Monoprotic Acid-Base Equilibria: Review of Fundamentals

Monoprotic Acid-Base Equilibria
Review of Fundamentals
1.) Acids and Bases are essential to virtually every application of chemistry
 Analytical procedures such as chromatography and electrophoresis
 Protein purification, chemical reactions, environmental issues
Forest Destruction
Pollutants Contribute to Acid Rain
Urban Stone Decay
Yellowstone Air Pollution (same view)

Monoprotic Acid-Base Equilibria Protein activity is
pH dependent
2.) Knowledge of Acid-Base Equilibrium is Necessary to

Understand:
 Buffer preparation and pH control
 Acid-Base Titrations
 Complexation, etc.
 Illustration:
Protein function and stability depends on pH, temperature and other conditions.
- Blood and milk have high protein concentrations
- Common problem in mechanical heart valve is clot formation
- Protein precipitation from milk provides a cheap and easy mimic of blood clotting for testing new
heart valves  avoids expensive and long animal studies
Blood clot formation Milk precipitation on

on heart valve heart valve
3.) Strong Acids and Bases

 Completely dissociates
 [H3O+] or [OH-] equals concentration of strong acid or base

- What is the pH of a 0.1M solution of HCl?
[H ]  [HCl]  0.1M

pH  log[H ]  log(0.1M)  1.00
- What is the pH of a 0.1M solution of KOH?
[OH- ]  [KOH]  0.1M
  Kw 1 10 -14
-
K w  [H ][OH ]  1 10 -14
 [H ]    1.0  10 13 M
[OH ] 0.10
pH  log[H ]  log(1.0  1013 M)  13.00

 pH at other concentrations of a strong base
[OH-] (M) [H+] (M) pH

Acid Ka
1x10-1 1x10-13 13.0
HCl 103.9
1x10 -2
1x10 -12
12.0
HBr 105.8
1x10 -3
1x10 -11
11
HI 1010.4
1x10-4 1x10-10 10
HNO3 101.4
1x10-5 1x10-9 9
 Relationship between pH and pOH:
pH  pOH  log K w  14.00 at 25o C


 Dilemma:
What is the pH of 1.0x10-8 M KOH?
[OH- ]  [KOH]  1.0  10 -8 M
 Kw 1 10 -14 6
[H ]    1.0  10 M
[OH ] 1.0  10 -8
pH  log[H ]  log(1.0  10  6 M)  6.00
How can a base
produce an
acidic solution?
 Wrong Assumption!!
[OH- ]  [KOH]  1.0  10 -8 M


 Wrong Assumption!!
For large concentration of acid or base,
[H+] = [acid] or [OH-] = [base]

For small concentration, must account for water dissociation
In pure water [OH-] = 1.0x10-7M, which is greater than [KOH] = 1x10-8M
Must Use Systematic Treatment of Equilibrium


 Systematic Treatment of Equilibrium
Step 1: Pertinent reactions:

Kw
Completely dissociates,
not pertinent
Step 2: Charge Balance:
[K  ]  [H  ]  [OH - ]
Step 3: Mass Balance:
[K  ]  [1.0  10 8 ] All K+ comes from KOH


Step 4: Equilibrium constant expression (one for each reaction):
Kw  [H  ][OH  ]  1.0  10 14
Step 5: Count equations and unknowns:

Three equations:   -
(1) [K ]  [H ]  [OH ]
 8
(2) [K ]  [1.0  10 ]
(3) Kw  [H  ][OH  ]  1.0  10 14

Three unknowns:
[K  ], [H  ], [OH - ]

Step 6: Solve (Seeking pH [H+]):
Set [H+] =x, and substitute mass balance equation into charge balance equation:
[K  ]  [1.0  10 8 ]
From mass
balance
[OH - ]  [K  ]  [H  ]  1.0  10 -8  x
Substitute OH- equation into equilibrium equation:
[OH - ]  1.0  10 -8  x Kw  [H  ][OH  ]  1.0  10 14
( x )(1.0  10 -8  x )  1.0  10 14


Step 6: Solve (Seeking pH [H+]):
Solve the quadratic equation:

x 2  (1.0  10 8 ) x  1.0  10 14  0
Use quadratic equation
 1.0  10  8  (1.0  10  8 )2  4 (1)( -1.0  10 -14 )

x
2 (1)
x  9.6  10  8 M or  1.1  10 7 M
Negative number is
physically meaningless
[H  ]  9 .6  10 -8 M pH slightly basic,
pH   log [H  ]   log (9 .6  10 -8 )  7 .02 consistent with low [KOH]

 Three Regions depending on acid/base concentrations
intermediate concentrations, (10-

6
-10-8M), H2O ionization ≈ H+,OH-
 systematic equilibrium
High concentrations (≥10-6M), calculation necessary
pH considered just from the
added H+,OH-
low concentrations (≤10-8M),

pH=7 not enough H+,OH- added
to change pH
4.) Water Almost Never Produces 10-7 M H+ and OH-

 pH=7 only true for pure water
 Any acid or base suppresses water ionization

- Follows Le Châtelier’s principal
[HBr ]  [1.0  10 4 ]  pH  4  [OH  ]  1  10 10
In 10-4 M HBr solution, water dissociation produces only 10-10 M OH- and H+
5.) Weak Acids and Bases

 Weak acid/base do not completely dissociate
 Dissociation Ka for the acid HA:
[H  ][ A  ]
Ka 
[HA]
 Base Hydrolysis constant Kb
[BH  ][OH  ]
Kb 
[B]
pK a   log( K a ) pK b   log( K b )
 pK is negative logarithm of equilibrium constant
5.) Weak Acids and Bases

 Conjugate acid-base pair – related by the gain or loss of a proton
Formic acid (pKa 3.744)

stronger acid than
benzoic acid (pKa=4.202)
Acid-base pair
- Conjugate base of a weak acid is a weak base

- Conjugate acid of a weak base is a weak acid
- Conjugate base of a strong acid is a very weak base or salt
Weak Acid Equilibria
1.) Any Effect that Increases the Stability of the Product Drives the Reaction
Forward
 Formation of internal hydrogen bond for an acid/base
Can’t form internal

hydrogen bond
Ortho isomer is stronger acid because

product forms internal hydrogen bond
2.) General Systematic Treatment of Equilibrium

 Unlike concentrated strong acid, need to account for water ionization
 Find pH for a solution of a general weak acid HA

Ka Kw

[H  ]  [OH - ]  [ A- ]
F  [HA]  [ A- ] F – formal concentration of acid

[H  ][ A  ]
Ka  Kw  [H  ][OH  ]  1.0  10 14
[HA]

Step 5: Count equations and unknowns:
 - -
Four Equations: (1) [H ]  [OH ]  [ A ] (2) F  [HA]  [ A ] - [H  ][ A  ]
(3) K a 
[HA]
  14
(4) Kw  [H ][OH ]  1.0  10
Four Unknowns: [A ], [HA], [H  ] , [OH - ]
Step 6: Solve (Not easy to solve  cubic equation results!):

- Again, need to make assumptions to simplify equations
- The goal is to determine [H+], so we can measure pH

Make Some Initial Assumptions:

 For a typical weak acid, [H+] from HA will be much greater than [H+] from H2O
 If dissociation of HA is much greater than H O, [H+] >> [OH-]
2
[H  ]  [OH - ]  [ A- ]  [H  ]  [ A- ]
Set [H+]=x:
[H  ]  x  [ A - ]  x
substitute
[HA]  F  [ A- ]  F  x


Substitute into Equilibrium Equation:
[H  ]  [ A - ]  x [HA]  F  x
[H  ][ A  ] ( x )( x )
Ka  
[HA] Fx
Rearrange:
x 2  ( K a ) x  ( F )( K a )  0
Solve quadratic equation:
 K a  K a2  4 ( 1 )( F )( K a )
x  [ x ]
2( 1 )

Step 7: Verify Assumption:

Was the approximation [H+] ≈ [A-] justified ([H+] >>[OH-])?
Setting F = 0.050 M and Ka = 1.07x10-3 for o-hydroxybenzoic acid:
 K a  K a2  4 ( 1 )( F )( K a )  1.07  10  3  ( 1.07  10  3 )2  4 ( 1 )( 0.0500 )( 1.07  10  3 )

x 
2( 1 ) 2( 1 )
x  6.8  10  3 M  [ H  ]  [ A  ]
pH   log x  2.17 [H+] >> [OH-]

6.8x10-3M >> 1.5x10-12M
Determine [OH-] from water dissociation: assumption is justified!
 Kw 1  10 14 12
[ OH ]    1 . 5  10
[H ] 6.8  10  3
3.) Fraction of Dissociation

 Fraction of acid HA in the form A-():
[A ] x x
  
[ A  ]  [HA] x  (F  x ) F
 Example:
What is the percent fraction dissociation for F = 0.050

M and Ka = 1.07x10-3 for o-hydroxybenzoic acid?
x 6.8  10 3 M
   0.14  14%
F 0.0500 M
 Percent dissociation increases with dilution

Weak Base Equilibria
1.) Treatment of Weak Base is Very Similar to Weak Acid

 Assume all OH- comes from base and not dissociation of water

Kb Kw

[H  ]  [BH  ]  [OH - ]

F  [B]  [BH  ]  [B]  F - [BH  ] F – formal concentration of base

[BH  ][OH  ] Kw  [H  ][OH  ]  1.0  10 14
Kb 
[B ]
1.) Treatment of Weak Base is Very Similar to Weak Acid

 Assume all OH- comes from base and not dissociation of water
Step 6: Solve (Assume [BH+] >> [H+]  [BH+] ≈ [OH-]):
Set [OH-]=x and substitute into Equilibrium Equation:

[BH  ]  [OH - ]  x [B ]  F  x
[BH  ][OH  ] ( x )( x ) x2
Kb   
[B] Fx Fx
Rearrange:
x 2  ( K b ) x  ( F )( K b )  0
Solve quadratic equation:
 K b  K b2  4 ( 1 )( F )( K b )
x  [ OH  ]
2( 1 )
2.) Example
What is the pH of cocaine dissolved in water? F = 0.0372 M and Kb
= 2.6x10-6 for cocaine?
Kb=2.6x10-4
0.0372-x x x
x2
 2.6  10 6  x  3.1  10  4
0.0372  x
2.) Example
What is the pH of cocaine dissolved in water? F = 0.0372 M and Kb
= 2.6x10-6 for cocaine?
Because x=[OH-], we need to solve for [H+]
Kw 14
[H ]  1.0  10 11
   3 . 2  10
[ OH ] 3.1  10  4
pH   log[ H  ]   log( 3.2  10 11 )  10.49

Consider an Illegal Drug Lab (pictured)
3.) Illustration
Criminal Investigation of the

illegal lab will require identifying:
 What drugs are present?
 How much of each drug is
present?
 What is the purity of the drugs?
pH change or titration indicator

may help identify/quantify drug.
(positive field test for cocaine)
http://www.stopmethaddiction.com/meth-lab-photos.htm
4.) Fraction of Association

 Fraction of Base B in BH+ form ():
[BH  ] x x
  
[BH  ]  [B] x  (F  x ) F
 Example:
What is the percent fraction dissociation of cocaine

reacted with water? F = 0.0372 M and Kb = 2.6x10-6
for cocaine?
x 3.1  10 4 M
   0.0083  0.83%
F 0.0372 M
Weak Acid Base Equilibria
5.) Example
A 0.0450 M solution of benzoic acid has a pH of 2.78. Calculate
pKa for this acid. What is the percent fraction dissociation?
Buffers
1.) A buffered solution resists changes in pH when acids or bases are added
 Buffer: is a mixture of a weak acid and its conjugate base
- Must be comparable amounts of acid & base
 For an organism to survive, it must control the pH of each subcellular
compartments
- Enzyme-catalyzed reactions are pH dependent
Bacteria growing in hot
springs (acidic pH)
Bacteria growing in lung

tissues (neutral pH)
Thermophilic archaea Picrophilus oshimae
and Picrophilus torridus grow at pH =0.7
(Stomach acid 1-3 pH)
Nature (London) (1995), 375(6534), 741-2.

Buffers
2.) Mixing a Weak Acid and Its Conjugated Base

 Very little reaction occurs
 Very little change in concentrations
 Example:
Consider a 0.10 M of acid with pKa of 4.00
0.10-x x x
x2
 K a  x  3.1  10  3
Fx
x 3.1  10 3 M
   0.031  3.1%
F 0.10 M
Buffers
2.) Mixing a Weak Acid and Its Conjugated Base

 Example:
Consider adding 0.10 M of conjugate base with pKb of 10.00
0.10-x x x
x2
 K b  x  3.2  10 6
Fx
x 3.2  10 6 M
   3.2  10  5
F 0.10 M
HA dissociates very little and A- reacts very little with water

Buffers
3.) Henderson-Hasselbalch Equation

 Rearranged form of Ka equilibrium equation:
[H  ][ A  ]
Ka 
[HA]
Take log of both sides:
[H  ][ A  ]  [ A ]
log K a  log  log[H ]  log
[HA] [HA]
rearrange:
 [ A ]
 log[H ]   log K a  log
[HA]
pH pKa
 [ A ] 
pH  pK a  log  
 [HA] 
 
Buffers
[A-]/[HA] pH
100:1 pKa + 2
 Determines pH of buffered solution
- Need to know ratio of conjugate [acid] and [base] 10:1 pKa + 1
 [ A ]  1:1 pKa
pH  pK a  log   1:10 pKa - 1
 [HA] 
  1:100 pKa - 2
- If [A ] = [HA], pH = pKa
-
- All equilibria must be satisfied simultaneously in any solution at equilibrium

- Only one concentration of H+ in a solution
 Similar equation for weak base and conjugate acid
 [B] 
pH  pK a  log  
 [BH  ]  pKa is for this acid
 
Buffers

 A strong acid and a weak base react “completely” to give the conjugate acid:
Weak Strong conjugate

base acid acid
 Also, a strong base and a weak acid react “completely” to give the conjugate
base:
Weak Strong conjugate

acid base base
Buffers

 Example:
Calculate how many milliters of 0.626 M KOH should be added to

5.00 g of MOBS to give a pH of 7.40?
pKa = 7.48
FW = 223.29
What is the pH if an additional 5 mL of the KOH solution is added?

Buffers
4.) Why Does a Buffer Resist Changes in pH?

 Strong acid or base is consumed by B or BH+
 Maximum capacity to resist pH change occurs at pH=pKa
 Buffer Capacity (): measure of a solutions resistance to pH change
dCb dCa
 
dpH dpH
where Ca and Cb are the number of moles of strong acid and
strong base per liter needed to produce a unit change in pH
5.) Choosing a Buffer

 Choose a buffer with pKa as close as possible to
desired pH
 Useful buffer range is pKa ± 1 pH units
 Buffer pH depends on temperature
and ionic strength  activity coefficients
When preparing a
buffer, you need to
monitor the pH.
Can not assume the

added HA and A- will
yield the desired pH.
pH dependent on:
- activity
- temperature
- ionic strength
Wide number of buffers
available that cover an
essential complete range
of pHs.
Choose a buffer with a

pKa as close as possible
to the desired pH.

Monoprotic Acid-Base Equilibria: Review of Fundamentals

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Monoprotic Acid-Base Equilibria

Yellowstone Air Pollution (same view)

2.) Knowledge of Acid-Base Equilibrium is Necessary to

Blood clot formation Milk precipitation on

3.) Strong Acids and Bases

 [H3O+] or [OH-] equals concentration of strong acid or base

[H ]  [HCl]  0.1M

- What is the pH of a 0.1M solution of KOH?

[OH- ]  [KOH]  0.1M

3.) Strong Acids and Bases

[OH-] (M) [H+] (M) pH

 Relationship between pH and pOH:

pH  pOH  log K w  14.00 at 25o C

3.) Strong Acids and Bases

[OH- ]  [KOH]  1.0  10 -8 M

3.) Strong Acids and Bases

[H+] = [acid] or [OH-] = [base]

In pure water [OH-] = 1.0x10-7M, which is greater than [KOH] = 1x10-8M

Must Use Systematic Treatment of Equilibrium

3.) Strong Acids and Bases

Step 1: Pertinent reactions:

Step 3: Mass Balance:

[K  ]  [1.0  10 8 ] All K+ comes from KOH

3.) Strong Acids and Bases

Step 4: Equilibrium constant expression (one for each reaction):

Kw  [H  ][OH  ]  1.0  10 14

Step 5: Count equations and unknowns:

(3) Kw  [H  ][OH  ]  1.0  10 14

3.) Strong Acids and Bases

Step 6: Solve (Seeking pH [H+]):

Substitute OH- equation into equilibrium equation:

[OH - ]  1.0  10 -8  x Kw  [H  ][OH  ]  1.0  10 14

( x )(1.0  10 -8  x )  1.0  10 14

3.) Strong Acids and Bases

Step 6: Solve (Seeking pH [H+]):

Solve the quadratic equation:

 1.0  10  8  (1.0  10  8 )2  4 (1)( -1.0  10 -14 )

3.) Strong Acids and Bases

intermediate concentrations, (10-

low concentrations (≤10-8M),

4.) Water Almost Never Produces 10-7 M H+ and OH-

 Any acid or base suppresses water ionization

[HBr ]  [1.0  10 4 ]  pH  4  [OH  ]  1  10 10

5.) Weak Acids and Bases

5.) Weak Acids and Bases

Formic acid (pKa 3.744)

- Conjugate base of a weak acid is a weak base

Can’t form internal

Ortho isomer is stronger acid because

2.) General Systematic Treatment of Equilibrium

Step 1: Pertinent reactions:

Step 2: Charge Balance:

Step 4: Equilibrium constant expression (one for each reaction):

2.) General Systematic Treatment of Equilibrium

Step 5: Count equations and unknowns:

Four Unknowns: [A ], [HA], [H  ] , [OH - ]

Step 6: Solve (Not easy to solve  cubic equation results!):

2.) General Systematic Treatment of Equilibrium

Step 6: Solve (Not easy to solve  cubic equation results!):

Make Some Initial Assumptions:

2.) General Systematic Treatment of Equilibrium

Step 6: Solve (Not easy to solve  cubic equation results!):