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    Chapter 15 Applications of Aqueous Equilibria 2022

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    Chapter 15 Applications of Aqueous Equilibria 2022

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    Chapter 15 Applications of Aqueous Equilibria 2022

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    iB13e

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    of 38

    Applications of Aqueous

    Equilibria

    Dr. Sulaiman Al-Isaee


    Department of Engineering
    College of Applied Sciences
    © 2018
    The common ion effect is the shift in equilibrium caused by the
    addition of a compound having an ion in common with the
    dissolved substance.
    The presence of a common ion suppresses
    the ionization of a weak acid or a weak base.

    Consider mixture of CH3COONa (strong electrolyte) and


    CH3COOH (weak acid).
    CH3COONa (s) Na+ (aq) + CH3COO- (aq)
    common
    ion
    CH3COOH (aq) H+ (aq) + CH3COO- (aq)

    NaCl CH3COOH
    KCl CH3COONa
    Acid dissociation
    Solubility pH
    A buffer solution is a solution of:
    1. A weak acid or a weak base and
    2. The salt of the weak acid or weak base
    Both must be present!

    A buffer solution has the ability to resist changes in pH upon


    the addition of small amounts of either acid or base.
    The effect of addition of acid or base to …

    acid added base added

    an unbuffered solution

    acid added base added

    or a buffered solution
    4
    How a Buffer Works: Le Chatelier’s Principle

    CH3COOH(aq) + H2O(l) CH3COO–(aq) + H3O+(aq)

    Added OH– reacts with Added H3O+ reacts with


    CH3COOH, causing a shift to CH3COO–, causing a
    the right. shift to the left.
    How a buffer works.
    Buffer has more HA after Buffer has equal Buffer has more A- after
    addition of H3O+. concentrations of A– and HA. addition of OH–.

    H3O+ OH-

    Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

    H2O + CH3COOH ← H3O+ + CH3COO- CH3COOH + OH- → CH3COO- + H2O


    Types of buffers
    Generally buffers are of two types:
    • Acidic buffers
    • Basic buffers

    Acidic Buffers:
    An acidic buffer is a combination of a weak acid and its
    salts with a strong conjugated base.
    Examples:
    CH3COOH/CH3COONa
    H2CO3/NaHCO3
    H3PO4/NaH2PO4
    Types of buffers
    Generally buffers are of two types:
    • Acidic buffers
    • Basic buffers

    Basic Buffers:
    A basic buffer is a combination of a weak base and its
    salts with a strong conjugated acid.
    Examples:
    NH4OH/NH4Cl
    NH3/(NH4)2CO3
    Which of the following are buffer systems? (a) KF/HF
    (b) KCl/HCl, (c) Na2CO3/NaHCO3

    (a) KF is a weak acid and F- is its conjugate base


    buffer solution
    (b) HCl is a strong acid
    not a buffer solution
    (c) CO32- is a weak base and HCO3- is it conjugate acid
    buffer solution
    3. A few drops of 0.10 M NaOH is added to a buffer solution at pH = 5.00.
    The new pH could be:

    A 4.98

    B. 5.02

    C. 8.05

    D. 2.11
    3. A few drops of 0.10 M NaOH is added to a buffer solution at pH = 5.00.
    The new pH could be:

    A 4.98

    B. 5.02

    C. 8.05

    D. 2.11
    Acid–Base Titrations
    • In a titration, a substance in a solution
    of known concentration is reacted with
    another substance in a solution of unknown
    concentration.
    • At this point, called the endpoint, the
    reactants are in their stoichiometric ratio.
    – The unknown solution is added slowly from an
    instrument called a burette.
    • A long glass tube with precise volume markings that allows
    small additions of solution
    • The titrant is the solution in the burette.
    Acid–Base Titrations
    • In acid–base titrations, because both the reactant
    and product solutions are colorless, a chemical is
    added that changes color when the solution
    undergoes large changes in acidity/alkalinity.
    – The chemical is called an indicator.
    • At the endpoint of an acid–base titration, the
    number of moles of H+ equals the number of moles
    of OH.
    – This is also known as the equivalence point.
    Acid–Base Titration
    Titration

    • In this titration, NaOH is added to a dilute HCl solution. When


    the NaOH and HCl reach stoichiometric proportions (the
    equivalence point), the phenolphthalein indicator changes
    color to pink.
    Strong Acid-Strong Base Titrations
    100%
    NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq) ionization!
    OH- (aq) + H+ (aq) H2O (l) No equilibrium
    Weak Acid-Strong Base Titrations
    CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
    CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
    At equivalence point (pH > 7):
    CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)
    Strong Acid-Weak Base Titrations
    HCl (aq) + NH3 (aq) NH4Cl (aq)
    H+ (aq) + NH3 (aq) NH4Cl (aq)
    At equivalence point (pH < 7):
    NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)
    Which indicator(s) would you use for a titration of HNO2
    with KOH ?

    Weak acid titrated with strong base.


    At equivalence point, will have conjugate base of weak acid.
    At equivalence point, pH > 7
    Use cresol red or phenolphthalein
    Solubility Equilibrium
    • In saturated solutions dynamic equilibrium
    exists between undissolved solids and ionic
    species in solutions
    • Solids continue to dissolve and ion-pairs
    continue to form solids.
    • The rate of dissolution process is equal to the
    rate of precipitation.
    Solubility Product Constant
    • General expression:
    • MmXn(s) ⇄ mMn+(aq) + nXm-(aq)
    • Solubility product, Ksp = [Mn+]m[Xm-]n
    Solubility and Solubility Products

    Examples:
    • AgCl(s) ⇌ Ag+(aq) + Cl-(aq)
    • Ksp = [Ag+][Cl-] = 1.6 x 10-10
    • If s is the solubility of AgCl, then:
    • [Ag+] = s and [Cl-] = s
    • Ksp = (s)(s) = s2 = 1.6 x 10-10
    • s = 1.3 x 10-5 mol/L
    Solubility and Solubility Products

    • Ag2CrO4(s) ⇌ 2Ag+(aq) + CrO42-(aq)


    • Ksp = [Ag+]2[CrO42-] = 9.0 x 10-12
    • If s is the solubility of Ag2CrO4, then:
    • [Ag+] = 2s and [CrO42-] = s
    • Ksp = (2s)2(s) = 4s3 = 9.0 x 10-12
    • s = 1.3 x 10-4 mol/L
    Factors that affect solubility
    • Temperature
    – Solubility generally increases with temperature;
    • Common ion effect
    – Common ions reduce solubility
    • pH of solution
    – pH affects the solubility of ionic compounds in which the
    anions are conjugate bases of weak acids;
    • Formation of complex ion
    – The formation of complex ion increases solubility
    Common Ion Effect

    • Consider the following solubility equilibrium:


    • AgCl(s) ⇌ Ag+(aq) + Cl-(aq); Ksp = 1.6 x 10-10;

    • The solubility of AgCl is 1.3 x 10-5 mol/L at 25oC.


    • If NaCl is added, equilibrium shifts left due to
    increase in [Cl-] and some AgCl will precipitate out.
    • For example, if [Cl-] = 1.0 x 10-2 M,
    • Solubility of AgCl = (1.6 x 10-10)/(1.0 x 10-2)
    • = 1.6 x 10-8 mol/L
    Effect of pH on Solubility
    • Consider the following equilibrium:
    Ag3PO4(s) ⇌ 3Ag+(aq) + PO43-(aq);

    • If HNO3 is added, the following reaction occurs:


    H3O+(aq) + PO43-(aq) ⇌ HPO42-(aq) + H2O
    • This reaction reduces PO43- in solution, causing more
    solid Ag3PO4 to dissolve.
    • In general, the solubility of compounds such as
    Ag3PO4, which anions are conjugate bases of weak
    acids, increases as the pH is lowered by adding nitric
    acid.
    Effect of pH on Solubility
    • Consider the following equilibrium:
    Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH-(aq);

    • Increasing the pH means increasing [OH-] and


    equilibrium will shift to the left, causing some of
    Mg(OH)2 to precipitate out.
    • If the pH is lowered, [OH-] decreases and equilibrium
    shifts to the right, causing solid Mg(OH)2 to dissolve.
    • The solubility of compounds of the type M(OH) n
    decreases as pH is increased, and increases as pH is
    decreased.
    Formation of Complex Ions on Solubility

    • Many transition metals ions have strong affinity for


    ligands to form complex ions.
    • Ligands are molecules, such as H2O, NH3 and CO, or
    anions, such as F-and CN-.
    • Complex ions are soluble – thus, the formation of
    complex ions increases solubility of slightly soluble
    ionic compounds.
    Effect of complex ion formation on solubility
    • Consider the following equilibria:
    • AgCl(s) ⇌ Ag+(aq) + Cl-(aq); Ksp = 1.6 x 10-10
    • Ag+(aq) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) ; Kf = 1.7 x 107

    • Combining the two equations yields:


    • AgCl(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl-(aq);
    • Knet = Ksp x Kf = (1.6 x 10-10) x (1.7 x 107)
    = 2.7 x 10-3
    • Knet > Ksp implies that AgCl is more soluble in
    aqueous NH3 than in water.
    Example1

    • Calculate the solubility of AgCl in water and in 1.0 M


    NH3 solution at 25oC.

    • Solutions:
    Solubility in water = (Ksp)
    = (1.6 x 10-10) = 1.3 x 10-5 mol/L
    Example1

    • Solubility of AgCl in 1.0 NH3:


    • AgCl(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl-(aq)
    
    • [Initial], M - 1.0 0.0 0.0
    • [Change] - -2S +S +S
    • [Equilm.] - (1 – 2S) S S
    

    [Ag(NH 3 ) 2 ][ Cl - ] S2
    K net    2.7 x 10 -3

    [ NH 3 ]2 (1 - 2 S ) 2
    Example1
    • Solubility of AgCl in 1.0 NH3 (continued):
    S
     2.7 x 10 -3  0.052
    (1 - 2 S )
    • S = 0.052 – 0.104S;
    • S = 0.052/1.104 = 0.047 mol/L
    • AgCl is much more soluble in NH3 solution than in
    water.
    Predicting Formation of Precipitate
    • Qsp is ion product expressed in the same way as Ksp for a
    particular system except that initial concentrations are
    used instead of equilibrium concentrations.

    • Qsp = Ksp  saturated solution, but no precipitate


    • Qsp > Ksp  saturated solution, with precipitate
    • Qsp < Ksp  unsaturated solution,
    Predicting Precipitation

    • Consider the following case:


    20.0 mL of 0.025 M Pb(NO3)2 is added to 30.0 mL of 0.10
    M NaCl. Predict if precipitate of PbCl2 will form.
    (Ksp for PbCl2 = 1.6 x 10-5)
    Predicting Precipitation

    • Calculation:
    • [Pb2+]0 = (20.0 mL x 0.025 M)/(50.0 mL) = 0.010 M
    • [Cl-]0 = (30.0 mL x 0.10 M)/(50.0 mL) = 0.060 M
    • Qsp = [Pb2+][Cl-]2 = (0.010 M)(0.060 M)2
    • = 3.6 x 10-5
    • Qsp > Ksp  precipitate of PbCl2 will form.

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