Unit 3 Test for anions (the end part of a salt) X+ YAnion Carbonate (CO32-) Distinguish between Hydrogen Carbonate

(HCO31-) and Carbonate (CO32-) Test Add dil. Acid 1. Add U.I. 2. Additionally you can add Phenolphthalein 3. Add Calcium Chloride to CO32- or HCO34. MgSO4, then heat Test Result Effervescence, CO2 produced

1. if the solution is blue you

have carbonate (pH 12), if it is dark green you have hydrogen carbonate (pH 9). 2. If the solution is dark pink you have a carbonate and light pink with hydrogen carbonate 3. White ppt with carbonate 4. Cloudy solution 1. White ppt produced (AgCl) 2. Cream ppt produced(AgBr) 3. Yellow ppt produced (AgI) 1. Silver Chloride ppt will dissolve 2. Silver bromide will dissolve 3. Silver iodide is insoluble in both Bright yellow ppt produced, PbI2

1. Chloride in solution (Cl-1) 2. Bromide in solution (Br-1) 3. Iodide in solution (I-1) Further test for halogens (confirmation test)

Acidify with dil. nitric acid and add silver nitrate

1. Add dilute ammonia 2. Add conc ammonia 3. In conc ammonia Iodide in solution (I-1) Acidify with dil. nitric acid and add lead (II) nitrate Nitrate in solution (NO3-1) Add sodium hydroxide and Ammonia gas produced aluminium foil and heat gently 2Sulphate in solution (SO4 ) Acidify with dil nitric acid White precipitate, BaSO4 and add barium nitrate Test for cations (the front part of a salt) X+ YExamples are NaCl or AlCl3 Transition Metal reactions with NH3 and NaOH Cation Aluminium (Al3+) Ammonium (NH4+) Calcium (Ca2+) Copper (Cu2+) Iron (II) (Fe2+) Iron (III) (Fe3+) Zinc (Zn2+) Effect of aqueous NaOH White ppt., soluble in X.S. giving colourless solution Ammonia produced on warming Slight White ppt., insoluble in X.S. Light blue ppt., insoluble in X.S. Dark green ppt., insoluble in X.S. Brown/orange ppt., insoluble in X.S. White ppt., soluble in X.S. giving colourless solution

Effect of aqueous NH3 White ppt., insoluble in X.S.

No ppt or very slight white ppt. Light blue ppt., soluble in X.S. giving a dark blue solution Dark green ppt., insoluble in X.S. Brown/orange ppt., insoluble in X.S. White ppt., soluble in X.S. giving colourless solution

Flame tests for metal cations Lithium = Red Sodium = Yellow Potassium = lilac Calcium = brick red (orange) Strontium = crimson (dark red) Barium = apple green Mg no colour

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The tests for gases Gas Ammonia Hydrogen chloride gas (Same for Hydrogen bromide/iodide) Carbon dioxide Chlorine (same for Br2 and I2) Hydrogen Oxygen Nitrogen dioxide Sulphur dioxide Test and result Turns damp red litmus paper blue (Alkaline gas) Misty fumes turns blue litmus red Turns limewater milky Turns damp blue litmus paper red then bleaches Pops with a lighted splint Relights a glowing splint Brown gas turns blue litmus red (Acidic gas tested in fume cupboard) Yellow gas turns blue litmus red (Acidic gas tested in fume cupboard) Turns potassium chromate paper from orange to green

Organic compound tests Organic molecule Alkenes Test

Alcohols

Aldehyde Organic acids Haloalkanes Test for Water Test Cobalt chloride paper Copper Sulphate (anhydrous)

Shake with bromine water, goes from orange/brown to colourless Alkanes do not react and the solution remains orange/brown Also alkaline KMnO4 can be added, it goes from purple to colourless and a diol is made. Also when burned alkenes make a sooty flame Acidified K2Cr2O7 is added Primary go from orange to green and aldehyde then organic acids are made Secondary go from orange to green and ketones are made Tertiary do not oxidise and it stays orange Additionally you can add PCl5 and misty fumes of HCl are produced Addition of Benedicts or Fehlings solution causes a red/orange ppt of Cu2O to be produced (Ketones dont react) Add a carbonate, effervescence of CO2 is observed Add sodium hydroxide and heat, then acidified silver nitrate (see anion test for results)

Result Blue paper turns pink with water White compound goes blue with water

Titration information Indicators: Phenolphthalein goes from colourless to pink (acid to alkali) and methyl orange goes from yellow to pink/orange Concordance: Two titres need to be within 0.20cm3 of each other, take an average and then multiply by the concentration to get the moles Sources of error: misreading meniscus, parallax error, bubbles in the burette, not rinsing with reactant before the start, leaving the funnel at the top Points to consider: Ratio of reactants in the equation, e.g. 2:1 for NaOH + H2SO4
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Essential Chemical reactions and information needed Unit 1 (plus some unit 3) Definitions Ionisation energy
The enthalpy change when 1 mole of electrons are removed from 1 mole of a gaseous element to make a single positive ion
This generally increases from left to right as nuclear charge increases

Second ionisation energy

The enthalpy change when 1 mole of electrons are removed from 1 mole of a gaseous ions to make a divalent positive ion

Electron affinity
The enthalpy change when 1 mole of electrons are added to 1 mole of a gaseous element to make a single negative ion
This generally increases from left to right as effective nuclear charge increases

Atomic radius
The distance from the nucleus to the outmost electrons.
This decreases from left to right as nuclear charge increases and increases as you go down a group as effective charge decreases.

Electronegativity
The ability of an atom to attract electrons towards itself in a covalent bond.
This increase from left to right and from bottom to top (F is highest)

Atom economy Mass of the target molecule over the mass of all reactants PPM Mass of component/mass of the solution X by 1 million
Used for small amounts when you dont want to have an expression with large negative integers

Unit 2 (plus some unit 3) Mechanisms needed Cl2 + Alkanes = Chloroalkanes + HCl (UV light) This is a free radical substitution reaction. Homolytic fission Cl2 = 2Cl (free radical production). This is initiation, followed by propagation using single headed arrow for movement of 1 electron. Termination is where 2 radical react with each other. This is the same mechanism for polymerisation. Br2 + Alkene = Dibromoalkane. This is electrophilic addition reaction. There is a partial charge on the Br2 which leads to it being attracted to the double bond. Br adds and the other Br takes both electrons making it Br-. A carbocation* is produced. Br- then adds to this. *(When using HBr this influences the product made see stability of carbcations). Haloalkane + NaOH = Alcohol + NaX. This is a nucleophilic substitution reaction. There is a permanent charge on the C-X bond due to the high difference in electronegativity. This attracts the OH and displaces the halogen. SN2 (Same for other nuc CN/NH3) Tertiary Haloalkane + NaOH = Alcohol + NaX. This is a nucleophilic substitution reaction but the OH does not displace the halogen, the C-X bond breaks and forms a stable carbocation which then attracts the OH. This is an SN1 mechanism Reduction
2Fe2O3 + 3C = 4Fe + 3CO2 Blast furnace Zinc Blend (ZnS + O2 = ZnO + SO2) ZnO + CO = Zn + CO2 If a metal is made then reduction has taken place

Moles Moles = mass /Mr (g) Moles = vol x conc (dm3) 1 of mole of gas = 24 dm3 Enthalpy of combustion
The enthalpy change when 1 mole of substance (element or compound) is burned completely in an excess of oxygen at 298oK and 1 atmos

Oxidation
2Mg + O2 = 2MgO Ethanol + K2Cr2O7 = Ethanoic acid (H2SO4 catalyst)

Hydrolysis and Condensation CH3COOH + C2H5OH = CH3COOC2H5 + H2O

This is a reversible reaction catalysed by acid

Shapes of molecules
Linear Bond angles are 180o e.g. CO2/ BeCl2 Trigonal planar Bond angles are 120o e.g. BCl3/ SO3/NO3Tetrahedral Bond angles are 109.5o e.g. CH4/ NH4+/SO42Trigonal bipyramidal Bond angles are 120/180o e.g. PCl5 Octahedral Bond angles are 90/180o e.g. SF6 Bent or V shaped Bond angles are 104.5o e.g. H2O /SO2 Pyramidal Bond angles are 107o e.g. NH3?/SO32T shape Bond angles are 90o e.g. BrF3 Square planar Bond angles are 90o e.g. ICl4-

Enthalpy of formation
The enthalpy change when 1 mole of product is formed from its elements in their standard states at 298oK and 1 atmos

Enthalpy of neutralisation
The enthalpy change when 1 mole of hydrogen ions reacts with 1 mole of hydroxide to make water at 298oK and 1 atmos

Hesss law
Enthalpy change is independent of the route taken

Bond Polarity H2O has polar bonds and overall is polar as it is not

Combustion data
Reactants - products

Formation data

Products - reactants Qatar International School analysis and summary sheet. Devised by Dr Warrilow & Mr Parry

symmetrical CO2 /CH4 /CCl4 has polar bonds and overall is not polar as it is symmetrical CH3Cl has polar bonds and overall is polar as not symmetrical

NH3 has polar bonds and overall is polar as it is not symmetrical If the molecule is symmetrical it will not have an overall polarity. If each polar bond is a vector and it is symmetrical these effectively cancel each other out therefore no overall polarity.

Organic reactions Alkenes C2H4 + Br2 = C2H4Br2 Electrophilic addition C2H4 + H2O = C2H5OH Acid catalyst hydration C2H4 + H2 = C2H6 Hydrogenation with Ni
catalyst

Halogens as reducing agents NaCl + H2SO4 = NaHSO4 + HCl

(misty fumes turns blue litmus red)

Cl1- to Cl1-

C2H4 + C2H4 = -[C2H4]- Polymerisation Alkanes with UV light or 200oC C2H6 + Cl2 = C2H5Cl + HCl Free radical
Substitution

NaBr + H2SO4 = NaHSO4 + HBr 2Br1- to Br20 2HBr(g) + H2SO4 (aq) = 2H2O(l) + Br2 + SO2 (misty fumes turns blue litmus red then Br2 bleaches) S6+ = S4+ NaI(s) + H2SO4 (aq) = HI(g) + NaHSO4(aq) 2HI(g) + H2SO4 (aq) = 2H2O(l) + I2(g) + SO2(g) H2SO4(l) + 8HI(g) = H2S(g) + 4I2(g) + 4H2O (l)
(misty fumes turns blue litmus red then I2 bleaches, also accompanied by rotten egg smell of H2S) 2I1- to I20 and S6+ = S2-

CH4 + 2O2 = CO2 + 2H2O

combustion

Oxidation or

Stability of carbo-cations 1o 2o 3o This means that for an unsymmetrical

alkene that reacts with HBr two possible products will be formed. 2o or 3o will be preferred. Primary carbocations are not stable

Reducing ability increases down the group, Iodide adds 8e- to sulphur to reduce it from 6+ to 2-

Solubility of hydroxides and sulphates

Group 2 increase as you go down the group, Be(OH)2 -most insoluble Group 2 decrease as you go down the group, BaSO4 most insoluble

Patterns in periodic table Explain the patterns in: IE increases going down and across the table Li-Cs it reduces and as a result the group 1 metals become more reactive Na-Ar IE increase as the number of protons increase in the nucleus. 2 exceptions group 3 and 6 have a slight drop due to shielding of the p sub shell and Hunds rule for electrons that have to share orbitals with others. Electronegativity and electron affinity shows a similar pattern to IE

Thermal decomposition -Breaks down with heat

All Carbonates break down except Na/K/Rb/Cs

CaCO3 = CaO + CO2

Nitrates decompose differently due to the group they are in.

All except Na/K/Rb/Cs

2Cu(NO3)2 = 2CuO + 4NO2 + O2 NaNO3 = NaNO2 + O2

Only Na/K/Rb/Cs

Nitrates and carbonates increase in stability as you go down the group as cations are less polarising

Alkanes and Alkenes uses and properties Alkanes are used as fuels, lubricants and road building (fractional distillation from last year) Properties their bpts increase with increasing chain length as there are more London forces. Straight chains have high bpts as the forces interact more than with branched molecules Alkenes are used to make plastics and can make alcohols with steam Only 1 bond per molecule and the name is based on the position of this. E.g. But-1-ene

Intermolecular forces Decreasing in strength as we go down Hydrogen bonds (1/10 of a covalent bond) e.g. H2O/NH3/HF Permanent dipole-dipole interactions (1/10 of HBond) e.g. CO2/CH3Cl London forces (1/10 of a dipole- dipole) CH4/O2/Cl2/He Organic reactions Haloalkanes with nucleophiles CN- / OH- / NH3 C2H5Br + NaOH = C2H5OH + NaBr (Nuc Sub) Haloalkanes with hydroxide under ethanolic conditions C2H5Br + NaOH = C2H4 + NaBr + H2O
C-X Bond strength increases as you go up the group, hence reactivity decreases. C-F bond does not break easily.

Halogenation of alcohols PCl5 + C2H5OH = POCl3 + C2H5Cl + HCl

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or but-2-ene are different. Isomers of but-2-ene. E and Z.

NaBr in Conc H2SO4 makes HBr which brominates the -OH Phosphorus and Iodine makes PI3 which iodinates the --OH Redox Always use OILRIG 0 Mg (s) + Cu2+(aq) = Mg2+(aq) + Cu0(s)

This is E as the priority groups are on opposite sides This is Z but-2-ene which means priority groups are on the zame zide (hydrogens are not shown on the diagram)
Polymer problems and solutions They do not decompose naturally, when burnt they give off toxic fumes HCN/HCl etc. Recycling plastic allows for the reduction of the companies carbon footprint Also biodegradable plastics are used which do not persist in the environment for long periods Energy can be derived form plastic by incineration

(For metals)

Cl20(l) + 2Br-1(aq) = 2Cl-1(aq) + Br20 (l)

(For non-metals)

Oxidation states
Chloride = Cl1- = 1- oxidation state Chlorite = ClO1- = 1+ oxidation state Chlorate = Cl3O1- = 5+ oxidation state Manganate = KMnO4 = 7+ oxidation state Chromate = K2Cr2O7 = 6+ oxidation state

New definition of oxidation -if the number becomes more positive it is oxidation and less positive then that is reduction.
E.g. S to SO2 is oxidation as S = 0 in sulphur, O is generally O2-, so 2times two is 4-. The compound is neutral so S has to = 4+. Becomes more positive therefore oxidation.

Electronic structure Use the periodic table to highlight the subgroups in each energy level E.g. Na = 1s2 2s2 2p6 3s1 Cl = 1s2 2s2 2p6 3s2 3p6 Mass spec Tells us the isotopic constitution of an atom e.g. 35 Cl 75% and 37 Cl 25% It works by Ionising the sample Accelerating Deflecting Detecting Patterns in periodic table: Atomic radius and ionic radius Patterns in isoelectric ions like Al3+ and Fhow do their sizes compare and why? Al has more protons so it is smaller. Anion tend to be larger as the number of electrons is more than the number of protons The more electrons to protons the bigger the ion or the reverse argument for cations Borne Haber cycle and Lattice enthalpy LE is the enthalpy change when gaseous ions form a crystal lattice it is always exothermic

Disproportionation Cl20 + H2O = HCl1- + HClO1+

With NaOH

2NaOH + Cl20 = NaCl1- + NaClO1+ (bleach) + H2O 3ClO- = 2Cl- + ClO3- at temps above 75oC
Chlorite 1+ Chloride 1- Chlorate 5+

Haber process (Making ammonia)

CH4(g) + H2O(g) = CO(g) + 3H2(g) Heat/ Ni Catalyst N2 + 3H2 = 2NH3 (Fe catalyst/300 atmos/ 450oC) Heat shifts equilibrium to the left Pressure to the right

Contact process (Making sulphuric acid) 1. S + O2 = SO2 2. SO2 + O2 = SO3 (V2O5 catalyst/2-5 atmos/ 450oC) Exo 3. SO3 + H2SO4 = H2S2O7 4. H2S2O7 + H2O = 2H2SO4
Heat shifts equilibrium to the left Pressure to the right

N2O4 = 2NO2 Increasing the pressure shifts the equilibrium to the left as there are less moles of gas Cl2 + I2 =2ICl Cl2 + ICl =ICl3 Increasing the Cl2 conc shifts the equilibrium to the right to get rid of the Cl2 Solubility Glucose dissolves in water as it has similar bonding due to presence of OH groups I2 dissolves in organic solvents in preference to water as its

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How exothermic it is depends on the size and charge. The smaller and larger the charge the larger the value. E.g. AlCl3 is very large LE figure due to 3+ and small ion Thermodynamic stability Concerned with the levels of the reactants compared to products

predominate intermolecular forces is London forces To dissolve a solid in a solvent the forces must be compatible Kinetics Temperature
KE is gained, more collisions occur per second, this leads to more particles over the EA and this leads to more successful collisions

Catalyst
EA is lowered by providing an alternative route, more particles have greater than the EA required when compared to the uncatalysed reaction which leads to more successful collisions and an increased rate

Pressure/Concentration and Surface area

In this case the products are lower down so more stable than the reactants (opposite is true for endo change) The increase in particles in a given volume leads to more collisions of reactants which leads to more successful collisions

Kinetic stability

This is concerned with kinetics, which is speed, so what affect the rate? The energy of activation EA. If this is big, like in this case then the reaction will be slow. Mean/Average bond values are less accurate than experimental values as they use C-H bonds from lots of different compounds

Diagram for catalyst Diagram for temperature Remember to refer to the shaded area when discussing why the reaction is faster in both cases

Heat capacity and KJ/mol-1 Energy = temp change x mass of water used x specific heat capacity of water E.g. 15o x 100g x 4.18 = the energy This is for the sample used, to work out the per mole value divide the figure here by the moles used. Insulation improves the results as less heat loss or
pipetting correct amounts into the reaction Errors people forget to use the water properly e.g. 50 cm3 of NaOH was added to 50cm3 of HCl, this is 50 + 50 to make 100g. 1000g = 1000cm3

Green chemistry Compounds like CO2, HCFC and CFC have greenhouse gas properties so effect the environment. They have polar bonds so absorbs IR radiation and heat up the atmosphere. O2/N2 do not heat up and are not affect by IR. Carbon neutral means that the amount of carbon released is equal to the amount taken in e.g. a green fuel like bio-diesel and ethanol can be more neutral than petrol Carbon capture, deals with a process where CO2 is pumped underground and stored in their place where oil or gas was extracted Carbon footprint is the amount of carbon dioxide a person or company produces per year Carbon offsetting is the measure a company can do to reduce the footprint, by recycling or purchasing trees etc. Mass spec and IR
Mass spec is the fragments that are produced when an organic compound is analysed. For butane C4H10 the largest peak will be the actual mass which is 58, this is called the Molecular ion or M+. The fragments are stable cations and radicals that break off from this. E.g. =15 peak =

Bonding
Metallic, why does Al have a high bpt/mpt than Na? More protons in the nucleus, more valence electrons, a metallic bond is the electrostatic attraction between the cations and the sea of electrons. More electrons and more electronegative cation = stronger bond

Giant molecular
SiO2 and Carbon graphite/diamond/fullerene Separating strong bonds not intermolecular forces

Simple Molecular

P4, S8 and Cl2 you separate the molecules rather than breaking bonds therefore they have low mpts/bpts. The larger the molecule the larger the London forces and that is why S8 is the highest and Cl2 is the lowest. Ar is Qatar International School analysis and summary sheet. Devised by Dr Warrilow & Mr Parry

CH3+ (1 x 12, 3 x 1). Also 29 = CH3CH2+ and 43 = CH3CH2CH2+ IR analyses polar bonds and tells you the functional groups that are present. E.g. 1690-1750 cm-1 = Ketones /Aldehydes and Carboxylic acids C=C 1620-1680 cm-1 C-O 1000-1300 cm-1 C-H 2850-3300

lower but is not a molecule

cm-1 O-H 3230-3550 (broad) 2500-3000 (COOH broad) Tables provided in the exam

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