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Chapter 2

Chemical equilibrium and
classical methods for analysis
- Gravimetric methods and Titrations

Holler, Crouch, “Skoog and West’s Fundamentals of Analytical Chemistry”, 9th Ed., Brook/Cole, 2014.
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• Among the strong electrolytes listed are acids, bases, and salts.
• A salt is produced in the reaction of an acid with a base.
• Ex., NaCl, Na2SO4, and NaOOCCH3 (sodium acetate).
 Acids and bases
According to the Brønsted-Lowry theory, an acid is a proton donor, and a
base is a proton acceptor. For a molecule to behave as an acid, it must
encounter a proton acceptor (or base) and vice versa.
 Conjugate Acids and Bases
• A conjugate base is formed when an acid loses a proton.
• For example, acetate ion is the conjugate base of acetic acid.
• A conjugate acid is formed when a base accepts a proton.
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Acids and bases

 Acid1 and base1 act as a conjugate acid/base pair, or just a conjugate pair.
 Similarly, every base accepts a proton to produce a conjugate acid. When
these two processes are combined, the result is an acid/base, or
neutralization reaction.
 This reaction proceeds to an extent that depends on the relative
tendencies of the two bases to accept a proton (or the two acids to
donate a proton).

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Water/ Aqueous solution
 An aqueous solution of ammonia

Ammonia (base1) reacts with water (acid2) to give the conjugate acid
ammonium ion (acid1) and hydroxide ion (base2) of the acid water.

 An aqueous solution of nitrous acid




Water acts as a proton acceptor, or base
The conjugate base of the acid HNO2 is nitrite ion.
The conjugate acid of water is the hydrated proton written as H3O+.
This species is called the hydronium ion, and it consists of a proton
covalently bonded to a single water molecule.

 Water is the classic example of an amphiprotic solvent.
(Species that have both acidic and basic properties are amphiprotic. )
 Common amphiprotic solvents include methanol, ethanol, and
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anhydrous acetic acid.

Chemical equilibrium
 Many reactions never result in complete conversion of reactants to
products. They proceed to a state of chemical equilibrium in which
the ratio of concentrations of reactants and products is constant.
 Equilibrium-constant expressions are algebraic equations that
describe the concentration relationships among reactants and
products at equilibrium.
The Equilibrium State
 The final position of a chemical equilibrium is independent of the
route to the equilibrium state.
 This relationship can be altered by applying stressors such as
changes in temperature, in pressure, or in total concentration of a
reactant or a product.
 These effects can be predicted qualitatively by the Le Châtelier’s
principle.
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Types of Equilibrium Constants in Analytical Chemistry

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CHA and CNaA. The effect of dilution 7 Calculating the pH of Buffer Solutions A solution containing a weak acid.Buffer solutions  A buffer solution resists changes in pH when it is diluted or when acids or bases are added to it. and its conjugate base. A-. To find the pH of a solution containing both an acid. or basic. neutral. HA. the equilibrium concentrations of HA and NaA need to expressed in terms of their analytical concentrations. depending on the positions of two competitive equilibria: These two equilibrium-constant expressions show that the relative concentrations of the hydronium and hydroxide ions depend not only on the magnitudes of Ka and Kb but also on the ratio between the concentrations of the acid and its conjugate base. may be acidic. 8 . and conjugated base (NaA). HA.  Buffers are used in chemical applications whenever it is important to maintain the pH of a solution at a constant and predetermined level.  Bsolutions are prepared from a conjugate acid/base pair.

 The Henderson-Hasselbalch Equation . this ratio is independent of dilution because the concentration of each component changes proportionally when the volume changes.The dissociation-constant expression can then be expressed as: The hydronium ion concentration of a solution containing a weak acid and its conjugate base depends only on the ratio of the molar concentrations of these two solutes. Furthermore.calculate the pH of buffer solution 9 10 .

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14 .The effect of Added Acids and Bases 13 Buffers do not maintain pH at an absolutely constant value. but changes in pH are relatively small when small amounts of acid or base are added.

They are based on mass measurements with an analytical balance. In precipitation gravimetry. In electrogravimetry. the analyte is separated from a solution of the sample as a precipitate and is converted to a compound of known composition that can be weighed. an instrument that yields highly accurate and precise data. In volatilization gravimetry.Gravimetric Methods of Analysis • • • • • Gravimetric methods are quantitative methods that are based on determining the mass of a pure compound to which the analyte is chemically related. The mass of this product then provides a measure of the analyte concentration 15 Calculation of results from gravimetric data 16 . The mass of the gas then serves as a measure of the analyte concentration. the analyte is separated by deposition on an electrode by an electrical current. the analyte is separated from other constituents of a sample by converting it to a gas of known chemical composition.

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Applications of gravimetric methods • • Gravimetric methods do not require a calibration or standardization step because the results are calculated directly from the experimental data and atomic masses. a gravimetric procedure may be the method of choice because it requires less time and effort than a procedure that requires preparation of standards and calibration. Thus. when only one or two samples are to be analyzed. 21 Inorganic Precipitating Agents 22 .

24 .23 Reducing Agents Reducing agents: convert an analyte to its elemental form for weighing.

Metal chelates are relatively nonpolar and have solubilities that are low in water but high in organic liquid. The four six-membered rings ate formed with Fe2+. and their products are called chelates. The functional groups are located in the molecule such that a five. Each of these groups is capable of bonding with a cation by donating a pair of electrons. 25 Chelates  Chelates are cyclical metal-organic compounds in which the metal is a part of one or more five. Heme 26 .or six-membered rings.  Heme is a part of homoglobin.or six-membered ring results from the reaction. Organic reagents that yield sparingly soluble coordination compounds typically contain at least two functional groups. Reagents that form compounds of this type are called chelating agents. and the other forms products in which the bonding between the inorganic species and the reagent is largely ionic.Organic Precipitating Agents There are two types of organic reagents: one forms slightly soluble nonionic products called coordination compounds. the oxygen-carrying molecule in human blood.

Widely used chelating agents  8-hydroxyquinoline (oxine)  Dimethylglyoxine Considerable degree of selectivity in the use of 8-hydroxyquinoline by controlling pH.  Sodium Tetraphenylborate 27 Organic Functional Group Analysis 28 .

The equivalence point of a titration cannot be determined experimentally. 30 . Indicators are often added to the analyte solution to produce an observable physical change (signaling the end point) at or near the equivalence point. Volumetric titrations involve measuring the volume of a solution of known concentration that is needed to react completely with the analyte. the “reagent” is a constant direct electrical current of known magnitude that consumes the analyte. It can only be estimated by observing some physical change associated with the condition of chemical equivalence called the end point for the titration. The difference in volume or mass between the equivalence point and the end point is the titration error. 29 Equivalence Points and End Points • • • • • • The equivalence point is the point in a titration when the amount of added standard reagent is equivalent to the amount of analyte. The reagent may be a standard solution of a chemical or an electric current of known magnitude. the mass of the reagent is measured instead of its volume. In coulometric titrations. The titration error is given as: Et = Vep − Veq where Vep is the actual volume of reagent required to reach the end point and Veq is the theoretical volume necessary to reach the equivalence point. In Gravimetric titrations.Titrations in Analytical Chemistry • • • • • Titration methods are based on determining the quantity of a reagent of known concentration that is required to react completely with the analyte.

1. The titration of a weak base. Weak acids and bases are never used as standard reagents because they react incompletely with analytes. such as HCl. HClO4. with a strong base. such as acetic or lactic acid. Standard solutions of acids are prepared by diluting concentrated hydrochloric. Nitric acid is seldom used because its oxidizing properties offer the potential for undesirable side reactions. such as sodium hydroxide. and KOH. 32 . 3. with a strong acid. such as sodium cyanide or sodium salicylate. 31 Standard Solutions • • • • • The standard reagents used in acid/base titrations are always strong acids or strong bases. or sulfuric acid. Hot concentrated perchloric and sulfuric acids are potent oxidizing agents and are very hazardous. The titration of a weak acid. There are several different types of acid/base titrations. such as hydrochloric or sulfuric acid. The titration of a strong acid. NaOH. H2SO4. 2. Solutions and indicators for acid/base titrations • Neutralization titrations depend on a chemical reaction of the analyte with a standard reagent. with a strong base.Principles of Neutralization Titrations • Neutralization titrations are widely used to determine the amounts of acids and bases and to monitor the progress of reactions that produce or consume hydrogen ions. perchloric.

(b) Basic form. (a) Acidic form after hydrolysis of the lactone form. the behavior of an acid-type indicator. In: In + H2O ⇔ InH+ + OH- • The equilibrium-constant expression for the dissociation of an acidtype indicator takes the form Ka = [H3O+][In-] [HIN] [H3O+] =Ka [HIN] [In-] 33 Figure 14-1 Color change and molecular modes for phenolphthalein.+ H3O+ • The equilibrium for a base-type indicator.Acid/Base Indicators • • An acid/base indicator is a weak organic acid or a weak organic base whose undissociated form differs in color from its conjugate base or its conjugate acid form. HIn: HIn + H2O ⇔ In. 34 . For example.

1 pH (basic color) = -log(0. on the concentration of the indicator. and the presence of organic solvents and colloidal particles. exhibits its pure acid color when [HIn]/[In-] ≥ 10/1 and its base color when [HIn]/[In-] ≤ 1/10  The range of hydronium ion concentrations needed for the indicator to change color can be estimated. It can usually be minimized by choosing the indicator carefully or by making a blank correction. particularly when the ratio [HIn]/[In-] is greater than about 10 or smaller than about 0. and for the full base color. The magnitude of this error depends on the change in pH per milliliter of reagent at the equivalence point.1Ka  To obtain the indicator pH range. The human eye is not very sensitive to color differences in a solution containing a mixture of HIn and In-. 36 . For full acid color.0). the ionic strength of the medium. Some of these effects can cause the transition range to shift by one or more pH units. Indicator color as a function of pH (pKa=5. and on the sensitivity of the eye to the two indicator colors. Variables That Influence the Behavior of Indicators The pH interval over which a given indicator exhibits a color change is influenced by temperature.1. we take the negative logarithms of the two expressions: pH (acid color) = -log(10Ka) = pKa . [H3O+] = 10Ka. • Indeterminate error that originates from the limited ability of the human eye to distinguish reproducibly the intermediate color of the indicator. [H3O+] = 0.  HIn.1Ka) = pKa + 1 Indicator pH range = pKa ± 1  An indicator with an acid dissociation constant of 1x10-5 (pKa=5) typically shows a complete color change the pH of the solution in which it is dissolved changes from 4 to 6. 35 Titration Errors with Acid/Base Indicators There are two types of titration error in acid/base titrations: • Determinate error that occurs when the pH at which the indicator changes color differs from the pH at the equivalence point.

The Common Acid/Base Indicators 37 Titration of strong acids and bases The hydronium ions in an aqueous solution of a strong acid have two sources: (1) the reaction of the acid with water (2) the dissociation of water itself. such as sodium hydroxide: [OH-] = cNAOH + [H3O+] ≈ cNAOH 38 . For a solution of HCl with a concentration greater than about 10-6 M: [H3O+] = cHCL + [OH-] ≈ cHCL where [OH-] represents the contribution of hydronium ions from the dissociation of water. For a solution of a strong base.

and the hydroxide ion concentration is assumed to be equal to or a multiple of the analytical concentration.  Postequivalence: the analytical concentration of the excess base is computed.Titrating a Strong Acid with a Strong Base Three types of calculations must be done to construct the hypothetical curve for titrating a solution of a strong acid with a strong base.  Equivalence: the hydronium ion concentration can be calculated directly from the ion-product constant for water. Kw. Kw = [H3O+][OH-] -log Kw = -log [H3O+][OH-] = -log[H3O+] – log[OH-] pKw = pH + pOH 39 40 .  Preequivalence: compute the concentration of the acid from its starting concentration and the amount of base added.

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43 Titrating a Strong Base with a Strong Acid 44 . • Figure 14-3 shows that the selection of an indicator is not critical when the reagent concentration is approximately 0.1 M. • The volume differences in titrations with the three indicators shown are of the same magnitude as the uncertainties associated with reading the buret and so are negligible. • The bromocresol green (also phenolphalein) is unsuited for a titration involving the 0.The Effect of Concentration/Choosing an Indicator • The effects of reagent and analyte concentration on the neutralization titration curves for strong acids are shown in Table 14-2 and Figure 14-3. • Bromocresol blue provides a satifactory end point with a minimal systematic error in the titration of 0.001M reagent because the color change occurs over a 5-mL range well before the equivalence point. Figure 14-3 Titration curves for HCl with NaOH.001M NaOH.

00500M NaOH with 0.00 mL of 0. and the pH is calculated from the concentration of this product. 46 . 3. the solution consists of a series of buffers.Figure 14. the solution contains only a weak acid or a weak base. The pH of each buffer can be calculated from the analytical concentrations of the conjugate base or acid and the concentrations of the weak acid or base that remains. but not including. At the beginning.0500M NaOH with 0.1000M HCl. and the pH is calculated from the concentration of that solute and its dissociation constant. the solution contains only the conjugate of the weak acid or base being titrated (that is. After various increments of titrant have been added (up to. 2. the equivalence point). 45 Titration curves for weak acids • Four distinctly different types of calculations are needed to compute values for a weak acid (or a weak base) titration curve: 1. 4. Beyond the equivalence point. a salt).01000M HCl. At the equivalence point. Curve A: 50. the excess of strong acid or base titrant suppresses the acidic or basic character of the reaction product to such an extent that the pH is governed largely by the concentration of the excess titrant. Curve B: 50.00 mL of 0.4 Titration curves for NaOH with HCl.

47 Hydronium Ion Concentration of Solutions of Weak Acids When the weak acid HA is dissolved in water. The sum of the molar concentrations of the weak acid and its conjugate base must equal the analytical concentration of the acid cHA Thus. two equilibria produce hydronium ions: The hydronium ions produced from the first reaction suppress the dissociation of water to such an extent that the contribution of hydronium ions from the second equilibrium is negligible. we get the mass-balance equation Substituting [H3O+] for [A-] yields which rearranges to 48 .

Thus. the equilibrium-constant expression becomes Which rearranges to The positive solution to this quadratic equation is Assume: dissociation does not appreciably decrease the molar conc. of HA This can be simplified and expressed as 49 50 .

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 At the half-titration point in a weak-base titration.  At the half-titration point in a weak-acid titration. often called the half-titration points. and pOH = pKb (recall Kb=Kw/Ka) Figure 14-5 Curve for the titration of acetic acid with sodium hydroxide.53  The analytical concentrations of acid and conjugate base are identical when an acid has been half neutralized.1000M acid with 0. 54 . Curve A: 0. the buffer capacities of each of the solutions are at a maximum at this point.00100M acid with 0. [OH-] = Kb. Curve B: 0. the hydroxide ion concentration is numerically equal to the dissociation constant of the base at the midpoint in the titration curve. [H3O+] = Ka and pH = pKa  In the titration of a weak base.1000M base. These points.01000M base.  In addition.

• The pH change in the equivalencepoint region becomes smaller as the acid becomes weaker. the pH values differ only slightly because of the buffering action of the acetic acid/sodium acetate system that is present in this region.1000M strong base.1000 M solutions of acids with different dissociation constants are shown. however. 55 Titration curves for weak bases 56 .The Effect of Concentration • • The initial pH values are higher and the equivalence-point pH is lower for the more dilute solution (Curve B).1000M weak acid with 0. Each curve represents the titration of 50. Choosing an Indicator • The choice of indicator is more limited in the cases of Figures 14-5 and 14-6. The Effect of Reaction Completeness • Titration curves for 0.00 mL of 0. Figure 14-6 The effect of acid strength (dissociation constant) on titration curves. At intermediate titrant volumes.

1000M HCl.1000M base with 0. The curves show that indicators with mostly acidic transition ranges must be used for weak bases. 58 . Figure 14-7 Hypothetical titration curves for a series of weak bases of different strengths.57 The effect of base strength (Kb) on titration curves Each curve represents the titration of 50.00 mL of 0.

(α1) during the titration of 50.00 mL of 0. the fraction dissociated Alpha values are unitless ratios whose sum must equal unity. The straight lines show the change in relative amounts of HOAc (α0) and OAc. If cT is the sum of the analytical concentrations of acetic acid and sodium acetate in a typical buffer solution. Figure 14-8 Plots of relative amounts of acetic acid and acetate ion during a titration. These relative concentrations are called alpha values. 59 The Composition of Buffer Solutions as a Function of pH: Alpha Values The composition of buffer solutions can be visualized by plotting the relative equilibrium concentrations of the two components of a conjugate acid/base as a function of the pH of the solution. we can write: α0 the fraction of the total concentration of acid that is undissociated α1.The composition of solutions during acid/base titrations The changes in composition that occur while a solution of a weak acid or a weak base is being titrated can be visualized by plotting the relative equilibrium concentration α0 of the weak acid as well as the relative equilibrium concentration of the conjugate base α1 as functions of the pH of the solution. .1000 M acetic acid. The curved line is the titration curve for the system. These values depend only on [H3O+] and Ka.

1000 M weak acid with 0. Locating Titration End point from pH Measurements Figure 14F-4 (a) the titration curve of 50.5 occurs when pH = pKHOAc = 4. The crossover point where α0 = α1 = 0.74. Similarly.The re-arranged equation becomes [HOAc]/cT = α0 Thus.00 mL of 0. Figure 9-5 Variation in α with pH. (b) The second derivative is shown on expanded scale. Note that most of the transition between α0 and α1 occurs within ±1 pH unit of the crossover point of the two curves. 62 .1000 M NaOH is shown as collected by a pH meter.