Contributed by: 
            
            
            
            
              
                
                  The highlights are:
1. Arrhenius Definition 
2. Bronsted-Lowry Definitions 
3. What happens when an acid dissolves in water?
4. Conjugate acid and bases 
5. Acid and base strength 
6. Autoionization of water 
7. pH and pOH 
8. Organic lesson 
9. Titrations 
10. Lewis acids and bases 
                
                
             
          
  
       
        
            
            
            
            
              
                2. 
                            Arrhenius Definition
   Acids are substances that produce
    hydrogen ions when dissolved in water.
    HCl → H+ + Cl-
   Bases are substances that produce
    hydroxide ions when dissolved in water.
    NaOH → Na+ + OH-
   Problem: NH3 (ammonia) when dissolved in water
    forms NH4OH, a weak base, but NH3 could not be an
    Arrhenius base based on traditional definition because
    NH3 does not have a hydroxide to donate.
              
             
            
            
            
              
                3. 
                    Brønsted-Lowry Definitions
A Brønsted–Lowry acid…
       …must have a removable (acidic)
                              proton.
A Brønsted–Lowry base…
      …must have a pair of nonbonding
                             electrons.
              
             
            
            
            
              
                4. 
                  Brønsted-Lowry Definitions
According to this theory, an acid is a
proton (hydrogen ion, H+) donor
and a base is a proton (hydrogen
ion, H+) acceptor.
…Consider introducing HCl(g) into
                                         EOS
              
             
            
            
            
              
                5. 
                What Happens When an Acid
   Dissolves in Water?
             Water acts as a
              Brønsted–Lowry base
              and extracts a proton
              (H+) from the acid,
              becoming a proton
              acceptor.
             As a result, the
              conjugate base of the
              acid and a hydronium
              ion (H3O+) are formed.
              
             
            
            
            
              
                6. 
                   NH3 works under this definition as a
    base. Let’s see how.
Notice that water now behaves as an
              
             
            
            
            
              
                7. 
                If it can be either an acid or base…
               ...it is amphiprotic
                      (amphoteric).
               HCO3−
               HSO4−
                H2O
              
             
            
            
            
              
                8. 
                       Conjugate Acids and Bases:
    From the Latin word conjugare, meaning “to
     join together.”
    Reactions between acids and bases always
     yield their conjugate bases and acids.
Conjugate acid and
base pairs are related
by a hydrogen ion on
either side of the
 If the reaction proceeds in the forward direction, then HNO2 acts as
 an acid by donating a hydrogen ion (proton). However, if the
 reaction were to then go backwards, then NO2-1 would act as a
 base by accepting a hydrogen ion (proton)
              
             
            
            
            
              
                9. 
                The conjugate acid of a base is the base
PLUS the attached proton and the
conjugate base of an acid is the acid
MINUS the proton
              
             
            
            
            
              
                10. 
                   Identify the acid, base, conjugate
    acid, conjugate base and pairs
   HCN + NH3  CN- +NH4+
       Acid – HCN
       Base – NH3
       Conjugate Base - CN-
       Conjugate Acid - NH4+
              
             
            
            
            
              
                11. 
                            Acid and Base Strength
   A strong acid/base undergoes complete
    ionization
       Reaction goes to completion
       Full dissociation. Equilibrium lies
        completely to the product side
       LARGE value of Kc
         Ex: HCl(aq)   H3O+(aq) +      Cl-(aq)
         Ex: NaOH                Na+(aq) +   OH-(aq)
                     (aq)  
   The conjugate base/acid therefore is
    extremely weak
       Ex: Cl- has VERY poor ability to attract
        protons to itself
              
             
            
            
            
              
                12. 
                Acid and Base Strength
            Weak acids/bases have
             very little ionization.
                Very little (partial)
                 dissociation in water
                Equilibria lies mostly to
                 the LEFT. SMALL value
                 of Kc
                Their conjugate
                 bases/acidss are weak to
                 exceedingly strong
            As acid/base strength
             decreases, the
             conjugate base/acid
             strength increases
              
             
            
            
            
              
                13. 
                    Acid and Base Strength
                     Substances with
                      negligible acidity do
                      not dissociate in
                      water.
                         Their conjugate bases
                          are exceedingly
                          strong.
CH4 + H2O   CH3- + H3O+
CH3- is a VERY strong base due to its
                           +
              
             
            
            
            
              
                14. 
                    Acid and Base Strength
In any acid-base reaction, the
equilibrium will favor the reaction
that moves the proton to the
stronger base.
  HCl(aq) + H2O(l)  H3O+(aq) + Cl−(aq)
H2O is a much stronger base than Cl−, so
the equilibrium lies so far to the right K is
not measured (K>>1).
ASSUMPTION: 100% dissociation. [H+] or
[H3O+] = [ACID given] ** important when
calculating pH
              
             
            
            
            
              
                15. 
                       Acid and Base Strength
HC2H3O2(aq) + H2O(l)            H3O+(aq) + C2H3O2−(aq)
   Acetate ion is a stronger base than H2O,
   Predict K>>>1 K>1 K<1 K<<<1
   equilibrium favors the left side (K<<<1).
              
             
            
            
            
              
                16. 
                    Consider the four diagrams where in each
     case, HA is an acid, H+ is a hydrogen ion,
     A- is an anion, and water molecules
   HA H+
   A- H2O
1. Which diagram represents a relatively concentrated weak acid?
   Explain
2. Which diagram represents a relatively concentrated strong acid?
   Explain
3. Assign relative strengths and concentrations to the two remaining
              
             
            
            
            
              
                17. 
                   Carefully note that the concentration of
    H+ and OH- are dependent upon TWO,
    separate factors.
       Strength of acid or base, i.e, degree of
        dissociation/ionization
       Amount of water present, i.e.
        concentration of sample solution
   It is possible to have a dilute, strong
    acid and a weak, concentrated acid
    with the SAME hydronium ion
    concentration
       Therefore, the same pH value
              
             
            
            
            
              
                18. 
                  Examples of Acids and Bases
Weak Acids     Organic (carboxylic)
               acids, such as
               butanoic, propanoic,
               ethanoic and
               methanoic
Strong Acids   HCl, HBr, HI, HClO4,
               HNO3, H2SO4
Weak Bases     Ammonia, and organic
               bases such as amines
               and pyridines
Strong Bases   Group 1 and Group 2
               hydroxides
              
             
            
            
            
              
                19. 
                         Autoionization of Water
   As we have seen, water is
    amphoteric.
   In pure water, a few molecules act as
    bases and a few act as acids.
    H2O(l) + H2O(l)       H3O+(aq) + OH−(aq)
   This is referred to as autoionization.
              
             
            
            
            
              
                20. 
                     pH (power of Hydrogen)
   Many of the concentration measurements
    in acid-base problems are given to us in
    terms of pH (power of H+) and pOH (power
    of OH-).
        p (anything) = -log (anything)
                   pH = -log [H+]
                pOH = -log [OH-]
                  pKa = -log Ka
              
             
            
            
            
              
                21. 
                              pH (power of H)
   pH scale is used to indicate the
    strength of an acid or base
    SAMPLE.
   Traditional range 0-14
       Negative pH is possible
       0- <7 Acidic
       7> - 14 Basic
       7 Neutral
              
             
            
            
            
              
                22. 
                   Recall: For a strong acid/base, ionization is
    considered to be 100%. Therefore
       H+ or OH- concentration can be determined directly
        from the stoichiometric ratio in the balanced
        equation and the concentration of acid or base.
       Ex: HNO3 is a strong acid. If 0.10 M HNO3
        dissociates, [H+] is ALSO 0.10 M
           HNO3     H+ + NO3-
          0.10 M 0.10 M        0.10M
   Calculate pH of above sample
       pH = -log[H+]
       pH = -log [0.10]
       pH = 1.00
              
             
            
            
            
              
                23. 
                                   pH
   pH= -log[H+]
   Used because [H+] is usually very
    small
   As pH decreases, [H+] increases
    exponentially
              
             
            
            
            
              
                24. 
                                       Practice
   Calculate pH of each of the following
    solutions
       0.0030 M HCl
       0.030 M HCl
       0.30 M HCl
       3.0 M HCl
   Carefully note that since pH is based on a
    log scale, there is a 10 fold change in
    concentration associated with a pH change
    of 1 unit (EXPONENTIAL)
              
             
            
            
            
              
                25. 
                               pH – cont.
    pH of 3 = 10 times more
     concentrated than pH of ???, and ???
     times more concentrated than pH of
     5
    pH of 3 = 10 times more
    concentrated than pH of 4, and 100
    times more concentrated than pH of
    5
              
             
            
            
            
              
                26. 
                   Determining [conc] from
                pH/pOH
pH is a measure of the pOH is a measure of the
strength of an acid strength of a base
sample;                sample;
low pH = stronger acid low pOH = stronger
 pH = –log[H3O+] and   base
                        pOH = –log[OH–]
 [H3O+] = 10(–pH)      (also means HIGH   pH
                        and [OH ] = 10
                               –      (–pOH)
                                         EOS
              
             
            
            
            
              
                27. 
                   Practice: Predict the following from
    highest to lowest [H+]. Then
    determine [H+] if pH is
    1.58
    9.5
    14
    -0.87
    4.2
              
             
            
            
            
              
                28. 
                   Additionally, at 298 K,
           14 = pH + pOH
       Therefore, ALL values (pH, pOH, OH- or
        H+ ) can be determined based on ANY
        one known value
              
             
            
            
            
              
                29. 
                                Practice
   Calculate the pH of a 0.010 M
    solution of Lithium hydroxide
   Calculate the hydrogen ion
    concentration in a solution with a pH
    of 4.32
   Calculate the pH of a solution made
    by dissolving 2.00g KOH in water to a
    total volume of 250. mL
              
             
            
            
            
              
                30. 
                          pH of weak acids
•What is the definition of a weak acid?
  •Incomplete dissociation
•What does the pH and/or strength of sample
depend on?
  • amount of acid dissociated [H+] AND
  amount of water present.
   Weak acids do not completely
    dissociate in water.
   Equilibrate!!
   Problems solved similar to
    equilibrium problems.
              
             
            
            
            
              
                31. 
                      HA(aq)   + H2O(l)      H3O+(aq)   +   A-(aq)
               
 I      X                             0           0
 C      -x                           +x           +x
 E    X-x                           0+x        0+x
• We do NOT know how much acid actually
   •Therefore, CANNOT use pH = - log [H+] because
   CANNOT assume the [H+] = [acid].
•Carefully note that since ionization is minimal, value
of x (dissociation) is small.
   •Considered NEGLIGIBLE in terms of (X – x)
              
             
            
            
            
              
                32. 
                •   Additionally
     • [H+] = [A-]
     • H2O (pure liquid) does not appear in Ka (Acid
       dissociation constant) expression
•   Therefore, the following Ka expression can be
    derived
                   [H+][A-]                  [H  ]
                                                + 2
                                       Ka =
                    [HA]                     [HA]
    Ka =     OR
                                     Mathematically
   And                              equal. MUST NOT
      pKa = -log Ka                  use as the
                                     EQUATION on ap
                                     frq. SHOW the
                                     ACTUAL equation.
              
             
            
            
            
              
                33. 
                             Practice Problems
   If ethanoic acid has a pKa 0f 4.74, what is its Ka?
   If propanoic acid has a Ka of 1.38 X 10-5, what is
    it’s pKa?
   Which is a stronger acid, propanoic or
    ethanoic?
   What is the pH of a 1.00 M solution of ethanoic
    acid?
   Calculate the Ka value of a 0.100 M solution of a
    weak acid with a [H+] of 1.75 X 10-3 M
   Calculate the Ka of a solution of 0.250 M of a
    weak acid with a pH of 5.11
              
             
            
            
            
              
                34. 
                                 ORGANIC LESSON
   Carboxylic acid (organic acid)
       General makeup
         R-COOH
         Example: ethanoic
                Ethane (C2H6): remove methyl (CH3) and add –COOH
                Formula: CH3COOH
           Example: propanoic
                propane: (C3H8): remove methyl (CH3) and add –
                 COOH
                Formula: C2H5COOH
           Determine formula for methanoic and butanoic
            acids. Draw Structure.
              
             
            
            
            
              
                35. 
                   Strength of carboxylic acid depends upon the
    stability of the anion (called: ___oate) formed
    when labile (mobile) proton is lost.
       All carboxylic acids that dissociates, give the following
        equilibrium, where R (hydrocarbon chain) can vary
            RCOOH  RCOO-              +     H+
          Anions may form, releasing H+ to form acidic solution
               Stability of anion depends on size of R group.
                   Smaller R group = FEWER electrons “pumped” to COO-
                    anion = HIGHER the stability of anion = STRONGER acid
                    = LARGER Ka = SMALLER pKa
               Explain in terms of polarity:
                   Higher polarity of a smaller particle (methanoate) will
                    cause greater attraction to water, therefore higher
                    chance of H+ ionizing. Lower polarity of a larger non-
                    polar R group (butanoate) will have far less attraction to
                    water, therefore smaller chance of H+ ionizing.
                   RECALL: carboxylic acids up to 4 carbons are
                    soluble/acidic
              
             
            
            
            
              
                36. 
                   Carefully note: as carboxylic acid R
    group increases in size, acid strength
    decreases.
       Ka decreases, pKa increases.
              
             
            
            
            
              
                37. 
                   Other related
    molecules
       Similar effects are
        observed when
        comparing relative
        strenghts of halogen
        substituted carboxylic
        acids.
         As the number of
          chlorine atoms present
          increases, so does the
          acid strength.
         The high
          electronegativity of Cl
          atoms attract electron
          density away from
          COO-
              
             
            
            
            
              
                38. 
                   High Halogen Electronegativity = high Ka =
    Stronger Acid = Low pKa
   Why?
       Greater attraction for electrons, so flourine pulls
        electrons away from the COO-, allowing easier
        removal of H+
              
             
            
            
            
              
                39. 
                Kb: Equilibrium Constant for Weak Bases
   Similar to weak acid equilibria, weak base
    ionization is incomplete
       Cannot directly determine amount of base
        dissociated based on Molarity of solution
       Cannot use pOH = -log [Base]
           Must determine and use ACTUAL [OH-]
   Same assumptions as weak acid equilibria
    calculations
       Assume x (dissociated ion) is negligible relative to
        X (base molarity)
       Assume [cation] = [OH-]
              
             
            
            
            
              
                40. 
                  NH3 + H2O  NH4+ + OH-
 Kb =  [OH -
             ][NH 4
                   +
                    ]
            [NH3]
                        DO NOT USE ON AP FRQ.
Often written as        Use ACTUAL Kb expression.
                        CLEARLY SPECIFY that you
 Kb =     [OH-]2        are ASSUMING [OH-] =
                        [Cation]
          [NH3]         CLEARLY SPECIFY that you
                        are ASSUMING [OH-] to be
And                     negligible, therefore using
                        [Base] as given
 pKb = -log Kb
              
             
            
            
            
            
            
            
              
                42. 
                         Autoionization of Water
   Although pure water is essentially
    covalent, a small amount of self-
    ionization occurs
   Water autoionizes, by donating a
    proton to another water molecule:
         H2O + H2O  H3O+ + OH-
                        or
                 H2O  H+ + OH-
   No individual ion remains ionized for long
   At 298 K, only about 2 out of every 109
    molecules are ionized at any given
    moment
              
             
            
            
            
              
                43. 
                         Autoionization of Water
   Equilibrium constant, Kw, written as
                Kw = [H+][OH-]
   At 298 K, Kw = 1.0 X 10-14
   Since [H+] = [OH-], therefore
       1.0 X 10-14 = [H+][OH-]
                        √1.0
        and [H ] = [OH ] =
              +        -       X 10-14
                                        = 1.0 X 10-7
        M
       Therefore, pH = -log [1.0 X 10-7 M] = 7
              
             
            
            
            
              
                44. 
                   Determine pKw
       pKw   = -log Kw
              = -log [1.0 X 10-14]
              = 14
   Since we know that
       Kw = [H+][OH-]                therefore
       K w = K a · Kb                therefore
       pKw = pKa + pKb               therefore
       14 = pH + pOH
       *** KNOW THIS
              
             
            
            
            
              
                45. 
                   Temperature dependent
       Carefully note that at temperatures
        other than 298 K, Kw value may be
        different, HOWEVER,
               [H+] = [OH-]
       pH may be different from 7
           HOWEVER, still considered NEUTRAL due to
            [H+] = [OH-] (no excess H+ or OH-)
              
             
            
            
            
              
                46. 
                       Autoionization of Water
                H2O  H+ + OH-
   Since this is specifically for the
    autoionization of water we use Kw as
    the equilibrium constant.
   At 25oC:
         Kw = [H+][OH-] = 1.0 x 10-14
   [H+] > [OH-]  acid
   [H+] < [OH-]  base
   [H+] = [OH-]  neutral
              
             
            
            
            
              
                47. 
                        Autoionization of Water
                 H2O  H+ + OH-
          Kw = [H+][OH-] = 1.0 x 10-14
   At this point it is very useful to
    remember that pH = - log [H+]
   Since Kw is a constant, if we are given
    [OH-] it is a very simple matter to
    calculate pH
   Since pH, pOH, [H+], [OH-], pKa, pKb,
    pKw and Kw are ALL related, knowing
    ANY of these values is sufficient to
    calculate ALL others.
              
             
            
            
            
              
                48. 
                                      Titrations
   Titration: experimental technique to
    perform a stoichiometrically
    balanced neutralization reaction.
       Accurately graduated glassware
        (volumetric flasks, graduated glass
        pipets and burets) is used in
        quantitative manner
           Helps determine unknown concentration of
            an acid or a base
              
             
            
            
            
              
                49. 
                Titrations             Terms to Know:
               Titrant:solution added
                        FROM the buret
                Titrate: solution that
                    titrant is added to.
                  Equivalence point:
                 100% neutralization.
                           [H+] = [OH-]
                End point: Change in
                      color of indicator
              Half Equivalence point:
                   1/2 total amount of
                         titrant added.
                  Buffer solution pH =
                                     pKa
              
             
            
            
            
              
                50. 
                                   Titrations
   As acid or base is added, there is
       Very little change in pH
       pH change of less than 1.5 units
        expected upto the point where 90% of
        acid/base is neutralized
       At equivalence point, when 100% of acid
        or base is neutralized, RAPID change in
        pH is observed
       Summarized using titration curve plots
              
             
            
            
            
              
                51. 
                            Strong acid-Strong base
                    Titration
   At equivalence point,
    pH = 7
   Carefully note: IF and
    ONLY IF concentrations
    of monoprotic acid and
    base are equal, then
    VOLUME of acid and
    base will also be equal.
   Generally, expect
    questions where
    EITHER concentration
    OR volume of acid OR     DUMB QUESTION: In the above
    base is UNKNOWN, and example, which is the titrate and which
    you are asked to solve is the titrant? How would you know if
                              labels were not given?
              
             
            
            
            
              
                52. 
                Weak acid-Strong
Base Titration
   PREDICT: How will a
    weak acid-strong
    base curve differ
    from strong acid-
    strong base curve?
       Starts at a HIGHER
        pH
       Plateaus at relatively
        HIGH basic pH      Weak acids doesn’t ionize fully. Removal
       Equivalence point  of dissociated H +
                                              due to neutralization
                           FORCES equilibrium shift towards
        ABOVE 7. Why? dissociation of acid. Reaction rate SLOWS
                           down as 100% neutralization approaches.
                           Need EXCESS base to FULLY ionize the
                           weak acid for complete neutralization
              
             
            
            
            
              
                53. 
                    Strong acid-Weak base Titration
   PREDICT: How will a
    strong acid-weak
    base curve differ
    from strong acid-
    strong base curve?
       Starts at LOW pH
       Equivalence point
        BELOW 7
       Plateaus at relatively
        LOW basic pH
              
             
            
            
            
              
                54. 
                     Weak acid-Weak base Titration
   Starts at relatively
    HIGH acid pH
   Plateaus at relatively
    LOW basic pH
   No sharp change in pH
    at equivalence point
   Equivalence point likely
     at pH = 7
       May be variable based
        on relative strength of
        acid and base.
              
             
            
            
            
              
                55. 
                         Polyprotic acid neutralization
   Multiple
    equivalence
    points
       Recall: Acid
        strength
        decreases with
        EACH hydrogen
        ion removal
       H3PO4 > H2PO4-1
        > HPO4-2
              
             
            
            
            
              
                56. 
                                       Indicators
   Most acids and bases form colorless
    solutions
       Driving force of neutralization reaction
        (formation of water) does not produce an
        observable change.
       Need a method of determining when
        equivalence point has been reached.
   Indicator: chemical that changes color at
    various pH’s
       Often weak acids, where ionized and unionized
        form have different colors.
       Ideal indicators change color over a small, given
              
             
            
            
            
              
                57. 
                                                    Indicators
   Choose an indicator that changes color at a pH value as close to the
    equivalence point as possible
       End point should correspond closely to equivalence point.
•   Suitable Indicators:
     • Strong acid-Strong base most
     • Weak Acid-Strong base phenolphthalein
     • Strong acid-Weak base   methyl orange
     • Weak acid-Weak base     none due to lack of
        sharp change in pH (use
        pH meter)
    
              
             
            
            
            
              
                58. 
                                 Buffer Solutions
   A buffer solution is one that resists
    changes in pH, when either a small
    amount of acid or base is added to it.
   General composition
       Weak acid and one of its salts (i.e. its
        conjugate base)
       Weak base and one of its salts (i.e its
        conjugate acid)
       Example: ethanoic acid and sodium
        ethanoate
              
             
            
            
            
              
                59. 
                   Ethanoic acid acts as the acid in the
    buffer solution. Absorbs base
     CH3COOH + OH-  CH3COO- + H2O
   Ethanoate ion acts as the base.
    Absorbs acid
     CH3COO- + H3O+  CH3COOH + H2O
   Process of “mopping up” of added
    acids and bases allows pH to remain
    relatively unchanged.
              
             
            
            
            
              
                60. 
                               Capacity of buffers
   Capacity defined as the ability to
    continue reacting as extra acid/base
    is added. Depends upon
       Concentration of components
           Higher the concentration, the more acid or
            base it can absorb, the higher its capacity
              
             
            
            
            
              
                61. 
                                   pH of Buffers
   pH of buffer is determined by the
       pKa or pKb of the weak acid or base, and
       Ratio of concentrations of each component
   To calculate pH of buffer solution, use
    Henderson-Hasselbach equation
     pH = pKafor    [salt]
              + acidic  buffer
                   [acid]
     log
pOH = pKfor+basic [salt]
                  buffer
         b
                 [base]
              
             
            
            
            
              
                62. 
                   Carefully note a crucial application of buffer
    solutions (expect ** AP ** question)
       Weak acid-strong base or weak base-strong acid
        titrations produce a buffer region on the graph
         Gradual  addition of Strong base to weak
          acid results in
            Some weak acid neutralization =
                                                 BU
            Production of the salt of weak acid   FF
                                             S       ER
            Production of water              OL
                                                 U
                                                TIO
                                                   N
              
             
            
            
            
            
            
            
              
                64. 
                   When 1/2 the acid is neutralized, what
    is the ratio of acid to salt?
       1:1
   Plugging into Henderson-Hasselbach,
    we get log (1) = 0
       Therefore when acid to salt ratio 1:1, then
        pH = pKa
           True at ½ equivalence point
              
             
            
            
            
              
                65. 
                                 Practice
   Ethanoic acid has a pKa of 4.75. Find
    the pH of the solution that results
    from the addition of 40.0 mL of 0.040
    M NaOH to 50.0 mL of 0.075 M
    ethanoic acid
   Methanoic acid has a Ka = 1.60 X 10-
    4. Calculate the pH of the final
    solution when 23.90 mL of 0.100 M
    sodium h
              
             
            
            
            
              
                66. 
                    Acid dissociation constant = Ka
       Acid dissociation constant is the
        equilibrium constant for an acid.
       HA(aq) + H2O(l)     H3O+(aq) + A-(aq)
       Ka = [H3O+][A-]
               [HA]
       H3O+ is often written H+ , ignore the
        water in equation.
              
             
            
            
            
              
                67. 
                    Acid dissociation constant Ka
   HA(aq)     H+(aq) + A-(aq)
   Ka = [H+][A-]        [HA]
   We can write the expression for any
    acid.
   Strong acids dissociate completely.
   Equilibrium far to right.
   Conjugate base is weak.
              
             
            
            
            
              
                68. 
                   Write the acid dissociation/ionization
    reaction and its Ka (omit water)
   HC2H3O2 for Acetic Acid
              
             
            
            
            
              
                69. 
                Kb = Base dissociation constant
   B(aq) + H2O(l)  BH+(aq) + OH-(aq)
   Kb =[BH+][OH-]
            [B]
              
             
            
            
            
              
                70. 
                               Strong Acids
   Equilibrium lies far to the right
   Almost 100% dissociation
       HA  H+ + A-
       1%       99%
   Gives a weak conjugate base
    (weaker than water)
   Large Ka
              
             
            
            
            
              
                71. 
                                Weak acids
   Equilibrium lies to the left
   Very little H+
    HA  H+ + A-
    99% 1%
   Strong conjugate base (stronger than
    water)
   Small Ka
              
             
            
            
            
              
                72. 
                                  Back to Pairs
   Strong acids             Weak acids
   Ka is large              Ka is small
   [H+] is >>> to [HA]      [H+] <<< [HA]
   A- is a weaker base      A- is a stronger
    than water                base than water
              
             
            
            
            
              
                73. 
                     Weak Acids and Bases
For weak acids and bases, equations can be
written to describe equilibrium conditions
                                             EOS
              
             
            
            
            
              
                74. 
                   Acid–Base Strength (cont’d)
Ka values are used to compare the strengths
of weak acids;  K,  strength
For strong acids, water has a leveling effect; that
is, when the strong acids are dissolved in water,
they all completely ionize to the hydronium ion
                                                      EOS
              
             
            
            
            
              
                75. 
                             Strong Bases
   Large Kb
   Almost completely dissociated
   Conjugate acid is weak
   Alkali metal hydroxides NaOH, LiOH,
    KOH
   Ba(OH)2
   Ca(OH)2 or Sr(OH)2
              
             
            
            
            
              
                76. 
                            Kw, Ka, Kb, pH, Oh my!
    How does this all relate and tie
      together???
    The symbols are actually very basic:
     K is the equilibrium constant for water
       w
     K is the acid-dissociation constant
       a
       Kb is the base-dissociation constant
       pH (power of hydrogen) is the –log of
        the concentration of hydrogen
              
             
            
            
            
              
                77. 
                         Kw, Ka, Kb, Oh my!
Given an acid reaction:
      HA(aq) + H2O(l)  H+(aq) + A-(aq)
Ka = [H+] [A-]
      [HA]
Given a base reaction:
      B(aq) + H2O(l)  HB+(aq) + OH-(aq)
Kb = [HB+] [OH-]
         [B]
              
             
            
            
            
              
                78. 
                         Kw, Ka, Kb, Oh my!
Here we have a conjugate acid-base pair:
         NH4+(aq)  NH3 (aq) + H+ (aq)
     NH3(aq) + H2O(l)  NH4+ (aq) + OH- (aq)
Ka = [NH3] [H+]
    [NH4+]
Kb = [NH4+] [OH-]
      [NH3]
              
             
            
            
            
              
                79. 
                          Mathematical Approach
   We can add the two equations together:
           NH4+(aq)  NH3 (aq) + H+ (aq)
       NH3(aq) + H2O(l)  NH4+ (aq) + OH- (aq)
NH3(aq) + H2O(l) + NH4+(aq)  NH3 (aq) + H+(aq) + NH4+(aq) + OH- (aq)
   Cancel out the duplicate terms on
    opposite sides of the arrows…
NH3(aq) + H2O(l) + NH4+(aq)  NH3 (aq) + H+(aq) + NH4+(aq) + OH- (aq)
   You are now left with:
                H2O  H+ + OH-
              
             
            
            
            
              
                80. 
                       Mathematical Approach
 If we try to multiply Ka and Kb. this is
  what we get:
  Ka             x       Kb
[NH3] [H+] x         [NH4+] [OH-] =
  [NH4+]            [NH3]
 Ka x Kb = [H+] x [OH-]
 Ka x Kb = 1.0 x 10-14 = Kw
              
             
            
            
            
              
                81. 
                             Watch This!
    [H3O+] [OH−] = Kw = 1.0  10−14,
we know that
 −log [H3O+] + −log [OH−] = −log Kw =
                 14.00
or, in other words,
         pH + pOH = pKw = 14.00
              
             
            
            
            
              
                82. 
                    Mathematical Approach
   KW = [H+][OH-] = 1.0 x 10-14
           Ka × Kb = Kw
In many books you will find a table
  for Ka they rarely are given for Kb
 since it is such an easy calculation
              
             
            
            
            
              
                83. 
                           Relationships
 Kw = [H+][OH-]
 -log K = -log([H+][OH-])
        w
 -log K = -log[H+]+ -log[OH-]
        w
 pK = pH + pOH
      w
 K = 1.0 x10-14
    w
 14.00 = pH + pOH
 Given any one of these we can find the
  other three:
[H+], [OH-], pH and pOH
              
             
            
            
            
              
                84. 
                                   Lewis Acids
   Lewis acids are defined as electron-pair acceptors.
   Includes cations and incomplete octets.
   Atoms with an empty valence orbital can be Lewis
    acids.
              
             
            
            
            
              
                85. 
                                   Lewis Bases
   Lewis bases are defined as electron-pair donors.
   Should have a lone pair of electrons.
   Anything that could be a Brønsted–Lowry base is a
    Lewis base.
   Lewis bases can interact with things other than
    protons, however.
              
             
            
            
            
              
                86. 
                          Lewis Acids and Bases
   Boron triflouride wants more
    electrons, because it has an
    incomplete octet.
F                           F           H
                    H
      B    F   :N   H   F       B   N   H
F                   H       F           H
              
             
            
            
            
              
                87. 
                           pH of strong acids
   Finding the pH of strong acids is easy
    since there is almost complete
    dissociation
   Common strong acids include:
      HCl, HBr, HI, HNO3, H2SO4, HClO4
ASSUMPTION: [H+] = [acid given]
              
             
            
            
            
              
                88. 
                                    Example
   ASSUMPTION: [H+] = [acid given]
   HCl (aq) + H2O(l)        H3O+(aq) + Cl-
    (aq)
    0.0004% at                99.996% at
    equilibrium
    equilibrium
              
             
            
            
            
              
                89. 
                                      Example
   Determine the pH of a 0.5 M HBr solution
       First,write the equilibrium reaction
       For strong acids, we assume 100%
        dissociation, therefore
        [H+] = [HBr] =         0.5 M
       Determine pH
         pH = - log [H+]
         pH = - log [0.5]
         pH = 0.3