Electrolytes

Electrolytes are chemical substances that conduct electricity either in the molten state or when dissolved in water, and are decomposed by electric current. e.g., acids, bases and salts. The conductivity of electrolytes is due to the movement of free ions when the substances are in the molten state or in an aqueous solution. In the solid state, electrolytes do not conduct electricity because the ions are immobile. In the molten state or aqueous solution, the ions are set free. It is the ions that carry the electricity through the electrolytes.

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Electrolytes
Electrolytes are sometimes called electrolytic conductors. They are different from solid conductors where the conduction of electricity is due to the movement of delocalized electrons. Strong electrolytes dissociate fully into ions when in an aqueous solution, (i.e. their degree of dissociation is almost 100% or 1). e.g., NaOH, HCl, NaCl, and others. Weak electrolytes dissociate only partially into ions when dissolved in water (i.e. their degree of dissociation is less than 1 or less than 100%). e.g., CH3COOH, NH3 and others. The degree of dissociation of a 0.100 moldm-3 CH3COOH is only 0.0134 or 1.34% at 298K.

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Electrolytes
The degree of dissociation of an electrolyte also depends on the solvent used. e.g., hydrogen chloride dissociates completely in water but does not undergo dissociation at all when dissolved in tetrachloromethane, CCl4.

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Ostwald Dilution Law

In 1888, a German chemist by the name of Ostwald derived a relationship between the degree of dissociation and the concentration constant for weak electrolytes. Consider an aqueous solution of a weak binary electrolyte, AB, of concentration C moldm-3 and degree of dissociation, . AB(aq) == A+(aq) + B-(aq)

The equilibrium constant, Kc for the system is given by: Kc = [A+][B-]/[AB], Kc = CxC/C(1-), Kc = C2/1-

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Ostwald Dilution Law

The final expression is known as the Ostwald Dilution Law and Kc is called the dissociation constant. For most weak electrolytes, the degree of dissociation, , is very small. Hence, 1-1. Therefore, Kc C2 or = Kc/C. Hence, the degree of dissociation of weak electrolytes increases when the concentration of the electrolyte decreases (or with increasing dilution). At infinite dilution (where concentration approaches zero), all weak electrolytes will dissociate completely.

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Acids and Bases

Acids are chemical substances with the following properties:

Acids have sour taste. Acids change the colour of blue litmus paper to red. Acids react with carbonates or bicarbonates to liberate carbon dioxide gas. Acids react with bases to form salts and water only.

Bases are chemical substances with the following properties:

Bases are slippery to the touch. Bases change the colour of red litmus to blue. Bases react with ammonium salt to produce ammonia gas. Bases react with acids to form salts and water only.

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Acids and Bases

Three important definitions for acids and bases:

Arrhenius definition Bronsted-Lowrys definition Lewis definition

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Acids and Bases

The Arrhenius Definition of Acids and Bases

In 1884, a Swedish chemist, Svante Arrhenius defined acids as substances which dissociate in water to produce hydrogen ions (H+). e.g., Arrhenius acids: + HCl(aq) H (aq) + Cl (aq) + 2H2SO4(aq) 2H (aq) + SO4 (aq) Bases are substances which dissociate in water to produce OH ions. e.g., Arrhenius bases: + NaOH(aq) Na (aq) + OH (aq) 2+ Ba(OH)2(aq) Ba (aq) + 2OH (aq) However, Arrhenius definition has its limitation. It cannot account for the basic properties of certain compounds which do not contain OH- group or ion in their molecules.

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Acids and Bases

The Arrhenius Definition of Acids and Bases

e.g., ammonia, NH3. When ammonia gas dissolves in water, the molecule does not dissociate to give the OH- ions. An aqueous solution of sodium carbonate or sodium ethoxide shows relatively strong basic properties. However, they do not contain the OH- ions. According to Arrhenius definition, ammonia, sodium carbonate and sodium ethoxide are not bases. + 2Na2CO3(aq) 2Na (aq) + CO3 (aq) + C2H5ONa(aq) Na (aq) + C2H5O (aq)

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Acids and Bases

The Bronsted-Lowry Definition of Acids and Bases

In order to overcome the shortcoming of the Arrhenius definition, J.N. Bronsted and T.M. Lowry put forward their proton transfer theory for acids and bases in 1923. According to the Bronsted-Lowry theory, an acid is a proton donor. An acid is a chemical substance which donates proton (the hydrogen ion, H+) to another substance. A base is a proton acceptor. A base is a chemical substance which takes protons from another substance. Hydrogen chloride gas dissolves in water according to the equation: HCl(g) + H2O(l) H3O+(aq) + Cl-(aq). HCl gives a proton to the H2O molecule. Therefore, HCl is an acid (proton donor) while H2O is a base (proton acceptor). The H3O+ ion (the hydrated proton) is called the oxonium ion.

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Acids and Bases

The Bronsted-Lowry Definition of Acids and Bases

e.g., Bronsted-Lowry acids: + CH3COOH(aq) + H2O(l) == CH3COO (aq) + H3O (aq) + + NH4 (aq) + H2O(l) == NH3 (aq) + H3O (aq) When ammonia dissolves in water, it accepts a proton from the water molecule, producing the OH- ions. Hence, ammonia is a Bronsted-Lowry base. + NH3(aq) + H2O(l) == NH4 (aq) + OH (aq) e.g., Bronsted-Lowry bases: + CH3NH2 + H2O == CH3NH3 + OH 2- + H O == HCO - + OHCO3 2 3 C2H5O + H2O == C2H5OH + OH

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Acids and Bases

The Bronsted-Lowry Definition of Acids and Bases

It can be seen that water can act both as a Bronsted-Lowry acid as well as a Bronsted-Lowry base. Water is known as an amphoteric solvent. One major difference between the Arrhenius definition and the Bronsted-Lowrys definition is that, in the Bronsted-Lowrys definition, water is not necessarily involved. e.g., the gas phase reaction between hydrogen chloride and ammonia, or in organic solvents, can be explained using the Bronsted-Lowrys definition. NH3(g) + HCl(g) NH4Cl(s) NH3 (l) + HCl(l) NH4Cl(s) (in CCl4)

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Acids and Bases

The Bronsted-Lowry Definition of Acids and Bases

The ammonia molecule receives a proton from the hydrogen chloride molecule. Hence, ammonia is a base (proton acceptor) while hydrogen chloride is an acid (proton donor).

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Acids and Bases

Conjugate Acid-Base Pair

Consider the reaction between ethanoic acid and water: CH3COOH + H2O == CH3COO- + H3O+. In the forward reaction, CH3COOH is the acid which donates a proton to H2O. In the reverse reaction, the CH3COO- acts as a base and accepts a proton from the H3O+ ion. Hence, the acid, CH3COOH is transformed into a base, CH3COO- when it donates a proton. H2O, which is a base is transformed into an acid, H3O+ when it accepts a proton. CH3COOH and CH3COO are known as a conjugate acid-base pair, and so are H2O and H3O+. CH3COO- is the conjugate base of CH3COOH, and H3O+ is the conjugate acid of H2O. CH3COOH + H2O == CH3COO- + H3O+ acid base conjugate base conjugate acid

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Acids and Bases

Conjugate Acid-Base Pair

The relationship of conjugate represented by the equation:

acid-base

pair

can

be

Acid1 + Base2 == Conjugate base 1 + Conjugate acid 2 HA + B == A+ HB+ acid base conjugate base conjugate acid It should be noted that no substance can act as an acid unless a base is present to accept a proton. Similarly, no substance can act as a base unless an acid is present to donate a proton.

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Acids and Bases

Relative Strength of Bronsted-Lowry Acids/Bases and their Conjugate Pairs

The relative strength of acids depends on their readiness to donate protons. The strength of bases depends on their readiness to accept protons. When hydrogen chloride dissolves in water, it dissociates almost completely: HCl(aq) + H2O H3O+ + Cl-. This shows that the ability for Cl- to receive protons from H3O+ is very low. Hence, Cl- is the weak conjugate base of HCl. Consider an aqueous solution of ammonia (a weak base): NH3 + (aq) + H2O(l) == NH4 (aq) + OH (aq). The equilibrium is largely shifted to the left hand side, showing that the ability for the NH4+ ion to donate protons is high. Hence, NH4+ is a strong conjugate acid of ammonia.

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Acids and Bases

Relative Strength of Bronsted-Lowry Acids/Bases and their Conjugate Pairs

Generally, a strong acid (HCl) will usually produce a weak conjugate base (Cl-), a weak base (NH3) will usually produce a strong conjugate acid (NH4+).

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Acids and Bases

Lewis Acids and Bases

In 1938, an American chemist, G.N. Lewis introduced another theory which extends the concept of acids and bases further than those of Arrhenius or Bronsted and Lowry. Lewis defined an acid as an electron pair acceptor and a base as an electron pair donor. The reaction between ammonia, NH3 and boron trifluoride, BF3 is a classic example involving a Lewis acid and base: BF3 + NH3 BF3.NH3

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Acids and Bases

Lewis Acids and Bases

The BF3 molecule accepts a lone pair of electron from NH3. Hence, BF3 is a Lewis acid while NH3 is a Lewis base. The formation of complex ions by transition metals is an example of reactions involving Lewis acids and Lewis bases. 2+ 2+ Cu (aq) + 4NH3(aq) == [Cu(NH3)4] (aq) 2+ . Hence, NH is NH3 donates a lone pair of electron to Cu 3 2+ is Lewis acid. Lewis base, and Cu

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Relative Strength of Bronsted-Lowry Acids and Bases

Degree of Dissociation
We can compare the relative strength of acids on their ability to form the oxonium ions in aqueous solutions. HA(aq) + H2O(l) == H3O+(aq) + A-(aq) A strong acid will have a higher tendency to dissociate to form the H3O+ ions as compared to a weaker acid. Hence, the higher the degree of dissociation, the stronger the acid. However, when comparing the degree of dissociation of acids, their concentration must be the same. This is because the degree of dissociation is dependent on the concentration of the acid. The table lists the degree of dissociation of four acids of 0.10 moldm-3 concentration.

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Relative Strength of Bronsted-Lowry Acids and Bases

Degree of Dissociation

The acids in order of increasing strength is: CH3COOH < HNO2 < HSO4 < HCl The strength of bases depends on their ability to form the OH ions in aqueous solutions: B + H2O HB- + OH-. A strong base will react completely with water to produce the OH- ions. Only a small portion of a weak base will react with water to form OH- ions. Hence, a strong base will have a higher degree of dissociation (i.e. % that will react with water) than weak bases.

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Relative Strength of Bronsted-Lowry Acids and Bases

Degree of Dissociation
The table below lists the degree of dissociation of three bases of concentration 0.10 moldm-3.

The base in order of increasing strength is: NO2 < CH3COO < NH3

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Relative Strength of Bronsted-Lowry Acids and Bases

Acid/Base Dissociation Constant (Ka and Kb)

Consider a weak monoprotic acid, HA, which dissociates partially in water. HA + H2O == H3O++ A+ At equilibrium, [H3O ][A ]/[HA] = constant. This constant is called the acid dissociation constant, Ka. The concentration of water is not included in the expression because water is present in large excess and its concentration is virtually unchanged. The higher the value of Ka, i.e. the equilibrium position is more towards the right hand side, the stronger the acid. Like all other equilibrium constants, the value of Ka for a particular acid is dependent on temperature. Through international agreement, 298K is used as a standard temperature for the measurement of Ka.

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Relative Strength of Bronsted-Lowry Acids and Bases

Acid/Base Dissociation Constant (Ka and Kb)

Consider a weak base, B, which dissociates partially in water: + B+ H2O == HB + OH + At equilibrium, [HB ][OH ]/[B] = constant. This constant is called the base dissociation constant, Kb. The higher the value of Kb, the stronger the base.

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Relative Strength of Bronsted-Lowry Acids and Bases

pKa and pKb

Another convenient way of expressing the acid / base dissociation constant is pKa and pKb. pKa = -logKa and pKb = -logKb. The larger the value of Ka or Kb, the smaller the value of pKa or pKb.

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Relative Strength of Bronsted-Lowry Acids and Bases

Acid Dissociation Constant of Polyprotic Acids

A polyprotic acid is an acid which can donate more than one H+ ion per acid molecule to other substances. e.g. a strong polyprotic acid (diprotic acid), sulphuric acid: H2SO4 + 2H2O 2H3O+ + SO42- or H2SO4 2H+ + SO42-. For weak polyprotic acids, the molecules dissociate in stages and each stage has its own Ka value. e.g., phosphoric(V) acid, H3PO4. The molecule dissociate in three distinct stages as follows:

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Relative Strength of Bronsted-Lowry Acids and Bases

Acid Dissociation Constant of Polyprotic Acids

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Ostwald Dilution Law and Dissociation Constant

Consider a weak acid, HA, of concentration C moldm-3 and degree of dissociation of .

At equilibrium: Ka = CC/C(1-). However, is very small, hence, (1- )1, Ka = C2, = Ka/C. Since [H+] = C, [H+] = KaC. For a weak base: B + H2O == HB+ + OH-, [OH-] = KbC

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Ionic Product of Water and the pH Scale

Since all acids and bases are aqueous solutions, pure water is considered the universal solvent for these compounds. The electric conductivity of even the purest water is not zero. This is due to the self-ionization of water: H2O(l) == H+(aq) + OH-(aq) Applying the equilibrium law, Kc=[H+][OH-]/[H2O]. Since the degree of dissociation of water is extremely small, the concentration of water, [H2O] can be considered a constant i.e. Kc[H2O] = [H+][OH-] = Kw. Kw is the ionic product of water.

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Ionic Product of Water and the pH Scale

From conductivity measurement, the [H+] and [OH-] of water at 25oC are 1.0x10-7 moldm-3 respectively. Hence, Kw= [H+][OH-] = (1.0x10-7)2 = 1.0x10-14 mol2dm-6. The ionic product of water can also be expressed in terms of pKw, where pKw = -logKw = -log(1.0x10-14) = 14 + From the expression: Kw = [H ][OH ]. Taking log to base 10 throughout, we obtain: pKw = pH + pOH = 14. Thus, if the pOH of a solution is known, its pH value can be calculated from the above relationship. Therefore, it is not necessary to have two scales to denote the acidity (or basicity) of acids and bases.

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Ionic Product of Water and the pH Scale

The concentration of the H+ ions in pure water at 298K is 1.0x10-7 moldm-3. Therefore, the pH of pure water at 298K is pH = -log(1.0x10-7) = 7.0. In acidic solutions, the [H+]>[OH-]>1.0x10-7moldm-3; pH<7.0. In basic solutions, the [H+]<[OH-]<1.0x10-7moldm-3; pH>7.0. In neutral solutions, [H+]=[OH-]=1.0x10-7moldm-3; pH=7.0.

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Ionic Product of Water and the pH Scale

A pH scale is shown.

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Relationship between pKa, pKb and pKw

Consider an aqueous solution of ethanoic acid: CH3COOH + H2O == CH3COO- + H3O+, Ka= [CH3COO][H3O+]/[CH3COOH] Consider an aqueous solution containing the ethanoate ion (which is the conjugate base of CH3COOH): CH3COO- + H2O == CH3COOH + OH-, Kb = [CH3COOH][OH-]/[CH3COO-] Multiplying Ka and Kb: Ka x Kb = [H3O+][OH-] or simply written as: [H+][OH-] Ka x Kb = Kw (for a acid/base conjugate pair) Taking log throughout: -log[H+] + (-log[OH-]) = logKw. Hence, for a acid/base conjugate pair: pH + pOH = pKw 4/29/2012 33

Acid-Base Titration

Acid-Base Indicators
The main aim of an acid-base titration is to determine the volume of two solutions (acid and base) which will exactly neutralize each other. Most acids and bases as well as their salts are colourless in water. Therefore, an indicator is necessary to pin-point the end point of the titration. Acid-base indicators (pH indicators) are substances which change colour according to the pH of the solution to which they are added. The indicators are usually weak acids or weak bases which dissociate partially in water.

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Acid-Base Titration

Acid-Base Indicators
Consider a weak monoprotic acid, Hln, which acts as an indicator: Hln(aq) == H+(aq) + ln-(aq). The undissociated molecule, Hln must have a different colour from its anion, ln-. + + e.g., methyl orange, HMe. Me + H == HMe . Addition of acid (H+) shifts the equilibrium to the right, so that [HMe+] >>[Me] and the solution becomes red. Addition of alkali (OH-) shifts the equilibrium to the left, so that [Me] >> [HMe+] and the solution becomes yellow. + e.g., phenolphthalein, HPh. HPh == H + Ph . In the presence of an acid, the equilibrium is pushed to the left and the solution turns colourless. In the presence of a base, the equilibrium is pushed to the right and the solution turns pink.

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Acid-Base Titration

Acid-Base Indicators
Applying the equilibrium law to the system: Hln == H+ + ln-. Kln = [H+][ln-]/[Hln]. Kln is known as the indicator dissociation constant. The indicator changes colour at the point when [Hln] = [ln ]. At this point, Kln = [H+], pKln = pH. Therefore, the pH at which the indicator changes colour is equal to the pKln of the indicator. In practice, the observable colour change actually takes place over a range of pH and not a particular pH. For most indicators, the pH range is around +/- 1 of the pKln value.

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Acid-Base Titration

Acid-Base Indicators
Generally, we can use the following ratios of concentration to predict the colour of the indicator: [Hln] / [ln ] 1.0, the colour of Hln will predominate. [Hln] / [ln ] 1.0, the colour of ln will predominate. [Hln] / [ln ] 1.0, the colour will be a combination of the colours of Hln and ln-. The table gives the pH range of some common indicators.

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Acid-Base Titration

Acid-Base Indicators
A universal indicator is a mixture of several indicators which gives a gradual change in colour over a wide range of pH.

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Acid-Base Titration

Equivalent Point and End Point of Acid-Base Titration

The equivalent point is when the amount of acid and base present exactly neutralizes one another. At this point, neither acid nor alkali are present in excess. The solution consists of salt and water only. The end point of titration is when the indicator changes colour. Thus, in an acid-base titration, the choice of indicator is important. The end point indicated by the indicator must coincide with the equivalent point. The choice of indicator in an acid-base titration depends on the type of acid or base used.

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Acid-Base Titration

Equivalent Point and End Point of Acid-Base Titration

e.g., in the titration of 25.0 cm3 of 0.10 moldm-3 HCl against a 0.15 moldm-3 solution of NaOH. NaOH + HCl NaCl + H2O -3 Number of moles of HCl used = (25.0x10 ) x 0.10 = 0.0025 mol Number of moles of NaOH required = 0.0025 mol 3 Let the volume of NaOH which contains 0.0025 mol = V cm 3 V/1000 x 0.15 = 0.0025, V = 16.67 cm 3 of Hence, the equivalent point is reached when 16.67 cm NaOH has been added from the burette. If the indicator used changes colour before the equivalent point, the volume recorded would be less than 16.67 cm3. If the indicator changes colour well after the equivalent point, the volume recorded will be more than 16.67 cm3.

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Acid-Base Titration

The Titration Graph

Assuming that a titration is carried out by adding a base (from the burette) to an acid (in the conical flask), the pH changes during the titration can be followed using a pH meter. A graph of pH against the volume of base added is then plotted. Four types of curve are obtained.

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The Titration Graph

Strong Acid-Strong Base Titration

The graph of pH against volume of NaOH added during the titration between 25.0 cm3 of 0.10 moldm-3 HCl and a solution of NaOH of concentration 0.10 moldm-3 is shown. Near the equivalent point, the pH of the solution jumps from about 3.7 to 10.6. The pH at the equivalent point is 7.0 because the NaCl formed is not hydrolyzed. NaOH + HCl NaCl + H2O Both methyl orange and phenolphthalein are suitable indicators.

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The Titration Graph

Strong Acid-Strong Base Titration

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The Titration Graph

Strong Acid-Weak Base Titration

The graph of pH against volume of NH3 added during the titration between 25.0 cm3 of 0.10 moldm-3 HCl and a solution of ammonia of concentration 0.10 moldm-3 is shown. Near the equivalent point, the pH of the solution jumps from about 3.0 to 7.0. The pH at the equivalent point is about 5.3 due to the hydrolysis of the NH4Cl formed. NH3(aq) + HCl(aq) NH4Cl(aq) + + NH4 (aq) + H2O(l) == NH3(aq) + H3O (aq) Methyl orange (pH range of 3.2-4.4) is a suitable indicator because it changes colour within the range of pH 3-7. Phenolphthalein is not suitable because it changes colour well after the equivalent point.

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The Titration Graph

Strong Acid-Weak Base Titration

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The Titration Graph

Weak Acid-Strong Base Titration

The graph of pH against volume of NaOH added during the titration between 25.0 cm3 of 0.10 moldm-3 CH3COOH and a solution of NaOH of concentration 0.10 moldm-3 is shown. As CH3COOH is a weak acid, the graph starts at a pH 2.8. Near the equivalent point, the pH of the solution jumps from about 6.5 to 11.0. The pH at the equivalent point is about 9.0 due to the hydrolysis of the sodium ethanoate formed. CH3COOH + NaOH CH3COONa + H2O CH3COO (aq) + H2O(l) == CH3COOH(aq) + OH (aq) Phenolphthalein (with pH range of 8.2 10.0) is a suitable indicator because it will change colour within the range of pH 6.5-11.0. Methyl orange is not suitable because it changes colour too early, i.e. before the equivalent point.

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The Titration Graph

Weak Acid-Strong Base Titration

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The Titration Graph

Weak Acid-Weak Base Titration

The graph of pH against volume of NH3 added during the titration between 25.0 cm3 of 0.10 moldm-3 CH3COOH and a solution of ammonia of concentration 0.10 moldm-3 is shown. There is no sharp rise in pH at the equivalent point of the titration. Hence, there is no suitable indicator for this type of titration.

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The Titration Graph

Weak Acid-Weak Base Titration

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The Titration Graph

Titration Strong acid+ weak base Weak acid + strong base Strong acid + strong base

Weak acid + weak base

Suitable Indicator Methyl orange Phenolphthalein Methyl orange / Phenolphthalein No suitable indicator

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Titration involving Weak Polybasic Acids/ Bases

The pH graph involving polybasic acids or bases usually consists of two or more equivalent points (or inflexion points) corresponding to the formation of acidic salts and normal salts. The pH graph for the titration between 25.0 cm3 of a solution of 0.10 moldm-3 sodium carbonate and a 0.10 moldm-3 solution of hydrochloric acid is shown. The first inflexion point (when 25.0 cm3 of HCl has been added) corresponds to the formation of the acidic salt, sodium hydrogen carbonate: Na2CO3 + HCl NaHCO3 + NaCl.

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Titration involving Weak Polybasic Acids/ Bases

The second inflexion point (when a total of 50.0 cm3 of HCl has been added) corresponds to the formation of the normal salt, sodium chloride: NaHCO3 + HCl NaCl + H2O + CO2. It can be seen from the graph that phenolphthalein will indicate the completion of the first reaction while methyl orange will indicate the completion of the second reaction.

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Titration involving Weak Polybasic Acids/ Bases

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Salt Hydrolysis
Salts can be defined as products formed from the neutralization between acids and bases. Some salts form neutral solutions (pH=7.0) when dissolved in water while others form either an acidic (pH<7.0) or basic solutions (pH>7.0). Salts that form acidic/basic solutions undergo hydrolysis by water. This is due to a reversible reaction between the aqueous salt ions with water to produce either H+ ions or OH- ions. Whether a salt solution is neutral, acidic or alkaline depends on the type of salt.

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Salt Hydrolysis

Salt Formed from a Strong Acid and Weak Base

When a salt formed from a strong acid and weak base dissolved in water, it forms an acidic solution. e.g., ammonium chloride, NH4Cl, which is formed from HCl (a strong acid) and ammonia (a weak base). NH3(aq) + HCl(aq) NH4Cl(aq) In water, ammonium chloride dissociates completely into ammonium ions and chloride ions: NH4Cl(aq) + aq NH4+(aq) + Cl-(aq). The ammonium ion, NH4+, acts as a Bronsted-Lowry acid and donates a proton to water: + + NH4 (aq) + H2O(l) == NH3(aq) + H3O (aq) + ions from the hydrolysis of the NH + The production of H3O 4 ions causes the solution to be acidic. This is also known as cationic hydrolysis.

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Salt Hydrolysis

Salt Formed from a Weak Acid and Strong Base

When a salt formed from a weak acid and strong base dissolved in water, it forms an alkaline solution. e.g., sodium ethanoate, which is formed from ethanoic acid (a weak acid) and NaOH (a strong base). In water, sodium ethanoate dissociates completely into sodium ions and ethanoate ions. CH3COONa(aq) CH3COO- (aq) + Na+ (aq). The ethanoate ion acts as a Bronsted-Lowry base by accepting a proton from water: CH3COO (aq) + H2O(l) == CH3COOH(aq) + OH (aq) The production of OH from the hydrolysis of the CH3COO ions causes the solution to be basic. This is also known as an anionic hydrolysis.

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Salt Hydrolysis

Salt Formed from Strong Acid and Strong Base

When a salt formed from a strong acid and a strong base dissolved in water, it forms a neutral solution. e.g., sodium chloride, which is formed from HCl (a strong acid) and NaOH (a strong base). NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) In water, sodium chloride dissociates completely to sodium ions and chloride ions: NaCl(aq) Na+(aq) + Cl-(aq). Both the Na+ ions and Cl- ions are not hydrolyzed by water. There is no production of extra H+ ions or OH- ions. Hence, the solution is neutral.

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Salt Hydrolysis

Salt Formed from a Weak Acid and Weak Base

An example of a salt formed from a weak base and weak acid is ammonium ethanoate formed from aqueous ammonia (a weak base) and ethanoic acid (a weak acid). CH3COOH(aq) + NH3(aq) CH3COONH4(aq) When dissolved in water, it dissociates completely into ammonium ions and ethanoate ions: CH3COONH4(aq) CH3COO-(aq) + NH4+(aq). The ethanoate ion undergoes anionic hydrolysis to produce OH- ions: CH3COO-(aq) + H2O(l) == CH3COOH(aq) + OH-(aq) The ammonium ion undergoes cationic hydrolysis to produce H+ ions: NH4+(aq) + H2O(l) == NH3(aq) + H3O+(aq).

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Salt Hydrolysis

Salt Formed from a Weak Acid and Weak Base

An aqueous solution of a salt of a weak acid and a weak base may be neutral, slightly acidic or basic depending on the relative amount of H3O+ and OH- ions formed. This in turn depends on the extent of the cationic hydrolysis and the anionic hydrolysis. The extent of the hydrolysis depends on the relative values of acid dissociation of the cation, Ka, and the base dissociation constant of the anion, Kb. If Ka > Kb, the solution will be acidic because the cation will be hydrolyzed to a greater extent than the anion. At equilibrium, more H3O+ will be produced.

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Salt Hydrolysis

Salt Formed from a Weak Acid and Weak Base

If Ka < Kb, the solution will be basic because the anion will be hydrolyzed to a greater extent than the cation. At equilibrium, more OH- will be produced. If Ka Kb, the solution will be neutral because both the cation and anion will be hydrolyzed to the same extent. For the case of aqueous ammonium ethanoate, the solution is neutral because the acid dissociation constant, Ka, for NH4+ and the base dissociation constant, Kb, for CH3COO- are almost the same (about 1.8 x 10-5 moldm-3).

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Salt Hydrolysis

Summary

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Buffer Solution
A buffer solution is a solution of which the pH does not change significantly on the addition of a little acid or base. When 1 cm3 of 1.0 moldm-3 HCl is added to 1 dm3 of water, the pH changes from 7.0 to 3.0, a change of 4 units. If this happens in the biological systems of living organisms, the organism will perish instantly. Under most circumstances, a change of 0.4 unit in the pH of the blood (which can occur when one takes medication or during sickness) can be fatal. Fortunately, living organisms are protected against sharp pH changes when a small amount of acid or base is added to the biological system of plants and animals including humans.

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Buffer Solution
Buffers are also important in many industrial processes. Certain processed food has to be prepared in a buffered form so that when consumed it does not cause undue changes in pH. A buffer solution must contain a relatively large quantity of acid to react with any OH- ions that might be added to it and also a relatively large quantity of base to react with any H+ ions that might be added to it. Furthermore, the acid and base components of the buffer solution must not neutralize one another.

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Buffer Solution

Acidic Buffer Solution

An acidic buffer solution (with pH between 4 and 7) can be prepared from a weak acid and its conjugate base. e.g., an aqueous mixture of ethanoic acid and sodium ethanoate. Sodium ethanoate dissociates fully in water: + CH3COONa(aq) CH3COO (aq) + Na (aq). Ethanoic acid dissociates partially in water: + CH3COOH(aq) == CH3COO (aq) + H (aq) An aqueous mixture of ethanoic acid and sodium ethanoate contains a large quantity of the undissociated CH3COOH molecule (the acid) and a large quantity of the CH3COO- ions (the conjugate base).

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Buffer Solution

Acidic Buffer Solution

When a little acid is added, the equilibrium will shift to the left to mop up the added H+ ions. H+(added) + CH3COO- CH3COOH. The presence of sodium ethanoate ensures that there is a large reservoir of CH3COO- ions to remove all of the added H+, and the pH remains constant. When a little base is added, it is removed by the reaction: OH (added) + CH3COOH CH3COO + H2O. The presence of ethanoic acid ensures that there is a large reservoir of undissocaited CH3COOH molecules to remove all of the added OH-, and the pH remains constant.

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Buffer Solution

Basic Buffer Solution

A basic buffer solution (with pH between 7 and 10) can be prepared from a weak base and its conjugate acid. An example of an aqueous mixture of ammonia (the base) and ammonium chloride (the conjugate acid). Ammonium chloride dissociates fully in water: + NH4Cl(aq) NH4 (aq) + Cl (aq) Ammonia dissociates partially in water: + NH3(aq) + H2O(l) == NH4 (aq) + OH (aq) An aqueous mixture of ammonia and ammonium chloride contains a large quantity of the undissociated NH3 molecules (the base component) and a large quantity of the NH4+ ions (the acid component).

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Buffer Solution

Basic Buffer Solution

When a little base is added, the equilibrium will shift to the left to mop up the added OH- ions. OH-(added) + NH4+ NH3 + H2O. The presence of ammonium chloride ensures that there is a large reservoir of NH4+ ions to remove all of the added OH-, and the pH remains constant. + When a little acid is added, it is removed by the reaction: H + (added) + NH3 NH4 . The presence of ammonia ensures that there is a large reservoir of undissociated NH3 molecules to remove all of the added H+, and the pH remains constant.

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Buffer Solution

pH of Buffer Solutions
Consider an aqueous mixture of a weak acid, HA and its salt MA. MA M+ + A-, HA == H+ + A-. Applying the equilibrium law to the equilibrium system, Ka= [H+][A-]/[HA]. The [A-] at equilibrium can be assumed to be the concentration of MA which dissociates 100%. The [HA] at equilibrium can be assumed to be equal to the original concentration of HA (since the degree of association is very small). + Rearranging the equation: [H ] = Ka [Acid]/[Salt]. Taking log throughout, pH = pKa log [Acid]/[Salt] Similarly, for a basic buffer solution: [OH ] = Kb [Base]/[Salt]. Taking log throughout, pOH = pKb log [Base]/[Salt].

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Buffer Solution

Buffer Action in Acid-Base Titration

The graph shows the variation in pH in a titration involving ethanoic acid and sodium hydroxide. At first, the pH changes only very slightly on the addition of NaOH to the ethanoic acid (section AB). However, at the equivalent point (when 50.0 cm3 NaOH was added), there is a large increase in the pH from about 6.5 to 10.5. Along section AB, some of the ethanoic acid is neutralized by the NaOH to form water and sodium ethanoate: CH3COOH + NaOH CH3COONa + H2O. Hence, the solution along section AB contains a mixture of ethanoic acid and sodium ethanoate which acts as a buffer solution. Therefore, the pH of the solution along section AB changes only slightly on addition of NaOH.

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Buffer Solution

Buffer Action in Acid-Base Titration

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Buffer Solution

Buffer Action in Acid-Base Titration

At mid-way neutralization (when 25.0 cm3 NaOH had been added), half of the original amount of ethanoic acid is neutralized. Hence, mid-way neutralization is: [CH3COOH]=[CH3COONa]. From the equation, pH = pKa log [CH3COOH]/[CH3COO ], at mid-way neutralization, [CH3COOH]/[CH3COO-] =1 and log (1) = 0. Therefore, pH = pKa. Hence, the pH of the solution at mid-way neutralization is equal to the pKa of the weak acid (ethanoic acid).

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Buffer Solution

Preparation of Buffer Solution

Choose a suitable weak acid (or weak base) whose pKa or pKb is almost equal to the required pH of the buffer solution. Calculate the ratio of the concentration of the acid (or base) to the concentration of the salt. Add the required amount of salt to the acid (or base) as determined.

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Buffer Solution

Preparation of Acidic Buffer Solution

Example:

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Buffer Solution

Preparation of Basic Buffer Solution

Example:

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Buffer Solution

Buffer Capacity
Buffer solutions have limited capacity to resist pH changes. If too much acid is added such that the weak base (or conjugate base) is used up, no more buffering action against acid is possible. On the other hand, if too much base is added such that the weak acid (or conjugate acid) is used up, no more buffering action against base is possible. The buffer capacity of a buffer solution is the amount of acid or base that can be added to a given amount of the buffer solution before the pH of the buffer solution changes by 1 unit. The buffer capacity depends on the actual amount of acid/conjugate base or base/conjugate acid present in the buffer solution.

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Sparingly Soluble Salts and Solubility Product

When a sparingly soluble salt (a salt which has very low solubility in water) is added a little at a time to water, a saturated solution is eventually formed. The solution is in equilibrium with excess undissolved solid. When a saturated solution of silver chloride is in contact with solid silver chloride, the following equilibrium is established. AgCl(s) == Ag+(aq) + Cl-(aq) . The product of the concentration of silver ions and chloride ions is known as the solubility product (Ksp) of silver chloride. Ksp = [Ag+][Cl-]

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Sparingly Soluble Salts and Solubility Product

The solubility product of a sparingly soluble salt is defined as the product of the concentration of the ions in a saturated solution of the salt, raised to the power of the stoichiometric coefficient of the respective ions. e.g., NiS(s) == Ni2+(aq) + S2-(aq) Ksp = [Ni2+][S2-] PbCl2(s) == Pb2+(aq) + 2Cl-(aq) Ksp = [Pb2+][Cl-]2 Ca3(PO4)2(s) == 3Ca2+(aq) + 2PO43-(aq) Ksp = [Ca2+]3[PO43-]2

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Sparingly Soluble Salts and Solubility Product

For a sparingly soluble salt AxBy, the Ksp is given by: y+ xAxBy(s) == xA (aq) + yB (aq) Ksp = [Ay+]x[Bx-]y Like other equilibrium constants, the solubility product varies with temperature. Thus, the solubility products are sometimes expressed as Ksp 298K. The solubility products (at 298K) of some common salts are given in the table.

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Sparingly Soluble Salts and Solubility Product

Solubility Product and Precipitation

When an aqueous solution of calcium nitrate is added to an aqueous solution of sodium sulphate, one of the products is calcium sulphate, a sparingly soluble salt. Ca(NO3)2(aq) + Na2SO4(aq) CaSO4(s) + 2NaNO3(aq), or Ca2+(aq) + SO42-(aq) CaSO4(s) Whether a precipitate of CaSO4 will be formed or not depends on the concentration of the Ca2+ ions and SO42- ions in the mixture. If [Ca2+][SO42-] > Ksp, precipitate will occur. If [Ca2+ ][SO42-] < Ksp, no precipitation takes place.

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Sparingly Soluble Salts and Solubility Product

Common Ion Effect

Consider a saturated solution of silver chloride: AgCl(s) == Ag+ (aq) + Cl (aq). If a little sodium chloride is added to the above solution, according to Le Chateliers Principle, the equilibrium will shift to the left to get rid of some of the Cl- ions added. Hence, the amount of solid silver chloride will increase. In other words, the solubility of silver chloride is decreased by the addition of sodium chloride (which contains the Cl- ions). This phenomenon is known as the common ion effect. The decrease in the solubility of a sparingly soluble salt in a solution which already contains one of the ions from the dissociation of the salt is known as the common ion effect.

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Sparingly Soluble Salts and Solubility Product

Common Ion Effect

Another way to look at the common ion effect is from the point of view of the Ksp values. The Ksp for AgCl is 1.0 x 10-10 mol2dm-6. In a saturated solution of silver chloride in water, the concentration of the Ag+ ions and Cl- ions are respectively 1.0 x 10-5 moldm-3. AgCl(s) == Ag+(aq) + Cl- (aq), [Ag+][Cl-] = 1.0 x 10-10 mol2dm-6. If a little sodium chloride is added to the saturated solution, the total Cl- concentration will increase: [Cl-] > 1.0 x 10-5 moldm-3. In order for the ionic product to remain constant (Ksp is a constant at a constant temperature), the Ag+ ion must decrease. Therefore, some of the Ag+ ions must combine with some of the added Cl- ions to form AgCl(s) until the value of the ionic product is again 1.0 x 10-10.

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Summary
Electrolytes are chemical substances which conduct electricity either in the molten state or when dissolved in water, and are decomposed by electrical current. Arrhenius definition of acids and bases:

Acids are substances that dissociate to produce H+ ions when dissolved in water. - ions Bases are substances that dissociate to produce OH when dissolved in water.

Bronsted-Lowry definition of acids and bases:

Acids are proton donors. Bases are proton acceptors.

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Summary

Lewis definition of acids and bases.

Acids are lone-pair electron acceptors. Bases are lone-pair electron donors.

The higher the Ka (or the lower the pKa), the stronger the acid. The higher the Kb (or the lower the pKb), the stronger the base. For a weak acid: [H+]=KaC For a weak base: [OH ]=KbC pH= -log[H+] pOH= -log[OH-]

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Summary
K = [H+][OH-] = 1.0 x 10-14 mol2dm-6 at 298K. pH + pOH = 14 For a conjugate acid/base pair: pKa + pKb = pKw = 14.0 at 298K. Buffer solution is a solution whose pH does not change much on the addition of a little acid or base. An acidic buffer solution consists of a mixture of a weak acid and its conjugate base. A basic buffer solution consists of a mixture of a weak base and its conjugate acid.
w

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Summary
For an acidic buffer solution: pH=pKa- log[Acid]/[Salt] For a basic buffer solution: pOH=pKb- log[Base]/[Salt] The buffer capacity of a buffer solution is the amount of acid or base that can be added to a given volume of the buffer solution before the pH of the solution changes by 1 unit. The solubility product of a sparingly soluble salt is defined as the product of the concentration of the ions in a saturated solution of the salt, raised to the power of the stoichiometric coefficient of the respective ions.

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Summary
The decrease in the solubility of a sparingly soluble salt in a solution which already contains one of the ions from the dissociation of the salt is known as the common ion effect. If the ionic product > Ksp, precipitation will occur. If the ionic product < Ksp, no precipitation will occur.

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