DF Flashcards
Define “thermochemistry”
The study of energy and heat associated with chemical reactions
Define “exothermic”
A reaction that gives out energy and heats surroundings
What are the main features of an exothermic reaction?
What does an enthalpy profile for one look like?
Bond making
ΔH negative - products end up with less energy than reactants
Gives out energy to surroundings
Heats up surroundings
Reactants above products, AE arrow up, ΔH arrow down
Define “endothermic”
A reaction that takes in energy and cools the surroundings
What are the main features of an endothermic reaction?
What does an enthalpy profile for one look like?
Bond breaking
ΔH Positive - products end up with more energy than reactants
Takes in energy from surroundings
Cools surroundings
Reactants below products, both arrows up
Define “enthalpy change”
The energy transferred to/from the surroundings when the reaction is carried out in an open container
Why are standard conditions used when calculating enthalpy change?
They are set conditions which allows us to compare enthalpy changes
What are standard conditions?
Pressure: 1 atmoshpere (101kPa/1.01Nm-2)
Temp: 298K
Concs: 1.00moldm-3
State: Whatever state at 298K
How do you convert K to degrees C?
Minus 273
What are the 4 types of enthalpy change?
- Standard enthalpy change of a reaction
- Standard enthalpy change of formation
- Standard enthalpy change of combustion
- Standard enthalpy change of neutralisation
Define “standard enthalpy change of a reaction”
Enthalpy change when one mole of matter is transformed by a chemical reaction under standard conditions
Define “standard enthalpy change of a formation”
Enthalpy change when 1 mol of a compound is formed from its elements in their standard states, under standard conditions
Define “standard enthalpy change of a combustion”
Enthalpy change when 1 mol of a substance is completely burned in oxygen, under standard conditions
Define “standard enthalpy change of a neutralisation”
Enthalpy change when acid reacts with alkali to form 1 mol of water under standard conditions
Are all combustion reactions positive/negative and why?
Negative because they are all exothermic
What formula is used to measure enthalpy change?
E = mcΔT
E = energy transfered (KJmol-1)
m = mass (g)
c = specific heat capacity (Jg-1K-1)
ΔT = temp. change (K)
What is the specific heat capacity of water?
4.18Jg-1k-1
How does a bomb calorimeter work?
- Fuel is ignited electrically and burns oxygen inside the pressurised vessel
- Energy is transferred to the surrounding water
What is measured in a bomb calorimeter?
Temperature rise
How is the experiment conducted in a bomb calorimeter?
At a constant volume in a closed container
Why is the fuel in a bomb calorimeter burnt under pressure?
To increase the number of successful collisions leading to complete combustion of the sample
Why is a bomb calorimeter more accurate than a simple calorimeter?
Low heat losses
What is Hess’s Law?
ΔH for any reaction will be the same if the start + end conditions are the same
What is the formula for finding the enthalpy change of reaction from enthalpy changes of combustion?
Change in H1 = Change in H2 - Change in H3
What is the formula for finding the enthalpy change of reaction from enthalpy changes of formation?
Enthalpy change of reaction = sum of enthalpy changes of formation of products - sum of enthalpy changes of formation of reactants
Which ways do the arrows point in an enthalpy cycle for combustion?
Down
What is placed at the bottom in an enthalpy cycle for combustion?
Combustion products - CO2 + H2O usually
Which ways do the arrows point in an enthalpy cycle for formation?
Up
What is placed at the bottom in an enthalpy cycle for formation?
The elements that formed the compound reactants
Why is the amount of oxygen used in combustion not critical?
It is normally used in excess
Why are the enthalpy changes for elements always 0?
They have already been formed and do not change their amount so enthalpy change is 0
What is crude oil?
A thick black liquid consisting of a mixture of hydrocarbons
Explain the process of fractional distillation
- At the refinery, the crude oil is heated to vapourise it
- vapour passes into the distillation column
- Vapour rises up through the column, separating into different fractions
- as different ones condense into liquids and run off at different levels
Does density increase/decrease up a fractionating column?
Decrease
Does boiling point increase/decrease up a fractionating column?
Decrease
Does chain length increase/decrease up a fractionating column?
Decrease
Does volatility increase/decrease up a fractionating column?
Increase
Does flammability increase/decrease up a fractionating column?
Increase
Why does each fraction not have an exact boiling point?
Each one is a mixture of many different hydrocarbons
Why is organic chemistry named so?
Many carbon compounds are found in living organisms
What does organic chemistry include?
All carbon compounds except CO, CO2 and carbonates
How many electrons does carbon have in its outershell?
4
Why does carbon generally form covalent bonds?
If it achieved stability by becoming an ion it would be too highly charged (4+ or 4-)
What is catenation?
Carbon’s ability to form strong covalent bonds with itself to give chains and rings of itself
What does catenation lead to?
The limitless variety of organic compounds
Define “hydrocarbon”
Compounds containing only carbon or hydrogen
What is the general formula for hydrocarbons?
CxHy
Define “aromatic”
Compounds containing one/more benzene rings
Define “aliphatic”
Compounds not containing any benzene rings
Define “functional group”
Modifiers responsible for the characteristic chemical reactions of molecules
Define “saturated”
A compound with no bonds available for bonding
Define “unsaturated”
A compound containing bonds that can be broken open
Define “homologous series”
A group of compounds with the same functional group
Are alkanes aliphatic?
Yes
What is the general formula for alkanes?
CnH2n+2
Name the first ten alkanes
- Methane
- Ethane
- Propane
- Butane
- Pentane
- Hexane
- Heptane
- Octane
- Nonane
- Decane
What is the relationship between alkane chain length and tendency to become a solid and why?
As chain length increases, the tendency towards a solid also increases because the boiling point increases
What state are alkanes n= 1 - 4 in?
Colourless gases
What state are alkanes n=5 - 16 in?
Colourless liquids
What state are alkanes n=17+ in?
White waxy solids
Do alkanes mix well with water?
No they form two separate layers
Why do alkanes not mix well with water?
Water contains polar molecules that attract each other and prevent alkane molecules mixing with them
What is a cycloalkane?
A saturated hydrocarbon where the carbon atoms are joined in a ring
What is the general formula for alkanes?
CnH2n+2
Are cycloalkanes saturated?
Yes
Are alkenes saturated and why?
No - the carbon double bond can open up and bond with more hydrogens
What is the general formula for alkenes?
CnH2n
Are alkenes aliphatic?
Yes
What is the general formula for cycloalkenes?
CnH2n-2
Are cycloalkenes aliphatic?
Yes
Are cycloalkenes saturated?
No
What is the formula of benzene?
C6H6
How many carbons and double bonds does a benzene ring contain?
6 carbons and 3 double bonds
Why are benzene rings more stable (less reactive) than expected?
The double bond electrons are delocalised around the carbon ring, unattached to any particular carbon
Is benzene aliphatic?
No - aromatic
Is benzene saturated?
No
Is alcohol a hydrocarbon?
No
What is the general formula for alcohols?
CnH2n+1OH
What is the functional group for alcohols?
The hydroxl group (-OH) which can be attached to any carbon atom on the chain
What is a general formula?
A formula that can describe any member of a family of compounds
What is a molecular formula?
The actual number of atoms of each element in a molecule
What is the shortened structural formula?
A formula showing the atoms, carbon by carbon with the attached hydrogens and functional groups
What is the structural formula?
Shows how all the atoms are arranged and all the bonds between them
What is the skeletal formula?
Shows the bond between the carbon skeleton only, with any functional groups. The hydrogen and carbon atoms are not shown.
Why is giving systematic names important?
It allows for the full structural formula of a compound to be determined.
What is the formula of methyl?
CH3
What is the formula for all alkyls after methyl?
CH3 + CH2 for every carbon atom
What is the prefix for two identical sidechains?
Di
What is the prefix for three identical sidechains?
Tri
What is the prefix for four identical sidechains?
Tetra
Define “energy density”
The amount of energy obtained per kg of fuel when burnt
What is the equation for energy density?
(1000/relative molecular mass) x standard enthalpy change
Define “bond enthalpy”
The energy needed to break 1 mol of a bond in the gaseous state
Define “average bond enthalpy”
The energy needed to break 1 mol of a bond gaseous state, averaged over many different compounds
Is bond forming exothermic/endothermic?
endothermic
Is bond making exothermic/endothermic?
exothermic
What is the relationship between bond strength and bond enthalpy and why?
The stronger a bond, the more energy needed to break it so the higher its bond enthalpy
Explain the forces which determine a bonds length in covalent molecules
- The positive nucleui are attracted to the shared electrons so the atoms move together
- The two positive nucleui also repel each other, these forces become greater until the atoms stop moving together
- The distance between the 2 nucleui is the distance where the attractive and repulsive forces balance each other out : equilibrium bond length
What is the relationship between bond length and bond enthalpy and why?
The shorter the bond length, the higher the bond enthalpy as there is a stronger attraction between the two atoms in the covalent bond.
Order these types of bonds in order of increasing bond enthalpy:
- Double bond
- Single Bond
- Triple Bond
- Triple bond
- Double bond
- Single Bond
Why do triple bonds have a higher bond enthalpy than double and single bonds?
- More electrons are shared with more bonds so electron density between the two atoms is greater
- Therefore the positive nucleui are more attracted to the electrons and so the atoms move closer together
What is the formula for bond enthalpy change?
Bond enthalpy change = total amount of bonds broken + total amount of bonds made
What do all reactions initially need and why?
Energy to stretch and break bonds as some must be broken before product molecules can begin to form
Why do some reactions such as neutralisation need barely be heated before they start?
They need only a little energy with enough available in their surroundings of room temperature
Why do you not need to break all bonds before a reaction occurs?
Once a few bonds have been broken, new bonds start to form and this gives out enough energy to keep reactions going
Why do some reactions need continuous heating?
They are only slightly exothermic
Why is there some variation between experimental and theoretical bond enthalpies?
- The bond enthalpy value is not actual standard value, e.g as under standard conditions water is a liquid but when calculating bond enthalpies you must work in a gaseous state
- Bond enthalpies in theory are given out as averages of several different bonds from different compounds
Why are bond enthalpies useful?
They enable enthalpy changes to be measured when there is little specific data for the compound
Why is it difficult to measure bond enthalpy?
- There is often more than one type of bond in a compound
- Difficult to make measurements when everything is in the gaseous state.
Hence an average taken across several different compounds
How are bond enthalpies measured?
Indirectly using enthalpy cycles
Explain two problems with fractions from fractional distillation
- “Straight run” -fractions from primary distillation makes for poor petrol and need to be treated further
- Supply and demand - crude oil contains a surplus of the high boiling fractions e.g gas oil and not enough of the lower boiling fractions e.g gasoline for the demand
How does cracking solve the problem for the demand of petrol?
- Alkanes with larger molecules too large for use in petrol are broken down into alkanes with shorter chains that can be used
- Alkanes are also broken down into cycloalkanes, arenes and alkenes which are blended to produce high grade petrol
Name 4 types of cracking reactions
- alkanes —-> branched alkanes + branched alkenes
- alkanes —-> smaller alkenes + cycloalkanes
- cycloalkanes —-> alkenes + branched alkenes
- alkenes —–> smaller alkenes
Are the products of cracking predictable?
No, they are random, with the same molecule giving different cracking products
Without a catalyst, what would the cracking process need?
It would require extremely high temperatures and pressures and would take far longer, which would be more expensive
Give details of an experimental procedure to crack a hydrocarbon vapour over a heated catalyst (in the lab).
- If using a liquid alkane mixture: Place 2 cm depth of mineral wool into a boiling tube, then use a dropper pipette to add approximately 1 cm3 of liquid alkane mix. Rotate the tube to ensure that the liquid alkane mixture soaks into the mineral wool.
- Set up the apparatus as shown in the picture
- Use a spatula to place some of the catalyst into the middle of the reaction tube. Keep it separate from the alkane mixture + mineral wool. Make sure there is space above the catalyst for gases to pass freely over it.
- Heat the catalyst strongly with a Bunsen flame. Once it’s hot, gently warm the alkane mixture to produce alkane vapour.
- Move the Bunsen burner backwards and forwards between the catalyst and the alkane mixture until you have collected several tubes of gas.
Stopper the tubes for testing later. The first tube can be discarded because it will contain mainly displaced air from the apparatus - Do not allow water to suck back from the trough
- When finished, lift the delivery tube out of the water + leave the apparatus to cool before dismantling it in a fume cupboard
What temperature does catalytic cracking take place at?
450 - 500 degrees
What catalyst is used normally in catalytic cracking?
Zeolite
Where does cracking take place?
In a riser reactor: a 60m high vertical tube around 2m in diameter
What is the mixture in the riser reactor like?
A moving fluidised bed where solid particles flow like a liquid
Explain the process of catalyctic cracking in detail
1) The hot vapourised hydrocarbons and the zeolite catalyst are fed into the bottom of the tube and forced upwards by the stream
2) The mixture takes 2 seconds to flow from the bottom to the top of the tube
3) After the riser reactor, the mixture passes into a separator where the steam carries away cracking products leaving behind the solid catalyst
4) The catalyst goes into the regenerator where it takes 10 minutes for coke to burn off in the hot air blown into the regenerator
5) The catalyst is then re-introduced into the base of the riser reactor, ready to repeat the cycle
What does the mixture only taking 2 seconds to flow from the bottom to the top of the tube mean?
The hydrocarbons are in contact with the catalyst for only a very short period of time
Why does the coke need to be burnt off in the regenerator?
Coke forms on the catalyst surface during cracking making it eventually go inactive and unable to catalyse reactions
What does energy released from burning the coke do?
Heats up the catalyst, this energy is then transferred to the feedstock so that the cracking can occur without additional heating
Define “catalyst”
Substance which speeds up the rate of chemical reaction by providing an alternate reaction pathway with a lower EA
Is not chemically changed/used up at the end of the reaction
(Although may form intermediates or be poisoned)
Define “catalysis”
The process of speeding up a chemical reaction using a catalyst
Do catalysts undergo any permanent chemical change during a reaction?
No
Do catalysts change physically?
Yes, they crumble/become roughened
What does catalysts changing physically suggest?
That they take part somewhat in the reaction, although they can be regenerated
How much of a catalyst is usually required?
Only small amounts
What do catalysts affect in the reaction?
Its rate, not the amount of product formed
Do catalysts appear as reactants in the overall equation?
No
Define “homogeneous catalyst”
A catalyst which is in the same physical state as the reactants
Give one example of homogeneous catalysis
Enzyme catalysed reactions in cells take part in an aqueous solution
Define “heterogeneous catalyst”
A catalyst which is in a different physical state to the reactants
What does heterogeneous catalysis usually involve?
A mixture of gases/liquids in the presence of a solid catalyst, providing a surface for the reaction to take part on
What shape does a single carbon bond have?
Tetrahedral
What is the angle between two carbon atoms in a single covalent bond?
109.5 degrees
What shape does a carbon double bond have?
Trigonal Planar
What are the bond angles around the C=C bond?
Why?
All bond angles around C=C bond 120º
Because there are 3 groups of e- around each C atom - 2 single bonds + 1 double bond
These groups repel each other as far as possible
Do all the carbon atoms in an alkene compound lie in a planar shape?
No only those in the double bond e.g ethene is completely planar but in propene only the C=C unit is
How is a sigma bond formed?
When two s orbitals overlap in the space between two atoms
Why are sigma bonds very strong?
There is the highest possible electron density between the two positive nucleui as the two s orbitals overlap
How is a pi bond formed?
When two p orbitals overlap sideways
What does a pi bond consist of?
2 areas of negative charge, one above and one below the line of atoms
Why is a double bond not twice as strong as a single bond?
Because pi bonds are weaker than sigma bonds
Define an “electrophile”
A positive ion or molecule with a partial positive charge on one of the atoms
This causes it to be attracted to a negatively charged area
It will react by accepting a lone-pair to form a dative covalent bond
Define an “addition reaction”
Two or more molecules reacting to form a larger single molecule
Why does the C=C have a highly negative region?
The four electrons in the double bond of ethene give the region between the two atoms a higher than normal negative charge density
What can be used to test for unsaturation?
Shaking the compound with bromine water
Bromine - is decolorised if unsaturated.
Goes from orange to colourless
Write a formula for the electrophilic addition of bromine to an alkene
H2C=CH2 + Br2 ====> CH2BrCH2Br
Describe the first step of electrophilic addition with bromine (polarisation)
The bromine molecule moves closer to the negative C=C bond which repels electrons to the bottom of the Br-Br bond, polarising the molecule and creating a postively charged (an electrophile) Br atom
Describe the second step of electrophilic addition with bromine (carbocation)
An electron pair from the C=C bond attacks the positive bromine atom, forming a dative covalent bond, the carbon atom the electron pair came from becomes a carbocation
Describe the third step of electrophilic addition with bromine (new covalent bond)
A pair of electrons moves from the now negative bromide ion to the carbocation to form a new carbon-bromine covalent bond