Paper 2 Flashcards

1
Q

What is a hydrocarbon

A

A compound which contains hydrogen or carbon only

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2
Q

Homologous series

A

A series of compounds that contain the same functional group and have the same general formula which differs by CH2

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3
Q

Functional group

A

Small group of atoms or a single halogen atom that give the compounds in the series particular chemical properties

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4
Q

Hydrolysis

A

H+ or OH- ions break a bond in a molecule splitting into two parts

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5
Q

How do you obtain alkane fuels

A

Fractional distillation of alkanes produces large amounts of heavier fuel. These are then cracked over suitable catalysts into smaller alkanes. these straight chained hydrocarbons are reformed into branched chain and cyclic hydrocarbons for efficient combustion by passing them over a suitable catalyst. These have a higher octane and therefore are more suitable for petrol driven cars

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6
Q

Problems which arise from the pollutants of combustion of fuels

A

Carbon monoxide
Sulphates of sulphur and nitrogen
Carbon particulates
Unburnt hydrocarbons are formed

CO is toxic
Oxides of nitrogen and sulphur are acidic

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7
Q

Alternative fuels

A

Biodiesel and alcohols
Renewable
Offset carbon released when grown
Some can be made from waste products eg coffee beans

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8
Q

What is a radical

A

Unpaired electron represented by a single dot

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9
Q

How are free radicals formed

A

Homolytic fission of a covalent bond

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10
Q

Alkanes plus oxygen in air

A

Burns balance with oxygen co2 and water

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11
Q

Alkane plus halogens

A

UV light or bright white light - chlorine and bromine

Free radical substitution

Initiation( homolytic fission of halogen)
Propagation - numerous number of products one radial reacts with one non radical to produce a radical and a non radical. The radical can be organic or a halogen)
Termination - two free radicals come together to produce a non free radical

Unhelpful in organic synthesis as there is a variety of products and further reactions would occur

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12
Q

Electrophile

A

Electron pair acceptor

Electron is attracted to the e- rich site

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13
Q

Alkenes plus hydrogen

Application

A

150degrees
Nickel catalyst

Forms alkane

Vegetable oil becomes margarine

Free radical addition

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14
Q

Alkene plus halogen

A

Room temperature, mix

In organic solvent
Halogen added across double bond

In aqueous solution
One halogen added one OH added

Chlorine and bromine

However iodine is not a strong enough electrophile unless the C=C bond is activated by an oxygen atom

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15
Q

Alkane plus hydrogen halide

A

Forms halogenoalkane
One halogen and one H added across double bond m
Mix gases at room temperature

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16
Q

Alkene plus steam

A

H3PO4 acid catalyst
Alkene vaporised

Forms alcohol

Reversible reaction so alcohol is removed by cooling and remaining gases repossessed over catalyst

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17
Q

Alkene plus potassium manganate (VII)

A

Shake at room temp
alkene + [O] + H20 -> diol

Purple manganate (VII) ions are reduced to ppt of brown manganese ( IV) oxide in neutral or colourless Mn^2+ ions in acid

NOT DICHROMATE

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18
Q

Formation of ions from covalent molecule

A

Heterolytic fission of the covalent bond

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19
Q

Addition of binary compounds to an alkene

A

Arrow from double bond to molecule (draw dipole on molecule if polar)

Covalent bond opens, one carbon has the halogen, the other carbon is positive

The negative ion (lone pair) arrow to carbon

Then compound

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20
Q

Markovnikov’s rule

A

Addition to an A-symmetric alkene, the hydrogen goes to the carbon which already has more hydrogen atoms directly attached

This is because he secondary carbocation is stabilised by the electron pushing affect compared to the primary

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21
Q

Stability of primary secondary and tertiary carbonation intermediated

A

tertiary is more stable than secondary which is more stable than primary due to the electron pushing effect

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22
Q

Test for C=C bond

A

Bromine water decolourises from orange

Mix at room temp

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23
Q

Waste polymers

A

Can be separated into specific types of polymer for
•recycling,
•incineration - producing energy (can produce toxic compounds eg CO)
•feedstock for cracking - producing a mixture of short chain alkene

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24
Q

How do chemists contribute to better use of polymers

A
  • more sustainable use of materials - less energy used making them or not using limited resources
  • developing biodegradable polymers
  • removing toxic waste gas from the incineration of plastics
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25
What is a nucleophile
Lone pair donor, forms covalent bond with δ+ atom in another molecule
26
Halogenoalkane plus potassium hydroxide
Hydroxide ion acts as nucleophile Heat under reflux and aqueous R-BX + KOH -> R-OH + KX
27
Halogenoalkane plus aqueous silver nitrate in ethanol
Water acts as nucleophile R-X + H20 -> R-OH + H+ + X- Ag+ X -> AgX ethanol !! 60 degrees
28
Halogenoalkane plus potassium cyanide
Reflux, aq and ethanol R-X + KCN -> R-CN +KX
29
Halogenoalkane plus ammonia
R-X + 2NH3 -> R-NH2 + NH4X Conc ammonia at room temp Or heat in sealed tube Heat in sealed tube so that it reacts fast but ammonia liberated if it was under reflux, ammonia gas would not be condensed by the reflux condenser
30
Halogenoalkane plus Ethanolic potassium hydroxide
R-Br + KOH -> alkene Of chain length R + H20 + KX Hydroxide ion acts as a base Heat under reflux with ethanol conc KOH
31
Experiment to determine relative rates of reaction of primary secondary and tertiary halogenoalkanes and chloro bromo and iodo halogenoalkanes
Equal amount of the halogenoalkanes are placed in a test tube water bath 60 degrees ethanol and silver nitrate and time how long it takes the ppt to appear Tertiary fastest secondary then primary SN1 faster than SN2 Iodo after than bromo faster than chloro because C-I bond enthalpy is the weakest, then bromo then chloro
32
Mechanism primary halogenoalkane and KOH
Lone pair on OH arrow from that to δ+ carbon, δ- on Br - attacks from opposite side of bromine arrow from C-Br bond to Br -> Forms intermediate with five bonds, square bracket and Br and OH bonds dotted lines, remember charge on intermediate, -> final product and Br-
33
Primary halogenoalknes and ammonia mechanism
Lone pair on ammonia, dipole on c-Cl Lone pair on ammonia arrow to carbon, then arrow from C-Cl bond to Cl Intermediate with five bonds around carbon and four around ammonia Then forms 3HN-C-RHH + Cl- ammonia has a positive charge Another ammonia lone pair arrow attacks hydrogen, arrow from H-N bond to N Forms NH4Cl + 2HN-CRHH
34
Alcohol plus oxygen in the air
Burning !
35
Alcohol plus PCl5
Dry alcohol solid PCl5 R-OH + PCl5 -> R-Cl + POCl3 + HCl This is the test for alcohol as steamy fumes of HCl is given off
36
Alcohol plus KBr H2SO4
50% conc H2SO4 to prevent HBr being oxidised, heat under reflux KBr + H2SO4 -> KHSO4 + HBr R-OH + HBr -> R-Br + H20
37
Alcohol plus red phosphorus and I2
Warm, moist red phosphorous 2P + 3I2 -> 2PI3 3R-OH + PI3 -> 3R-I + H3PO3
38
Alcohol plus potassium dichromate (VI)
Dilute sulphuric acid R-OH + [O] -> R=O + H20 distill as produced (hot ethanol 60 degrees) R-OH + 2[O] -> R-OOH + H20 heat under reflux Secondary -> just to ketone - can be refluxed HUF, electric heater, then use test for aldehyde to determine if it was primary or secondary secondary Dichromate orange to green
39
Phosphoric acid + alcohol
Warm, conc H3PO4 Alcohol -> alkene + H2O (Or heat over aluminium oxide - separate reaction)
40
Heating under reflux
Volatile/ flammable / toxic substancesthe •Place in round bottomed flask with vertical reflux condenser •Water in at bottom and out at top •top of reflux condenser being open •use electric heater No I reacted reagent escapes Add antibumping granules Distill off wanted product at bp
41
Solvent extraction
``` Sparingly soluable organic product •shake reaction mixture in separating funnel with solvent eg ethanol, cyclohexane, Dry ether. Depends on circumstance •organic layer collected only •wash and dry organic layer •still off solvent ``` Suitable solvent dissolves the organic and is low boiling point so can be easily removed
42
Boiling point determination
* Place a small about of a test liquid in an ignition tube and attach to thermometer with rubber band. * Place in beaker with water. Clamp thermometer * Place empty capillary tube in liquid, open end below surface * Heat water and stir, slowly heat until rapid stream of bubbles comes out. Note temp and stop heating * allow to cool, stir until bubbles stop and liquid sucked into capillary tube. Note temp
43
Drying
Use an anhydrous salt such as calcium chloride to remove any water from a crystal product. Anhydrous sodium sulphate or calcium chloride Initial mixture is cloudy, clear when dry. Then filter organic liquid
44
Chirality
Optical isomerism is a result of chirality in molecules with a single chiral centre. This results in optical isomerism. Where the optical isomers are object and non superimposable mirror images
45
What is optical activity
The ability of a single optical isomer to rotate the plane of polarisation of the plane-polarised monochromatic light in molecules containing a single chiral centre
46
Racemic mixture
A solution containing equimolar amounts of the two enantiomers does not rotate the plane of plane polarised light
47
Optical activity as evidence for Sn1 and Sn2 reactions
SN1 - chance of attack is identical from top or bottom - racemic mix. The carbocation has three pairs of bonding electrons and no lone pairs, so it’s shape is triangular planar around the positive carbon atom SN2 - nucleophile attacks from the opposite side to the halogen therefore single optical isomer
48
Boiling and melting point of aldehydes and ketones
Lower than alcohols because does not hydrogen bond intermolecular
49
Solubility of aldehydes and ketones
Solvable as can hydrogen bond with water | They cannot hydrogen bond with themselves
50
Carbonyl compounds with Fehling/Benedicts
Copper sulphate and potassium tartrate Deep blue solution Aldehydes only -> deep blue solution forms red ppt of Cu2O copper (I) oxide Aldehyde oxidised R=O + [O] + OH- -> ROO- +H20 Salt of carboxlyic acid Test for aldehyde
51
Carbonyl compounds and Tollen’s
Sodium hydroxide and silver nitrate dissolved in dilute ammonia, warm Only aldehyde Silver mirror produced R=O + [O] + OH- -> ROO- +H20 Ag(NH3)2^+ -> Ag + 2NH3
52
Carbonyl compounds and acidified dichromate (VI) ions
R=O + [O] + OH- -> ROO- +H20 Aldehyde only Orange reduced to green (If it was manganate (VII) purple to colourless in acidic or brown ppt in alkaline)
53
Carbonyl compounds lithium aluminium hydride
In dry ether Aldehyde -> primary alcohol Ketone -> secondary R=O + 2[H] -> R-OH R1-CO-R2 + 2[H] -> R-CHOH-R2 Also works with hydrogen with a platinum catalyst Does not reduce double bonds (hydrogen with platinum catalyst does)
54
Carbonyl compounds plus HCN
In the presence of HCN pH 8 R=O + HCN -> ROHCN Excess potassium cyanide and some dilute sulfuric acid or hydrogen cyanide and some sodium hydroxide pH allows enough of CN- and HCN
55
Carbonyl + HCN mechanism
Dipole on C=O lone pair on CN- from the KCN but as ion Arrow from CN lone pair to carbon, arrow from double bond to oxygen CRHCNO- Lone pair on negative oxygen attacks hydrogen on HCN molecule, arrow from H-CN bond to the carbon Forms CRHCNOH and CN- If pH is too low not enough CN- if too high not enough HCN
56
Optical activity of product of HCN KCN and carbonyl compound
Racemic minxture, planar around C=O group, equal chance of attack from left right of planar centre (Not the intermediate which is tetrahedral). The initial aldehyde is the planar one
57
Carbonyl plus (2,4-DNPH)
Test for carbonyl group Brady’s reagent Orange ppt Filter off and recrystallise and do melting point determination to indentify compound Does not do carboxylic acids
58
Iodine in the presence of alkali plus carbonyl compound
Does ethanal, methyl ketones, ethanol also(gets oxidised first) and secondary methyl alcohols, gently warm with iodine and sodium hydroxide CH3COR + 3I2 + 4NaOH -> CHI3 + RCOO-Na+ + 3NaI + 3H2O Stepwise I2 + 2OH- -> IO- + I- + H2O CH3COR + IO- CI3COR IO withdrawing weakens σ bond with carbon -> CHI3 + RCOO- Pale yellow ppt of iodoform is produced
59
Boiling point of carboxylic acid
Higher as it can hydrogen bond
60
Solubility of carboxylic acids
Soluble ad can hydrogen bond
61
Preparation of carboxylic acids
•R-OH + 2[O] -> RCOOH + H2O •R=O + [O] -> RCOOH heat under reflux with acidified potassium dichromate primary alcohol RCN + H+ + 2H2O -> RCOOH + NH4+ Reflux with dilute acid Or hydrolysis of an Ester
62
Carboxylic acid plus lithium aluminium hydride
RCOOH + 4[H] -> ROH + H20 Dry ether
63
Carboxylic acid plus base
RCOOH + NaOH -> H2O + RCOO-Na+
64
Carboxylic acid plus PCl5
Solid, dry acid RCOOH + PCl5 -> ROCl + POCl3 + HCl
65
carboxylic acid plus alcohol
Acid catalyst conc H2SO4 RCOOH + R’OH reversible RCOOR’
66
Acyl chloride plus water
RCOCl + H20 -> RCOOH + HCl Vigorous
67
Acyl chloride plus alcohol
RCOCl + R’OH -> RCOOR’ + HCl Not reversible and Cl is a better leaving group therefore better than wth carboxylic acid Dry
68
Acyl chloride with ammonia
Conc ammonia, dry RCOCl + NH3 -> HCL + RONH2 HCl + NH3 -> NH4Cl
69
Acyl chloride plus amine
RCOCl + R’NH2 -> RCONHR’ + HCl Dry
70
Hydrolysis of esters
Acid RCOOR’ + H20 ⇌ RCOOH + R’OH acid cat, low yield Alkali RCOOR’ + NaOH -> RCOO-Na+ + R’OH Goes to completion
71
Polyester formation
Condensation - water is lost Acyl chloride then HCl lost Monomers join together with the elimination of a simple molecule such as water or hydrogen
72
Bonding in benzene
Kekule model and delocalised model Overlap of p-orbitals to form π-bonds
73
Evidence for the delocalised model of the bonding in benzene
•Enthalpy of hydrogenation : The predicted value is lower, more exothermic than the true value because benzene is stabilised because of the delocalisation of the π-electrons Predicted -357 real -207 KJmol^-1 •c-c bond lengths, C=C is slightly shorter than C-C in aliphatic compounds, x-ray diffraction shows that the bond lengths between the C atoms are the same •does not undergo the typical electrophilic addition reactions of unsaturated compounds
74
Why is benzene resistance to bromination
The π-bonds are delocalised in benzene and localised in π-bond of alkene The compound is more stable Substitution rather than addition
75
Benzene plus oxygen in air
Burns
76
Bromine plus benzene
Iron catalyst 2Fe + 3Br2 -> 2FeBr3 FeBr3 + Br2 -> FeBr4- + Br+ Bromine liquid Dry conditions Heat under reflux Br substitutes onto ring for hydrogen Benzene + Br2 -> bromobenzene + HBr Or UV light - heat under reflux, addition occurs from free radicals
77
Benzene and nitric acid
Sulphuric acid conc Of H2SO4 and HNO3 catalyst warm to 50degrees in flask with reflux condenser HNO3 + H2SO4 -> H2NO3^+ + HSO4- H2NO3^ -> NO2+ + H2O NO2 substitutes on ring H lost replaces in HSO4-
78
Fridel-Crafts reaction
Alkylation Dry R-Cl + AlCl3 -> R+ + AlCl4- R+ substitutes on ring, H takes a Cl forming HCl and reforming the AlCl3 Acylation Dry Acyl chloride, anhydrous aluminium chloride R-OCl + AlCl3 -> R+=O + AlCl4-
79
Mechanism of electrophilic substitutions
Generate electrophile 1) Kekule •arrow from a double bond to the electrophile •intermediate has positive charge on the carbon next to the one the electrophile has attached too, arrow from the hydrogen carbon bond next to electrophile back to where double bond is reformed •double bond reformed •show catalyst regenerated by hydrogen 2) delocalised -> instead of coming from double bond, comes from Armstrong inner circle •gets circle turns into horseshoe open opposite where the electrophile has attached, positive charge inside horseshoe, •arrow from hydrogen bond carbon bond to positive charge in horse shoe •show solvent getting reformed
80
Phenol and bromine water
Lone pair in OH is delocalised in the π-system electron density is increased. More susceptible to electrophilic substitution Ortho and para directing Bromine water water works, no need for FeBr3 ROOM TEMP 3 substitutes instead of one (Same with nitration) C6H6OHBr3 + 3HBr White ppt
81
Amines
-NH2
82
Amides
R-CONH2
83
Amino acids
H2N-CHR-COOH
84
Amine plus water
R-NH2 + H2O -> RNH3^+ + OH-
85
Amine plus acid
R-NH2 + HCl -> R-NH3^+Cl- Strong acid
86
Amines plus ethanoyl chloride
R-NH2 + CH3COCl -> R-NH-COCH3 + HCl
87
Amines plus halogenoalkanes
Dropwise R-NH2 + R’Cl -> R-NH2-R’ pos charge on nitrogen and Cl- Excess R-NHR’R’ + HCl
88
Order of strength of base ammonia aromatic amines and aliphatic amines
Aliphatic - electron density pushes into nitro group - more available lone pair. More basic Ammonia Aromatic lone pair delocalised in the ring, less available lone pair , less basic
89
Preparation of primary aliphatic amines
•halogenoalkane conc ammonia and aqueous ethanolic solution, long time in a sealed tube R-Cl + 2NH3 -> R-NH2 + NH4Cl •reduction of nitriles warm with LiAlH4 in dry ether, hydrolyse with dil acid R-CN + 4[H] -> R-NH2
90
Forming aromatic amides
Benzene plus nitric acid plus sulphuric acid forms benzene-no2 Then heat under reflux with conc HCl and Tin to reduce to benzene-NH2 Add excess NaOH Steam distill Then place in separating funnel and sodium chloride added to reduce solubility, the phenyl-amine later is run off and some solid anhydrous potassium carbonate is added to dry
91
Preparation of amides
•ethanoyl chloride + ammonia CH3COCl + NH3 -> CH3CONH2 + HCl
92
Formation of polyamides
Condensation reaction Acyl chloride and amine HCl lost Amino acids - water lost
93
Acidity and basisity of 2-amino acid
Zwitterions are formed (solid at room temp) The ammonia group is protonated, the carboxylic acid is deprotonated Therefore can act as an acid or base (Also strongly attracted)
94
Are 2-amino acids optically active or racemic mixture
Only one isomer is naturally occurring therefore it rotates the plane of plane polarised monochromatic light
95
Proteins
•contain a peptide bond when amino acids combine, by condensation polymerisation. One hydrogen is lost on the NH2 group and the nitrogen bonds with a carbon from the carboxylic acid group Water is lost the same no of waters as no of monomers •can be hydrolysed to form the constituent amino acids, which can be separated by chromatography
96
Gringard reagents
•halogenoalkane + magnesium in dry ether with trace iodine R-I + Mg -> R-MgI Then with carbonyl compounds R-MgI + R’R’’CO -> R-CR’R”-OMgI (R is opposite O) Dil acid O-H of MgI Carbon dioxide R-MgI + CO2 -> RCOOMgI Dilute acid - RCOOH All in dry ether until it is hydrolysed with dilute acid (and water -hydrolysed)
97
Purification by washing
* wash with sodium hydrogencarbonate in separating funnel, removes acidic impurities, release pressure CO2. Stop when no further gas produced * discard aq layer. Wash organic layer with water to remove unreacted sodium salts and soluable organic substances e.g ethanol * discard aqueous layer. Dry with anhydrous salt eg calcium chloride complete when goes clear from cloudy * distill and collect in range of 2 degrees either side of boiling point
98
Recrystallisation
* filter * dissolve ppt in minimum about of suitable solvent when solubility is high when hot and low when cold * filter hot solution again through fluted filter paper using warmed stemless funnel into conical flask-> removes insoluable impurities * cool solution * filter solvent + pure solid under reduced pressure in Buchner funnel * collect solid on filter paper, discard liquid- removes soluable impurities * wash solid, ice cold solvent and leave to drypp
99
Melting point determination
* Insert solid into capillary tube and attach tube, open end up to thermometer with a rubber band * place thermometer into bath of liquid with higher bp than mp of solid * heat liquid bath, stir and note temp where solid melts * the smaller the range the purer the solid
100
Steam distillation
* used to extract a volatile liquid that is immiscible with water from a Complex mixture, partially for a substance that would decompose at its boiling point or just for convenience of it boiling bellow it’s boiling point * heat water to form steam which enters a round bottomed flask with the substance and water. Then distill with a condenser * have a safety vent * electric heater
101
Heights of peaks in proton NMR
Relative heights relate to the relative numbers of hydrogens in each environment
102
Splitting pattern proton NMR
If the proton of a hydrogen atom has n hydrogen atoms on neighbouring carbon atom, its peak will be split into (n+1) subpeaks
103
What is chromatography
Separates components of a mixture between a mobile phase and a stationary phase The sample dissolved in a solvent and washed through a stationary phase by a mobile phase called an eluent The competition between the sample molecules adsorbed by the stationary phase and dissolved by the eluent results in separation depending on how soluable they are in eluent and less adsorbed by stationary phase as these move faster through apparatus
104
Calculating Rf values
For a one way chromograph Rf=distance moved by substance/ distance moved by eluent
105
Types of column chromatography
TLC - thin layer chromatography HPLC - high performance liquid chromatographs GC - gas chromatography Different substances have different retention times due to their strengths attractions with the mobile and stationary phase These can be used in conjunction with mass spectrometry (in applications such as forensics and sport)
106
Affect of concentration on rate of reaction
Increase in concentration causes an increase in reaction rate. Collisions occur more frequently as more in the same volume Successful collisions also occur more frequently
107
Affect of temperature on rate of reaction
Molecules have higher KE large fraction possess activation energy greater the activation energy, larger proportion of collisions result in reaction. Also a increase in collision frequency
108
Affect of pressure on rate of reaction
Increases no of moles per cm^3 -> frequency of collisions increased KE sameX frequency of successful collisions increases. Therefore rate increases However if the reaction is gaseous catalysed by a solid catalyst, the rate is determined by the number of active sites on the catalyst surface, so increasing pressure does not alter the rate
109
Affect of surface area on the rate of reaction
Only surface area can react, larger SA increased frequency of collisions, increased frequency of collisions, increased frequency of successful collision
110
Activation energy
Minimum KE the colliding molecules must posses for the collisions to be successful and result in the formation of product molecules
111
How to calculate rate of reaction
DProduct/Dt Or -Dreactant/ Gradient of graph, either initial rate or at time t
112
In terms of maxwell Boltzmann
Ecat is lower than initial Ea, larger fraction of molecules above ecat line T hot line has peak shifted to the right but lower peak
113
Reaction profiles for catalysed and uncatalysed reactions
Reactants products AH and Ea | For catalysed add a middle transition state
114
Rate of reaction
Rate of change of concentration of product or reactant with time
115
Half life chem
Time taken for reactants to half
116
Rate determining step
Slowest step in a multi step mechanism
117
Obtaining rate equation by titration
* Measure out samples of reactants with known conc, * Mix and start clock * stir throughly * at regular time intervals, withdraw samples using a pipettes and quench stop reaction either with ice or cold water or solution to react with one of the reactants. Note time where half the contents of the pipette have been added to the quenching solution * titrate solutions to find conc of reactant
118
Obtaining rate equation by colorimetry
Spectrophotometer can be used to measure conc of coloured species amount of light of frequency absorbed is measured at set time intervals this depends on conc
119
Measuring rate equation by mass change
Average rate = mass lost/time Do the reaction in a conical flaks tarred when t=O, record mass loss over time in gradual intervals (Some liquid may be lost as spray, plug it with cotton wool, mass change is v small)
120
Measuring rate equation by volume of gas involved
The moles of gas measured of product when less than ten percent of acid used up Rate inversely proportional to time for certain volume of gas to be produced
121
Initial rates method Give example
Initial rate = gradient of a conc time graph at t=0 Conc recatants falls by 10% or less to make initial rates valid, measure change in conc over time ``` Example: Iodine clock reaction H2O2 + 2I- -> I2 + 2H2O With starch and thiosulphate The thiosulphate reacts with the produced iodine. Thererefore the blue black colour is perceived only after the set amount of thiosulphate has been used up Blue black end point ``` Vary concentrations but keep total volume constant Sulphur clock S2O3^2- + 2H+ -> S + SO2 + H20 With nitric acid Time taken for a large X on a white tile to become Invisible
122
Conc time graph is flat
No reaction
123
Conc time graph is linear
Zero Order
124
Conc time graph has a constant half life
First order
125
Conc time graph where half lives increase in a regular geometric manner
Second order
126
Rate conc graph horizontal
Zero order
127
Rate conc graph straight
First order
128
Rate conc graph where rate - reactant squares is straight
Second order
129
How to determine rate determining step from a rate equation or vice-versa
Anything involved in the rate equation is involved in or before the rate determining step
130
How to gather data on the iodonation of propanone
Colorimeter Acid catalyst - dark brown I2 -> colourless Vary concentrations and keep total volume constant Rate = k [propanone] [H+]
131
How to determine mechanism for the iodonation of propanone
Iodine not involved in or before the rate determining step •Lone pair on oxygen attacks H+ pos charge moves onto carbon (CH3)2C+OH), arrow from one of the hydrogens on CH3 to form double bond - this is slow step as C-H bond is broken CH2=C(CH3)OH •arrow from OH bond to carbon, then from double bond to I , from the I-I bond to the other I, Forms H3C-CO-CH2I + I-
132
Rate equations for SN1 and SN2
SN1 R=k[halogenoalkane] not involved in rate determining step - tertiary SN2 R=k[halogenoalkene][nucleophile] - primary Evidence for the mechanisms involved
133
How can a reaction be zero order with respect to all gaseous reactants
If it is catalysed by something in the solid state, the limiting factor is the availability of active sites. Unless the pressure is extremely low Adsorption fast Slow step is adsorbed reactants to adsorbed products Adsorbed products to gaseous products is fast
134
How can a regent which appears in the slow step not appear in the rate equation for
If the conc of the reagent is at least ten times that of the other reagent, the change in conc during reaction will be negligible. This means that within experimental error it appears to be constant and rate equation. Is r = k * what appears to be constant [B]^q * [A]
135
Structural isomer
Compounds with the same molecular formula but different structural formula
136
Stereoisomers
Compounds with the same structural formula but which have the atoms arranged differently in space Split into geometric and optical isomerism
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Geometric isomerism
Is a type of stereoisomerism caused by the presence of a functional group that restricts rotation Eg double bonds or cyclic compounds
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Optical isomer
Do not have a plane of symmetry. They are chiral. They are two isomers which are non superimposable mirror images, two enantiomers.
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Factors which effect the angle through which the plane of plane polarised light is rotated through
* The nature of the enantiomer * The concentration of the enantiomer in the solution * The length of reaction tube
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How to distinguish between primary and secondary and tertiary alcohols
* primary and secondary alcohols turn orange acidified potassium dichromate (VI) solution to a green Cr3+ solution. Tertiary are not oxidised, remains orange * by distilling off the product as the former, and then doing a test with tollens, only aldehyde would reduce silver ion complex to give silver mirror, this would come from the secondary alcohol
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Test for carboxylic acid
Addition of sodium hydrogencarbonate or sodium carbonate. Has evolved RCOOH + NaHCO3 -> RCOONa + H20 + CO2 Gas turns limewater cloudy CO2 + Ca(OH)2 -> CaCO3 + H20
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Fingerprint region
Region below 1500cm^-1, it shows a series of peaks that dependant on the exact compound being analysed.
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How can an infrared spectrum test purity
The purer the compound the closer it matches database. Any stray peaks will be due to impurities
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Why is there a need for standard in NMR
The extend of the splitting depends on the strength of the magnetic field. Therefore there must be some comparison. TMS is used - dissolved in solvent which does not contain any protons
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Chemical shift in NMR
Caused by the extent to which the electrons in orbit around the hydrogen nucleus are pulled away from the hydrogen (deshielding) the chemical shift is less for Ch3 than CH2 because the carbon is pulling electrons away from theee groups
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Why does splitting occur
The magnetic environment of a proton in one group is affected by the magnetic field of protons on the neighbouring carbon atoms •if a neighbouring group have opposite spin from another compound it results in two different fields affecting the CH2 so their peaks are split in two
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Why is there no splitting in carbon 13 NMR What do peak heights represent
The change of two C-13 atoms being next to each other in the carbon chain is about 1 in 1000 This is also why peak heights are not prioritising to the number of carbon in each environment
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High performance liquid chromatography
* column packed with a solid of inform particle size- stationary phase * sample is dissolved in suitable solvent and added to top of column, liquid eluent is forced through column under high pressure * it has a high resolution because the high pressure increases the speed at which the eluent passes through the column and so reduces the extent to which the band of a component spreads out due to diffusion * non polar stationary phase, polar eluent * connect column to infrared spectrometry
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Retention time
The time taken for a component in the sample mixture to pass through the column
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Gas chromatography
* inject a sample into a chromatography column in a thermostatically controlled oven * sample evaporated and is forced through column by flow of inert, gaseous mobile phase, called carrier gas (hydrogen, argon, oxygen, nitrogen or air). Column contains a liquid stationary phase that is adsorbed onto surface of inert solid * useful for separating mixtures of gases or volatile liquids. * remove the samples, measure mass and use NMR/IR compare with database Useful for forensic work and detention of drugs in urine sample
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Which have higher boiling points | Alkene or alkane or halogenoalkane
Alkanes have higher bp because the rigidity of the double bond does not allow the molecules to pack together as efficiently Halogenoalkanes are the highest because they contain more electrons so have more London forces
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Solubility of halogenoalkanes
Insoluble because they cannot hydrogen bond
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Distillation
Large enough difference in the boiling temps of organic substances then distillation can be used to separate them •round bottomed or pear-shaped flask •a still-headed fitted with a thermometer the bulb must be positioned level with outlet of still head •condenser with water going in at bottom and leaving at the top •open receiving vessel •electric heater Collect 2 degrees either side
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Nitriles in synthesis
Hydrolysed to salt of carboxylic acid heat under reflux with NaOH RCN + H20 + NaOH -> RCOO-Na+ + NH3 (To then get carboxylic acid use a strong acid after) Acidic hydrolysis dilute HCl RCN + 2H2O + HCl -> RCOOH + NH4Cl under reflux with lithium aluminium hydride LiAlH4 in dry ether and then hydrolyse with H2SO4 aq to form amine
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Acyl chlorides plus LiAlH4
rR-OCl + 4[H] -> rRHOH + HCl dry ether
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Are esters soluable
No as they cannot hydrogen bond
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Presence of a alkyl group on a benzene
Ortho Para Directing
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Melting temp of phenol
Can hydrogen bond so melts higher than benzene which only has london forces Also soluable unlike Benzene as can hydrogen bond
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Phenol plus acyl chlorides
Not Friedel crafts Oxygen atom acts as nucleophile and attacks carbon atom forming an Easter
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Boiling temps of amines
Hydrogen bonding therefore higher than comparison alkane (also soluable)
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TLC
•thin layer chromatography Stationary phase is either silica gel aluminium oxide immobilised on a flat inert sheet made from class or plastic •unknown amino acid mixture is dissolved in suitable solvent and a spot of dissolved known amino acid is placed separately on the same plate at the same level •the plate is then dipped in suitable eluent with spots above the level of liquid eluent •place in sealed container •capillary action draws up eluent •plate left until eluent has risen up to the top of the plate •remove plate and spray with ninhydrin and heat •ninhydrin reacts with amino acids producing a blue purple colour Compare with the heights reacted by known amino acids
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Which is more acidic Phenol Alchohol Carboxylic acid
Carboxylic acid is strongest -> two oxygen groups Phenol is second as the lone pair can be delocalised into pi system -> stabilises conjugate base Alcohol weakest
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Drawing enantiomers
Use two lines, one solid triangle and one dashed line The entanioner has the same type of line drawn to each group but the groups are reversed like a mirror image
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Why would you wash with ice cold water
To remove soluble impurities but to ensure as little solid as possible dissolves
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Benefit of Grignard
Source of nucleophile can carbon
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How do anti bumping granules prevent bumping
They provide a surface for bubbles to form They distribute the heat more evenly
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Cracking
Collection over water/ gas syringe Ceramic fibre/ wool soaked in substance to be cracked Aluminium oxide Heat under catalyst
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Why should hydrogen not be above lithium
The rest of group one are metals Hydrogen does not react in the same way, has different chemical properties Forms H- ion
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Which halogens react with alkenes
Chlorine and bromine | Iodine only if the C=C bond is activated by an oxygen atom
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Rates of addition of hydrogen halides to alkenes
HI > HBr > HCl because the HCl bond the weakest Gaseous
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Polymerisation of an alkene
Heat under 1000 atm pressure in the presence of trace of oxygen Causes radicals to be formed that initiate the polymerisation reaction Or mix with a solution containing alkylaluminium and titanium chloride
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What is the difference between hazard and risk
Hazard is the potential to do harm | Risk is the probability of harm occurring
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State of halogenoalkanes
Chloro bromo methane and chloroethane are gases at RTP Iodomethane and higher members are liquids
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Alcohol and HCl
Only works for tertiary Conc HCL heat under reflux Chloroalkane plus H20
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Obtaining rate by production of a solid
The time taken to produce enough solid to hide a cross on a piece of paper
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Rate of reaction using change in pH or conductivity
Measure pH at time intervals Remember pH is logorithmic Or when no of ions change measures electrical conductivity
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How to make an aldehyde
Heat at 60 degrees using an electric heater Add potassium dichromate and did sulphuric acid Collect ethanol in flask surrounded by iced water Distill off directly to prevent further oxidation Electric heater as organic stuff is flammable
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Preparation of ketones
Potassium dichromate sulphuric acid Round bottomed flask Reflux condenser Heat Aromatic can be done using Fredel-crafts
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Reduction of alkene group
H2/Pt
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Steps of iodoform
Sodium hydroxide reacts withs with iodine to form IO- and I- and H20 The IO- ions substitute into the CH3 group next to the C=O group forming CI3COR the electron withdrawing effect of the three halogen atoms and the oxygen atom weakens the σ bond which then breaks, and then OH- adds forming iodoform
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How to prepare a carboxylic acid
* oxidation of primary alcohol * oxidation of aldehyde * hydrolysis of an Easter * hydrolysis of a nitrile * iodoform then add excess strong acid
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Test for cabrolyxic acid
Carboxylic acid + sodium carbonate -> salt of acid plus co2 plus h20 Turns limewater cloudy
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Preparation of acyl chlorides
Carboxylic acid plus PCl5 -> POCl3 plus acyl chloride plus HCl
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Advantages of forming esters using acyl chloride
HCl gas is lost hence irreversible Lower activation energy Cl is a better leaving group
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Benzene plus hydrogen
Nickel catalyst and heat
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Why plus temp of nitration be 50
Bellow 50 too slow | Above 60 Second NO2 group substitutes
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Melting temp of phenol compared to bromine
Can hydrogen bond hence higher melting temp | Also soluble
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Nitration of phenol
Reacts with dilute nitric acid | 1,4
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Relative acidity of alcohols phenols and carboxylic acid
Alcohol not very acidic - no litmus no sodium hydroxide no sodium carbonate Phenol - litmus goes red, salt formed with NaOH, no reaction with sodium carbonate Carboxylic acid does all three
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Hydrolysis of amides
Heat under reflux with aq acid or alkali Acid Amide + H+ + H20 -> CH3COOH + NH4+ Alkali Amide + OH- ->salt of carboxylic acid plus NH3
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Chromatography of amino acids
TLC Stationary phase is either silica gel or aluminium oxide immobilised on a flat inert sheet that is usually made from glass or plastic •acid or mixture dissolved in a suitable solvent and a spot of the test solution is placed 2cm from bottom •known amino acid placed at the same level •plate dipped in mobile phase with the spots above the level of the liquid eluent •plate placed in sealed container •the eluent is drawn up by capillary action •plate left until eluent has risen to top •plate removed and sprayed with a solution of ninhydrin and then heated •ninhydrin reacts with amino acids producing a blue purple colour
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Describe the bonding in benzene
Head on overlap between orbitals from neighbouring carbon atoms to form a sigma bond The remaining orbitals overlap sideways and so electrons delocalise around the ring
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How can chemists contribute to a more sustainable use of polymers
* Reprocessing polymers into simpler compounds for use in feedstock and chemical industry * Capture and use of energy from incineration * sorting and recycling of polymers * removal of toxic products formed during incineration
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Why does stereoisomerism occur in alkenes
Restricted rotation around the C=C bond because the π bond prevents it
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Describe the bonding in benzene
Head on overlap between orbitals from neighbouring carbon atoms to form a sigma bond The remaining orbitals overlap sideways and so electrons delocalise around the ring
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How can chemists contribute to a more sustainable use of polymers
* Reprocessing polymers into simpler compounds for use in feedstock and chemical industry * Capture and use of energy from incineration * sorting and recycling of polymers * removal of toxic products formed during incineration
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Why does stereoisomerism occur in alkenes
Restricted rotation around the C=C bond because the π bond prevents it
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Equation for hydrolysis of nitrile
Nitrile + 2H20 + H+ -> Carboxylic acid plus NH4+ Strong acid heat under reflux
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Addition across cyclohexene
Transisomer is formed | Providing that the second chlorine for example adds on opposite side to the first chlorine