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# Chemistry revision Kinetics Rate of Change is the change in concentration with unit time.

The order of reaction with respect to one of the species is the power of the concentration. The overall order is the sum of the orders For example 2A + B ---> 3C + D has a rate equation rate = k[A]2 [B] order respect to A = 2 , respect to B =1 and the overall = 3 The order can also be calculated using a graph y=n is 0 order , y=x is 1st order and y=x2 is 2nd order It also can be calculate using an initial rate in a table form In the rate equation the constant k can be affected by temperatures, the hotter it is the faster the rate so higher K is The increase in temperature increase the speed of particles so there is more collisions with higher energies hence the rate is increase. *The rate determining step is the slowest step in a long reaction. Otherwise it depends on the reactants in the rate equation. The reactant with the highest order has the greater affect

Equilibrium
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An equilibrium mixture will always form the same ratio of products and reactants so long as the conditions are maintained. Hence there is an equilibrium constant Kc which is calculate by aA + bB <-----> xX + yY = [X]x [Y]y [B]b [A]a

For an exothermic reaction (-H) increasing the temperature decrease the equilibrium constant. For an endothermic reaction (H) increasing the temperature increase the equilibrium constant If Kc is greater than 1 there is more products than reactants so the equilibrium over to the right. Catalyst and change in concentration have no effect on Kc. Catalyst affects the forward and backward reaction equally hence only the rate is increased.

Optical isomerism
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They occur when four different substituents are attached to one carbon atom. They are mirror images of each other They are said to be chiral and the two isomers are called enantiomers The carbon is the chiral centre Polarised light can be passed through the enantiomers rotate the light in opposite directions. This occurs in a polarimeter. The + isomer produces a clockwise rotation, the - isomer produces a anticlockwise rotation. Many reactions which involve optical isomers produce a racemic mixture which is 50% of each enantiomers. Hence there is no optical activity it cancels out

Racemic mixtures are produced because a nucleophile can attack from above or below the double bond carbons. Optical isomers in the drug industry means one enantiomers might not work or be dangerous. To sort this out they can be separated which is difficult and expensive, keep it in which is wasteful or find a new synthetic root.

Carbonyl Compounds (C=O) The polar C=O means it has a higher boiling point than alkanes, but no hydrogen bonds occur. Shorter chains can dissolve in water. They Undergo Nucleophile addition. Aldehydes can be oxidised to carboxylic acid using acidified (dilute H2SO4) potassium dichromate K2Cr2O7/H+. In ketones a C-C bond has to be broken for this to occur and so it does not. Fehlings test contains Cu2+ which is coloured blue, when warmed with an aldehyde a brick red precipitate (copper oxide is formed), Ketones have no reaction. Tollens silver mirror test contains a reagent [Ag (NH3)2]+, when added to an aldehyde, the aldehyde is oxidised to a carboxylic acid. The Ag+ is reduced to metallic silver, Ketones do not react. A reduction of an aldehyde produces a primary alcohol and a ketone a secondary alcohol. The reaction requires H+ form a solvent (NaBH4)

Carboxylic acid + esters Carboxylic acid forms hydrogen bonds with water and in there solid state meaning they have a higher boiling point than there alkanes. To identify carboxylic acid you can measure there melting point Esters name by the alcohol first then the carboxylic acid, for example Ethanoic acid + Propanol --- > Propylethanoate The carboxylic acid can dissociate to form a carboxylate ion. The negative charge is shared, the delocalisation makes the ion more stable. Esters are formed by adding carboxylic acid and an alcohol with a strong acid catalyst. To from an ester and water. The reaction is reversible and the ester can be hydrolysed. This can happen at room temperature. By adding NaOH instead of a strong acid to catalyse the reaction the salt of the acid is produced and water Uses of esters , involves glycerol and 3 fatty acids to produce an ester adding this to NaoH produces soap (salt). These dissociate and hence have two distinct ends. The hydrocarbon is non-polar and mixes with grease whilst the COO- does not allowing grease and water to mix. Propane 1,2,3-triol is used in pharmaceutical and cosmetic preparation, medicines and toothpaste, a solvent in food. And is used to plastics various materials. Biodiesel is also an ester.

Acylation Acyl groups is R-C=O Acid derivatives all have acyl groups (these are derived from carboxylic acids and from a groups called ethanoyl) This is attacked from nucleophiles which hence are acylated. This occurs more readily depending on the magnitude of the charge on the carbonyl carbon, which depends on the electron releasing or attacking of the power of the side group. How easily the side group is lost and how good the nucleophile is. It follows the mechanism nucleophile addition-elimination Nucleophiles consist of either ammonia (amide), primary amine (N-substituted amide) , alcohol ( ester) and water ( carboxylic acid), this is order of the reactivity. Using an acid chloride HCl is a by-product using an anhydride produce ethanoic acid. The anhydride is cheaper, less corrosive, does not react with water readily, it has a safer byproduct.

Benzene Arenes are hydrocarbons based on benzene C6H6 It forms addition compounds The electrons are delocalised. They form a region of density above and below the ring. It produces an aromatic stability This can be proven as more energy is released by 3 double bonds than the benzene when its hydrogenated. Benzene is a colourless liquid boils at 353K and freezers at 279K. Because its flat they pack closer together and so are harder to separate. The ring is an area of high electron density and so attacked by electrophiles. The ring is very stable and so does not break They react by electrophilic substation Arenes can undergo combustion and their flames are very smoky Nitration uses the substitution of NO2+ it is made from the following reaction H2SO4 + HNO3 --- > H2NO3+ + HSO4- (The sulphuric acid is the stronger acid so the nitric acid acts as a Bronstead-Lowry base) The H2NO3+ then loses a molecule of water to produce the NO2+ ( Nitronium ion) Molecule Nitration is important to make explosives such as TNT Friedal-crafts acylation has a catalyst of aluminium chloride The acyl chloride is made by RCOCl + AlCl3 --- > RCO+ + AlCl4The aluminium atom accepts another chloride as the chloride gives a lone pair. The aluminium chloride is a catalyst AlCl4- + H+ --- > AlCl3 + HCl

Amines -

A primary amine has one R group connected to the nitrogen , secondary two R groups and so on. Ammonia has a bond angle of 107 as t is a pyramidal shape ( The lone pair makes it act like a tetrahedral) Amines are polar and can accept hydrogen bonds but they are not as strong as water as nitrogen has a lower electronegativity than oxygen