1 . L 1 = L 1 . 1 t h e n* 7 . 4 = 1 . 5 C 88.9* 12 = 7.4 then + 7.4= 1 Multiply both by 2 to get whole numbers = [3] .'. E.F.is CrH. tll

It

Sodium chloride has a lattice structure t l l . The bonding is ionic [l.]. Your diagram must show a 3-D arrangement = [3] of ions, Na. alternating with Cl-. [1]

.l

:1ffi A r q s w e n s
b HI has more electrons tll .'. induced dipole or dispersion or London or v.d.Waals = I2f are stronger [1] 3 bond pairs and 1 lone pair repel to get c i as far apart as possible [1] see diagram = l2l below [1] ii 4 bond pairs around Al repel to get as far apart as possible [1] see diagram = I2l below [t] (i) d i [L] for the electrons around S and [1] for the = l2l electrons around both Cl atoms.
t a a t

** *. .* .. ++CI + +CI ++ + + The 2 bond pairs and the 2 lone pairs [L] repel each other to get as far apart as = I2l possible [.] Cl is more electronegative than S, so the bonds are polar [1], but as the molecule is = fzl bent, the polarities do not cancel [1]

t/l---t
@

(ii)i Tj

F-h

lll

Moles of gas = volume + molar volume = 8.0 ,mt/2.4 x 10ncm' mol-' = 3.33 x 10" mol

U n i2 t
I Topic2.1- Energetics
Gasesat a pressure of t atmosphete, a stated temperature (298 K) and all solutions of concentration 1".00mol dm-'. Substancesin their most stable state. zC(s) + ZH,(g) + O,(8) - CHaCOOH(I) i ii CH,COOH(I) + 2O,(g) - 2CO,(8) + 2H,O(l) iii CH3COOH(aq)+ NaOH(aQ)- CH,COONa(aq) + H,O(l) or CH,COOH(aq) + OH-(aq) - CH,COO-(aq) + H,O(l)

= Itr"o., of molecules 6.0 x 10" x numberof = fzl moles = z.o x 1o'o 1t1

mass Hl is larger. of the b Donotsaybecause molar pa n t er i c R e m e m b h a t t i st h ee l e c t r o n i r s o tt h e m t h r a t o m n o rt h eb o n dts a t e p e lo g i v e a x i m u m s separation.

5 a i
ll

b i
ll

lll

is The oxidation number of sulphur: in HrSOn +6 [1], in H,S is +2 [1], in SO, is +a [1] = [3] The I- ion is the stronger reducing agent becauseit reduces sulphur from +6 to +2 fAl, = l2f whereas Br- only reduces it to +4 [1] 'lrcl, = [1] * eZCl- - Cl, + 2e- or Cl- OCI-+2H-+2e--Cl-+HrO = I2l species[1], balance [t] = [1] OCf + 2H. + Cl- -'Cl, + HrO

acid, so its and acid that Note ethanoic is a weak n n f o r m u lm u s b ew r i t t ein f u l la n d o ta sH ' . a t

No(g) +tboz(g) are the reaction, electrons i & ii For oxidation an they and ontheright, for reduction areontheleft. o or n w i i i Y o u o u l d o tb ep e n a l i sfe df a i l i ntg c a n c e l h h i o n e f t h eC l - o n si,. e . a v i ntg ee q u a t i o n . o + O C l+ 2 H . 2 C l - C l , + H , 0+ C l 6 a 2,8,6 SS(S)+ e --+ (g) trl b i = [1]

Enthalpy

t I

t/,

Nr(g) + oz(g)

ii

S(g)- S.(g)+ e- [1]

and [1] for state symbols in both equations = [3] A big jump in ionisation energy means that an electron has been removed from a new shell [1] The first big jump is after 6 electrons and so there are six electrons in the outer shell [1] The second big jump is after 8 electrons and so = [3] there are 8 in the 2nd shell [1]

MI,= +90.3 kJ + (-57.1) kJ = +33.2 kJ mol-'

ir i i t N o t eh a t h e+ s i g n s g i v e nnt h ea n s w en o r d e r in ha t o e m p h a s its e t h er e a c t i os e n d o t h e r m i c .

ANswERs 127
Nf, 2NOr(g) ---------------+ \ *'\ \ / / ,/*, Nz(g) + zOzG) 20zG) LH, = AH, + LH, = -2 x (+33.9) + (+9.7) = -58.1 kJ mol-'

NzOn(g)

r--r\--\-

H
f

H HO-H-+

//
H

\\ H

H-C-C-O-H

t
l

l
H

Make (exo) x C-C = -348 kJ x C-H = -4I2 kJ x C-O = -360 kJ = - 1120 kJ = +1075 kJ Total Total NI = net result of bonds broken and bonds made = + 1075 - 1720 = -45 kJ mol -' . Break (endo) kJ 1 x C = C = + 6" 12 1 x H-O = +463 kJ

= 2 t of of L H , m i n u s t i m e sh ee n t h a l p yf o r m a t i o n rn t te N 0 , ( g ) ,e c a u sh er e a c t i o e p r e s e nh s te b of f o r m a t i o nN 0 , ( gr)e v e r s e d d L H 2 = n t h a l p y an e of f o r m a t i o nN , 0 , ( g ) . of

I Topic2.2 Organicchemistry
L a B r F F b CI OHH Br-C-C-C-H

l l

l l

l l

H-C-C-C-C-H H

t
t

l
l

aHr 12C(s) lZHr(g) + Oz(g)------------>CH3(CHTt6COOH(s) +

2 a
Nf1

C I C I

a C H , , C H . C H , O Hn d C H , C H ( O H ) C H , .

r2COr(g) + rzHzo(l)
= where A-FI, 12 x enthalpy of combustion of carbon (graphite) + 12 x enthalpy of combustion of hydrogen and LH, = minus the enthalpy of combustion of lauric acid. LH,= 12x(-394) +12x(-286) -(-7377) = -783 kJ mol-'. 6 HCI + NaOH -- NaCl + HrO Amount of HCI = corC(mol dm-') x vol(dm') = 1 .0 0x 1 0 0 1000 = 0.100mol Ris ein t em p e ra tu r= + 6 .8 0 ' C Heat produced when 0.100 mol reacts = total mass x specific heat capacity x rise in temperature =2OOgx4.18Jg-' x 6 .8 0 " C = 5 6 8 5 J = 5 . 6 8 5k J Heat produced when 1 mol reacts = = 5.685/0.100 56.9kJ mol-' = therefore AFI"",, -56.9 kJ mol-' (exothermic).
3 a b

s un a t 0rs T h i sy p e f u n a m b i g uf0 u m u lia a l l o w e d l e s s o s o fo f u l ls t r u c t u r a lr m u lia a s k efd r .

and cH3c(cHr)rcH, cH.cHrcH.cH.cH,, cH.cH=cH(cH,)cH.

c

C H ,C H = C H C H ,(both the ci s and tr ans and C H .C H TCH=CH, i somers),(C H ,).C = C H , A free radical is a specieswith a single unpaired e l e c t r o n ,e . g . C l . . Homolytic fission is when a bond breaks with one electron going to each atom. An electrophile is a specieswhich seeksout negative centres and acceptsa lone pair of electrons to form a new covalent bond. Heterolytic fission is when a bond breaks with the two electrons going to one atom. C.Hn+ Cl, -* CrH.Cl + HCI then: CrH.Cl + Cl, - CrH*Cl, + HCI etc conditions: ultraviolet light c.H ,,+ 3' l ror- ZC o, + 3H ro conditions: flame or a spark C H ,C H = C H ,+ H , - C H .C H TC H , conditions: heat and Pt catalyst CH.CH=CH, + Br, -' CH3CHBTCHTBT conditions: solution in hexane observation: goes from brown to colourless CH.,CH=CH,+ HI - CH..CHICH. conditions: mix gasesat room temperature CH,CH=CH, + [O] + H,O -- CH.,CH(OH)CH,OH condition: aqueous observation: goes from purple to brown precipitate

4 a

5 a

6 a b

is the hotter, reaction the Because mixture became The o e x o t h e r m i c . m a s s s e ds t h em a s s ft h ew h o l e u i g c s o l u t i o n , 1 0 0 +1 0 0 m 3 2 0 0 m ' = 2 0 0 , n o t h e cm' c = m a s s ft h eH C l . o

c d

rsrr

128 7 a b c

ANswERs C H .C H (O H )C H ,+ N aI propan-2-ol CH3CHICH.+ KOH--'CH.CH=CHz + KI + HrO propene CH3CHICH, + ZNH, - CH.CH(NHr)CH3 + NH4I 2-aminopropane CH. CHI CH. + N a OH ' Pressure. As the pressure is increased, the number of molecules in a given volume increases,and the frequency of collision increasesand hence the rate of reaction, which is dependent upon this frequency of collision, increasestoo. Temperature. If the temperature is increased, the average kinetic energy of the molecules is also increased. This means that a greater proportion of the colliding molecules will have, between them, energy greater than or equal to the activation energy. There will be a larger number of successful collisions and a faster rate of reaction. Catalyst. This increasesthe rate of reaction by providing an alternative path with a lower activation energy, thus a greater proportion of the colliding molecules have energy greater than or equal to the lower catalysed activation energy.
ttt (u

8 CH.CH(OH)CH, - H,O -'CH.CH-CH, conditions: concentrated acid at l7O "C 9 a

H
H-

C-C-C

l t / l l \

b c

H O - H Propanoic acid observation: solution goes from orange to green No reaction observation: solution stays orange CH3CHCICH3 2-chloropropane observation: steamy fumes

U q.)

1O The n carbon-carbon bond in ethene is weaker than the o carbon-carbon bond in ethane. This makes the activation energy less, and so the reaction is faster. 1,1 The C-Br bond is stronger than the C-I bond. This makes the activation energy more, and so the reaction is slower. + L2 C6H1o Br, - CuH,oBr, = 5. 67 g of CuH, o 5 .6 7 1 8 2= 0 .0 6 9 1 m o I Because the reaction is a L:L reaction, the amount of product is also 0.0691 mol. Therefore the theoretical yield of CuH,oBr, = 0. 0691 x 242 = 1 6 .7 g yield = 15.4 g x 100 = 92o/o. The o/o 1 6 . 7g They are stable in air owing to the strong C-Cl 13 and C-F bonds. They then diffuse into the stratosphere where they form radicals and destroy the ozone layer.

(|{
(J

Ea Energy Bacterial and enzyme reactions are also slowed down by a decreasein temperature for exactly the same reason as ordinary chemical reactions, which is that fewer colliding molecules will have the necessaryactivation energy to react on collision. So the low temperature in the refrigerator will slow down the biological decay reactions. i i i

>.
@ OJ

Tonic2.3 KineticsI
I

1 i

ii

The activation energy is the minimum energy that the reacting molecules must have when they collide in order for them to react. It is measured in kJ mol-'. A catalyst is a substance that speedsup a chemical reaction without being used up. It works by providing an alternatlve route with a smaller activation enetgy.

tll

lv

bo q)
ar-l

energy. lowers activation the Never that catalyst say a it becauseis nota substance Light nota catalyst, is form up. andit is used lt is justa specific of energy.

R is the reactant and P is the product.

AusweRs 129

Topic2.4 Chemical equilibriaI

i true ii false iii true i Position moves R-L, becausethat is the exothermic direction. ii Pressure increases, therefore position moves R-L as fewer gas moles on left iii None, catalyst speedsup the forward and reverse reactions equally, reducing the time taken to reach equilibrium. 3 i Alkali removes ethanoic acid, therefore position moves R--L. ii No change becauseAH is zero 4 Solid dissolvesbecausehigh [Cll drives equilibrium L-R. 5 Too high a temperature produces too low a yield. Too low a temperature produces too slow a rate Catalyst allows reaction to proceed at a fast rate at a temperature where the yield is high.

L a It is a seriesof compounds with the same general formula [1] which differ by CH, [L], and have = [3] the same functional group [1] b -(C H (C H ,)C H r).-: correct carbon cha in [ 1] wit h = l2l extension bonds at both ends [.] c i SeeFig 2.4 on page 38. [1] for each = I2l isomer ii Rotation around the z bond is restricted = [1]

the in b Donothave 3 carbon atoms a straight n c h a i. c D on o td r a wh es t r u c t uwe t h b o n d n g l eo f t r i a a s g th 9 0 ' a r o u n d eC = C r o u p .

2 a SeeFig 2.9 on page 45: [1] for having the axes correct (y-axis labelled fraction of molecules, x-axis energy), [1] for having the curves with the correct shape, and [1] for having the T, curve = [3] flatter with the peak moved to the right b Draw the activation energy on the graph to the ri ght of both peaks [1,],expl anati on t hat t he ar ea under the curve to the ri ght of the E . line measures the number of mol ecul esw it h E > E. , [1], w hi ch i s l arger at T, than at T,[1] , so t her e are a greaterproporti on of successfucollisions l = [4]

Topic2.5 Industrialinorganic chemistry

L Reaction is slow at moderate temperatures. Therefore a catalyst is used which allows a fast rate and reasonableyield at 400 "C, that is, an economic rate and yield. A very high pressure (200 atm) is used, even though this is very expensivebecause the yield at ordinary pressures very low. A very is high pressure drives the equilibrium L'R to the side with fewer gas moles. After NH, is separated, the unreacted gasesare recycled. 2 The ammonia liquefies under the high pressureand is removed from the unreacted nitrogen and hydrogen, which are then put back through the reaction chamber. 3 Anode: zcl-(aq) - Cl,(B) + 2eCathode: 2H,O(1) + 2e- -- ZOH-(aq) + H,(g) or 2H'(aq) + 2e- - H,(B)

tu

t l h a T h e o t aa r e a n d etr et w oc u r v es h o u lb et h e u s d same. m t e b M e n t i o n u s b em a d o f c o l l i s i o n s .
3 a i The reagent is HBr [1] and the conditions are = I2f in the gas phase [l.] = [ 1] i i S i s C H ,C H B TC H , = [ 1] b i P i s C H .C H (OH )C H , ii The type of reaction in step 1 is electrophilic = l2l lr,l addition [L] in the conversion of S to P the type is = [21 nucleophilic [1] substitution [1] i For step 2, the reagent is conc sulphuric (or phosphoric) acid or aluminium oxide [1] and = f?l the condition is heat [L] ii For step 3, the reagentsare potassium dichromate(Vl) [1] and sulphuric acid [1] and the conditions are heat under reflux [1] = [3] = [1] d Q is CH,CH(OH)CH,OH [r.]

Answersto PracticeTestUnit 2
The allocation of marks follows Edexcelmark schemes. The marks that you will need each grade are approximately:

rtul

130 Auswens
tl

Dynamic means that the reaction is occurring in both directions [1] and equilibrium means that there is no change in concentrations A lower temperature will move the position to the right [1], becausethat is the exothermic direction (or this produces heat)

yo fo a b a a l f t h ef u l ls t r u c t u r a lr m u lh a d e e n s k e d , u with atom separately, all must then show each b o n ds h o w n . s you make for are b Asthere 2 marks each, must 2 points. iVl ) iv ma c i i P o t a s s i u m n g a n a t e ( s alna l t e r n a t t o e p o t a s s i u m h r o m a t e ( V l ) . yg i v e i t h e r e th Alwa s e dic e f u l ln a m eo rt h e f u l lf o r m u l ae .,g .n o t s 'reflux' 'acidified Also n0r'Crr0,'-lHr'. dichromate' h f n b yi t s e ld o e s o ti m p l y e a t .
4 a Hess'slaw statesthat the enthalpy change for a reaction [1] is independent of the route [1] = [2] b The definition is the enthalpy (or heat but not energy) change when 1 mole [1] of a substance is completely burnt in oxygen (or burnt in excess oxygen) [.] under standard conditions (at L atm = [3] pressure) [1] bonds made i Bonds broken =-2972 4 x C=O 1xC-C =+348 =-2778 6xO-H 5xC-H =+206O Total = -5750 kJ tll 1xC-O =+360 1xO-H =+463 3 Q=O=l-1-a88 " Total = + 47L9 kJ tU = [3] L,H = + 47t9 - 5750 = -103t kJ mol-' [t] ii S eeF ig. 2.1 o n p a g e 3 3 . Labelling of reactants and products [1], with energy of reactants higher than = f2l products and AFI shown [L]

tlI

= l2f

C I

ll

Decreasingthe volume increasesthe pressure and so moves the equilibrium to the right [1] as the right has fewer gas molecules [1] = [2]

tll

= fzl

pr h o a i i I n i n d u s t r i a l o c e s s ets ,ec h o i c e f t e m p e r a t ud e p e n do n r a t e( h i g h r s n a t e m p e r a t ug e o d ) n dp o s i t i o o f ro (h t ra e q u i l i b r i u m i g h e m p e r a t ub e df o r A al a reacti ons).catal yst l ows exothermi c temperature. at fastrate a l ow er

6 a b c d

= [1] ZOt- - O, + 4e-(or Ot- --'lrO, + 2e-) = [1] Al'. + 3e-'Al = [1] The reaction at the anode. The oxygen produced at the anode reacts with = [1] the carbon anode and eats it away e Aluminium oxide (pure bauxite) has an extremely high melting temperature [.], and so = l2l the process would be too expensive [1]

i a e t er a R e m e m b h a t h eo x i d eo nh a s c h a r go f 2 - . c s , e si d b I n b o t h l e c t r o l ya nsc e l l so x i d a t i o n c u ra t v a t h ea n o d ( oa n d a r eb o t h o w e l s ) . e ig t er b b c i R e m e m b h a t o n d r e a k i ns a l w a y s (i) m g b e n d o t h e m+ca n d o n d a k i ne x o t h e r m i c (-) profile been for, had asked ii lf thereaction y (t t y t h e n o um u ss h o w ne n e r gb a r r i e r h e a level energy) your in enthalpy activation The marks that you will need for each grade are diagram. approximately:
5 a i Your answer for the temperature should be between 350 and 500 "C (623 and 773K) = [1] ll A high temperature favours a high rate of reaction [1], but gives a low yield [1], so a temperature is chosen which gives a balance = [3] between rate and yield [1] = [1] is iron tll The catalvst used lv A catalyst provides an alternative pathway [1], which has a lower activation energy [1]

Answersto PracticeTest Unit 38

= I2l

b i

Homogeneous means that all the substances are in the same phase (here all are in the = [U gaseousstate)

Hydrogen: burns with a squeaky pop [1] Oxygen: relights splint [1] Carbon dioxide turns lime-water [f.] milky [1] Sulphur dioxide: the solution turns green [1] The gas which turns moist litmus red then bleaches = [6] it is chlorine [1] 2 a i There is a loss in mass becauseCO, gas [1] is = I2l lost from the flask [1] ii At first the slope of the graph is steep, so the . reaction is fast, then as the slope gets less it

ArusweRs 131
slows down [1], when the line is horizontal (after 6 or 7 minutes) the reaction has stopped (all the acid has been used up) [1]

= f2f

b For experiment 2: your graph should initially be steeperthan in 1 but is horizontal earlier, but with the same mass loss (1 B) as in 1. [1] For experiment 3: your graph should initially be less steep. It should become horizontal later, but at t he s a me m a s s l o s s a s i n 1 . [1 ] For experiment 4: your graph should be steeper than in 1 and become horizontal at twice the = [3] mass loss (2 8) as in 1. [f.] c i Amount of HCI = 1.00 mol dm-" x 50/1 0 0 0 d m' = 0 .0 5 0 0 mo l [L ], a m o u n t o f C a C O 3= ' 1 , , 0 . 0 5 0 0 m o l = 0. 0 2 5 0 mo l [L ]: mass of CaCO, = = [3] 0.0250 mol x 100 g mol-' = 2.5O g tll ii As the amount of acid in experiment 4 is twice that of the other experiments [1], the mass of CaCO. must be at least =[2] 2x2.50=5.009tl]

b T h et e m p e r a t ug e e s . r p , h e a t s p r o d u c e d , d r0 L s0 i an s '; t h er e a c t i oin e x o t h e r m i.c . A H i s n e g a t i v e . 4 a i Any one of: use a larger beaker [1] as this will prevent acid spray escaping [1]; powder the limestone [1] as this speedsup the reaction [1,]; use more acid [L] as this gives larger and = [21 hence more accuratetitres [,]. Choose titres 1 and 3 [1]; ' 1, (14.9O+ 14.85) = 14.8 7 cm ' 1L1 mean = 5

ll

b i

a T oa n s w eh i s o uh a v eo w o r k u ti f t h e tr y t o r e a c t i os f a s t eo r s l o w e r a nn 1 a n d h e t h e r in r th i w t h em a s s f C 0 ,l o s t s t h es a m e , o r e r l e s s i m o o t h a nn 1 . i have halve moles HCI c i You to the of because t h e r e r eh a l a sm a n v o l eo f C a C 0 ,s a f m s a m o l eo f H C l . s

3 a Any two of: use a pipette to measure out the CuSO, solution [1] as the volume is measuredmore accurately; [1] use smaller piecesof iron [1] as there will be less heat loss in a faster reaction [1]; use a polystyrene (or plastic) cup [f.] as this reducesheat loss [1]; measure temperature for several minutes before addition of iron [f.] as this allows for a more accuratedetermination of the initial temperature [1,]; measure temperature more frequently [1] as this makes the extrapolation more accurate [1]; use a thermometer which reads to 0.5 or 0.1 O C [1] as this gives a more accurate temperature [1]; stir the reaction mixture gently [1] as this ensures an even temperature in the liquid [1]. = [4] -' d .g-' x 15.2' C b i Heat given out = 50.09 x 4.18Jg = 3 L 8 0J o r 3 . 1 8 k J = [1] = ii Amount of CuSOn 0.500 mol d m - ' x 5 0 / 1 0 0 0 = [1] dm'= 0.025mol = [zl iii -3.18 kJ + 0.025 mol = -L27 kJ mol-' (Lmark for the negative sign and 1.for the number)

A mount of N aOH i n ti tre = 0.100 m ol dm - ''x = [1] 1 4 . 8 7 5 1 7 0 0d m ' = 0 . 0 0 1 4 8 7 5 o l 0 m ll A mount of H C I i n porti on = 0.001488m o1 = [1] iii Total amount of HCI remaining = = [ 11 10 x 0.001488= 0.0L488 mol iv Original amount of HCI = 2.0 mol dm-' x = [ 1] 50/1000 dm" = 0.100 mol v A mount of H C I used = 0.100 - 0 . 01488 = 0.08512 mol = [1] ' 1r r 0.085L2 = O . O 4256 vi A mount of C aC O. = mol [1] = 0.04256 mol x 100 g mol- ' = 4. 256g viiPurity= 100x 4.256915.249=8t.2o/o = [1] = [ 1] i C w hi ch i s betw een I4.75 and 14 . 95 ii One of: not reading from bottom of meniscus, not reading meniscus at eye level, burette not vertical, air bubble below tap, funnel left in = [U top of burette

-- r2l

tll

= l2l

i n a i l f p o s s i b ltet r a t i o e x p e r i m e n th o u l d e ss b to t d e s i g n e d g i v e i t r e s f a b o u2 5 c m ' . o t i i Y o us h o u l d n l yc h o o s t i t r a t i o v a l u e t h a t n o e s t a r el e s s h a n0 . 2c m 3 p a r t . a forget thatthe rati oof H CI o CaCO , b vi D on' t t is 2 ' .1 . 5 a Place the chemicals in a round bottomed flask [1], fitted with a reflux condenser [1]. Heat for severalminutes [1]. Distil off the propan-2-ol [1]. Collect the fraction that boils off around = [5] 82 "C [1] b A mount = 6.15 g + 123 g mol -' = 0.0500 m ol [ 1] vol of NaOH = 0.0500 mol * 2.O mol dm-' = = f}l 0.025 dm' = 25 cm' [L] yield would give 0.0500 mol of propan-2c 100o/o ol = 0.0500 mol x 60 g mol -' = 3.00 g t ll. = I2-l yield = 3.00 x 80/1,00 = 2.4 g [1] 80o/o d One of: the reaction did not go to completion; it is an equilibrium reaction; some propene was formed by elimination. = [1]

lll

,uErr

132 AnsweRs
ii AH, of CaCl(s) = + 193 + 590 + LZt + (-36a) + (-650) = - 110 kJ mol-t iii AH, of (ZCaCl(s) -' CaCl,(s) + Ca(s)) = -790 -2 x (-L10) = -57O kJ mol-' Therefore products are more thermodynamically stable than reactants. Thus CaCl will disproportionate. 2 NaF: Experimental lattice energy = theoretical lattice energy. Therefore it is nearly t0oo/oionic. MgIr: Experimental >> theoretical. Therefore it is considerably covalent, becausethe doubly charged Mg"'ion is much more polarising than the singly charged Na- ion. Also the much bigger I- ion is more polarisable than the smaller F- ion.

(a)The is be reactionslow, it must heated. so x is ne e, 1 - b r o m o p r 0 p av o l a t i ls oa r e f l uc o n d e n s e r m t y m u s b eu s e dF i n a ltl h ep r o d u c t u s b ed i s t i l l e d t . mixure. it from reaction the offto separate

Unit4
II Topic4.7 Energetics
1 a i Ca*(g) + Cl(g) -364

Topic4.2 The PeriodicTableII

l a i
lt lll

Ca(g) + Cl(g)

|.'no l+nt

Ca*(g) + CI(g)

ca(g)+lrcb1sy

NaCl(s) + aq - Na'(aq) + Cl-(aq) S i c l n+ Z H r O - S i O z + 4 H C l PCl, + H.,O-' HrPOn+ 5HC1.

| +res
+'lrclr(g) Ca(s)
CaCl(s)
It

e td t y D on o tb et e m p t e o g i v eh et o t a l lw r o n g q u a t i o n : H N a C l H , 0 - -N a O + H C l . +
NaCl is ionic and so iust dissolves Sicln and PCl, are covalent and so react to give H C I. A lone pair of electrons on the oxygen atom of HrO forms a dative bond into the empty 3d orbital in the silicon atom. This releases enough energy to break the Si-Cl bond. In CCln, the carbon atom has no 2d orbital and so a dative bond cannot form before the C-Cl bond breaks, and the four large chlorine atoms around the small carbon atom sterically hinder the approach of a water molecule. As a base: Al(OH).(s) + 3H.(aq) -'Al'.(aq) +3H,O(|) and as an acid: A t(OH ),(s)+ 3OH -(aq)' [A I(OH ),]' -(aq)

ca'*(g) + 2cl(g)

Ca-(g)+ 2cl(g)
l

.,,,0 J
| +seo
+ x2 l+I2I

-364 x 2

ca'*(g)+ zcl-(g)

Ca(g) + 2Cl(g)

Ca(g) + Clr(g)

+1e3 | + Ca(s) Clr(g)

CaClr(s)

i of Not e hatth e e n th a l po f a to m i s a ti o n c h l ori nes t y /,C -f or t he r e a c ti o'n 1 ,(g ) C l (g ).

NIr of CaCl,(s) = + L93 + 5 9 0 + 1 L 5 0 + 2 x I2 ' 1 .+ 2 x (-3 64) + (-2237) = -79O kJ mol-'

ionic and of For reactionsoxides hydroxides, the Basic easier. oxides/hydroxides are equations usually ie , a t s e r e a cw i t hH -i o n so g i v e i m p lp o s i t i v o n sa n d c i d i c t to negative react 0H-ions give with oxides/hydroxides ions.

ANswERs 133
3 a i ii iii b i ii iii 4 a b Mg(OH),(s) + 2H.(ae) * Mg'.(aq) + 2H,O(l) PbO(s)+ 2H.(aq) --'Pb'.(aq) + H,O(l) SO, + acid: no reaction. Mg(OH), + alkali: no reaction PbO(s) + ZOH-(aq) + H,O(l) - Pb(OH),'-(aq) SO,(g) + ZOH-(aq)* SO,'-(aq) H,O(l) + b i Becausereaction L*R is exothermic, a decrease in temperature causesK. to increase,and so the position of equilibrium moves to the right. As the reaction going from right to left causesan increasein the number of moles of gas, a decrease pressurewill causethe in position of equilibrium to shift from right to left. K. is unaltered. There will be no effect on either. A catalyst speedsup the rate of both forward and back reactions equally, and so equilibrium is reached sooner.

ii

PbO, + 4HCl -' PbCl, + ZH'O + Cl, Sn'.(aq) + 2Fe'.(aq)-* Snn.(aq)+ 2Fe'.(aq) iii

Topic4.3 Chemical equilibriaII

1, 2SO3+ Start(moles) 0.0200 Change(moles) -0.0058 2SO, + 0 +0.0058

o,
0 +0.0029

Topic4.4 Acid-base equilibria

1. C,H.COOH + H . + C T H . C O O = PK,, 4'87 ThereforeK , = i n v e r s e l o g ( - 4 . 8 7 ) = 7 . 3 5 x 1 0 - ' m o l dm-' [ H - ] = [ C , H . C O OI K " = [H -l x [C .H .C OO I =

1 m o l e f S 0 ,g i v e s m o l e f S 0 ,a n d' / , m o l e f 0 , o 1 o o Equilib.moles 0.0142 0.0058 0.0029 0.074217.52 0.0058/1.s2 0.002917.s2 il*/mol dm= 0 .0 0 9 3 4 = 0.00382 = 0.00191 ^ 4= [SOJ" x [O,]

lc.H.cooHl
[Hl'

= 1 . 3 5x 1 0 ' m o l d m '

Ic.H.cooHl
[H]= (K"x[C,H'COOH]) --l.7zx1o-'moldm-' =@

rsoT
= (0.00382)'zx 0..00191 (0.00e34)' = 3.L9x 10" mol dm-'' zNO(g)+O,(g) + 2NO,(g) 1.0 1.0 0 Total = 2 mol -0.60 -0.30 +0.60 0.40 0.70 0.60 Total= 1.7 mol
O.4Oll.7 = 0 .2 3 5 O . 7 O | I . 7 0.6011..7 = 0 .4 ' 1 ,2 = 0 . 3 5 3 O .4 1 2x 4 = L.65 0.353 x 4 = I.4l

= pH=trtoslHt 2.76
2 a End poi nt i s at 25 cm' N aOH .

Start (moles) Change (moles) Equilib. (moles) Equilib. mole fraction

l2 11 10 9 p H 8 7 6 5 4 Half way End point

Partial pr es s ur e/ a tm O .2 3 5 4 x o.g4 ^= Kn = (p of NOr)'

(p of No) x p o f O ,
= (1.41)'

20
VolumeNaOH/cm3 H al f w ay to end poi nt i s 12.5 cm' , which is when [HA] = [A-]. pH at this point is 4.95. ThereforepK = 4.95.
b 3 a

25

(oe4)TT.6s
= 1. 4 at m - ' 3 a
ISOr],"no,'

ffi
=

(q.2\,

( o . 2 ) "x 0 . 1 = 10 mol-t dm' which is not equal to K., so it is not at equilibrium. As the quotient <K., the reaction moves left to right, until equilibrium is reached.

P henol phthal ei n. A buffer is a solution of known pH, which will

T h e ] t e r m n l y q u a lK w h e nh es y s t e m i n o e s t is [ equilibrium.

T h i si s a s u i t a b lie d i c a t o re c a u sies r a n g e f p H n b t o f o r i t s e n t i r e o l o u c h a n g ie w i t h i n h ev e r t i c a l a r t p c r s t o f t h eg r a p h .

134

ANswERS resist change in pH when contaminated with small amounts of either acid or base. It consists of any weak acid and its coniugate base, such as ethanoic acid and sodium ethanoate.

(b)

cHs

CHs

I
F

I
HO(/ H

--c(-'--

U O H H

.-';c\

'Nearly constant' that Donotsay thepHis constant. is acceotable.

The salt is fully ionised: + CH'COONa(aq) - CH,.COO-(aq) Na-(aq) The weak acid is partially ionised: CH.COOH(aq) + H.(aq) + CH.COO-(aq) ions from the salt suppressmost The CHTCOOof the ionisation of the acid. If H- ions are added to the solution, almost all of them are removed by reaction with the large reservoir of CH.COO- ions from the salt, thus the pH hardly alters. H.(aq) + CH.COO-(aq)-* CH.COOH(aq) If OH- ions are added, almost all of them are removed by reaction with the large reservoir of CHTCOOH molecules from the weak acid, thus the pH hardly alters. OH-(aq) + CH,COOH -' CH.COO-(aq) + HrO(l)

ii o o f i l f t h e r es a d o u b lb o n dl , o ko rg e o m e t r sc m e r s . e not bond them with correct angles, 90". the Draw s d n d nt L o o ko rf o u r i f f e r eg r o u pa r o u na c a r b oa t o m f il f o ro p t i c as o m e r i s m .

Ms/drv ether CH3CHICHT----:---------+ CO2(s)then HCI(aq)

CH3CH(MgI)CH3

CH3CH(MgI)CH,

CH3CH(CHJCOOH

or KCN CH3CHICH: +

CH3CH(CH3)CN

CH

heat under reflux with HCI(aq)

3cH(cH3)cooH

ry F our equa ti o na ren e c e s s a fo r a g o o da n s w er, s e w i t ho n eo f t h e ma s a n e o u i l i b r i urm a c t i o n . 3 a

i a n r A n i n c r e a si e t h en u m b eo f c a r b o n t o m s n a c h a i n e o ts i n d i c a t e h eu s eo f a G r i g n a rrd a g e n tr a c y a n i d e . Add water to each: ethanoyl chloride gives off steamy fumes of HCI; ethanoic acid shows no visible reaction. Add PCl, to each: ethanoic acid gives off steamy fumes of HCI; ethanoyl chloride shows no visible reaction. Add to a solution of iodine and sodium hydroxide: propanone gives a pale yellow precipitate; propanal gives no precipitate. Add ammoniacal silver nitrate solution and warm: propanal gives a silver mirror; propanone gives no mirror.

[H] = K" x [weak acid]/[salt] [weak acid] = 0.44 mol dm-' A m ount of s alt = 4 .4 1 8 2= 0 .0 5 3 7 m o l . 1 T her ef or e [ s alt ] = 0 .0 5 3 7 /0 .L= 0 .5 3 7 m o l om [H] = I.74xlO-s x0.44 0.537 = 1.43 x 10-' mol dm-' Therefore pH = -log (1.43 x 1,0*;= 4.85.

n tt o s d T h e o n c e n t r a t i o nh en u m b e rf m o l es h o u lb e c u s e dn b u f f ec a l c u l a t i o n s . i r

Answersto PracticeTestUnit 4
The allocation of marks follows Edexcel mark schemes. The marks that you will need for each grade are approximately:

II Topic4.5 Organicchemistry
1 a

(a) H \

CI

C-C / \ CHs CHs

H \

CH" /

C-C / \ ct cHs

ArusweRs 1.a

1v t 5 te

Mg'.(g)

Ms"(g)
Mg(s) +

r r

zcl- (g

iii One of: the reaction is faster, or no catalyst is required, or with ethanol the reaction is an = [1] equilibrium
I \ r H H

zcl(s)
Cl,(g) -* MgClr(s)

t t

H
H-C-f H

r o - ? - c| - H |
\ H H
o

Correct cycle with all state symbols [2]

Mfo,.ution = SU[l Of all Othef ChangeS

- 6 4 2 = + L 5 0 + 7 3 6 + 1 4 5 0+ 2 x 1 2 1 +2x(-364)+LE[2] = [5] LE = -2492 kJ mol-' [1,] b i The ionic radius of Sr'* is < that of Ba'' [1], and so there is a stronger force of attraction bet ween c a ti o n a n d a n i o n i n S r(O H ) .than i n

Ba(OH), [r.]
ii

= l2'l = I2l
3 a

fl w a A s a f u l ls t r u c t u r ao r m u l a a sn o ta s k e dv, 0 un e e d n o ts h o w l lt h ea t o m s . a r lo b A n ya m i n e, v o u dd . o c F u l s t r u c t u rfa lr m u l ave e r e s k e d .o a l la t o m s l r a s m a n db o n d s u s tb es h o u r n .

Energy is releasedwhen the d-oxygen atom in water [1] is attracted to the positive cation [.]

CtH.t C.
I

C.Ht

= -L?ttice energy + A-F1n,.,,o,inn iii A.Ff,oru,,on of cation + Mhyd,u,ion the anions [.] of AI1,,, Ba(OH), = +2228 - 1360 - 92O = -52kJ

'..

CHs

AI1,.,Sr(OH), = +2354 - 1480 - 920 = -46kJ

tll

t
H

'oH

Ho I
H

...c_ -.n,

tll
so A-F/,o,u,,u. of Ba(OH), is 6 kJ more exothermic = l4l and so it is more soluble [,]

a R e m e m b h a t a t t i ce n e r g i e sen e g a t i v e . t er l e ar b i i i l f y o uf o r g otto m u l t i p- y 6 0b y2 ( t h e r e l4 a r e 0 H - o n sy o uw o u l do s e m a r k . 2 i ) l 1 Another to score 3rdand way the 4th m a r kis :f r o m r - - B a t h el a t t i ce n e r g y s , e S decreases126kJ [1],butAHnro,,,,o. by of the cation decreases120kJ [1] only by
2 a i ii iii b i ii c
I

b Reagents: C,H.CHO[l] and CH.MgBr [1] or CH*CHO [1] and C,H,MgBr [1] = [3] Conditions; dry ether solvent [1] =[1] ci YiSCH,CHTCOCH, =[1] ii Yisaketone iii Add 2,4-dinitrophenylhydrazine [1] which gives an orange ppt. [1] Add Fehling's solution (or ammoniacal silver nitrate) [1] which stays blue (does not give a = [4] silver mirror) [L] = IZf iv CH[,, [f.] and C,H.COONa [1]

= [1] cH.cHrcHrc=N = [1] LiAlHn or NaBHn = [1] cH3cH2cHzcHzNH2 The lone pair of electrons on the N atom = [1] make it a base = [1] RNH, + H* - RNH3. H H H H 4 a

m t a Y o u u s m a k e na t t e m p t a 3 - Dd r a w i n g d a a an t h et w oi s o m e r s u s b em i r r oirm a g e sf e a c h m t o other. m t t i b i i i Y o u u s s h o wh a t t i s a c a r b o n y l c o m o o u n d d h e nh a t t i s n o ta n an t t i a l dh y d . e e b i v C , H . C 0 0 H u l d ea c c e p t e dt h eo t h e r wo b as organproduct. ic

= [1]

/ H - C - (^ t \ I
H ii

N
\

l l -C-C-H
l
H H

o
= [1]

It forms a substituted amide

b Amount of AtCl = 0.63g162.5g mol-' = 0.01 mol Amount of Alcl, = 0.67 9/133.5 $ rnol-' = 0.005mo1 [1] total moles = 0.015 mole fractions: AlCl = O.667,AlCl, = 0.333 [1] p(AlCl) = O.667 x 2 = 1.33 atm partial pressures: = 2 x 0.333 = 0.667 atm [L] P (A l C l .) K " = (1.33 atm)' 10.667atm = 3.56 atm' 1f 1 = 1+1

--

e
tal

-e;
A '

\-

ir

136 AxsweRs
c An increase in temperature shifts the equilibrium in the endothermic direction. .'.AH is positive = [1] d Ko stays constant [1] The position of equilibrium moves to the side with fewer gas molecules [1], = [3] which is to the left [1] Mix scrap aluminium metal with AlCl, and heat to form AlCl [U, remove from excessAl, then cool (or increase pressure)and pure Al and AlCl3 are formed. The latter is then used again [1] = [2]

t4 12 10 pH8 6 4 2 0 25 Vol. NaOH/cmE

Shape of curve correct [L], start at pH = 4 llf, vertical at 25 cm' [1] and at a pH of between 7 and = [5] 11 [f.], curve flattening off at pH 13 [1]
i HrSOl --' H* + HSO.,- [L] HSO.*-+ H* + SOn^ [1]

ir e a S o l i dd on o ta p p e an K o x p r e s s i 0 n s . s pressure. pressuremole x is fraction total b Partial a d c K i s o n l y l t e r eb yt e m p e r a u r e . 5 a i -+ MgO(s)+ H,SOn(aQ) MgSO.,(aq) H,O(l) Correctequation [1] statesymbols[L] = lz'J ii A white solid [1] reactsto form a colourless

= fz'l solution [1.] + 4NarPOn 6HrO + b i PnO,o L2NaOfl ---+ + + 2NasPOn 3HrO or PrO., 6NaOH ---+ = I2f All speciescorrect [l.], balanced [1] (or HCI) ii For having 2 equations, one with H' and the other with OH- (or NaOH) [1,] and: AI(OH)3 + 3H* -- Al''* + 3HrO or AI(OH)3+ 3HCl --' AICIr + 3H,O [1.] plus AI(OH), + 3OH- -r Al(OH)u'-or = [3] AI(OH), + 3NaOH -'Na,Al(OH). [1] is MgO is basic, AI(OH). is amphoteric and PnO,o acidic [L] showing the metallic character of the = f2l element decreasingacrossthe period tll get more As a Group is descendedthe oxides basic [1]. Indium is in the same Group as amphoteric aluminium, so indium oxide will be = I2l basic [1]

= [2]

ii

The second ionisation is incomplete and is suppressedby the H. from the first ionisation, = [1] and so produces very few H. ions

(how ionised) dilute with conf a Don't useweak (how any oles). m m p b n f b T og e t r o m Ht o [ H - ]u s e h e1 0 " u t t oo n , t your alculator. c n s a i d S u l p h u r i c i ds o n l y t r o n ig i t s1 s t n ha a s o, i o n i s a t i o n t h i ss o l u t i o n s p Ho f 0 . 9 8 o t 0.699.

equations. are bad Many students very atwriting n n m t s t t Y o u u s m a k e u r eh a y o ul e a r t h ee q u a t i oin s T o p i4 . 2o l t h es p e ci ic a t i o n . c f you you what would to a Whenever areasked state bef e te t s e ey o um u s d e s c r i bh ea p p e a r a n c e o ra n d , reaction. after
6 a An acid is a proton donor [,], Weak means that it is incompletely dissociated (ionised) [L], but dilute means that its = [3] concentration is small [1] b i pH = -log,u [H.] ii Ku = 3.72 x lO-" = [H.]tOCl-l = [ H] = 10- o n 5 .8 9 x 1 0 -' mo l d m = 0.0932 mol dm-' [1]

U n i5 t
equilibria Topic5 .7 Redox
1 a i ii iii iv CrrOr'- (aq) + 14H'(aq) + 6e- -- 2Cr"(aq) + THrO Snn.(aq)+ 2e- -- Sn'.(aq) IO, (aq) + 6H .(aq) + 5e- -' 1,1,+ 3H rO l, + 2e- -- Zl-(ag)

=[u
tU
tll

lHocll

-r

lHl = [octl tl] = * x .'. tHOCll (5.89 10-')' 3.72x 1 0 *

ns ns s A l la r er e d u c t i oa n d oh a v e l e c t r o o nt h el e f t . n l o ns th T h e u m b e rf e l e c t r o e q u a l s et o t ac h a n gi e n nu oxidation mber.

= [41

ANswERs 137
b i CrrO,'-(aq)+. 14H.(ag) + 3Sn'.(aq) - zCr'.(aq) + TH.,O+ 3Snn"(aq) = E,"".tio.+1.33 - 0.15 = +1.18 V. Feasible as E,"u.tion > 0.

Topic5.2 Transitionmetal chemistry

t The water ligands split the d orbitals into two of higher energy and three of lower energy. When white light shines on the solution, an electron absorbs visible light energy and moves (jumps) from the lower to the higher energy level, absorbing some of the red/green light and leaving blue light. 2 a + [C r(H ,O).]" (aq) 3OH -(ag)-C r(OH ) , ( s) + 6H, O

E q u a t i o ni i s m u l t i p l i e d3 , r e v e r s e d d ai by an added equation to a i.
Ior(aq) + 6H.(aq) + Sl-(aq)- 3I, + 3H,O = *1.19 - 0.54 = +0.65 V. E,"u.tion Feasibleas E"u..,o. 0. >

T h i s e a c t i os d e p r o t o n a t i o n . r in E q u a t i o nv i s m u l t i p l i e d5 1 2r,e v e r s e d d ai by an a d d etd e q u a t i o ni i . o ai
Equations are: Fe(s^) 2H.(aq) * Fe'*(aq)+ H,(g) + SFe"(aq)+ MnOf(ae) + 8H'(aq) - SFe*(aq)+ Mn'.(aq) + 4HrO Amount of MnOn- = 0.0235 x 0.0200 = 4 . 7 Ox 1 0 * m o l Amount of Fe'*in 25 cm' sample = 4.70 x 10* x 5/1 = 0.00235 mol t h e n C r ( O H ) , ( s + 3 O H - ( a Q+ C r ( O H ) . ' - ( a q ) ) )

,/

T h i s c c u r b e c a u s er ( l l l i s a m p h o t e r i c o s C ,y + + [Fe(H ,O)u]" -(aq)ZOH -(aq)- Fe(OH) : ( s) 6H, O then no further reaction. [Zn(H,O),]'.(aq)+ ZOH-(ag)'Zn(OH).(s) + 4H.O then Zn(OH),(s) + 2OH-(aq) - Zn(OH),r (aq) + [Fe(H,O),]'.(aq) 3NHr(ag) * Fe(OH),(s)+ 3NH; (aq) + 3H,o

c 3 a

5/ 1 bec auste e re re5 F e 2 - 1 M n 0 oi - th e e quati on. h a to n Amount of Fe" in 250 cm' sample = 0.0235 mol Mass of Fe'*= rl?ss of Fe = 0.0235 x 56 = 1.316 g Purity of iron in steel = 1.316 x L00 = 99.7o/o 132 Anode area: Fe(s)-- Fe'.(aq) + 2e-

This reactiondeprotonation. is then no further reaction. + + [Cu(H,O)J'.(aq) 2NH.(ae) Cu(OH),(s) 2NH; (aq) + 4H"O

This reactionalso is deprotonation. 0xidationtheAnode, electrons theright. at so on

'lrOr(aq) + HrO + 2e- -' 2OH-(ae) then Cu(OH),(s)+ 4NH,(aq) + 2H,O(l) --' [Cu(NH,)o(H,O)J'.(ag)+ 20H-(aq)

Cathode area:

Theoveralreacti on l i gand l is exchange.

Reduction Cathode,electrons theleft. atthe so on

Between anode and cathode: ZFe(OH),(s)+ 2OH-(aq) - Fe,O,(s)+ 3H,O(l) + 2e '|,O,(aq) + H,O(l) + 2e- - 2OH-(ag)

4 a

VOI(aq) + 4H.(aq) + 3e--- V'.(aq) + ZH,O

Vanadium(V) is reduced, electrons ontheleft. so are The o x i d a t i o n m b e r a n g e s 3 , s ot h e r e u s b et h r e e nu ch by m t electrons.

t a

138 ANsweRs b c d VOI(aq)+ ZH.(aq) e - VO"(aq)+ H,O 1 V"(aq) + HrO -- VO'.(aq)+ 2H.(ae)+ eVO"(aq) + H,O -- VOi (aq) + 2H.(aq)+ e'C), the If the temperature is too high (>5 benzene diazonium chloride will decompose. b but C.H'N=NC.H.,OH is C.H.N=NC6H*Oacceptable.

III Topic5.3 Organicchemistry

1 a The bromine reacts with the iron catalyst to form FeBr.: ZFe + 3Br, --' 2FeBr, The FeBr. then reacts with more bromine to form Br'(the electrophile) and FeBrn.

II kinetics Tonic5.4 Chemical

L v r P v v . ^

Rate = klHll' k = rate. = 2.0 x 10' mol dm-' s-' = 0.080 s' mol' dm'

tHI]"

The intermediate cation loses H. to the FeBr".

t- \ st

l-

GyB'l,,rl.-,, 1 v / l t l
L B r I

2 Cany out the following procedure: s* Placeequal volumes of solutiorl, e.8. 50 cm'of 0.1.0 mol dm-'ethanoic acid and methanol in flasks in a thermostatically controlled tank at 60 "C. ,,,:' Mix, start the clock and replace in the tank. 'ii:i intervals of time, pipette out 10 cmt portions At and add to 25 cm'iced water in a conical flask. + Rapidly titrate with standard sodium hydroxide solution using phenolphthalein as the indicator. .# Repeat several times. llr Plot a graph of the titre (which is proportional to the amount of ethanoic acid left) against time. 3 Time taken for the concentration to halve from 1.6 to 0.8 mol dm-' = 26 minutes. Time taken to halve again to 0.4 mol dm-'= 26 minutes. Time taken to halve again to O.2 mol dm-'= 26 minutes. tr,ris a constant, therefore reaction is 1st order.

O-u'*

+ nu, FeBr,

IV Topic5.5 Organicchemistry
that: Check ,s. arrow ring on the starts thedelocalised andgoes not the towards Br-(and to the+ of Br-) .'ffi intermediatea broken ring delocalised has the witha+insideit .r thearrow the of from o bond thering/H starts g o e sn s i dte eh e x a g o b u t o t (n n i h atom nd a to directly the+).
1 a Add 2,4-dinitrophenylhydrazine. Both give an orange precipitate. Add ammoniacal silver nitrate solution. Only pentanal will give a silver mirror on warming.

s F e h l i n g 'o l u t i ow , i c h i v e a r e dp r e c i p i t a t e , ss nh g silver in of be could used place ammoniacal nitrate.

Heat under reflux with aqueous sodium hydroxide.

It is energetically favourable for the intermediate cation to lose an H* and gain the stability of the benzene ring, rather than add Br- as happens with alkenes. The first step is the addition of a CN- ion. HCN is too weak an acid to produce a significant amount of CN- ions. NaOH will deprotonate HCN molecules, producing the necessaryCN- ions. 'C), the rate is 3 a If the temperature is too low (<5 too slow.

firstbe and arecovalent so must Halogenoalkanes o ha op h y d r o l y ste d r o d u c e l i die n s .

Cool and acidify with dilute nitric acid, then add silver nitrate solution.

ANswERs 139
The 2-bromo compound gives a cream precipitate insoluble in dilute ammonia but soluble in concentrated ammonia. The 2-chloro compound gives a white precipitate which dissolvesin dilute ammonia. Warm with dilute sulphuric acid and potassium dichromate(VI) solution and distill off any product into ammoniacal silver nitrate s olut ion. Methylpropan-Z-ol does not change the colour of the potassium dichromate(VI). Methylpropan-1-ol turns it from orange to green and the distillate gives a silver mirror. Butan-2-ol turns it from orange to green and the distillate has no effect on the silver nitrate solution. To confirm, add a few drops of the butan-2-ol to iodine and aqueous sodium hydroxide and warm gently. A yellow precipitate of iodoform will be produced. approximately:

a i

C onsi der experi ments1 & 2: w hen [ RCHr Cl]is i ncreased3 ti mes, rate al so i ncreas es t im es 3 .' . 1st order w i th respectto [R CHr Cl] .t ll [U , C o n s i d e re x p e r i m e n t s1 & 3 : w h e n concentrati onsof both are doubl ed, t he r at e is -l i ncreased ti mes [1], .' .1storder w it h r espect = [4] to [OH ] as n' el l [1] = [1] i i R a t e= k [ R C H . C l lx [ o H ] i i i k = r a t e / ( [ R C H - C lx [ O H - ] ) l -1.0 l0'mol dm ' s ' = x 0 . 0 5 0m o l d m x 0 . 1 0 r n o l d m - ' = l2'l = 0.080 [r] mol ' clm s ' [U m i v A s i t i s l st order i n both, i t i s a S ,,2 echanism

tu.
R

R
I I

lx T h e1 ' a l c o h o s p a r t i a l oy i d i s e d a n a l d e h y d e . il to T h e2 " a l c o h oi ls o x i d i s etd a k e t o n e . o T h e3 " a l c o h oi ls n o to x i d i s e d . g) B u t a n - 2 -c o n t a i nts eC H , C H ( 0 Hr o u p n ds o ol h a g i v e s p o s i t i vie d o f o r m s t . a o te

H -

()'

/--\

\
,(:-

Cl ---------------- H

() ----C---- Cl
D r

----------------

l
H H R CI

/ \
H -

:
J

/
The substanceis probably aromatic (> 6 carbon atoms and about the same number of hydrogen at om s ) . 120 is the molecular ion. 105 is 15 less than 12O and is probably causedby loss of CH,.. 77 is probably causedby the (CuH,).group (77 is 43 less than 720 and is probably caused by loss of
HO-C^ r\

Curlv arrows from O of OH- to C and from C-Cl o = [3] bond to Cl [1], correct transition state [L]

cocH.).
X is probably C.H.COCH.. The 120 peak is causedby (C.H.COCH3)., the 105 peak by (C.H.CO)', and the 77 peak by (CuH,).. 32OOcm-' is due to O-H, 1720 cm-' is due to C=O, and 1L50 c m -' i s d u e to C -O . Six of the carbon atoms are in a benzene ring. The remainder are either CrH, group or 2 x CH, groups. Y is C.H,CHrCH.. [5 H's in CoH.,2 H's in CH, and 3 H's in CH..] Z is CoH,(CH.)r. [6 H's in 2 x CH, groups, 4 H's in CuHr.] youar e i Y oumustmake t cl ear hatdata w u s i n g n dh o wy o ua r r i v e t e a c h r d e r . a a o i v Make surethatal l yourcurl yarows ar t st a e i t h ea t a b o n d n dg o t o a n a t o m0 r a t a n r a t o m n dg o t o a b o n d . a i

2 a The el ectrophi l ei s C H .C O* [1].The equat ion is:

CH,COCI + AlCl,,--+ CH,,CO.+ AICI*- [t]

= I2l

i At c+ _-_+ l ( * . I t
\
CH, -

H
.--.-}
CH,

v/\

^v\ l( )l
v

i
cH,
+ H *

Answersto Practice TestUnit 5

The allocation of marks follows Edexcel mark schemes. The marks that you will need for each grade are

Curly arrow from ring to C of CO' [1], correct intermediate [,], curly arrow from C-H o bond to = [3] ring [L] Reactthe phenylethanone, C.HTCOCH3, with HCN [1], with a trace of base (or in a solution buffered anywhere between pH 5 to 9 or add a mixture of HCN and KCN) tll. This produces

140 ANswERs
CHs CsHsC -CN 4 a Dip a platinum elec-trode[1] into a solution which is L mol dm-'in both Fe'*and Fe'. ions [1]. This is connected via a salt bridge (containing potassium chloride solution) [U to a standard hydrogen electrode [1]. The potential is measured with a high resistancevoltmeter (or a = [5] potentiometer) [L] - Au [1] b i Au''* + 3e= l2l Fe" -t Fe"*+ e- [1] = tll ii Au" + 3Fett- Au + 3Fet' E (gold) iii Au'. + 3e- - Au E ' = -0 . 77 v 3Fe' *-- 3Fet' + 3eadding the two half-equations gives E cell E (gold) + (-0.77) = E' (cell) = + 0.73 [U

I
I

oH
Now add aqueous sulphuric acid (or any named acid) [L] and heat under reflux [1]

tll

_ [51 = amounts of ester and oH- [1] d Mix known remove sample [t] at known time [1.] quench the reaction by adding ice cold water [1,] titrate unreacted OH- with acid [t] Calculate rate = change in [OH-] + time [1] Repeat with double [ester] and the same tOHl tll Repeat with double [OHl and the same[ester]-tl] = [8]

= E (gold)= * 0.73+ O.77 + 1.50V[1]

= [21

b i

go the must towards C of theC0nolthe curly arrow b The a T i a e t , C o f t h eC H g r o u p . h e n t e r m e d imtu s h a v e b r o k e n f g w a s r i n g o i n g c r o sa l lb u tt h eC a t o m h i c h a s o r m e d w t 0 t h eb o n d i t h h eC H , Cg r o u p . n p h y e, d T h e Hw o u l d a r d lc h a n g s oa m e t h oid v o l v i n g w s a ov r he m e a s u r itn g p Hc h a n g e e t i m e o u l d c o r e m a x i m uo f 6 . m
3 a The reagent for step 1 is magnesium [1], and the = l2l conditions are dry ether [1] Potassiumdichromate(Vl) [1] and sulphuric b i = f2l acid [1] = [1] ii Distil off D as it is formed [1] iti Ethanoic acid (CH.COOH) or ethanoate ions

(gain takes at Reduction of electrons) place the gold it acts thecathode. as because electrode g e n ns t T h u s u ' .i o n s a i n l e c t r o t h a f l o w eid t h e A w l it F e x t e r nc ilr c u f r o m e "i o n s h i c ho s t h e m . a n by n . he i i i M u l t i p l y itn g F e ' h a l f - e q u a t i o3 d o e s o t a l t eirt sF v a l u e . sn t w o A n o t h e ra y f d o i n gh ec a l c u l a t i o t o u s e potentials thus: reduction thestandard ag F o f o x i d i s i n g e n(tg o l d-) f o f r e d u c i n g ) a g e n(ti r o n= P o f t h ec e l l .
3d

5 a

Fe:rArl rutrntrtr

4s

(cH3coo) tll

= [1]

E is CHTCH,CH(OH)CH. [f.] for any secondary = f2l alcohol and [.] for the correct formula F is a carbonyl compound as it reacts with d i Z,4-dinitrophenyl hydrazine [U, but it must be a ketone and not an aldehyde as it does not react with ammoniacal silver nitrate [1] ii

cr: rA4 trtrtrtrtr

cr3*: trtrnII rArl
+ b FeCrOn 4C - Fe + Cr + 4CO = f2l species [1], balancing of equation [1] = [1] i [Fe(HrO)u]" - Fe(OH), + 6H,O ii [Fe(H,O).)'.+ ZOH+ or [Fe(H,O)u]'. ZOH- -' [Fe(OH),(H,O)J + ZH.O correct iron speciesin product [1] balance = [1] iii The precipitate's colour is pale green = [1] iv [Cr(OH)J'v The solution of R would first give a Sreen precipitate [1], which forms a green solution = I2l with excessacid [1] d i The standard electrode potential is the potential difference between a standard hydrogen electrode and the half-cell [1] where all concentrations are 1-mol dm-'and the = I2l pressure of all gasesis 1 atm. [L] = [l] ii All four halogens will oxidise Cr'* iii Both bromine and iodine will not oxidise Cr''* ' = [1] further

= I2l

In order to do the iodoform reaction F must have the CH.CO group [1] and the products = t3l are CHI,. [1] and CH.CH,COO- [U = r2l iii F is CH,CH,COCH. [2] = 72 [1], for e The speciesare: (CH.CHTCOCH..). m/e (COCH.). for 43 [1] and (CH3CH,)' for 29 tll _ t3l

tll

= fzf

o D b i i i T h ea l d e h y d e i s o x i d i s etd a n a c i db y t h e o s i l v e r / a m m o c oa p l eix n s . ni m re t e c G r ignar r eag e n ts a c w i tha n a l d e h y dto g i v ea d s e c o n d a ayc o h o l . rl re are to d ii T heonlys u b s ta n c e s d o th e i o d o fo rm a c ti on g) , s a l c o h o lw i t ha C H , C H ( 0 H r o u pk e t o n ew i t ha s gr a C H , , C 0 o u p n de t h a n a l . n s o t t e Don' f or gethec h a rg e nth es p e c i eis a ma s s pectrum.

A,NSwERS 141
lv

Mix the blue Cr'* solution separately with bromine and iodine [1], the solution goes green and stays green with excesshalogen

tll

= [2]

er t a R e m e m b t h a t3 d ' ,4 s ' i s m o r e t a b l eh a n3 d o , s i 4 s ' ( a n d i m i l a r lfy r C uw h i c h s 3 d ' 04 s ' ) .A l s o s o , are t he4 s e l e c tro na rel o s tfi rs tw h e nc ati ons s fo r m e d . n c i A l lt r a n s i t i om e t ailo n sa r eh y d r a t eid n w m s o l u t i o n , i t h6 w a t e r o l e c u l e s o r d i n a t e l y co b o n d eo n . d b i v C h r o m i u m a m p h o t e r iIc . r ( 0 H ) ,w o u l d e is C ]a n a c c e p ta bae s w e r. ln e v A d d i t i oo f a c i dw i l lf i r s tp r e c i p i t atth e n h y d r o x i d eh i c ha s i t i s b a s i cw i l lt h e nr e a c t w , , w i t he x c e sa c i d o f o r ma s o l u t i o o f t h e s t n h y d ra tem e ta il o n s . d

y a D o n ' f o r g etto m u l t i p l b y 1 0 t o g e tt h et o t a l t i a a m o u no f t h eN H , ' i o n s ,n dt h e nh a l v et a st h e r e t pe i s I a m o l e f a m m o n i u s u l p h a t e r1 m o lo f o m N H .i o n s . t r F o r g e t t i no d i v i d e y 2 g i v e sh ea n s w e9 7 . 3 Y o tg b ( o b t a i n e d a b o u 't/ ,o f t h ec a n d i d a t ew h i c h by s) score4 marks. s on h a c i I n a p r e c i p i t a t i r e a c t i otn e r e r ej u s tt w o i o n s a o o n t h el e f ta n dt h ef u l lf o r m u l o f t h es o l i d n t t h er i g h o f t h ee q u a t i o n 1 , t a e, d D o n ' g i v e g r 0 u p c a r b o n a tn o r B a C Oa,s i t n n t sn d o e s n d e c o m p o 0 e h e a t i nig t h el a b , o r ie es r B e C 0b e c a u s t d e c o m p o sb e l o w o o m rat temoe ure.

Answer any two of the section B questions 2 a A ny tw o of : i t i s consi derabl ycheape r[ 1] ; l essri sk of l eachi ng tU it does not effect the pH of the soil [1] = [21 the nitrogen slowly [L] it releases b The smaller the K" of the conjugate acid, the stronger the base [1]. Therefore ammonia is the = I2l stronger base [.] Polymerisation occurs when many molecules ioin to form a long chain [1]; condensation is with the elimination of water or a small inorganic molecule such as HCI [L]. A polyamide contains the -CONH- link [1] as in: O O H H

Answersto Practice TestUnit 68

The allocation of marks follow Edexcel mark schemes. The marks that you will need for each grade are approximately:

1 a Amount of NaOH = 0.100 mol dm-' x 0.0280 dm' = 0.00280 mol [f.] = moles of H. Ratio H. to NHn*= 1 : 1". Amount of NH.,.in 25 cm' = 0.00280 mol. Amount in 250 cm' = 0.0280 mol [L] - '1,, O.o280= 0.0140 mol Amount of (NHr)rSOn [ 1] , mass of (NHn)rSOn 0.0140 mol x 132 g mol-' = 1. 848 I [ 1] , o/o (NH*)'SO.* fertiliser = 1".848 100/3.80 = x in = [5] 48.60/ofaf b Any two of: not all ammonia driven off [1]; ammonia incompletely absorbed by the HCI [f,]; = I2l some ammonia gas escapes[1] (aq) - BaSO.(s) i Ba'.(aq)+ SOn'= f2l Species[1], state symbols [1.] ions were ii To ensure that all the sulphate = [U precipitated d Many carbonateswill decomposeon heating [L], and the CO, gas evolved will result in a lower mass being recorded [1]. An example is CaCO. [1] = [4] CaCO, - CaO + CO, [1]

l\ -( cH,)--i- n,),-*+ tu *-(. +.

/ll ,

ll |

d i

ll

e l

ii

The reagentsare : liquid bromine [1] and concentrated sodium hydroxide [1]. The = [3] condition is that it must be heated [1] = [u NH.NH, Solids are not included in Ko expressionsand = [1] ammonium nitrate is a solid. As the reaction is endothermic, the energy level of the products is higher than that of the reactants [1], therefore the reaction is said to

u ofu u a t s a The isadvantages ing rea re hat ome rea d is within days 4 if there norain of evaporates especially w ne l ca b a p p l i c a t i otn . n n o teb l e n d e di t hp h o s p h a to r p o t a s s i ue r t i l i s e as ,d t i s l e s s u i t a boe c h a l k y fm rn i s ln te l d n c e s o i l sl.t c a n a u sd a m a g o s e e d l i n gts . o e s o tw o r k i f t h es o i li s t o oc o l d . the the its acid. c The stronger base, weaker conjugate A k stab y d T h e r m o d y n a m i c i l i its t o d ow i t h Ha n d i n e t i c the is of stabilitv to dowith rate thereaction.

142

ANswERs be thermodynamically stable [1] and the equilibrium lies to the left [U. As the reaction proceeds on moderate heating, the activation energy is fairly small [1] and so the reaction is kinetically unstable [1] The reagents are potassium dichromate(Vl) [1] and sulphuric acid [1]. The conditions are careful heating and distil off the aldehyde as it = [3] is formed [.]. The conditions for the addition of HCN to a carbonyl compound are KCN in aqueous ethanol at a pH of 8 (or a mixture of KCN and HCN) [1] The mechanism is:

3 a i

ii

the to if has a i Care to betaken youwish stop oxidation a o f a p r i m a r yl c o h o ltt h ea l d e h y d e . a curly arows start on make that ii Asalways sure your t a o a g a na t o m n d ot o f o r m b o n d r s t a ro na b o n d g a n d ot o a na t o m . in y i i i t h er e a c t i os s i m p lR - C N R C O 0 H . tl es i v t h ec o n c u l p h u rd c h y d r a t h ea l c o h oo a C = C . s ie t H Y o u e r eo l di nt h es t e mh a t Ad e c o l o u r i s e d w t w r s b r o m i n ea t ea n d oi t i s u n s a t u r a t e d . to of of is answer themode action b ii This thestandard be a buffer must learnt. and
4 a The Fe ion is 3+ whereas the Na ion is only 1+ [1] The Fe'*ion is much more polarising than the Na. ion [L], and so it draws the electrons [.] from the large Cl- ion towards itself and the bond becomes

/ R- i {-'cN=---------n/\

\.--o
H

o- H-cN \-/

C-CN l I

t t n

R-

C -CN

+ +H,o o ;""tXt:,'ii;iil" * H,o* [Fe(H,o),oH]* [r]^

acid [Fe(HrO)J'.' coniugate base[Fe(HrO).OH]'. = [3] coniugate acid H.O. [1] base HrO: ii a red precipitate will form [.] which stayswith excessNaOH [1] -+ [Fe(HrO),]'. 3OH- Fe(OH). + 6HrO [1] or + + 3OH- -. [Fe(H,O).(OH).] 3H,O [Fe(H,O)u]". = [4] The reaction is deprotonation. [L] iii The bonding is dative covalent (coordinate)[1] The ligands split the d-orbitals into two levels

= f4l

I OH
[1] for a curly arrow going from the C in CN[1] for a curly arrow going from the C:O z bond to the oxygen atom = [4] [1] for the intermediate with its - charge iii CH,CH,CH,CH(CH.)CH(OH)CN+ HCI + zH,O -- CH.CH,CH,CH(CH3) CH(OH) COOH + NH'CI [.], = l2l correct formula of organic product [1] iv H cH,

tll

tll
The light is absorbed and a d electron promoted from the lower to the higher level.

\.-./
cHscHz/ cHz
HA

\/ c.

o
O-H = [1]

b i

K. = [H,O.] x [A-] or [H] instead of [H,O.] [1] IHA] = 6. 71x L 0 " m o l d m-' [1 ] = [3] pH = -log (6.7L x LO') = 3.L7 lll The acid is partially ionised: HA =. H* + AThe salt is totally ionised: NaA - Na. + A- tll This suppresses the ionisation of the acid and so both [HA] and [Al are large compared to any H* or OH- that may be added. [1] When H'is added, it is removed by the reaction: H. + A--- HA [1] If OH- is added, it is removed by: = [4] OH- + HA -- A- + H,O [1.]

lH.ol=[Al=./-(rrl=@

ll

c Each oxygen is -2, :. 4 oxygrrs= -8. The ion is 2-, and so the Fe is +6 (6+ and 8- make 2-) tll There are two ways. The first is: add excess acidified potassium iodide solution to an aliquot solution [1], then titrate the of the FeOn'liberated iodine against standard sodium thiosulphate solution [1], adding starch when the solution becomespale yellow and stopping when it is colourlesss[1] The second method is: add excessacid to an aliquot [1], then titrate against standard FeSOo solution [1] until the solution becomes very pale = [4] pink [1]

tll

= [3]

a A c o m p a r i sw in h a C l u s b em a d e . ot N m t pairs both sure you b i Make that identify acid-base and l a b e lh e m l e a r l y . t c s i i l r o n s n o ta m p h o t ea in d ot h ep p ts t a y i n e x c e s s . i r cs have they the excited gradually iii After electrons been giving heat, are to level out and fallback thelower photons. ready absorb to then power. like in and is very Mn0.,- colour in oxidising c FeO.,'method estimating the of either standard Soyoucanuse i i n) ag o x i d i s i n g e n t(so d i ntet r a t i o o r t h em a n g a n a t e ( V l l ) i ti w o m e t h ow h i c hs d i r e c t t r a t i o ni t hi r o n ( l li) n s . d

APPEN DIX

A
ffi reactions organic
1. AS and A2 (synoptic)
Alkanes, e.g. ethane CIITCII, . Ethane ---+ carbon dioxide and water oxygen (air) Reactant: Equation: 2CH,CH, + 7Or- 4CO, + 6H,O burn / spark Conditions: Classification: combustion o Ethane ---rchloroethane Reactant: chlorine + CH,CH, + Cl, - CH,CHTCI HCI Equation: Conditions: sunlight Classification: free radical substitution Alkenes, e.g. ethene, H'C{H, . Ethene ---+ ethane hydrogen Reactant: Equation: H2C={H, + Hr -+ CH,CH, heated nickel (or platinum) catalyst Conditions: Classification: addition or reduction or hydrogenation . Ethene + I,2-dlbromoethane bromine Reactant: HrC<H2 + Br, - CHTBTCH'Br Equation: bubble ethene into bromine dissolved in hexane Conditions: Classification: electrophilic addition a Ethene -> bromoethane hydrogen bromide Reactant: HrC<H, + HBr - CHTCHTBT Equation: mix gasesat room temperature Conditions: Classification: electrophilic addition o Ethene ---;ethan-1,2-diol potassium manganate(Vll) solution Reactant: HrC:CH, + [Ol + HrO - CHr(OH)CHTOH Equation: a solution made alkaline with sodium hvdroxide Conditions: . Ethene -+ poly(ethene) Reactant: ethene ---+ n HrCdH, Equation: fCHr-CHr),, 2000 atm pressure,250 "C Conditions: Classification: addition polymerisation e.g. l-bromopropane Halogenoalkanes, propan-l-ol o l-bromopropane ---+ Reactant: sodium (or potassium) hydroxide + CH3CHTCHTBTNaOH --- CHTCHTCHTOH Equation: heat under reflux in aqueous solution Conditions: Classification: nucleophilic substitution o l,-bromopropane ---' propene potassium hydroxide Reactant: + Equation: CH,CH,CHTBT KOH --r CHrCH:CH, + KBr + HrO heat under reflux in ethanolic solution Conditions: Classification: elimination o L-bromopropane --+ butanenitrile potassium cyanide Reactant: + + CH3CH,CH,BT KCN --+ CH.CH2CH2CN KBr Equation: heat under reflux in a solution of ethanol and water Conditions: Classification: nucleophilic substitution o L-bromopropane ---;1-aminopropane Reactant: ammonia + + Equation: CH.CHTCHTBT 2NH, + CH.CH2CH2NH2 NHnBr heat a solution of ammonia in ethanol in a sealedtube Conditions: Classification: nucleophilic substitution

APPENDIx . 1-bromopropane ---+ Grignard reagent (A2 only) Magnesium Reactant: + Equation: CH,CHTCH,BT Mg ---' CH,CH,CH,MgBT warm (in water bath) under reflux in dry ether Conditions:

Alcohols, .S. ethanol o ethanol ---;ethanal potassium dichromate(Vl) + dilute sulphuric acid Reactant: CH.CHO + HrO Equation: C,H,OH + [O] ----r heat carefully and distil out the aldehyde as it is formed Conditions: Classification: oxidation ethanoic acid o ethanol ---+ potassium dichromate(Vl) + dilute sulphuric acid Reactant: CH,COOH + H,O Equation: CTH,OH + 2lO) ---+ heat under reflux Conditions: Classification: oxidation NOTE: Secondaryalcohols are oxidised to ketones and tertiary alcohols are not oxidised. + CH3CH(OH)CH, [O] - CH,COCH. + H,O (CH.).COH + [O]----r reaction; potassium dichromate solution stays orange no o ethanol --+ ethene Reactant: concentrated sulphuric (orphosphoric) acid or aluminium oxide HrC:CH, Equation: CTH'OH - HrO ---+ Conditions: heat Classification: dehydration a ethanol -> chloroethane phosphorus pentachloride Reactant: Equation: CTH'OH + PClr --- CrHrCl + POCI. + HCI Conditions: dry o ethanol ---+ bromoethane Reactant: hydrogen bromide Equation: C,H.OH + HBr - CrH.Br+ H,O HBr made in sitttfrom 50(%sulphuric acid and solid potassium Conditions: bromide o ethanol ----r iodoethane hydrogen iodide Reactant: C,H.l + H,O Equation: CTH.OH+ HI ---+ HI made in situ from iodine and moist red phosphorus Conditions:

2. A2 only
bromide Grignard reagents, e.8. ethylmagnesium o Ethylmagnesium bromide ---+ ethane Reactant: water Equation: CrHrMgBr + HrO - CrHu+ Mg compounds o Ethylmagnesium bromide ---' a secondary alcohol Reactant: an aldehvde such as ethanal Equation: CrH,MgBr + CH.CHO --+ CH,CH(OH)C,H. Conditions: dry ether solution, then hydrolyse with dilute acid Classification: nucleophilic addition to the aldehyde o Ethylmagnesium bromide ---+ tertiary alcohol a Reactant: a ketone such as propanone Equation: CrHrMgBr+ CH,COCH. - (CH.),C(OH)C,H, Conditions: dry ether solution, then hydrolyse with dilute acid Classification: nucleophilic addition to the ketone o Ethylmagnesium bromide ---;a carboxylic acid (solid) carbon dioxide Reactant: Equation: CrHrMgBr + CO, ---tCTHTCOOH Conditions: dry ether solution, then hydrolyse with dilute acid Carboxylic acids, e.g. ethanoic acid o ethanoic acid ---+ ester an Reactant: ethanol Equation: CH,COOH + C,H,OH:CH.COOC,H, + H,O heat under reflux with a few drops of concentrated sulphuric acid Conditions: Classification: esterification

APPENDIX

an o ethanoic acid ----r alcohol lithium aluminium hydride (lithium tetrahydridoaluminate(III)) Reactant: CH,COOH + a[Hl - CH,CH'OH + H'O Equation: dry ether solution then hydrolyse with dilute acid Conditions: Classification: reduction an . ethanoic acid ---+ acid chloride phosphorus pentachloride (or PCl, or SOCIr) Reactant: CH.COOH + PCI, -J CH,COCI + POCI, + HCI EqUAtiON: dry Conditions: a . ethanoic acid ---+ salt sodium carbonate Reactant: 2CH,COOH(aq)+ Na'CO,(s) Equation: ---+ 2CH,CooNa(aq) + Co,(g) + H,o(l) Classification: neutralisation o ethanoic acid - a salt sodium hydrogencarbonate Reactant: CH.COOH(aq)+ NaHCO,(s)t Equation: Classification: neutralisation

CH,COONa(aq)+ CO.(8) + H'O(l)

Esters, e.g. ethyl ethanoate o ethyl ethanoate --+ acid + alcohol any aqueous stront acid such as dilute sulphuric acid Reactant: + C'H.OH CH,COOC'H, + Hp-CH,COOH Equation: heat under reflux Conditions: Classification: reversible hydrolysis salt + alcohol o ethyl ethanoate ----r aqueous sodium hydroxide Reactant: CH,COOCTH,+ NaOH - CH,COONa + C,H.OH Equation: heat under reflux Conditions: Classification: hydrolysis (saponification) Carbonyl compounds aldehydcs, e.g. CHTCHO, and ketones, e.g. CHtCOCH3 o Both react with: 2,4-dinitrophenylhydrazine Reactant: + H'o >c:N-NHC6H'(No')' + NH.NHC.H,(NO.): ---+ >c{ Equation: mix solutions: oranSe precipitate observed conditions: o Both react with: hydrogen cYanide Reactant: + HCN -+ >C(OH)CN >C{ Equation: potassium cyanide + some dilute sulphuric acid conditions: Classification: nucleophilic addition o Both react with: lithium aluminium hydride (or sodium borohydride) Reactant: cH,CHo + 2[Hl - CH'CH'OH (a primary alcohol) Equation: CH.coCH, + 2[Hl - CH'CH(OH)CH. (a secondaryalcohol) dry ether, then hydrolyse with dilute acid Conditions: Classification: reduction o Aldehydes only react with: Fehling's solution or ammoniacal silver nitrate Reactant: CH,CHO + [Ol + OH- ---rCH'COO- + H,O Equation: warm Conditions: Classification: oxidation o Carbonyl compounds with a CH,CO group give a yellow precipitate of iodoform with: Reactant: Equation: iodine and sodium hydroxide solution + CH3COO- CHI, + 3I- + 3HrO cH,cocH, + 31,+ 4OH- ---+

Acid chlorldes, .8. ethanoyl chloride o ethanoyl chloride ---'ethanoic acid water Reactant: CH,COCI + H.O --- CH.COOH + HCI Equation: Classification: hYdrolYsis o ethanoyl chloride ---tan ester an alcohol Reactant: + CH,COCI + C.H.OH --- CH.COOCTH' HCI Equation: rapid reaction at room temperature Conditions: Classification: esterification

APPENDIX

ethanoyl chloride ---+ ethanamide Reactant: ammonia Equation: CH.COCI + 2NH. -+ CH,CONH, + NH'CI ethanoyl chloride ---+ substituted amide a Reactant: an amine Equation: CH.COCI + CrH.NHr --+CH.CONHCTH. HCI + Amines, e.g. CrHrNH, o ethylamine --+ a salt Reactant: any acid such as hydrochloric Equation: C2H.NH2 HCI ---tCrHrNHr.Cl+ o ethylamine ---J substituted amide a Reactant: an acid chloride Equation: C2H.NH2 CH.COCI ---+ + CH.CONHCTH.+ HCI Nitrlles, e.g. CIITCN o ethanenitrile ----r ethanoic acid Reactant: dilute sulphuric acid (or sodium hydroxide followed by acidification) Equation: CH.CN + H* + zHrO ---+ CH,COOH + NHn. Conditions: heat under reflux Classification: hydrolysis . ethanenitrile --+ethylamine Reactant: lithium aluminium hydride Equation: CH3CN + a[H] --+ CH.CHTNH, Conditions: dry ether then hydrolyse with dilute acid Classification: reduction Amides, e.g. CHTCONH, o ethanamide ---+ methvlamine Reactant: bromine and sodium hydroxide Equation: CHTCONH, + Br, + 2NaOH ---+ CH.NH, + 2NaBr + HrO + CO, Conditions: liquid bromine and conc sodium hydroxide Classification: Hofmann degradation reaction. o ethanamide --+ ethanenitrile Reactant: phosphorus(V)oxide Equation: CH,CONH, - HrO ---+ CH.CN Conditions: warm Classification: dehydration Benzene o benzene---+ nitrobenzene Reactant: concentrated nitric acid Equation: CuHu HNO. -- CuHrNO,+ HrO + Conditions: mix with concentrated sulphuric acid at 50 'C Classification: electrophilic substitution a benzene ---;bromobenzene Reactant: bromine Equation: C.H. + Br, ----r CuHrBr+ HBr Conditions: liquid bromine with an iron catalyst Classification: electrophilic substitution o benzene --+ ethylbenzene Reactant: chloroethane Equation: C.Hu+ CrHrCl ----t CuHrCrH, HCI + Conditions: anhydrousaluminiumchloridecatalyst Classification: electrophilic substitution phenylethanone o benzene ---+ Reactant: ethanovl chloride Equation: + CuHu CH.COCI ---,C.HTCOCH,+ HCI Conditions: anhydrous aluminium chloride as catalyst Classification: electrophilic substitution Alkylbenzenes, e.g ethylbenzene o ethylbenzene ---)ethanoate ions Reactant: potassium manganate(Vll) + sodium hydroxide Equation: + C5H'C2H, 6[0] + OH- ---' C.HTCOO- 3H,O + CO, + Conditions: heat under reflux Classification: oxidation

APPENDIX

Phenol o phenol' sodium phenate sodium hydroxide Reactant: C.HTOH+ NaOH --- CuHrONa+ HrO Equation: Classification: neutralisation . phenol -"+ 2,4,6-tribromophenol bromine Reactant: C'H.OH + 3Br, -r HOCuHrBr.+ 3HBr Equation: aqueous; orange bromine water forms a white precipitate Conditions: Classification: electrophilic substitution o phenol -+ phenyl ethanoate ethanoyl chloride Reactant: C.H.OH + CH,COCI --+CH,COOC.H. + HCI Equation: Classification: esterification Nitrobenzene Nitrobenzene ---)phenylamine Reactant: tin and concentrated hydrochloric acid C'H,NO, + 6[Hl - C"H'NHr+ 2H.O Equation: heat under reflux, then add sodium hydroxide Conditions: Classification: reduction Phenylamine Phenylamine --r diazonium ion + azo dye 'C; step 2: phenol step 1: nitrous acid at 5 Reactant: + 2H' + NO, - C.H.N,' + 2H.O CuHsNH2 Equation: + H.O CoHrN2'+C"H.OH - HOC.H.-N:N-C"H. mix phenylamine with sodium nitrite and hydrochloric acid at Conditions: 5 "C, then add phenol in sodium hvdroxide solution.