Back To School

CHEMISTRY SUMMARY

1 EQUILIBRIA Chemical Equilibria

Reversible reactions, dynamic equilibrium. (a) Factors affecting chemical equilibria: Le Chateliers principle.

Back To School

The following examples are useful: (i) the hydrolysis of simple esters, (ii) the synthesis of ammonia, (iii) acid base behaviour. (b) Equilibrium constants, their definition and their calculation in terms of concentrations. The qualitative effect of temperature on equilibrium constants.

The concentration of solids and pure liquids are not included in the expression for the equilibrium constant. Careful distinction should be drawn between those cases where a change in the composition of the equilibrium mixture occurs (i) with the constant unchanged, e.g. in response to a change in concentration, (ii) because of change in the value of the equilibrium constant, in response to a change in temperature. 1.2 Ionic Equilibria (a) Bronsted-Lowry theory of acids and bases. Qualitative distinction between strong and weak acids in terms of conductivity.

Back To School
An appreciation that strong electrolytes, in contrast to weak electrolytes, are effectively fully dissociated in all but the most concentrated solutions is expected. Definition and details of the measurement of any form of conductivity are not required. Degree of dissociation a, described in terms of actual concentration of hydrogen (or hydroxide) ion relative to maximum theoretical concentration. No treatment of pKa, Kb or pKb is required. (b) The ionic product of water Kw. (c) pH. Calculation of pH from concentration for strong acids and from concentration and Ka for weak acids using Ka = a2/V (derivation not required). pH indicators: choice of indicators. (d) Buffer solutions a qualitative treatment only. Reference should be made to the importance of buffers in biological systems. 1.3 Chromatography Treated as an equilibrium between a stationary and a moving phase. Practical experience should be given in paper, thin layer and column chromatography. The use of R1 values. Gas chromatography, the use of peak heights and retention times. The widespread application of these methods in industry and medicine should be noted.

2 REACTION KINETICS

Back To School
(a) Simple rate equations; order of reaction; rate constants. Rate = k[A]n[B]m. Treatment should be limited to simple cases of single step reactions and of multi-step processes with a rate-determining step, for which n and m are both integral and are either 0, 1 or 2. The use of the integrated forms of firstand second-order rate equations is not required but the use of constancy of half-life as a test for first order kinetics is included. Simple calculations on half-life may be set. Questions will not be set requiring candidates to determine the order of a reaction using methods that involve drawing tangents to curves. Candidates will not be asked to determine the values of rate constants but should be able to construct a rate equation for a reaction by inspection of suitable data. The use of order of reaction in checking that a given reaction mechanism is consistent with the observed kinetics.

(b) The qualitative effect of temperature on rate constants; concept of activation energy as an energy barrier.

Back To School

Back To School

Interpreted qualitatively in terms of the variation with temperature of the Boltzmann distribution. (c) Catalysis

It should be appreciated that in the presence of a catalyst a reaction follows an alternative path, i.e. a different barrier of lower energy is involved.

Back To School
3 THERMOCHEMISTRY AND CHEMICAL ENERGETICS (a)

Back To School

Back To School

Back To School

(b) Lattice energies for simple ionic crystals. A qualitative appreciation of the effects of ionic charge and ionic radius on the magnitude of a lattice energy. A treatment of the Born-Haber cycle is not required.

4 THE PERIODIC TABLE: PRINCIPLES OF CHEMICAL PERIODICITY 4.1 Periodicity of Physical Properties

Back To School
A qualitative appreciation of the variation in physical properties with atomic number across the second and third periods (lithium to neon, sodium to argon). The variation in first ionisation energies, atomic radii, melting points. Interpretation and explanation or the above trends and gradations in terms of structure and bonding of the elements.

Ionic Bonds

Back To School

Back To School

Example of covalent bond

4.2 Periodic Patterns in the Chemical Properties of Compounds Study in this sub-section should be restricted to the oxides, chlorides and simple hydrides (also excluding 'MgH2' and 'AIH3') of the elements sodium to chlorine.

Back To School
The patterns and gradations in properties should be interpreted in terms of key atomic and electronic factors such as atomic and ionic radii, ionisation energies and electronegativities. (a) Variation in oxidation number illustrated by the oxides, chlorides and simple hydrides. (b) (i) Reaction of oxides, chlorides and simple hydrides with water. (ii) Acid/base behaviour of oxides. No treatment of peroxides or superoxides is required. 5 A STUDY OF THE ELEMENTS IN SOME GROUPS OF THE PERIODIC TABLE 5.1 Group II The elements magnesium, calcium, strontium and barium. A group of reactive metals which are essentially similar to each other with only gradual changes as their atomic numbers increase. (a) The fixed oxidation number of Group II elements in their compounds. Interpretation in terms of the electronic structure of the elements. (b) Thermal decomposition of nitrates, carbonates and hydroxides. The alkaline earth metals are a series of elements comprising Group 2 (IUPAC style) of the periodic table: beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra). The alkaline earth metals provide a good example of group trends in properties in the periodic table, with well characterised homologous behaviour down the group.

Back To School
beryllium is an exception: It does not react with water or steam, and its halides are covalent. All the alkaline earth metals have two electrons in their outermost shell, so the energetically preferred state of achieving a filled electron shell is to lose two electrons to form doubly charged positive ions. The alkaline earth metals are silvery colored, soft, low-density metals, which react readily with halogens to form ionic salts, and with water, though not as rapidly as the alkali metals, to form strongly alkaline (basic) hydroxides. For example, where sodium and potassium react with water at room temperature, magnesium reacts only with steam and calcium with hot water: Mg + 2 H2O Mg(OH)2 + H2

5.2 Nitrogen (a) The element: reasons for its lack of reactivity. (b) Ammonia (i) Manufacture by the Haber process. Reference should be made to application of the principles of kinetics and equilibria to this process. (ii) Formation from ammonium salts. (iii) Properties as a base. (iv) Uses, particularly in the manufacture of nitric acid and fertilisers.

Back To School
5.3 Group VII Halogens are highly reactive, and as such can be harmful or lethal to biological organisms in sufficient quantities. This high reactivity is due to their atoms being one electron short of a full outer shell of eight electrons. They can gain this electron by reacting with atoms of other elements. Fluorine is the most reactive element in existence, attacking such inert materials as glass, and forming compounds with the heavier noble gases. It is a corrosive and highly toxic gas. The reactivity of fluorine is such that, if used or stored in laboratory glassware, it can react with glass in the presence of small amounts of water to form SiF4. Thus fluorine must be handled with substances such as Teflon, extremely dry glass, or metals such as copper or steel which form a protective layer of fluoride on their surface. . 5.4 An Introduction to the Chemistry of some d-block Elements The first row d-block (transition) elements chromium, manganese, iron, nickel and copper. Emphasis should be place on the similarity of the elements to each other and the interpretation of their properties, where appropriate, in terms of incomplete d subshells. (a) The physical properties of transition metals: melting points, density, successive ionisation energies (up to the fourth, where appropriate). (b) Characteristic chemical properties of these elements.

Back To School
(i) Variable oxidation state and colour: the principal oxidation states/numbers of these elements in their common cations, oxides and oxoanions, the relative stabilities of these oxidation states. (ii) Formation of complex ions; exchange of ligands. No treatment of stability constants is expected. It is expected that candidates will be familiar with the hexa-aquo ions of the above elements, the corresponding ammine complexes, where appropriate, and the [CuCl4]2 ion. No treatment of the geometry of complexes is required. No treatment of bonding in complexes is required. (iii) Catalytic properties, transition metals and their compounds as important industrial catalysts, e.g. Fe/Fe2O3 in the Haber process, Ni in the hydrogenation of alkenes.

Back To School

6 THE STRUCTURES OF ORGANIC MOLECULES

Back To School

Back To School

7 ELECTRONIC EFFECTS AND REACTION TYPES The nature of the C-H, C-Br and > C = C < and > C = O bonds in terms of electron density distribution.

Back To School
Heterolytic and homolytic bond fission; nucleophiles and electrophiles. Reaction types; addition, substitution and elimination. Addition and substitution classified as electrophilic, nucleophilic (reference to SN1 and SN2 mechanisms is not required) or free radical.

8 GENERAL ORGANIC CHEMISTRY Wherever possible the above classification of reaction types should be indicated. 8.1 Hydrocarbons Alkanes Cracking reactions as a means of obtaining alkenes from crude oil fractions. Alkanes as being generally characterised by free radical reactions, e.g. reaction with bromine. Alkenes Characterised by electrophilic addition, e.g. HBr, Br2. Simple tests for alkenes by decolourisation of manganate (VII) ions and of bromine in an inert solvent. Catalytic hydrogenation to alkanes. Arenes Characterised by electrophilic substitution, e.g. AlBr3/Br2, conc. HNO3/H2SO4. (Monosubstitution only). 8.2 Halogen derivatives Halogenoalkanes characterised by nucleophilic substitution, e.g. OH , CN. Difficulties of nucleophilic substitution in halogenoarenes.

Back To School
Haloalkanes are reactive towards nucleophiles. They are polar molecules: the carbon to which the halogen is attached is slightly electropositive where the halogen is slightly electronegative. This results in an electron deficient (electrophilic) carbon which, inevitably, attracts nucleophiles. Substitution reactions Substitution reactions involve the replacement of the halogen with another molecule - thus leaving saturated hydrocarbons, as well as the halogen product. Hydrolysis - a reaction in which water breaks a bond--is a good example of the nucleophilic nature of halogenoalkanes. The polar bond attracts a hydroxide ion, OH-. (NaOH(aq) being a common source of this ion). This OH- is a nucleophile with a clearly negative charge, as it has excess electrons it donates them to the carbon, which results in a covalent bond between the two. Thus C-X is broken by heterolytic fission resulting in a halide ion, X-. As can be seen, the OH is now attached to the alkyl group, creating an alcohol. (Hydrolysis of bromoethane, for example, yields ethanol). One should note that within the halogen series, the C-X bond weakens as one goes to heavier halogens, and this affects the rate of reaction. Thus, the C-I of an iodoalkane generally reacts faster than the C-F of a fluoroalkane. Apart from hydrolysis, there are a few other isolated examples of nucleophilic substitution: Ammonia (NH3) and bromoethane yields a mixture of ethylamine, diethylamine, and triethylamine (as their bromide salts), and tetraethylammonium bromide. Cyanide (CN ) added to bromoethane will form propionitrile (CH3CH2CN), a nitrile, and Br . Nitriles can be further hydrolyzed into carboxylic acids.

Back To School
8.3 Hydroxy compounds Primary, secondary and tertiary alcohols; reactions with acids, e.g. HBr, H2SO4 leading to substitution and elimination. Oxidisation of primary and secondary alcohols resistance to mild oxidation by tertiary alcohols. Ester formation with organic acids and acyl chlorides. Tests for presence of hydroxyl group using sodium or phosphorus pentachloride. Phenols acidity compared to alcohols and carboxylic acids; ease of electrophilic substitution compared with benzene. 8.4 Carbonyl compounds (a) Aldehydes; ease of oxidation; reduction to primary alcohol; condensation with hydroxylamine. (b) Ketones; more resistant to oxidation, reduction to secondary alcohol; condensation with hydroxylamine. Tests based on alkaline Cu2+ complex to distinguish between aldehydes and ketones. 8.5 Carboxylic acids and derivatives Carboxylic acids; acidity compared to alcohols and phenols. Formation from alcohols. Reduction to alcohols. Conversion to esters, acyl chlorides. Acyl chlorides; treated as reactive derivatives carboxylic acids widely used in the synthesis of amides and esters. 8.6 Amines

Back To School
Aliphatic primary amines; basic properties. Reaction with nitrous acid. Formation from nitriles. Aromatic primary amines; their formation from aromatic nitro compounds; basic properties. Reaction with nitrous acid and production azo dyes.

As displayed in the image, primary aliphatic amines arise when one of three hydrogen atoms in ammonia is replaced by an organic substituent.

Back To School