Types of Equilibrium In chemistry, equilibrium may be classified into two categories, viz., physical equilibrium and chemical equilibrium, depending upon the type of change involved in the system. In physical equilibrium, two or more than two phases of the same substance exist in equilibrium with each other, whereas in chemical equilibrium, different chemical species exist in equilibrium with each other. As stated above, in physical equilibrium two or more than two phases of the same substance exist in equilibrium with each other. The commonly observed two-phase equilibria along with their main characteristics are described in the following.Consider a system containing solid water (ice) and liquid water. The equilibrium set up between the two phases may be represented as H20(y= H20¢) The following characteristics of the above equilibrium may be established. 1. At 1 atmospheric pressure, the two phases, namely, solid water (ice) and liquid water, exist together in equilibrium only when the temperature of the system has a constant value of 0°C. nv If the temperature of the system is more than 0°C, we find that all the ice has melted and the system contains only liquid water. o . If the temperature of the system is less than 0°C, we find that all the liquid water has solidified and the system contains only solid water. > For a thermally isolated system at 0°C, the masses of solid water and liquid water remain constant with time. However, as stated earlier, the system is at dynamic equilibrium where water molecules are being continuously exchanged between the two phases at equal rates, i.e. the rate of transfer of water molecules from liquid water to solid water is the same as that from solid water to liquid water . + Tee water t=0° Schematic diagram displayingdynamic equilibrium H20(y= H20() Normal Melting (or Freezing) Point of a Pure Substance. We have seen above that the solid and liquid phases of a pure substance exist at equilibrium only at one particular temperature for a given pressure. When the pressure is 1 atm this temperature is referred to as normal melting (or freezing) point of the substance.For any liquid, there exists equilibrium of the type liquid = vapour Taking any example of water, we have H20(1) = H20(9) The pressure caused by the vapour in equilibrium with its liquid is known as vapour pressure of liquid. Let an evacuated vessel fitted with a movable piston be placed in a thermostat whose temperature is a little above 0 C (say, 10 C) such as shown in Fig. The position of the piston can be held anywhere against a set of stops. Let liquid water be introduced in the vessel. The main characteristics of the above system at various stages of temperature and pressure are described in the following. System exhibiting liquid-vapour equilibrium of water 1. When the system has attained equilibrium, it is found that the pressure within the vessel attains a constant value. This pressure is known as vapour pressure of liquid water at the given temperature. At this stage, the rates of transfer of water molecules from liquid to vapour and vice versa are identical. N . For a given temperature, the liquid-vapour equilibrium exists only at a fixed pressure of vapours. If this pressure is increased or decreased, the equilibrium adjusts to have the same vapour pressure. This may be demonstrated as follows. If the volume of a system is increased at constant temperature by moving the position of the piston outward it will cause a decrease in the pressure of vapour phase. Since at a given» > a temperature the vapour pressure of liquid water has a fixed value, a little water will evaporate to keep the vapour pressure to a constant value. If the above process of expansion is continued, more and more liquid water evaporates till the entire liquid phase disappears. At this stage, the system contains only the gaseous phase. The expansion of the latter merely causes a decrease in its pressure. Similarly, if the volume of the system is gradually decreased, more and more vapour is condensed in order to keep the vapour pressure of liquid water to a constant value. If the compression is continued, eventually a stage is reached where the entire vapour phase is condensed and the system contains only the liquid phase. The piston of the vessel will be directly in contact with the liquid phase. Applying more pressure on the piston can increase the pressure on the liquid phase. The vapour pressure of a liquid is found to increase with increasing temperature of the system Fig. The expression connecting these two has the form given below. where A Hny vap is the molar enthalpy of vaporization, p is the standard unit pressure* and | is a constant factor. Variation of vapour pressure with temperature Boiling point of a liquid On continuous increase of temperature, a stage is reached where the vapour pressure of the liquid becomes equal to the external pressure on the liquid. At this stage, vapours start forming within the liquid and these on rising within the liquid disappear in the surroundings. The liquid is said to have started boiling. The temperature at which this happens is known as the boiling point of the liquid. The temperature remains constant till the entire liquid is converted into vapour phase. Obviously, changing the external pressure can change the boiling point of a liquid. Normal boiling point of a liquid When the external pressure on the liquid is the atmospheric pressure (1 atm), the boiling point is known as the normal boiling point. Obviously, a liquid with comparative low vapourpressure would require more heating so as to make its vapour pressure equal to the atmospheric pressure and thus such a liquid will have higher boiling point. For example, comparing ethanol (vapour pressure 5.85 kPa at 293 K) and acetone (vapour pressure 12.36 kPa at 293 K), ethanol is expected to have higher boiling point. a Process of evaporation When the liquid is exposed to atmosphere the vapours formed are dispersed to the larger volume of air. In order to keep the vapour pressure constant at the surface of liquid, more and more liquid is converted into vapour that, in turn, continues to disperse in air. This process of continuous conversion of liquid into vapour is known as evaporation. During this process, cooling of liquid is observed as the energy required to convert liquid molecule into vapour molecule comes from the liquid itself. The phenomenon of evaporation is faster in hot and airy weather as these factors help in evaporating and dispersing the gaseous molecules at a faster rate. Comment Comment ° Previous Next Previous Next m About Us (/mainsite/aboutus) News (/mainsite/news) is course is powered by Blog (/blog/) Contact Us (/mainsite/contact) Terms and Conditions (/mainsite/policy) Developers (/mainsite/developer) Publishers (/mainsite/publisher) mailus at contact@gradestack.com (mailto:contact@gradestack.com)Solid - Vapour Equilibrium The solid phase also exerts its vapour pressure though its value is much smaller than the corresponding liquid phase. Its value also increases with temperature in accordance with the expression ‘Hm subl 5 2.303 RT log (p /p®)= - where A Hm, sub| is the molar enthalpy of sublimation, p is standard unit pressure and | is a constant factor. In some cases, vapour pressure becomes equal to the atmospheric pressure and the solid is passed directly into vapour phase. Such a phenomenon is known as sublimation. Examples of a solid exhibiting such behaviour are iodine and ammonium chloride. Comment Previous Next Comment 9 Previous Next m About Us (/mainsite/aboutus) News (/mainsite/news) is course Is powered by Blog (/blog/) Contact Us (/mainsite/contact) Terms and Conditions (/mainsite/policy) Developers (/mainsite/developer) Publishers (/mainsite/publisher) mailus at contact@gradestack.com (mailto:contact@gradestack.com)If we dissolve a solid phase (say, sugar) in a liquid phase (say, water), we find that the solid phase stops dissolving after a certain stage. The resultant solution is said to be a saturated solution of the given solid in the given liquid. At this stage, un dissolved solid exists in equilibrium with the dissolved solid and can be represented as un dissolved solid dissolved solid As usual, this is a dynamic equilibrium. The dynamic nature can be demonstrated by adding solute containing radioactive species. After sometime, it is observed that the solution as well as the earlier un dissolved solute acquires radioactive species Fig. The maximum mass of solid dissolved per unit mass of liquid (sometime also expressed as mass per unit volume of liquid) is known as solubility of the solid in the said liquid. The process of dissolution is associated with the absorption (endothermic) or evolution (exothermic) of heat. The effect of temperature on the solubility depends upon whether the dissolution process is exothermic or endothermic. For exothermic dissolution, the solubility decreases with increase in temperature (for example, anhydrous sodium sulphate), whereas for endothermic dissolution, the solubility increases with increase in temperature (for examples, hydrated sodium sulphate, ammonium nitrite and ammonium nitrate).Solution Solid Comment Comment Like Share {0 Previous Next Previous Next This course is powered by-- About Us (/mainsite/aboutus) News (/mainsite/news) arr Blog (/blog/) Contact Us (/mainsite/contact) Terms and Conditions (/mainsite/policy) Everonn Education Limited Developers (/mainsite/developer) Publishers (/mainsite/publisher) mailus at contact@gradestack.com (mailto:contact@gradestack.com)At Gas-Dissolved Gas in Equilibrium Gases are soluble in liquids. For a given pair of gas and liquid, solubility depends on temperature and pressure. For a given temperature and pressure, the solubility of a gas increases with the ease of liquefaction of the gas. For example, hydrogen and helium are much less soluble in water than carbon dioxide and ammonia. Dissolution of a gas in a liquid is generally an exothermic process. Consequently, the solubility of a gas decreases with increase in temperature. The effect of gaseous pressure on its solubility as given by Henry's law is mporm=kp that is, at a given temperature, the mass of dissolved gas in a given volume of solvent is proportional to the pressure of the gas with which it is in equilibrium. There exists equilibrium between the gas in gaseous phase and the gas that has dissolved in the liquid phase, i.e Gas (gaseous phase) =Gas (in liquid phase) Comment Comment 0 Previous Next Previous Next m About Us (/mainsite/aboutus) News (/mainsite/news) is course is powered by ST rca ay Blog (/blog/) Contact Us (/mainsite/contact) Terms and Conditions (/mainsite/policy) Everonn Education LimitedChemical equilibrium involves different chemical species in equilibrium with each other. The chemical equilibrium may be classified as homogeneous and heterogeneous depending upon whether the reaction involves only one phase or more than one phase, respectively. A few examples are listed below. Homogenous Chemical Equilibria Ha(g) + l2(g) =2HI(g) N204(g) =2NO2(g) N2(g) + 3H2(g) = 2NH3(g) Ha(g) + CO2(g) =H20(g) + CO(g) Fe®*(aq) + SCN (aq) = FeSCN?*(aq) CH3COOH(aq) + H20(1) = CH3COO-(aq) + H30*(aq) Heterogeneous Chemical Equilibira CaCO3(s) CaO(s) + CO2(g) Essential Characteristics of Equilibrium . Equilibrium is possible only in a closed system at a given temperature. Nn Both the opposing processes occur at the same rate and there is a dynamic but stable condition. » All measurable properties of the system remain constant. > When equilibrium is attained for a physical process, it is characterised by constant value of one of its parameters at a given temperature. a The magnitude of such quantities at any stage indicates the extent to which the reaction has proceeded before reaching equilibrium.Equilibrium involving ions are known as lonic Equilibria. Acids, bases and salts come under this category. So, the next question that comes spontaneously to our mind is, how do we define acids and bases. The first theory was given by Arrhenius. According to him, acids are substances that donate a proton, H* in water. Thus, HCl, H2SO4, HNO3, CH3COOH, all fall under acids according to this theory. According to Arrhenius, bases are substances that donate a Hydroxyl lon in water. Hence, NaOH, Mg(OH)2, Al(OH)3 are bases according to Arrhenius. Limitation Cannot explain acidic and basic nature in non aqueous medium Cannot explain the basic character of NH3 and several molecules that do not possess OH group Similarly cannot explain the acidic nature of B, Al compounds Bronsted Lowry theory of Acids and Bases Acids: capable of donating a proton to give a conjugate base Bases: capable of accepting a proton to give a conjugate acid Explains, the basic nature of NH3 According to this theory, the conjugate base of a weak acid is strong and vice versa Similarly, the conjugate acid of a strong base is weak and vice versa This concept explains the strength of acids and bases based on how readily they accept or donate H*Limitation cannot explain the acidic nature of B, Al compounds Lewis Acids and Bases According to this theory, Acids are electron deficient compounds that accept a lone pair of electrons, and bases are compounds that donate a pair of electrons to form adducts. Thus, explains the acidic nature of B, Al compounds and basic nature of electron tich compounds such as NH3 lonization of Acids and Bases An Acid HA ionizes in water as HA +H 0 > H30* + A Where, A’ is the conjugate base of the acid HA. lonization constant of Water H20 + H20 —> H30* + OH” The dissociation constant, Ky = ([H30*][0H1])/[H20]? However, since the [H20] does not change for all practical reasons, as self ionization of water is very low, we omit the term, [H20]? in the denominator This ionization is dependent on temperature and at 298 K, the value of Ky is found to be 1.00 x10 M? Thus, water largely exists in unionized form PH: pH is defined as negative logarithm of the concentration of H* ion Mathematically, pH = - log [H30*] lonization constants of weak acids For weak acids, HX + H20 —> H30* + X° Let the initial concentrations of HX be a The initial concentration of H30* and X will respectively be 0 If, ais the extent of ionization, then; the concentration of HX at equilibrium will be, a (1- a) and the concentrations of H30* and X will be aa Thus, Ka = [H30*][ X]/[HX]=(a a)(aa)/a(1-a) Since for weak acids, a <<1, the above equation reduces to, Ka = aa/(1-a) Larger, the value of Ka, larger is the strength of the acid We can write a similar expression for weak bases as well, where K, is replaced by Kp Dissociation constant of base K, and Ky for a given species are related as KaxKp = Ky Factors affecting the strength of an Acid 1. Strength of H-A bond, the weaker the bond, the greater is the acid strength. 2. Nature of Polarity. The greater the electronegativity difference between H and A, the larger the acid strength However, within the same group, say Halogens,H-X bond strength overweighs the H-X Polarity. Thus, Hl is the strongest acid and HF is the weakest. Common lon effect When a strong acid or base is added to a weak acid or base, the degree of ionization of the weak acid or base is further suppressed. For example, consider the equation, CH3COOH + H20 — CH3CO0" + H30* When, a strong acid such as HCl is added to the above solution, then, Ac being a very strong conjugate base of weak Acid HAc will readily accept H* ions donated from the Strong acid HCl and therefore the equilibrium will shift towards the left, the undissociated form. Hydrolysis of SaltsSalts are formed by combination of acids and bases Case I: Salts of strong acids and strong bases - the pH of these solutions will be 7.0 Examples, HCI + NaOH —> NaCl + H20 These salts do not ionize in water and therefore, their pH remains 7.0 Case Il: Salts of Strong acids and Weak bases The pH of these solutions will be Acidic, for example- HCI + NH4 OH — NH4Cl + H20 NH,4Cl + H20 > NHq* + Cr The NH,* ions combine with water to give, NH4*+H20 > NH,OH + H* Since, NH4OH is a weak base, it largely exists in unionized form and the concentration of H* lons increases rapidly. Thus the pH is always < 7.0. Salts of weak acids and strong bases Consider CH3COONa — Ac’ and Na* in aqueous solutions. Ac’ + H20 — HAc + OH” Since, HAc is a weak acid, it largely remains in undissociated form, and thus [OH] increases rapidly. Hence, the solutions of these salts have a pH >7.0. For salts of weak acids and weak bases pH = 7.0 + (pK, + pKp) and the pH of these solutions depends on the relative strengths of the respective weak acids and weak bases Buffer solutions resist a change in pH on addition of a small amount of acids and bases. Solubility Product Constant is given by Ksp and is determined for sparingly soluble salts. If the solubility product is greater than ionic product, the substance is said to be soluble in water and if the solubility product is lesser than ionic product of water, then, the substance would precipitate in water. CommentClass-11th- Scipnpi Gleyieal/ 2kéHiple of equilibrium shift - oxygenation of hemoglobin in Studyg lood 1, Some Baste Rmaszionr that occurs in red blood cell Chemistry = HHb = - Hemoglobin E- (http: Harecesia fe Class-111th-Sciende/SMO-9e” Basic-ConceptsHbO = Oxygenated hemoglobin = oxyhemoglobin ion Seen ives! ViiPiet Blood cell (RBC) the following equilibrium occurs “Sew Hb + 02 > HbO2” + H* B. Effect of increasing [02] in the lungs by inhaling Shift toward oxygenation C. Effect of breathing oxygen rich air Shift toward oxygenation D. What happens if the blood is in acidosis i.e. it has too high a level of H*? Shift toward deoxygenation E. How the body forces this reaction toward oxygenation in lungs HCO;" + H* > H2CO3 H2CO3 > H20 + CO 2 The shift that causes oxygenation of Hb is called the isohydric shift. mm How exhaling air and lowering levels of CO2 in the lungs affect this Equilibrium? Oxygen goes on the Hb molecule Hz C03 H20 + CO» HCO3 - + H+ > H2CO3HHb + 07> HbO>.+ Ht 2 . In RBC at Tissue CO, +H20 — H,CO3 H,CO3 > H+ + HCO3, H* + HbO2. > HHb + 02 H. Equilibrium considerations at the tissue level Effect of elevated CO, at the tissue level Shift toward deoxygenation Isohydric shift at the tissue level Shift toward deoxygenation Effect of cell depleting the O, levels at tissue level Shift toward deoxygenation Detrimental effects of alkalosis (blood has too low a level of H*) upon 0, removal at the tissue level Makes it harder to remove oxygen from hemoglobin b. Capable of predicting the yield of a compound by varying the condition if the equilibrium constant is known c. Can take a reaction in the desired direction if we know the reversible reaction d. Used in the synthesis of the following compounds i. The Contact Process equilibrium You will remember that the equation for this is 2804) + Og) === 2804) Kp is given by 2 _ __Psog Ki = or Psa,” X Po, ii. The Haber Process equilibrium The equation for this is ...and the K, expression isThe equilibrium produced on heating calcium carbonate This equilibrium is only established if the calcium carbonate is heated in a closed system, preventing the carbon dioxide from escaping. The only thing in this equilibrium which isn't a solid is the carbon dioxide. That is all that is left in the equilibrium constant expression Comment Comment {0 Previous Next Previous Next m . About Us (/mainsite/aboutus) News (/mainsite/news) is course Is powered by nr Blog (/blog/) Contact Us (/mainsite/contact) Terms and Conditions (/mainsite/policy) Everonn Education Limited Developers (/mainsite/developer) Publishers (/mainsite/publisher) mail us at contact@gradestack.com (mailto:contact@gradestack.com)Law of Mass Action The rates of reaction (forward or backward) can be written on the basis of the law of mass action proposed by Guldberg and Waage in 1863. According to this law, the rate of reaction at constant temperature is directly proportional to the product of molar concentrations of reacting species, each raised to a power equal to the corresponding stoichiometric coefficient appearing in the chemical reaction Taking an example of the reaction N204(g) = 2NO2(g) we have Rate of forward reaction, r¢[N204] or r¢ = ke[N20,]Rate of backward reaction, rp [NO2]? or rh=kp[NO2]? where kt and kp are the constants of proportionality. These constants depend only on the temperature of the system. Comment Expression of Equilibrium Constant Since at equilibrium, rate of forward reaction = rate of backward reaction we will have k¢ [N20 4 eq = kp INO2 12q where the subscript eq stands for the concentration prevailing at equilibrium. The above expression can be rewritten as ke, Nz ka kb N204]eg Since ky and ky are constants of proportionality, the ratio k;/kp is also constant and is known as the equilibrium constant (symbol: K). Since for a given reaction kg and kp depend only on the temperature, the equilibrium constant K will also depend only on the temperature of the system. Its value will be independent of the concentrations of reactants (or/and products) taken at the start of the reaction. A given chemical equilibrium may be started by taking either reactants or products or a mixture of reactants and products and whatever may be their initial concentrations, the reaction at equilibrium satisfies the expression of equilibrium constant, i.e. the reaction will be adjusted in such a manner to give the same value of equilibrium constant. The expression for equilibrium constant can be written directly based on thegiven reaction. In the numerator, we take the product of molar concentrations of the right-hand species (i.e. products), whereas in the denominator we take the product of molar concentrations of the left-hand species (i.e. reactants) and each concentration term is raised to a power which is the stoichiometric number of the species involved in the reaction. Expressions for equilibrium constants of a few reactions Reaction Expression for equilibrium constant H2(g) + Io(g) = 2HI(g) HI?/[Holfla} No(g) + 3H2(g) == 2NH3(g) Keg = [NH3]?/[Nal[H2]? 2H20(g) == 2H,(g) + 02(g) Keg =[Hal?[02]/[H20]? 280,(g) + 02(g) = 280a(9) Keq=1SO]?/1S02]*{02] N20q(g) == 2NO2(a) Keq=[NOz]?/IN20a] Comment Expression of Equilibrium Constant At equilibrium, rate of forward reaction = rate of backward reaction we will have kg [N24 ]eq = kb INOzléq where the subscript eq stands for the concentration prevailing at equilibrium. The above expression can be rewritten as ke, Nz ka kb N204]eg Since ky and ky are constants of proportionality, the ratio k;/kp is also constant and is known as the equilibrium constant (symbol: K). Since for a given reaction kg and kp depend only on the temperature, the equilibrium constant K will alsodepend only on the temperature of the system. Its value will be independent of the concentrations of reactants (or/and products) taken at the start of the reaction. A given chemical equilibrium may be started by taking either reactants or products or a mixture of reactants and products and whatever may be their initial concentrations, the reaction at equilibrium satisfies the expression of equilibrium constant, i.e. the reaction will be adjusted in such a manner to give the same value of equilibrium constant. The expression for equilibrium constant can be written directly based on the given reaction. In the numerator, we take the product of molar concentrations of the right-hand species (i.e. products), whereas in the denominator we take the product of molar concentrations of the left-hand species (i.e. reactants) and each concentration term is raised to a power which is the stoichiometric number of the species involved in the reaction. Expressions for equilibrium constants of few reactions Reaction Expression for equilibrium constant H2(g) + lo(9) = 2HI(g) Keg = [HII?/Holllal No(a) + 3Ha(g) = 2NH3(9) INH3]/[Nal[H2]? 2H,0(g) =2H2(g) + 02(9) H2]?[02]/[H20]* 2802(g) + 02(g) = 2803(g) Keg=[S0s]?/[S02]*(0z] N204(g) = 2NO>(9) Keg=[NOz]?/IN204] Comment Comment ° Previous Next Previous Next This course is powered by: Please Register ever nn Everonn Education Limited —Le-Chatelier's Principle When a reaction at equilibrium is subjected to a change of temperature, pressure or concentration of one (or more) of the reacting substances, then the system adjusts to a new equilibrium stage as dictated by the change of variable. These changes can be predicted qualitatively by the general principle known as Le Chatelier's principle. This principle may be stated as follows. If a system at equilibrium is subjected to a change, the system adjusts to a new equilibrium stage in such a way so as to oppose or reduce the change. The applications of the above principle may be discussed one by one. Comment Change in ConcentrationIf the concentration of one of the reacting substances is increased, then according to Le Chatelier principle, the system will adjust in such way so as to decrease the concentration of the substance. Taking an example of the reactionFe**(aq) + SCN‘(aq) [Fe(SCN)]?*(aq) we may discuss the effects of adding more Fe°*(aq), SCN‘(aq) and Fe(SCN)** one by one. Adding More of Fe**(aq) or SCN‘(aq) The concentration of the ions Fe** or SCN is increased. To reduce the concentration, the equilibrium is shifted to right-hand side, i.e. more of Fe(SCN)3 is formed. This conclusion can also be verified from the expression for the equilibrium constant. We have Kk = Fecal Fe°"] [SCN™] If concentration of Fe** or SCN’ is increased, the denominator of the above expression is increased. Now since the equilibrium constant has a constant value at a given temperature, the only possibility is that the value of the numerator (i.e. [Fe(SCN)]?* should be increased, i.e. more [Fe(SCN)]* is formed with the consumption of added Fe** or SCN ions. Adding More of [Fe(SCN)]?* To reduce the concentration of this species, the equilibrium is shifted to the left- hand side, i.e. more Fe** and SCN‘are formed. This conclusion is also in agreement with the expression for the equilibrium constant. In this case, numerator is increased and in order to keep the equilibrium constant to the same value, the concentration terms appearing in the denominator are increased. It may be noted here that the reaction achieves a new equilibrium stage, the new concentrations of Fe®*, SCN” and [Fe(SCN)]*, when substituted in the expression for equilibrium constant, yield the same value of equilibrium constant, i.e. here equilibrium stage is adjusted and not its equilibrium constant as the latter depends only on the temperature of the system.Change in Temperature The effect of changing the temperature of a reaction at equilibrium depends on whether the reaction is exothermic or endothermic in nature. When the reactants are converted into products, heat is evolved in exothermic reactions, whereas heat is absorbed in endothermic reaction. To increase the temperature of the system we add heat to it. According to the Le Chatelier principle, the equilibrium is shifted in a direction so as to consume (or reduce) the heat added to the system. Thus, for an endothermic reaction, the equilibrium is shifted to the right-hand side and for an exothermic reaction; the equilibrium is shifted to the left-hand side, as these are the directions of consumption of heat. These effects may be easily followed if we treat heat as one of the constituents of the reaction as described below. 1. Exothermic reaction A+B=C+Dtq2. Endothermic reaction A+B+q=C+D where A, B, C and D are the reacting constituents and q is the heat involved in the reaction. Now the Le Chatelier principle as discussed earlier, in the case of the effect of adding one of the constituents, may be used directly. If we add q (or raise temperature), for an exothermic reaction, equilibrium is shifted to the left-hand side, whereas in an endothermic reaction, equilibrium is shifted to the right-hand side, as these directions are the directions in which heat is consumed (or reduced) We may also use the above way of writing chemical reactions to discuss the effects produced when the temperature of the system is lowered. Here, we are removing heat and thus reaction moves in a direction to produce more heat. Thus, for an exothermic reaction, the equilibrium is shifted to the right-hand side, whereas is an endothermic reaction, it is shifted to the left-hand side. Note that the equilibrium in the present case is primarily caused by the variation of the equilibrium constant of the reaction. From the conclusions drawn above, the effect of temperature on equilibrium constant may be deduced Effect of temperature on equilibrium constant Reaction Temperature | Concentration of species on Right-hand side Left-hand | Equilibrium side constant Exothermic Increase Decrease Increase Increase | Decrease Decrease Decrease | Increase Endothermic | Increase Increase Decrease Decrease | Increase Decrease Increase | Decrease Problem The ionic products of water at 273 K and 373 K are 1.1 10°'5 (mol dm’)? and 5.1 10713 (mol dm)2, respectively. Predict whether the ionization of water isChange in Pressure If pressure of the system is increased, then according to Le Chatelier's principle, the equilibrium is adjusted to decrease the pressure of the system. Since pressure is directly proportional to number of molecules present in the system, it follows that the equilibrium will be shifted in a direction where there are a lesser number of gaseous substances. Taking the example of N2(g) + 3H2(g) = 2NH3(9) we find that there are lesser number of gaseous species on the right-hand side as compared to the left-hand side. Thus, on increasing pressure, the equilibrium is shifted to the right-hand side. On the other hand, if we decrease pressure, the equilibrium will be shifted towards the left-hand side. Since the equilibrium constant of a reaction is independent of pressure, the above shift is not due to the change in equilibrium constant but is due to the change in partial pressures (or mole fractions) of the constituents. Taking anexample of the above reaction, we have 2 x, = Phas Pn2Pre Writing partial pressures in terms of total pressure (p), we have where x represents the mole fractions of the respective constituents. Since Kp has a constant value for a given temperature, it is obvious from the right-hand side that x depends on the pressure of the system. If pressure of the system is increased (say, by compressing the total volume), the denominator in the above expression is increased. Now in order to keep Kp constant, the value of the numerator will be increased. This means more ammonia will be formed, i.e. the equilibrium is shifted towards the lesser number of gaseous species. On the other side, if the pressure is decreased (say, by increasing the volume of the system), the value of xyy3 will also decrease to have the same value of equilibrium constant, i.e. the equilibrium is shifted towards larger number of gaseous species. For a reaction in which there occurs no change in gaseous molecules, i.e. =0 there will be no effect of pressure on the equilibrium stage of the reaction. One of the examples of such reaction is H2(g) + l2(g) = 2HI(g). Comment Comment {0 Previous Next Previous Next This course is powered by: Please Register ever nn Everonn Education Limited f > Facebook Connect About Us (/mainsite/aboutus) News (/mainsite/news) orEffect of an Inert Gas The effects produced on the addition of an inert gas on the equilibrium of a reaction can be predicted qualitatively as follows. Inert gas added keeping pressure of the system constant In this case, the addition of an inert gas increases the volume of the system, which in turn, causes the equilibrium position of the system to move in the direction of larger number of gaseous molecules. Thus, we will have Reaction with Direction of shift in equilibrium Ang positive right-hand side Ang negative left-hand side Ang zero remains unaffected Inert gas added keeping volume of the system constant. The effect of addinginert gas on equilibrium may be discussed by writing eq. (9.10) in terms of amount of substances, i.e. ky = me XN 2%he P? (rns / Matai)? a Cg /Meotal He “Motel Since pressure of the system is directly proportional to Ntotai (P = NRT/V), the ration of ntotal/P will remain constant on the addition of inert gas. Since the value of Ky is independent of pressure, it follows that the amounts of substances at equilibrium remain unaffected by the addition of inert gas, i.e. the equilibrium position of the reaction remains unaffected. Problem For the exothermic formation of sulphur trioxide from sulphur dioxide and oxygen in the gas phase 2802(g) + 02(g) 2S03(g) Kp = 40.5 atm at 900 K and H =-198 kJ mol. » Write the expression for the equilibrium constant for the reaction. ao . At room temperature (300K) will Kp be greater than, less than or equal to K, at 900 K. 2 . How will the equilibrium be affected if the volume of the vessel containing the three gases is reduced, keeping the temperature constant? a |. What is the effect of adding 1 mol of helium gas to a flask containing SO2 02 and SO3 at equilibrium, at constant pressure? Solution a. The expression for equilibrium constant is b. For an exothermic reaction, on decreasing the temperature the equilibrium position of the reaction is shifted to the right-hand side. Hence in the expression for Kp, the value of numerator is increased. Thus, the value of K, is increased, i.e. Kp at 300 K will be greater than K, at 900K. c. On reducing volume, the pressure of the system will be increased and it will affect the equilibrium by causing a shift towards the lesser number of molecules. Thus, the equilibrium will be shifted towards the right-hand side, i.e. more SO3 will be formed. d. The addition of inert gas at constant pressure will cause an increase in volume and this will shift the equilibrium towards the larger number of gaseous molecules. Thus, in the present case, the equilibrium will be shifted towards the left-hand side. Comment Comment ro) Previous Next Previous Next Please Register f > Facebook Connect or. FulName Emal Password Contact Number Create Account Account Already Exist? This course is powered by:- ever nn Everonn Education Limited About Us (/mainsite/aboutus) News (/mainsite/news) Blog (/blog/) Contact Us (/mainsite/contact) Terms and Conditions (/mainsite/policy) Developers (/mainsite/developer) Publishers (/mainsite/publisher) mail us at contact@gradestack.com (mailto:contact@gradestack.com)Dissolution Process and Classification of Electrolytes Most chemical reactions occur in solution. The study of such solutions constitutes one of the important branches of physical chemistry. In general, if we analyse the solubility of solutes in various solvents, we find that the polar solutes are more soluble in polar solvents, whereas non-polar solutes are more soluble in nonpolar solvents. For example, sodium chloride (polar solute) is soluble in water (polar solvent), whereas it is insoluble in carbon tetrachloride (nonpolar solvent) and naphthalene (nonpolar solute) is soluble in carbon tetrachloride, whereas it is insoluble in water. Because of its polar nature* and high dielectric constant * water serves as one of the important solvents for ionic solutes. The high dielectric constant (D = 80) weakens the forces of attraction between the oppositely charged ions of an ionic crystal and its polar nature generates the ion-dipole interaction in which the positive ion is attached to the negative end of the water dipole, whereas negativeion is attached to the positive end of the dipole as shown in Fig. The consequence of this is that the ions are pulled out of the crystal lattice and drift into water and thus a solution is formed. In solution, ions move in the hydrated form. Certain covalent molecules with relatively high dipole moments (e.g. HCl) can also dissolve in water to produce an ionic solution. This is due to the stronger ion-dipole interactions. : lon-dipole interactions A solute when dissolved in water may produce three different types of solution depending upon whether it is a good, poor or bad conductor of electricity. The conduction in the solution is due to the movement of ions. Hence a good conducting solution contains a larger number of ions, a poor one contains lesser number of ions and the bad one will not contain any ions. The ions in the solution are produced by dissolving the solute (also known as electrolyte) in water. Based on the conducting ability, an electrolyte may be classified into three categories as described below. Electrolyte Conducting ability Examples Strong electrolyte high NaCl, KCI, KBr, NH4Cl, HCl, H2S0q, NaOH Weak electrolyte low PbCl,HgClaHzCO3, CHyCOOH Non - electrolyte non conducting CH30H,CHCls, CCl The classification of compounds in terms of strong and weak electrolytes is based on their behaviour in a particular solvent, namely, water. However, such a classification suffers from a great disadvantage in the sense that a particular electrolyte, though weak in water, might behave as a strong one when dissolvedArrehenius Theory of Dissociation The total conducting ability of 1 molar aqueous solution of electrolytes is found to increase with dilution. Based on this observation, Arrhenius postulated that a chemical equilibrium exists between the undissociated electrolyte molecule and the ions that result from dissociation. For example, in case of acetic acid we have CH3COOH + H20 < CH3COO" + H30* On dilution, more of the acetic acid dissociates to give acetate and hydronium ions, which accounts for the increasing conducting ability. In dilute solutions it is known today that the above equilibrium is valid only for weak electrolytes. Strong electrolytes are already present in the form of ions in the solid state. The chemical equilibrium written above is, like any other equilibrium, dynamic in nature, i.e. the ionization of acetic acid to produce ions and the combination of these ions to produce acetic acid take place continuously. The rates of thesetwo processes are equal to equilibrium. Like any other equilibrium, the above equilibrium can be characterized by its equilibrium constant defined as kag + {HSC0O"I a0") [CH3COOH] 20] Water is present in larger amounts and whatever it has consumed in the above poor ionization is negligibly small and can be ignored. Hence, the concentration of water may be taken to remain constant. This constant may be combined with the equilibrium constant to give a new constant which is known as the ionization constant or dissociation constant of acetic acid. Thus, we have [cHCOO"]1H30*] Kone *K alto] = SeSoe The value of the ionization constant is a characteristic of the weak electrolyte and depends only on the temperature. It is independent of the individual concentrations of the species involved in the equilibrium. Comment Degree of Dissociation of a Weak Electrolyte The extent of dissociation of a substance can be expressed in terms of degree of dissociation, which is, by definition, equal to the fraction of the total substance that is present in the form of ions. If ais the degree of dissociation, it means that the amount a out of 1 mole of the substance is present in the form of ions and thus the remaining fraction of the undissociated species will be 1 -a. If cis the concentration of the solute then the concentrations of dissociated and undissociated electrolytes will be ca and c(1 - a), respectively. Taking the example of acetic acid, we have Reaction: CH3COOH + H20 CH3COO" + H30* Concentrations: c(1 -a) ca ca_ [C9007] BHg0"] [cH 3COOHT = (C9)(Ca) _ Co? Ca = 0) Kioniz Ostwald Dilution law The degree of dissociation is usually a very small quantity (unless Kioniz has a large value) and thus can be neglected in comparison to unity, i.e. 1 -a = 1. Thus, the above expression becomes cot Kioniz = =- T (ss]" C From the above expression it follows that as c decreases (dilution), a increases. In the limit when c — 0 (infinite dilution), a will approach 1, i.e. at infinite dilution, all of the weak electrolyte gets ionized. This is the Ostwald dilution law. Problem: Calculate the degree of dissociation and [H30*] of a 0.1 mol dm*® solution of acetic acid. Solution: Given: Ka(CH3COOH) = 1.8 x 10° mol dm. Let a be the degree of dissociation. The concentrations of various species involved in the equilibrium as follows. CH3COOH + H20 & CH3CHOO' + H30* e(1-a) caca Hence kK, = EHsC007] M20". (ca) (ca) | co? . TCH ,COOH] ca-a) T-a Ignoring a in comparison to 1, and rearranging we get Substituting the values, we get a= (1.8 x 10° mol dm/0.1 mol dm)'/2 = 1.34 107 Now [H30*] = ca = (0.1 mol dm) (1.34 x 10) = 1.34 « 103 mol dm?Some Concepts of Acids and Bases Some of the most important equilibria in chemistry are those involving acids and bases. With the advancement of science, various attempts have been made to define these acids and bases, starting from the phenomenological basis to the molecular composition and structure of the compound. A few of the currently accepted concepts are discussed below. Comment Arrhenius Concept Arrhenius classified a substance into an acid or a base in terms of the characteristic ions of water which it produces in aqueous solution. Thus, an acid is a substance which ionizes in water to produce H*(aq) or the hydronium ion; abase is a substance which produces hydroxide ion, OH (aq). The strength of an acid is defined in terms of the concentration of H*(aq) that is present in the aqueous solution of a given concentration of the acid. Likewise, the strength of a base depends upon the relative concentration of OH (aq) in an aqueous solution of the base. Comment Bronsted-Lowry Concept J. Bronsted and T. Lowry independently proposed a broader concept of acids and bases. According to them, "a substance is known as an acid if it can donate a proton and as a base if it can accept a proton”. The substance may be a molecule or an ion. The reaction of an acid with a base constitutes the transfer of a proton from the acid to the base. The dissolution of ammonia in water may be represented by the equation H20+NH3 NH + OH” In this reaction, H20 is serving as an acid as it donates a proton to the base NH3. If a solution of an ammonium salt is made strongly alkaline, ammonia gas is released. The reaction is therefore reversible and the system exists in equilibrium. In the reverse reaction, yy}, is serving as an acid and OH as a base. It follows, then, that in this Bronsted acid-base reaction, two acids (H20 and NH}) and two bases (OH and NHs) are involved. The base NH3 gains a proton and thereby forms the acid NH3 which on the loss of a proton forms the base NH3. Such an acid-base pair, related through the loss or gain of a proton, is called a conjugate pair. NH{, is the conjugate acid of the base NHs, and NHs is the conjugate base of the acid NH. Similarly, the acid H20 and the base OH constitute a second conjugate pair in the preceding reaction. We may indicate conjugate relationships by the use of subscripts in the following manner:-H20+NH3 NH + OH” Acid; Base2 Acid, Base; A few other examples are N . CH3COOH + H,0 & H30* + CH,COO" Acid, Base, Acid, Base; wo . HC] + H20 <> H30* + Ch Acid, Base, Acid, Base, 4, 20+ C02 3HC03 + OH Acid, Base Acid2 Base; Similar types of reactions can be written in a nonaqueous medium 5.7 +NHg Hp + NH Base2 Acid; Acid2 Base; There are many molecules and ions that can function as acids in certain reactions and as base in other reactions. Such species are called amphiprotic. For example, H20 acts as an acid in reactions (1) and (4) and as a base in reactions (2) and (3). Arrhenius acid-base type reactions are also covered by the Bronsted- Lowry reactions: a . H30* + OH" H20 + H20 Acid; Base Acidz Base; 7. NHS +NH3—GNHg +NHe Acid, Base, Acid, Base, - Strength of Bronsted Acids and Bases. The strength of a Bronsted acid is determined by its tendency to donate a proton, and the strength of Bronsted base is determined by its tendency to accept a proton. Consider the reaction HCI +H20 < H30* + Cr Acid, Base Acid2 Base; This reaction proceeds virtually to completion, i.e. the reactants are completely, ie. the reactants are completely converted into products. It can be concluded that 1. The acid HCl is stronger than H30* ion, since HCI has a greater tendencyto lose a proton than the H30* ion. 2. The base H0 is stronger than CI ions, since in the competition for holding the proton, HO shows a larger tendency and is thereby converted to H30*. Thus, we see that the strong acid HCl has a weak conjugate base CI ion and the strong base H20 has a weak conjugate acid H30*. The fact that a strong acid has a weak conjugate base and vice versa is always true since a strong acid with a high tendency to lose a proton is necessarily conjugate to a weak base with a small tendency to gain and hold a proton. Similarly, a strong base with a strong tendency to attract a proton is necessarily conjugate to a weak acid with a lower tendency to lose a proton. An aqueous solution of 0.1mol dm® acetic acid is only 1.33 per cent ionized at 25°C. The reaction is C2HgOzH + Hp0->H30* +CzH303 Acid; Base2 Acid; Base; or briefly HAc + H20 — H30* + Ac” Acid; Basez Acid, Base; which is largely displaced to the left. Once again, it can be concluded that: 1. The H30* is a stronger acid than HAc since at equilibrium more H30* ions than HAc molecules have lost protons. 2. The Ac’ is a stronger base than water since it shows greater tendency to attract the proton than H,0, thus converting itself into HAc. In the above example, we again notice that the stronger acid H30* is conjugate to the weaker base H20 and the stronger base Ac’ is conjugate to the weaker acid HAc. From the above two examples, one more conclusion can be drawn. This can be stated as follows: In a given reaction, the position of equilibrium favours the formation of a weak acid and a weak base.Thus, in the reaction between HCI and H20, the equilibrium concentrations of the weaker species H30* and CI’ are high, whereas in the solution of acetic acid, the equilibrium concentrations of the stronger species H30* and ¢,H303 are low. The Arrhenius concept of a strong and a weak acid in aqueous solution can be explained by the Bronsted concept. In Arrhenius theory, a strong acid is virtually 100 % ionized in aqueous solution and thus produces a very high concentration of H30*. In the Bronsted system, acids are classified according to their ability to donate protons to a specific base under consideration. |t is obvious that if water is used as the specific base, then the acid strengths of the Arrhenius concept can be explained in terms of the Bronsted concept. Thus, strong Arrhenius acids are those substances that are stronger acids than H30* and weak Arrhenius acids are those substances that are weaker acids than H30*. Problem (a) What is the conjugate base of () HS, (i) H30*, (iii) HOCI and (iv) CH30H? (b) What is the conjugate acid of (i) F (ii) OH, (ji) P03", (iv) NHg, (v) ng, (vi) HS" (a) The following relations give us the conjugate base. (i) HS +H20 H30* +S? Acid Base (ii) HOCI + H20 Hg0* + OCr Acid Base (iii) CH30H + Hy H30* + CH30" Acid Base (b) The following relations give us conjugate acid. () HO+F HF + OH Base Acid (ji) H20 «Pos HPO? + oH Base Acid (lil) #20 + NHy @ NH + OHM Base Acid (iv) Hp0+NHZ eNHs +OH7 Base Acid(v) H20 + HS" HyS + OH" Base Acid Problem: Identify the Bronsted acids and bases in the following: (a) NH3 +HCI-3NH§ cl” (b) NH4 + OH” SNH, +H20 (c) H30* HS HS + H20 (d) HpS04 + CN” HCN + HSO3 The identifications of Bronsted acids and bases in the given reactions are given below: (a) NHg + HCISNHY +c” Base, Acid Acid; Base (b) NHg + OH” SNH +H20 Acid; Base Base; Acid (c) H30* + HS H2S + H20 Acid; Basez Acid, Base; (d) HpS04 + CN HCN +HSO3 Acid; Base Acid2 Base; Comment Comment Previous Previous This course is powered by Please Register ever nn Everonn Education Limited f > Facebook Connect About Us (/mainsite/aboutus) or Full Name Blog (/blog/) Contact Us (/mainsite/contact) News (/mainsite/news)Strong And Weak Electrolytes A solute when dissolved in water may produce three different types of solution depending upon whether it is a good, poor or bad conductor of electricity. The conduction in the solution is due to the movement of ions. Hence a good conducting solution contains a larger number of ions, a poor one contains lesser number of ions and the bad one will not contain any ions. The ions in the solution are produced by dissolving the solute (also known as electrolyte) in water. Based on the conducting ability, an electrolyte may be classified into three categories as described below. Electrolyte Conducting Ability Examples Strong electrolyte high NaCl, KCI, KBr, NH4Cl, HCl, HySO4, NaOH Weak electrolyte low PbCh, HgCl, H2C0s, CH3COOH Non - electrolyte nonconducting CH3OH, CHCls, CClThe classification of compounds in terms of strong and weak electrolytes is based on their behaviour in a particular solvent, namely, water. However, such a classification suffers from a great disadvantage in the sense that a particular electrolyte, though weak in water, might behave as a strong one when dissolved in some other solvent or vice versa. For example, sodium chloride behaves as a strong electrolyte and acetic acid as a weak electrolyte when dissolved in water. However, when acetic acid and sodium chloride are dissolved in ammonia, their conducting abilities are comparable, indicating a strong electrolyte behaviour for acetic acid. Thus, the above classification depends upon the solvent used. Another classification that is largely based on the characteristics of the solute and not on that of the solvent is to label them as the true electrolyte and the potential electrolyte. The essential characteristic of a true electrolyte is that even in the pure liquid state it is an ionic conductor. In dissolution process, all that a polar solvent does is to use ion-dipole forces to disengage ions from their lattice sites, solvate them and disperse them into the solution. Examples are NaCl, KCI, etc. The potential electrolyte, however, does not conduct in the pure liquid state, though it provides a conducting solution on dissolution in an ionic solvent. Examples are hydrochloric acid, acetic acid, etc. Comment Comment 9 Previous Next Previous Next This course is powered by:- Please Register — 1Common lon Effect Weak acids and weak bases are ionized only to small extent in their aqueous solutions. In their solutions, unionized molecules are in dynamic equilibrium with ions. The degree of ionization of a weak electrolyte (weak acid or weak base) is further suppressed if some strong electrolyte which can furnish some ion common with the ions furnished by weak electrolyte, is added to its solution. This effect is called common ion effect. For example, degree of ionization of NH,OH (a weak base) is suppressed by the addition of NH4Cl. The ionization of NH4OH and NH,Cl in solution is represented as follows: NHgOH(aq) == NHg4*(aq) OH ‘(aq) .... Weakly ionized NH4Cl — NHg*(aq) + CI(aq) ... strongly ionized ....... (2) Due to the addition of NH4Cl, which is strongly ionized in the solution,concentration of NH,’ ions increases in the solution. Therefore, according to Le- Chatelier’s principle, equilibrium in equation (1) shifts in the backward direction in the favour of unionized NH4OH. Thus, the concentration of OH ions in the solution is considerably reduced and the weak base NH4OH becomes still weaker base. The suppression of the degree of ionisation of a weak electrolyte (weak acid or weak base) by the addition of some strong electrolyte having a common ion is called common ion effect. The solubility of salts of weak acids like phosphates increases at lower pH. This is because at lower pH the concentration of the anion decreases due to its protonation. This in turn increase the solubility of the salt so that Ksp = Qsp. Comment Comment {0 Previous Next Previous Next This course is powered by: Please Register ever nn Everonn Education Limited f > Facebook Connect L_- About Us (/mainsite/aboutus) News (/mainsite/news) or Blog (/blog/) Contact Us (/mainsite/contact) manne Terms and Conditions (/mainsite/policy) Ema Developers (/mainsite/developer) Publishers (/mainsite/publisher) mailus at contact@gradestack.com (mailto:contact@gradestack.com) Password Contact NumberBuffer Hydrogen ion concentration of water is largely changed by addition of very small quantity of an acid or a base to it. Thus, one drop of a strong concentrated acid (say HCl) added to a litre of water makes it sufficiently acidic raising its H* ion concentration to about 5000 times. Similarly, just two drops of strong alkali (say NaOH) added to water make it sufficiently basic, decreasing its H* ion concentration to about a million times. Yet for many purposes we may need a solution with a fixed pH which does not change much on dilution or adding to it a small amount of any acid or base. Such a solution is called a buffer solution or simply buffer. In simple words, a buffer solution is a system, which maintains its hydrogen (or hydroxyl) ion concentration at an approximately constant level, which does not change by adding water, any acid or base to it. It is not true that there is absolutely no change in the pH of a buffer solution by adding an acid or a baseto it. However, the change is negligible which can be taken as practically no change. In general, buffer solutions contain either a weak acid in presence of a rather high concentration of its conjugate base, or a weak base in presence of a rather high concentration of its conjugate acid. Strong acids and strong bases seldom form buffer because they are completely ionized. Following are some examples of common buffer solutions. Comment Applications of Buffers Buffers with varying pH-range find a wide application in various processes, as described below: In biological systems. Blood is the best example of a buffer solution. It consists of PO43, HCOs,, and proteins (bases) and has a pH = 7.35 to 7.45. Consequently the blood always remains slightly alkaline inspite of many acidic foods we take. 1. The pH of blood and other biological systems help the life processes go on normally. Sudden changes in their pH might prove fatal. Nn Buffers are highly useful in industrial processes, such as manufacture of paper, dyes, inks, paints, drugs, antibiotics, etc., and working of latex, tanning of leather, laundry and so on. 2 For healthy seeding and growth of crops; the soil needs to be maintained at a constant pH by means of suitable buffer solutions. Buffer of various PH are also of vital importance in the preparation of dairy products, such as condensed milk and processed cheese; and in preservation of various types of foods and fruits. CommentSome Buffer Solutions S.No. | Buffer pair PH Nature 1 CHgCOOH + CHgCOO™ 474 Acidic 2 HCOOH + HCOO" 37 Acidic COOH coo 1.42 Strongly 3. 1+ acidic COOH coo 7.0-9.1 HgB03 + BOs 9.25 Basic 4. NH4* +NHg 6.38 Basic 5. HCOs + C03 6.2- 8.2 Basic 6. HyPOg + HPO, Basic 7. Calculation of pH and pOH for buffer solutions: Acidic Buffer solution CH3COOH(aq) === CH3CO0 (aq) + H* (aq)Dissociation constant, i.e. Ka = SA22IHl = 1.8“ 10° (Known) [H"] = Ka x PH of the solution can be calculated as below: pH = og[H*] = {log Ka + log [Salt]/[Acid] pH = -log Ka + log (2) or pH = PK, + log [2) pH = PK, +log fb) This pH of the above mentioned buffer will not be affected much by dilution or by adding H ions from outside to it. If some water is added, the concentrations of CH3COOH and CH3COONa giving CH3CO0 ion will be affected equally such that the ratio [CH3COOH] / [CH3COO] is once again unity and hence pH will remain unchanged. Now, (i) if a small amount of any acid, i.e. H* ion is added, CH3COO ‘ions will react to produce CH3COOH, but as CH3CO0’ is taken away, more of CH3COONa, will ionize. So, again the ratio [CH3COOH] / [CH3CO0] will become 1 Similarly, (ii) if a small amount of a base, i.e. O H ion is added, the CHgCOOH in equilibrium will ionize to furnish a little more CH3COO ions. But the change is very negligible and the ratio [CH3COOHJ/ [ CH3COO] again remains nearly 1 Hence, the buffer maintains its pH (4.74) even on dilution or adding any acid or base to it. Similarly, the working of any other buffer can also be explained. Comment Alkaline Buffer solution(NH4Cl + NH40H) We can treat a mixture of ammonium chloride and ammonium hydroxide in two. ways. We can consider either the reaction.NH40H(aq) <> NHq*(aq) + OH(aq) Or we take the conjugate acid NH,* and consider the reaction: NH4*(aq) + H20(!) <> NH3(aq) + H30*(aq) Or NHq*(aq) + H20(1) <> NHa(aq) + H*(aq) To calculate the pH, we arrange this equation in the form [H*(aq)] = Ka [2 Taking negative logarithm on both sides, we get H= pK - log (2) It may be noted that pK, + PKp = 14 and pK, for NH4* = 9.25. Therefore, pH = 9.25 — log [2) Or pH = 9.25 + log [5) Or pH = 9.25 + log [ard [eonjagatexid] Itis to be noted that the highest buffer capacity should be around 9.25 and furthermore concentration of ammonia is actually the concentration of ammonium hydroxide. Comment Comment {0 Previous Next Previous Next This course is powered | Please Register ever nn Everonn Education Limited f > Facebook Connect L_- About Us (/mainsite/aboutus) News (/mainsite/news) orSummary Points to ponder Chemical equilibrium is dynamic in nature since the rate of forward and reverse reactions are equal. Law of mass action states that at constant temperature rate of a chemical reaction is directly proportional to the molar concentration of the reacting substances. Equilibrium constant (Kc) is defined as the ratio of the product of concentration of the products to that of reactants. More the value of this more faster is the reaction. Equilibrium constant for the reverse reaction is the reciprocal of that of the forward reaction. Reaction quotient (Qc) is defined as the ratio of product of initial concentration of the products to that of reactants. If Q > Kc the reaction is reverse where as the reaction is forward if Q< Ke. According to le-Chatlieur's principle, if a system at equilibrium is subjected to any constraints the system will act in such a way to nullify its effect . It plays an important role in the industrial processes. Electrolyte that gets completely ionized in solution is called a strong electrolyte and that which undergoes incomplete ionization is called a weak electrolyte. According to Arhenius theory substances furnishing H* ions in solution are acids, those furnishing OH- are called bases.Lewis theory defines acids as electron pair acceptors and bases as electron donors. All proton donors are acids and proton acceptors bases according to Lowry bronsted concept of acids and bases. The suppression of dissociation of weak electrolytes by adding their own ions is called common ion effect. Solutions which resist any change in the pH value are called buffer solutions Solubility product is the product of concentration of an anion and the cation in solution. This helps in predicting whether a particular salt will get precipitated or not