A galvanic cell is an electrochemical device that converts chemical energy into electrical energy through a spontaneous redox reaction (e.g. the Daniell cell). It has two electrodes: the anode, where oxidation (loss of electrons) takes place and which is the negative terminal; and the cathode, where reduction (gain of electrons) takes place and which is the positive terminal. A salt bridge connects the two half-cells and maintains electrical neutrality.

The standard electrode potential is the potential difference developed between an electrode and its solution of unit concentration (1 M) at 298 K and 1 bar pressure, measured with respect to a reference electrode. The standard hydrogen electrode (SHE) is taken as the reference electrode and is assigned a potential of exactly zero volt. Electrodes are compared with the SHE to obtain their standard potentials.

The standard Gibbs energy change of a cell reaction is related to the standard EMF by delta G(standard) = -n F E(standard), where n is the number of electrons transferred, F is the Faraday constant (96500 C/mol) and E(standard) is the standard cell EMF. A positive EMF gives a negative delta G, meaning the cell reaction is spontaneous. This relation also links electrochemistry with thermodynamics.

delta G(standard) = -n F E(standard)

Faraday's first law states that the mass of a substance deposited or liberated at an electrode during electrolysis is directly proportional to the quantity of electric charge passed through the electrolyte (m is proportional to Q = I t). Faraday's second law states that when the same quantity of charge is passed through different electrolytes, the masses of substances deposited or liberated are directly proportional to their chemical equivalent weights.

m proportional to Q = I t

Charge passed Q = I t = 5 x (30 x 60) = 5 x 1800 = 9000 C. Silver is deposited by Ag+ + e- -> Ag, so 1 mole of electrons (96500 C) deposits 108 g of silver. Mass of Ag = (108/96500) x 9000 = (108 x 9000)/96500 = 972000/96500 = 10.07 g.

mass = (equivalent mass x Q)/96500

A primary cell is one in which the redox reaction occurs only once and cannot be reversed, so it cannot be recharged and is discarded after use; e.g. the dry cell (Leclanche cell) and the mercury cell. A secondary cell is one that can be recharged by passing current through it in the opposite direction, so it can be used again and again; e.g. the lead storage battery and the nickel-cadmium cell.

The rate of a chemical reaction is the change in the concentration of a reactant or product per unit time. The average rate is the change in concentration over a measurable time interval (delta concentration/delta time). The instantaneous rate is the rate of the reaction at a particular instant of time, obtained by making the time interval very small (the derivative d[concentration]/dt). Its units are usually mol L^-1 s^-1.

rate = -d[R]/dt = +d[P]/dt

The rate of a chemical reaction is affected by: (1) the nature and concentration of the reactants (rate usually increases with concentration); (2) temperature (rate generally increases with a rise in temperature); (3) the presence of a catalyst (which increases the rate by providing an alternative path of lower activation energy); (4) the surface area of solid reactants (greater surface area gives a faster rate); and (5) for photochemical reactions, the intensity of light.

For a first order reaction, the half-life is independent of the initial concentration and is given by t(1/2) = 0.693/k. Substituting k = 6.93 x 10^-3 s^-1: t(1/2) = 0.693/(6.93 x 10^-3) = 100 s. Thus the half-life of the reaction is 100 seconds.

t(1/2) = 0.693/k

The Arrhenius equation relates the rate constant to temperature: k = A e^(-Ea/RT), where k is the rate constant, A is the frequency (pre-exponential) factor, Ea is the activation energy, R is the gas constant and T is the absolute temperature. Activation energy (Ea) is the minimum extra energy that the reactant molecules must possess (above their average energy) for a collision to be effective and lead to a reaction. A higher Ea means a slower reaction.

k = A e^(-Ea/RT)

A catalyst increases the rate of a reaction by providing an alternative reaction pathway with a lower activation energy. As a result, a larger fraction of the reactant molecules have enough energy to cross the (lowered) energy barrier, so more effective collisions occur and the reaction proceeds faster. The catalyst does not change the enthalpy or the equilibrium position of the reaction, and it is regenerated at the end of the reaction.

The units of the rate constant depend on the order of the reaction. For a zero order reaction, the rate = k, so the units of k are the same as the rate: mol L^-1 s^-1 (or mol L^-1 time^-1). For a first order reaction, rate = k[R], so k has units of s^-1 (or time^-1), which are independent of concentration. In general, the units of k are (mol L^-1)^(1-n) time^-1 for an nth order reaction.

units of k = (mol L^-1)^(1-n) time^-1

The Group 15 elements (the nitrogen family) are nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) and bismuth (Bi). Their general valence shell electronic configuration is ns2 np3 (a half-filled p subshell, which gives extra stability). Their common oxidation states are -3, +3 and +5; the stability of the +5 state decreases and that of the +3 state increases down the group due to the inert pair effect.

ns2 np3

Ammonia (NH3) has a lone pair of electrons on the nitrogen atom which it can donate to an electron-deficient species, so it acts as a Lewis base. It has a higher boiling point than phosphine because nitrogen is small and highly electronegative, so NH3 molecules form strong intermolecular hydrogen bonds, whereas PH3 molecules are held only by weak van der Waals forces; more energy is needed to separate the hydrogen-bonded NH3 molecules.

Nitric acid is manufactured by the Ostwald process, which uses ammonia as the starting material. The steps are: (1) catalytic oxidation of ammonia, 4NH3 + 5O2 -> 4NO + 6H2O, using a platinum-rhodium catalyst at about 500 K; (2) oxidation of nitric oxide, 2NO + O2 -> 2NO2; and (3) absorption of nitrogen dioxide in water, 3NO2 + H2O -> 2HNO3 + NO, where the NO produced is recycled. The dilute acid is then concentrated by distillation.

3NO2 + H2O -> 2HNO3 + NO

White phosphorus consists of discrete tetrahedral P4 molecules; it is soft, poisonous, very reactive, glows in the dark (chemiluminescence), catches fire in air spontaneously and is stored under water. Red phosphorus has a polymeric chain structure of linked P4 units; it is comparatively hard, non-poisonous, much less reactive, does not glow in the dark and does not catch fire spontaneously. Red phosphorus is more stable than white phosphorus.

Ozone (O3) is prepared by passing a silent electric discharge through pure, dry oxygen: 3O2 -> 2O3 (the reaction is endothermic). Ozone acts as a powerful oxidising agent because it is unstable and readily decomposes to give nascent oxygen: O3 -> O2 + [O]. This nascent oxygen is very reactive and readily oxidises other substances (for example, it turns moist starch-iodide paper blue by liberating iodine).

3O2 -> 2O3; O3 -> O2 + [O]

Fluorine is the strongest oxidising agent among the halogens because of its low bond dissociation energy (weak F-F bond), small atomic size and high hydration energy of the fluoride ion, which together make it accept electrons most readily. Chlorine acts as a bleaching agent because in the presence of moisture it produces nascent oxygen, Cl2 + H2O -> 2HCl + [O], and this nascent oxygen oxidises the coloured substance to a colourless one. The bleaching action of chlorine is permanent.

Cl2 + H2O -> 2HCl + [O]

Noble gases (Group 18) are chemically inert because they have completely filled valence shells (ns2 np6, except helium which is 1s2), which is a very stable electronic configuration. As a result they have very high ionisation enthalpies and almost zero electron gain enthalpy, so they have little tendency to gain, lose or share electrons. Xenon, being the largest and most easily ionised, does form some compounds, for example xenon difluoride (XeF2) and xenon tetrafluoride (XeF4).

Transition elements are the d-block elements whose atoms or stable ions have partially filled d orbitals (their general configuration is (n-1)d(1-10) ns(1-2)). They are called transition elements because they are placed between the s-block metals and the p-block non-metals in the periodic table and show a gradual transition of properties from the highly electropositive s-block metals to the less electropositive p-block elements.

(n-1)d(1-10) ns(1-2)