CHEMICAL EQUILIBRIUM Reversible Reactions Reversible Reactions: A chemical reaction in which the products can react to re-form the

reactants as indicated below with arrows pointing in both directions. Chemical Equilibrium: When the rate of the forward reaction equals the rate of the reverse reaction and the concentration of products and reactants remains unchanged 2HgO(s) 2Hg(l) + O2(g) Arrows going both directions ( ) indicates equilibrium in a chemical equation Reactions which are not reversible (irreversible) have the usual complete arrow only pointing to the right. Note: Reversing the reaction conditions reverses the direction of chemical change, typical of a reversible reaction. Example 1. Thermal decomposition means using 'heat' to 'break down' a molecule into smaller ones. The decomposition of NH4Cl is endothermic, H +ve (heat absorbed, taken in from the surroundings) and the formation of NH4Cl is exothermic, H -ve (heat released, given out to the surroundings). This means if the direction of chemical change is reversed, the energy change sign must also be reversed but its numerical value stays the same. Example 2 On heating the blue solid, hydrated copper(II) sulphate, steam is given off and the white solid of anhydrous copper(II) sulphate is formed. When the white solid is cooled and water added, blue hydrated copper(II) sulphate is reformed. CuSO4.5H2O(s) --------- CuSO4(s) + 5H2O(g) Note: The crystal structure is broken down on heating and the water of crystallisation is given off. Thermal decomposition is endothermic (H +ve) as heat is absorbed to drive off the water. The reverse reaction is exothermic (H +ve) i.e. on adding water to cold white anhydrous copper(II) sulphate the mixture heats up as the blue crystals reform. These are typical examples you encounter at an earlier study level, but it begs the question, "is it possible to have a situation, under suitable conditions, in which the reaction does not completely go in one direction or the other and both reactants and products co-exist?", and

the answer is yes! and the situation is called a dynamic chemical equilibrium. The word dynamic is used because the 'forward' (L to R) and 'backward' (R to L) reactions do not cease but match each other in rate so the concentrations of reactants and products are constant when the equilibrium is established. Reversible reactions and the concept of a dynamic chemical equilibrium Although most reactions you have encountered at an earlier academic level did go to 100% completion, it is a fact that many reactions do NOT go to completion i.e. 100% yield from the forward reaction. If ammonium chloride were heated in a closed system, over a certain temperature range, some of the NH4Cl will be sublimed into the gases NH3 and HCl and some of the solid salt remains. A closed system means nothing can enter or leave the system. When a reversible reaction occurs in a closed system, depending on conditions, a chemical equilibrium is formed, in which the original reactants and products formed coexist. In other words the reaction (i.e. from left to right as the equation is written) never goes to completion. Eventually the 'system settles down' and the net concentrations of the reactants and products remain constant i.e. a state of concentration balance exists. BUT the reactions don't stop! Reactants are continually forming products, and the products are continually re-forming the original reactants, hence the term dynamic equilibrium. In terms of kinetics ('rates of reaction'), it means that the rate of formation of product = rate of re-formation of reactants, or the rate of the forward reaction = rate of the backward reaction Example 2 The formation/decomposition of hydrogen iodide. o H2(g) + I2(g) ---------- 2HI(g) (all gases above 200 C) L to R forward reaction: If you start with pure hydrogen and pure iodine, so much of them combine to form hydrogen iodide. R to L backward reaction: If you start with pure hydrogen iodide, some, but not all of it, will decompose into hydrogen and iodine. Starting with the same total number of moles of either H2 + I2 or HI, the final equilibrium concentrations will be the same at the same temperature, volume and pressure. This is further illustrated in the diagram below. Put in figure 15.4 on page 262 of Ababio

Note: The final equilibrium composition is the same in each case no matter which direction you started from for the same total moles of of substance. Systems A and B show that the same equilibrium position can be reached irrespective of whether we dissolve the iodine in trichloromethane or in aqueous potassium iodide. Some important outcomes from experimentally studying dynamic equilibrium reactions It doesn't matter whether you start with the 'reactants' or the 'products', either way, if the conditions are suitable; both are present when a state of equilibrium exists. Eventually the net concentrations of the reactants and products remain the same BUT the forward and backward reactions don't stop. When a dynamic equilibrium is achieved there is a state of balance between the constant concentrations of the reactants and products because the rate at which the reactants change into products is exactly equal to the rate at which the products change back to the original reactants. However, the actual relative amounts of the original reactants left, and products formed, at equilibrium, depend on the particular reaction and reaction conditions e.g. the initial concentrations, temperature and pressure (if gaseous reactants or products are involved) and the value of the equilibrium constant A catalyst does not affect the position of the equilibrium, i.e. the final constant concentrations are the same with or without a catalyst, you simply get to the equilibrium point faster with a catalyst! In some cases you can adjust reaction conditions sufficiently to make the reaction go virtually 100% in one direction. At a given constant temperature, all the final equilibrium concentrations are mathematically governed by the equilibrium expression and the equilibrium constant. Equilibrium constant The effect of concentration on reaction rate was first stated by Gulberg and Waage. This law is known as the law of mass action. It states that at constant temperature, the rate of

reaction is proportional to the active masses of each of the reactants.

The active mass is given as the concentration of the substance raised to an appropriate power in moles per dm3 and if the substance is a gas, its partial pressure may be used instead of concentration. For a reaction in which n moles of a substance A reacts with m moles of substance B. Let the rate of the reaction be r. Then

mA + nB ---r--- Products
r & (concentration of A)m and r & (concentration of B)n

r & (concentration of A)m x (concentration of B)n i.e r & [A]m x [B]n Introducing a constant, r = k.[A]m . [B]n Where r is a constant called the Velocity Constant.

For a particular equation, mA + nB pC + qD

The rate of the left-to-right reaction, r1 = k1 . [A]m . [B]n

The rate of the right-to-left reaction, r2 = k2 . [C]p . [D]q

Where k1 and k2 are the velocity constants of the forward and backward reactions respectively. At equilibrium, then therefore k2
k1

r1 = r2 k1. [A]m . [B]n = k2. [C]p . [D]q

[C]p . [D]q [A]m . [B]n

Where K is the equilibrium constant of the reaction at that temperature. It is important to note the following: * K is the ratio of the two velocity constants k1 and k2 * Since the velocity constant usually vary with temperature, then it follows that K will vary with temperature. * The addition of a catalyst will however not cause any change in the value of K * Varying the concentration of any of the substances A,B,C or D will also not affect the value of

K. (this is because the reaction will automatically adjust itself to attain equilibrium again to give the same value of K) To do this, the position of the equilibrium shifts to the right when the concentration of A and B are increased favouring the formation of C and D thereby increasing their concentrations.
Le Chatelier's Principle As we can see, every reaction reaches its own specific equilibrium under a given set of conditions. This equilibrium state is dependent on: * temperature of the reacting system * pressure of the reacting system(for gases) * concentration of the reacting system. A change in any one of these factors will upset the balance of the system and result in a shift in the position of the equilibrium. These factors and their effects on chemical systems in equilibrium were studied by Le Chatelier (1850-1936) who formulated the Le Chatelier's principle. Le Chateliers's Principle states that if an 'instantaneous' change is imposed on an equilibrium, the position of the equilibrium will further change to minimize the 'enforced' change. Le Chatelier Translated: When you take something away from a system at equilibrium, the system shifts in such a way as to replace what youve taken away. When you add something to a system at equilibrium, the system shifts in such a way as to use up what youve added. In other words, if a change is 'instantaneously' imposed, the equilibrium attempts to restore the original situation, but it cannot do this completely BUT the change 'trend' can be predicted. Also, when considering the equilibrium rules outlined below, any change affects BOTH the rates of the forward and backward reactions. * This principle is of great importance in the chemical industry because it can help to: - define the optimum conditions for the chemical processes employed in industry; - reduce undesirable reversibility; - predict the effect of an altered factor of the equilibrium position of an untried reaction. Rule 1 - Temperature and energy changes (H) 1a. Raising the temperature favours the endothermic direction (H +ve) . The system absorbs

the heat energy from the surroundings to try to minimize the temperature increase. 1b. Decreasing the temperature favours the exothermic direction (H -ve). The system releases heat energy to the surroundings to try to minimize the temperature decrease. Rule 2 - Gas pressure changes at constant temperature (V) 2a. Increasing the pressure favours the side of the equilibrium with the least number of gaseous molecules as indicated by the balanced symbol equation. The system attempts to reduce the number of gas molecules present to reduce the pressure increase. 2b. Decreasing the pressure favours the side of the equilibrium with the most number of gaseous molecules as indicated by the balanced symbol equation. The system attempts to increase the number of gas molecules to minimize the pressure decrease. NOTE: States symbols (g/l/s/aq) are particularly important when considering equilibrium equations , if no (g) the pressure rule doesn't apply since solids and liquids are virtually in-compressible. Rule 2 ONLY applies to a reaction with one or more gaseous reactants or products because pressure has no real effect on the 'concentration' on the virtually incompressible liquids or solids. If there is NO net change in the number of gas molecules, gas pressure has NO effect on the position of the equilibrium, though pressure increase effectively increases gas concentration so both the forward and backward reactions will be speed-ed up. Over and above rule 2, all the individual partial pressures of the gases, must comply with the mathematics of the Kp equilibrium expression. The rest of the rules 1, 3 and 4 apply to ANY reaction, whatever the physical states of the reactants and products. Rule 3 - Concentration changes at constant temperature 3a. If the concentration of a reactant (on the left) is increased, then some of it must change to the products (on the right) to maintain a balanced equilibrium position. 3b. If the concentration of a reactant (on the left) is decreased, then some of the products (on the right) must change back to reactants to maintain a balanced equilibrium position. This means if you change ANY concentration, all the other concentrations must change too. Also, any net concentration changes must comply with the Kc equilibrium expression Rule 4 - Using a catalyst A catalyst does NOT affect the position of an equilibrium. What it does is to enable the reaction get to the point of equilibrium faster! A catalyst speeds up both the forward and reverse reactions by providing a mechanistic pathway with alower activation energy, but there is no way it can influence the final 'balanced' concentration ratios. The importance of a catalyst lies with economics of chemical production e.g. bringing about

reactions with high activation energies at lower temperatures and so reducing energy requirements and time, and both reductions save money! Applying Le Chatelier's Principle and the equilibrium rules Example 1. The thermal decomposition of calcium carbonate (limestone) to make calcium oxide (quicklime): CaCO3(s) CaO(s) + CO2(g) -1 (H = +178 kJ mol )

Note: By convention, the H value quoted corresponds to the forward reaction (L to R), reversing the sign gives the H for the backward reaction (R to L). Rule 1 - temperature and energy change (H) Increasing temperature favours the endothermic direction (RHS) so more quicklime is formed. Rule 2 - gas pressure (V) Decreasing the partial pressure of carbon dioxide increases the yield of quicklime (0 ==> 1 mole gas). Rule 3 - concentration Not applicable to the reactants because you can't decrease or increase the concentration of a solid but you can reduce the concentration of carbon dioxide by venting the gases to increase the yield of quicklime, a common strategy used in industries. Rule 4 - catalyst: Not applicable. Example 2. The synthesis of ammonia: nitrogen + hydrogen ammonia N2(g) + 3H2(g) 1mole 3 moles 2NH3(g) 2 moles -1 (H = -92 kJ mol )

Rule 1 - temperature and energy change (H) The forward, and desirable reaction, to form ammonia, is exothermic, so lowering the temperature favours its formation. Rule 2 - gas pressure (V) Increase in pressure favours ammonia formation since 4 mol of gaseous reactants ==> 2 mol

gaseous products. Rule 3 - concentration: In terms of enforced change => system response If the nitrogen or hydrogen concentration was increased, some of this 'extra' gases would change to ammonia. Likewise, if the nitrogen or hydrogen concentration was decreased, some of ammonia would change to nitrogen and hydrogen. Rule 4 - catalyst: An iron oxide catalyst is used, time = money for industrial chemical production! 3. The formation of hydrogen iodide from hydrogen and iodine: H2(g) + I2(g) ----- 2HI(g) -1 o (H = -10 kJ mol , iodine gaseous above 200 C)

Rule 1 - temperature and energy change (H) Increasing temperature favours the LHS, i.e. increases the endothermic decomposition of hydrogen iodide. Rule 2 - gas pressure (V): No effect on position of equilibrium, 2 mol gas ==> 2 mol gas, no net change in gas moles. Rule 3 - concentration e.g. if more iodine was added to a constant volume container, the hydrogen concentration or partial pressure would decrease as some reacts with added iodine to give more hydrogen iodide as the system tries to minimise the iodine increase. Please note that there would still be an overall increase in iodine at the new equilibrium point. Rule 4 - catalyst: Not applicable. 4. The formation of nitrogen (II) oxide. N2(g) + O2(g) -------- 2NO(g) -1 (H = +181 kJ mol )

Rule 1 - temperature and energy change (H) Increase in temperature favours the endothermic formation of NO. This reaction does not happen at room temperature but is formed at the high temperatures in car engines. Unfortunately when released through the car exhaust, it cools to normal temperatures when NO irreversibly reacts with oxygen in air to form nitrogen(IV) oxide, NO 2, which is acidic, a lung irritant and a reactive free radical molecule involved in the chemistry of photochemical smog not good!

Rule 2 - gas pressure (V) Since 2 mol gaseous reactants gives 2 mol gaseous products, pressure does not affect the position of the equilibrium. Rule 3 - concentration The concentration of nitrogen is high from air, but although the concentration of oxygen is low in the exhaust gases, there is sufficient present in the combustion process to ensure a small % of NO is formed. Rule 4 - catalyst: Not applicable. 5. One way to produce hydrogen for the Haber synthesis of ammonia is to react methane gas with steam. -1 CH4(g) + H2O(g) --------- 3H2(g) + CO(g) (H = +206 kJ mol ) Rule 1 - temperature and energy change (H) Increase in temperature favours the endothermic formation of hydrogen (and carbon monoxide). Rule 2 - gas pressure (V) For the desired forward reaction, 2 mol of reactant gases ==> 4 mol of product gases, so the increase in product volume is favoured by lower pressure. Rule 3 - concentration Theoretically increase in methane and steam concentrations will increase the hydrogen concentration, but this essentially means increasing pressure favouring the LHS, so you might not gain as much hydrogen as you like to! Rule 4 - catalyst A nickel catalyst is used, but cannot affect the yield. e.g. nitrogen + hydrogen ammonia or N2(g) + 3H2(g) -----2NH3(g)

If the nitrogen or hydrogen concentration was increased, some of this extra gas would change to ammonia. If the nitrogen or hydrogen concentration was decreased, some of ammonia would change back to nitrogen and hydrogen. So in terms of enforced change ==> system response: Increasing nitrogen ==> decreases hydrogen and increases ammonia. Increasing hydrogen ==> decreases nitrogen and increases ammonia. Increasing ammonia ==> increases nitrogen and hydrogen. Decreasing ammonia ==> decreases nitrogen and hydrogen. Decreasing nitrogen ==> increases hydrogen and decreases ammonia. Decreasing hydrogen ==> increases nitrogen and decreases ammonia.

Rule 4: A catalyst does NOT affect the position of equilibrium, you just get there faster! A catalyst usually speeds up both the forward and reverse reaction but there is no way it can influence the final 'balanced' concentrations. However, the importance of a catalyst lies with economics e.g. (i) bringing about reactions with high activation energies at lower temperatures and so saving energy or (ii) saving time is saving money. LeChatelier Example #1

A closed container of ice and water at equilibrium. The temperature is raised. Ice + Energy Water The equilibrium of the system shifts to the _______ to use up the added energy. right
LeChatelier Example #2

A closed container of N2O4 and NO2 at equilibrium. NO2 is added to the container. N2O4 (g) + Energy 2 NO2 (g) The equilibrium of the system shifts to the _______ to use up the added NO2. left
LeChatelier Example #3

A closed container of water and its vapor at equilibrium. Vapor is removed from the system. water + Energy vapor

The equilibrium of the system shifts to the _______ to replace the vapor. right

LeChatelier Example #4

A closed container of N2O4 and NO2 at equilibrium. The pressure is increased. N2O4 (g) + Energy 2 NO2 (g) The equilibrium of the system shifts to the _______ to lower the pressure, because there are fewer moles of gas on that side of the equation. left
Activity for practice ( solve the following on a separate piece of paper ) Show the effect of the four(4) rules on the following reactions 1. N2O4(g) 2NO2(g) 2. 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)

3. The effect of change in concentration on Iron(III) thiocyanate system and potassium heptaoxochromate (VI) system 4. Include the summary tables of Table 15.1; 15.2 and 15.3

EQUILIBRIUM IN PRACTICE Chemical equilibrium and Le Chatelier's Principle, are applied to decide on the optimum conditions of operation. These conditions, temperature, Pressure, Concentration and Catalysts, are chosen by industrial chemists with the aim of: * Minimizing cost of production by ensuring [a] the capital cost of the plant is not too high. [b] the starting materials are cheap.

* maximizing yield of product by: [a] shifting the equilibrium position in the desired direction. [b] increasing the value of the equilibrium constant K, for the process concerned. The Haber Process and the Contact Process are two important industrial processes that uses Le Chaterlier's Principle among others to determine their optimum operating condition. 3. The Synthesis of ammonia - The Haber Process Ammonia gas is synthesized in the chemical industry by reacting nitrogen gas with hydrogen gas in what is known as the Haber-Bosch Process, named after two highly inventive and subsequently famous chemists. The nitrogen is obtained from liquified air (80% N2). Air is cooled and compressed under high pressure to form liquid air (liquefaction). The liquid air is fractionally distilled at low temperature to separate oxygen (used in welding, hospitals etc.), nitrogen (for making ammonia), Noble Gases e.g. argon for light bulbs, helium for balloons). The hydrogen is made by reacting methane (natural gas) and water or from cracking hydrocarbons (both reactions are done at high temperature with a catalyst). CH4 + H2O ==> 3H2 + CO The synthesis equation for this reversible reaction is ... N2(g) + 3H2(g) 2NH3(g) .. which means an equilibrium will form, so there is no chance of 100% yield even if we use, as you actually do, the theoretical reactant ratio of nitrogen : hydrogen of 1 : 3 ! In forming ammonia 92kJ of heat energy is given out (i.e. exothermic, 46kJ of heat released per mole of ammonia formed). N2 + 3H2 2NH3 H = -92JK/mol Four moles of 'reactant' gas form two moles of 'product' gas, so there is net decrease in gas molecules on forming ammonia. N2 + 3H2 2NH3 1 mole 3 moles 2 moles So applying the equilibrium rules from section 2 above, the formation of ammonia is favoured by (a) Using high pressure because you are going from 4 to 2 gas molecules (the high pressure also speeds up the reaction because it effectively increases the concentration of the gas molecules), but higher pressure means more dangerous and more costly engineering. (b) Carrying out the reaction at a low temperature, because it is an exothermic reaction is favoured by low temperature, but this may produce too slow a rate of reaction,

So, the idea is to use a set of optimum conditions to get the most efficient yield of ammonia and this involves getting a low % yield (e.g. 8% conversion) but fast. Described below are the conditions to give the most economic production of ammonia. these arguments make the point that the yield* of an equilibrium reaction depends on the conditions used. * The word 'yield' means how much product you get compared to the theoretical maximum possible if the reaction goes 100%. In industry pressures of 200 - 300 times normal atmospheric pressure are used in line with the theory. Theoretically a low temperature would give a high yield of ammonia BUT ... Nitrogen is very stable molecule and not very reactive i.e. chemically inert, so the rate of reaction is too slow at low temperatures. To speed up the reaction an iron catalyst is used as well as a higher temperature (e.g. 400o 450 C). The higher temperature is an economic compromise, i.e. it is more economical to get a low yield fast, than a high yield slowly! Note: a catalyst does NOT affect the yield of a reaction, i.e. the equilibrium position BUT you do get there faster! At the end of the process, when the gases emerge from the iron catalyst reaction chamber, the gas mixture is cooled under high pressure, when only the ammonia liquefies and is so can be removed and stored in cylinders. Any unreacted nitrogen or hydrogen (NOT liquified), is recycled back through the reactor o o chamber, nothing is wasted! [nitrogen (-196 C) and hydrogen (-252 C) have much lower boiling o points than ammonia (-33 C). Boiling points increase with pressure, but these normal atmospheric pressure values offer a fair comparison]. To sum up: A low % yield of ammonia is produced quickly at moderate temperatures and pressure, and is more economic than getting a higher % equilibrium yield of ammonia at a more costly high pressure and a slower lower temperature reaction. Include Fig 15.8 on page 270 and table 15.4. in Ababio.

CONTACT PROCESS ( industrial production of sulphuric acid ) The oxidation of sulphur dioxide to sulphur trioxide e.g. in the Contact Process for manufacturing sulphuric acid. -1 2SO2(g) + O2(g) ----- 2SO3(g) (H = -196 kJ mol ) Rule 1 - temperature and energy change (H) The exothermic formation of sulphur trioxide is favoured by low temperature. Rule 2 - gas pressure (V) Higher pressure favours a higher yield of sulphur trioxide as 3 gas moles ==> 2 gas moles, though 1-2 only atm is used in practice because the equilibrium is already so far to the right (about 99%). Rule 3 - concentration Air is used as the source of oxygen and despite its dilution with nitrogen the concentration, the oxygen concentration is high enough to move the equilibrium very much to the RHS. Rule 4 - catalyst A vanadium(V) oxide, V2O5, catalyst ensures the high yield of 99% SO3 is attained fast, but no more! Include table 15.5 page 271 in Ababio.

EQUILIBRIUM CONSTANT FREE ENERGY AND ELECTRODE POTENTIAL At equilibrium, the free energy change of a closed system at constant temperature and pressure, is at its minimum {meaning that the system is at its utmost stability} At this stage, there is no net flow of heat or species occurs and no work can be done by the system as such we can strike a simple relationship between G of a reaction and the equilibrium constant, K.

Go = -RT InK G--- Standard free energy change of the system; K ---- is the equilibrium constant; R ----- is the gas constant; T ---- is the temperature of the system in kelvin

Since redox reactions occur in an electrochemical cell, at equilibrium, a reaction such as this is given as; Zn(s) + Pb2+(aq) Zn2+(aq) + Pb(s)

a relationship between Eo and K is given as, Eo = RT InK nF Eo is standard electrode potential of the reaction R is the gas constant; T is the temperature in kelvin; F is the Faraday's constant

K is the equilibrium constant;

n is the number of moles of electrons

The value of K usually used to effect electroplating of metals. For the reaction above, a higher value of K would favour the forward reaction resulting in a thicker coating of lead on the object in question. Go = -nFEo This is the relationship between electrode potential and free energy change of an electrochemical cell. A negative value of delta G shows that work is obtained from the electrochemical cell. ACID BASE EQUILIBRIUM This is a study of the chemical equilibrium that exists between acids and their associated bases. Two theories have been put forward on acid-base action. The earliest being that proposed by Arrhenius in the nineteenth century and the other by Bronsted-Lowry. According to Arrhenius, an acid is defined as a substance which dissociates in water to produce hydrogen ions, H+ e.g HCl H++ ClIn the same vein, a base is defined as a substance which gives hydroxide ions in solution NaOH(s) Na+(aq) + OH-

Chemist discovered that the hydrogen ion cannot exist on its own in solution and that each proton associates with a water molecule to form hydroxonium or Oxonium ion.Hence the dissociation of an acid in water is represented more accurately as; HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)

With these arguments, the Arrhenius theory recognized 1. The role of the Solvent water molecules in the dissociation of acids. 2. Why substance exhibit acidic properties in the presence of water. 3. that acidity is not an inherent property of the substance but rather the mode of behaviour of a substance under certain conditions. Bronsted-Lowry Theory According to the theory of Bronsted-Lowry, an acid is a substance which donates a proton, while a base is a molecule or ion which accepts the proton. This describes an acid-base reaction in a non-aqueous solution.

CH3COOH(aq) + OH-(aq) acid base

CH3COO-(aq) + H2O(l) base acid

In the forward reaction, an ethanoic acid molecule donates a proton to a hydroxide ion which accepts it. The ethanoic acid behaves as an acid while the hydroxide ion as a base. In the reverse reaction, the ethanoate ion accepts a proton from a water molecule acting as a base, and the water acting as an acid. The ethanoic acid and the ethanoate ion are a CONJUGATE acid-base pair similarly the water molecule and the hydroxide ion are also a CONJUGATE acid-base pair in the reverse reaction. Thus a Conjugate acid-base pair is an acid-base combination in which one is related to by a gain or loss of protons.
Other examples are HCl(g) + NH3(g)
acid base

NH4+ Cl-(s)
acid base

By the arrows, the equilibrium shifts to the right to favour the forward reaction because hydrogen chloride is a stronger acid than ammonium ion.

HCl(aq) + H2O(l)
acid base

Cl-(aq) + H3O+(aq
base acid

By the arrows it shows that equilibrium shifts to the right to favour the forward reaction because hydrogen chloride is a stronger acid than hydroxonium ion.

H2O(l) + H2O(l)
acid base

H3O+(aq) + OH-(aq)
acid base

The equilibrium is balanced because the conjugate acid and base are equal.

NOTE: The lengths of the arrows indicate the favour direction of the reaction. HYDROGEN ION CONCENTRATION Dissociation of Water At 250 C, pure water ionizes as follows; [H+] = [OH-] = (10-7 x 10-7) moldm
-3

Here the concentration of both hydrogen and hydroxide ions are both equal to 10-7 moldm-3. The ionic product of water is represented as Kw = [H+][OH-] = (10-7 x 10-7) (moldm-3)2 = 10-14 moldm-3 at 250C Kw is kept constant under all circumstances at 250C. Thus in all neutral, Acidic (i.e acid added to the solution), and alkaline solutions (i.e alkaline added to the solution), the concentrations of both hydrogen and hydroxide ions are jas reflected in the table below Table 15.6 Hydrogen ion concentration of solutions [Ababio page 273]

The increase and decrease in hydrogen and hydroxide concentrations conversely is in the attempt to maintain Kw at 10-14 mol dm-3.

pH Scale Sorensen devised the logarithmic pH scale in 1909 in order to: Avoid the clumsy ness in the handling of negative indices. Accommodate the wide range of H+ and OH- concentrations commonly encountered in acid-base reactions. He defined the pH of a solution as, as the negative logarithm of the hydrogen ion

concentration to the base 10.

Example; If the hydrogen ion concentration of a given aqueous medium is 10-5 moldm-3, then the acidity of the solution can be written as; [H+] = 10-5 Log[H+] = log 10-5 = -5 pH = -log [H+] = -(-5) =5 Thus if [H+] = 10-x, then pH = x Since concentration of [H+] is inversely proportional to [OH-], then the value of pH would indicate both acidity and alkalinity of a solution. [H+][OH-] = 10-14 Therefore, pH + pOH = 14 where pOH is the hydroxide ion concentration Then pOH = 14 pH Since [H+] = [OH-] = 10-7, then a high pH value would indicate a low hydrogen ion concentration i.e weak acidity and a high hydroxide ion concentration i.e strong alkalinity. Likewise, a low pH value indicates a high hydrogen ion concentration i.e strong acidity and a low hydroxide ion concentration i.e weak alkalinity.

Include examples 1 to 3 from pages 273 to 275

STRENGTHS OF ACIDS AND BASES Take for instance, HA(aq) + H2O H3O+(aq) + A-(aq)

The position of equilibrium indicates the strength of an acid. In a strong acid the reaction goes virtually to completion as below HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)

In a weak acid, most of the acid molecules are dissociated. CH3COOH(aq) + H2O(l) CH3COO-(aq) + H2O(aq)

Note that the reverse arrow is supposed to be longer than the forward arrow Read and follow the line of class discussion to make notes on: hydrolysis of salts * Indicators * Buffer solutions