MBBS Chapter 3 and Chapter 4 Electrolyte Solutions and Buffers

HCl HC
Nonelectrolyte strong 1O4 H2S

acid: O4 HNO
Strong strong 3NaOH
electrolyte base: KOH
Solution completely salt: NaCl
ionized Monoprotic a
weak cid: HAc
Electrolyte Diprotic acid
acid
: H2CO3
Weak Triprotic acid:
electrolyte H3PO4
partially weak NH3
ionized base
Chapter 3 and Chapter
4 Electrolyte Solution
s and Buffers (11h)
Chapter 3 Electrolyte Solutions
(8h)
3.1 Strong Electrolytic Solutions (cancel)
3.2 Brønsted-Lowry Acid-Base Theory
3.3 Solving Problems Involving Acid-Base Equilibri
a (monoprotic acids or bases)
3.4 Electron-Pair Donation and the Lewis Acid-Bas
e Definition (cancel)
3.5 Equilibria of Slightly Soluble Ionic (cancel)
Chapter 4 Buffers (4h)
Key Points:
 Identify conjugate acid-base pairs
 Calculate the concentrations of the species pr
esent in a solution of a weak acid or base
 Determine the relationship between Kb for a bas
e and the Ka of its conjugate acid
 Determine the pH of a buffer solution containi
ng a weak acid and its conjugate base
 Determine how the addition of small amounts of
acids or bases changes the pH of a buffer solu
tion
 Know how to prepare a buffer of a given pH
3.2 Brønsted-Lowry Acid-Base Th
eory
1. History of the Acid-Base Concept
 In 1680, Boyle noted that acids change the
color of certain natural dyes.
 In the eighteenth century it was recognize
d that acids have a sour taste.
eory
 Lavoisier, in 1787, proposed that aci
ds are binary compounds of oxygen .
 Davy, in 1811, proposed that acids a
re compounds of hydrogen.
 Arrhenius concept, the Brønsted-Lowry
protonic concept, the Lewis theory .
eory
2. Arrhenius Concept of Acids and Bases
 Definition: Acids are substances that produc
e H3O+ and bases are substances that produce
OH － in aqueous solutions.
HC1O4(aq)+H2O(l)→H3O+(aq)+ClO4-(aq)
NaOH(s) + H2O(l)→ Na+(aq) + OH-(aq)
CH3COOH + H2O H3O+ + CH3COO-
 Reactions: This neutralization of a acid by
a base is essentially the reaction of H3O+ (a
q) with OH-(aq) and always give the water.
eory
 Advantage and Disadvantage :
 The Arrhenius definition applies to
aqueous solutions, and does not scri
be the behavior of substances in oth
er solvents or in gas-phase.
 It singles out the OH- ion as the so
urce of base character.
eory
3. Brønsted -Lowry Concept of Acids and Bases
 Definition: An acid is a proton donor ， an
d a base is a proton acceptor.
HAc H+ + Ac －
NH4+ H+ + NH3
H3PO4 H+ + H2PO4 －
H2PO4 － H+ + HPO42 －
HPO42 － H+ + PO43 －
Acid Proton + Conjugate base
eory
 Notice:
 Acids contain hydrogen and all negative ions
must be considered as bases. When a acids los
es a proton, the species formed is base. The
two species are conjugate acid-base pair. Eve
ry Brønsted -Lowry acid has a conjugate base,
and every base has a+ conjugate acid.
-H
conjugate acid conjugate base
+H+
 Write the formula of the conjugate base of an
y acid simply by removing a proton .
eory
 Acids and bases can be ions as well as
molecular substances.
 Some species that can act as either ac
ids or bases are called amphiprotic. T
he proton-containing negative ions are
amphiprotic.
 A salt may be regarded as an ionic com
pound which can act as acids or bases.
eory
 Reactions: An acid-base reaction is the t
ransfer of a proton from a proton donor
(acid) to a proton acceptor (base).
 Neutralization
HCl(g) + NH3(g) → NH4Cl(s)
 Ionization or dissociation
CH3CO2H + H2O H3O+ + CH3CO2-
NH3 + H2O NH4+ + OH-
 Hydrolysis
Ac － + H2O HAc + OH －
NH4+ + H2O NH3 + H3O+
eory
eory
 Notice:
 For a given pair of reactants, write the equation for th
e transfer of one proton from one species to the other.
(Do not transfer two protons.) A Brønsted -Lowry acid-b
ase reaction produces a conjugate acid and base.
 The direction for an acid-base reaction is from the str
onger acid and base to the weaker acid and base.
HB1 + B2 - B1- + HB2
stronger stronger weaker weaker
acid base base
acid
eory
 The strongest acids have the weakest conjug
ate bases, and the strongest bases have the
weakest conjugate acids.
 Water is amphiprotic.
 Acid-base reactions are not restricted to a
queous solution.
 Example 1 What are the conjugate bases of
(a) H2SO3 and (b) H2PO4 － ?
 Example 2 What are the conjugate acids of
(a) CN － and (b) H2PO4 － ?
eory
 Example 3 Write the equations illustrating the
following Brønsted -Lowry acid-base reactions.
(a) H2S as an acid with H2O
(b) H2PO4 － as an acid with OH －
(c) H2PO4 － as an base with H3O+
(d) CN － as an base with H2O
 Example 4 In the following equations, label eac
h species as an acid or a base. Show the conjug
ate acid-base pairs.
HCO3-+ HF H2CO3+ F-
eory
4. Relative Strengths of Acids and Bases
 The terms stronger and weaker are used her
e only in a comparative sense.
HC1(aq)+H2O(l)→H3O+(aq)+Cl-(aq)
Notice
 It is important to understand that the terms stronger
and weaker are used here only in a comparative
sense. It relates to the types of solvent system.
eory
HC1+H2O→H3O++Cl-
HC1O4+H2O→H3O++ ClO4-
H2SO4 +H2O→H3O++HSO4-
HNO3+H2O→H3O++NO3-
HNO3(aq)+H2O(l)→H3O+(aq)+NO3-(aq)
HNO3 + HAc H2Ac+ +NO3-
HC1 + HNO3 H2NO3 + + Cl -
eory
Notice
 The strength of the acid is a measure of its tendency
to liberate proton.
 When you say an acid loses its proton readily, you
can also say that its conjugate base does not hold
the proton very tightly. The stronger the acid, the
weaker is its conjugate base.
 The direction for an acid-base reaction is from the
stronger acid and base to the weaker acid and base.
eory
 Leveling effect
HCl+H2O→H3O++Cl-
HClO4+H2O→H3O++ ClO4-
H2SO4 +H2O→H3O++HSO4-
HNO3+H2O→H3O++NO3-
 This phenomenon is called the leveling effect-- the
solvent makes the strong acids appear equal, or leve
l, in acidity.
eory
 H+ (aq) (or H3O+(aq)) is the strongest acid that can
exist in aqueous solution. Any acid stronger than
H+(aq) reacts with water completely to produce H +
(aq) and the weak conjugate base.
 The conjugate base of the solvent is the strongest ba
se that can be present. In water, OH - is the strongest
base.
eory
 Differentiating Effect: How to differenti
ate among the four strong acids?
HC1+HAc H2Ac+ + Cl-
HC1O4+HAc H2Ac+ + ClO4-
H2SO4 +HAc H2Ac+ + HSO4-
HNO3+HAc H2Ac+ + NO3-
 We could choose a different solvent that is a more a
cidic. The acid strengths are in the order
HC1O4> H2SO4 > HC1> HNO3
eory
 The relative strengths of acid stronger than hydromi
um ion can be determined by studying reaction in n
onaqueous solutions, using solvent more acidic than
water.
 The relative strengths of base stronger than hydroxi
de ion can be determined by studying reaction in no
naqueous solutions, using solvent more basic than
water.
Summary of Acid-Base Definitions
 Acid: proton donor (contain hydrogen )
Base: proton acceptor ( all negative
ions ) amphiprotic: (proton-containing negative
ions )
-H+
conjugate acid conjugate base
+H+
 Reaction: The Brønsted -Lowry concept considers
an acid-base reaction as a proton-transfer reac
tion.
 Relative Strengths of Acids and Bases: The stro
ngest acids have the weakest conjugate bases. T
he conjugate acid of the solvent is the stronge
st acid that can be present.
3.4 Solving Problems Involving
Acid-Base Equilibria
1. Self-Ionization of Water
 Ionization
NH3 + H2O NH4+ + OH-
 Self-Ionization of Water
H2O(l)+ H2O(l) H3O+ (aq) + OH-(aq)
[H 3 O  ][OH  ]
Kc 
[H 2 O]2
[H2O]2 Kc =[H3O+ ][OH-]=constant= Kw
 Notice
 Kw is the ion-product constant for water.
At 25℃, the value of Kw is 1.0 × 10-14.
 Like any equilibrium constant, Kw varies wi
th temperature. UNLESS OTHERWISE INDICATED,
ALL CALCULATIONS WILL BE AT 298.15 K
 If you add an acid or a base to water, the
concentrations of H+ and OH- will no longer
be equal. The equilibrium-constant equation
Kw =[H3O+ ][OH-] will still ho1d.
In an acidic solution, [H+] > 1.0 × 10-7 M.
In a neutral solution, [H+] = 1.0 × 10-7 M.
In a basic solution, [H+] < 1.0 × 10-7 M.
 Equation indicates an inverse relationship
between
[H +] and [OH -]; if we know either the hy
drogen or hydroxide ion concentration, we c
an, by Equation, find the other.
2. The pH of A Solution (important)
 Definition: pH is the negative logarithm of
the molar hydrogen ion concentration.
pH = -log[H+]
 Remember, a high pH (greater than 7) means b
asic and a low pH (less than 7) means acidic
. The higher the pH, the lower the acidity,
and vice versa.
 If [H+] = l0-x, then pH = x.
 [H+] = antilog(-pH) = 10-pH
 Relationship between pH and pOH
[H+][OH-] = Kw
(-log [H+]) + (-log [OH-]) = -log Kw
pH + pOH = pKw=14
 Just as we know that the product of the h
ydrogen ion and hydroxide ion concentrati
ons is 1.0× 10-14 , the sum of the pH and
pOH must always be 14.00 (at 25℃).
 The relationships among [H3O+], [OH-], pH,
and pOH can be summarized as fol1ows:
 The relationships among [H3O+], [OH-], pH, and
pOH can be summarized as fol1ows:
pH+pOH=14
pH
pOH
-log [H+]
-log [OH-]
[H+] [O
H- ]
[H+][OH-] = Kw = 1.0×10-14
EXAMPLE 1 A sample of orange juice has a hy
drogen-ion concentration of 2.9×10-4 M. W
hat is the pH? Is the solution acidic?
EXAMPLE 2 The pH of human arterial blood is
7.40. What is the hydrogen-ion concentra
tion?
 Measurement of pH
 Using a pH meter
 Using acid-base indicators

Questions
 What is the hydrogen-ion concentration
of 0.10M niacin (nicotinic acid)?
 What is the hydrogen-ion concentration
of the solution obtained by dissolving
one 5.00-gram tablet of aspirin (acety
lsalicylic acid) in 0.500 L of water?
 The pH of human blood remains very nea
rly 7.35. Why?
 How to prepare a buffer of a given pH?
3. The pH of Monoprotic Acids or Bases
 Acid-ionization Constant and Base-ionization C
onstant
 
acid: HA+H2O A- +H3O+ [H O ][A ]
K  3
a
[H 3O  ][A  ]  
[HA]
Kc  [H 3O ][A ]
K a  K c [H 2O] 
[HA][H 2O] [HA] 
[HA][OH ]
base: A +H2O
- HA +OH - Kb  
 Ka is the acid-ionization constant. Like any] eq
[A
uilibrium constant, Ka (or Kb) varies with temp
erature.
 If Ka is large, the acid is strong. If Kb is la
rge, the base is strong.
3. The pH of Monoprotic Acids or Bases
 Acid-ionization Constant and Base-ionizat
ion Constant
 The Degree of Ionization, α

Acid: [H 3O ] where ca is the the initial conce
α
ca ntration of the weak acid.
Base: [OH  ] where c is the the initial conce
α b
cb ntration of the weak base.
Question Although Ka and Kb are listed in some
tables, more frequently they are not. How d
o you determine Ka or Kb of an ionic acid, b
asic, or amphiprotic substance?
 The Relationship between Ka and Kb for Conju
gate Acid-Base Pairs (important) [H  ][A  ]
HA(aq) + H2O(l) H3O+(aq) + A-(Kaq 
a )
[HA]

A (aq) + H2O(l)
- HA(aq) + OHK(baq
- [HA][OH
) ]

[A - ]
If we multiply Ka(HA) by Kb(A -), we obtain
KaKb = Kw
Notice
 This relationship is general and shows that
the product of acid- and base-ionization con
stants in aqueous solution for conjugate aci
d-base pairs equals the ion-product constant
for water, Kw.
 As Ka decreases, Kb for the conjugate base mu
st increase, since Kw is a constant. We see t
hat the weaker an acid (the smaller Ka ), the
stronger its conjugate base (the larger Kb ).
 Obtain Ka from Kb or Kb from Ka .
Example Use Tables 3-3 to obtain the following
at 25℃: (a) Kb for CN-; (b) Ka for NH4+.
Solution
(a) The conjugate acid of CN- is HCN, whose Ka
is 6.2×10-10. Hence,
Kb=Kw/Ka=1.0×10–14/6.2×10-10=1.6×10–5
(b) The conjugate base of NH4+ is NH3, whose Kb
is 1.8×10-5. Hence,
Ka=Kw/Kb=1.0×10–14/1.8×10-5=5.6×10-10
3.4 Solving Problems Involving Aci
d-Base Equilibria (monoprotic acid)
Question: Once you know the value of Ka for an
acid HA, how can you calculate the equilibr
ium concentrations of species HA, A-, and H+
for solutions of different molarities?
 Calculating Concentrations of Species in a
Weak Acid Solution (Approximation Method)
Procedure
 Write the equilibrium equation.
 Set up a table in which you write the start
ing, change, and equilibrium values of each
substance under the balanced equation.
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
Starting ca
0 0
Change - x +
x + x
Equilibrium c a- x x
x


][H3O  ] x  x  equation
Substitute the[Aequilibrium-constant 5% x 2 for the
K a concentrations.
equilibrium 
[HA] ca  x ca
 Solve the equilibrium-constant equation for the equi
librium concentrations.x  [H O  ]  [A  ]  K c
3 a a
ca/Ka≥500 (or α< 5% ):
[HA]≈ ca pH=-log[H+ ] =-log[H3O+ ]
Question How do you know when you can use the
simplifying assumption, where you neglected x in the
denominator of the equilibrium equation?
Solution α<5% or ca/Ka ≥500
Notice Every time an approximation is introdu
ced in a calculation, you must check to see
if the approximation is valid (α<5% or ca/K
a ≥500 ). If you find you have made an inva
lid assumption, you can always solve the eq
uation using the quadratic formula.
K K  4K  c
2
[H  ]  a
 a a a
2 4
Example A 0.25 M solution of HCN has a pH of 5.
00. What is Ka? What is α of Hydrocyanic aci
d in this solution?
Procedure
 Convert pH to [H+] .
 Write the equilibrium equation.
 Set up a table in which you write the startin
g, change, and equilibrium values of each sub
stance under the balanced equation.
 Use these equilibrium values to calculate Ka
and α.
Solution [H+] = antilog (-5.00) = 1.0×
10-5
HCN (aq) + H2O(l) H3O+ (aq)+ CN -
(aq)
Starting 0.25
0  ][CN  ]
[H 3O 0 -5
[1  10 ][1 10 -5
] 10
K
Change
a  -1.0×10 -5   4  10
+1.0×10-5 +
1.0×10-5 [HCN] [0.25]
 5
[H
Equilibrium O ] 1  10
α 3  0.25  4  10 5  0.004% 1.0×1
0-5 1.0×10
ca -5 0.25
Example: What are the concentrations of nicoti
nic acid, hydrogen ion, and nicotinate ion in
a solution of 0.10M nicotinic acid, HC6H4NO
2, at 25℃? What is the pH of the solution? W
hat is the degree of ionization of nicotinic aci
d? The acid-ionization constant, Ka, is 1.4×1
0-5.
Solution HNic (aq) + H2O(l) H3O+ (aq)+
Nic
x -(aq)
[H  ]  [A  ]  K a ca [HA]≈ ca
[H  ]
pH=-log[H+ ] α
ca
x  [H  ]  [Nic  ]  K a ca
 0.1 1.4  105  0.0012 mol/L
[HNic]≈ ca =0.1 mol/L pH=-log[H+ ] = 2.92
[H  ] 0.0012
α   0.012  1.2%
ca 0.1
d-Base Equilibria (monoprotic base)
Monoprotic Acid[H3O+] Monoprotic Base[OH-]
HA+H2O A-+H3O+ A-+H2O HA +OH-
  
[H O ][A ] [HA][OH ]
Ka  3 Kb 
[HA] [A  ]
[H 3 O  ] [OH  ]
 
ca cb
If ca/Ka≥500 If cb/Kb≥500
[ H 3 O  ]  [ A  ]  K a ca [OH  ]  [HA]  K b cb
 Ka K a2  4 K a  c a  Kb K b2  4 K b  c b

[H ]   [OH  ]  
2 4 2 4
Example
 Morphine, C17H19NO3, is administered medically to rel
ieve pain. It is a naturally occurring base, or alk
aloid. What is the pH of a 0.0075 mol·L-1 solution o
f morphine at 25 ℃? The base-ionization constant,
Kb, is 1.6×10-6 at 25 ℃.
Solution
C17H19NO3 (aq) + H2O(l) HC17H19NO3 +(aq) + OH-(aq)
Starting 0.0075 0
0
Condition
Change   5% or
- cxb /K b  500 + x
+ x
 6
x  [OH ]  0.0075
Equilibrium K bcb - 1x .6≈10  0.0075  1.1x10  4 mol / L
0.0075
x
pOH  3.96 pH  10.04
Procedure
 Identify a salt solution is acidic or bas
ic.
 Obtain Ka or Kb for the ion that hydrolyze
s by using KaKb = Kw .
 Calculation of the concentrations of spec
ies present follows that for solutions of
weak acids or bases.

basic→Kb → [OH ]  K bCb

acidic→Ka → 3 ]  K a C a
[H O
d-Base Equilibria
 Shifting an Acid-Base Equilibrium
 Dilution Law
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
Starting ca
0 0
Change -caα c aα
caα
Equilibrium  ca -  caα c aα ca
[H 3O ][A ] c a  c a  c a  2   5%

Ka α    ca  2
[HA] c a c a  1
  K a / ca As ca gets smaller, αmust increas

ca/Ka≥500: e because Ka is a constant at a giv
en temperature.
3.4 Solving Problems Involving Acid-Base Equi
libria (Common-Ion
( Effect and Salt Effect)
 Common-Ion Effect and Salt Effect
Examples Question
HAc(aq) + H2O(l) H3
O+(aq) + Ac-(aq) Suppose you add NaAc(aq) to thi
s solution. What is the effect on the acid-ioni
zation equilibrium?
Solution HAc(aq) + H2O(l) H3O+(aq) + Ac-(aq)
NaAc → Na+
+ Ac-
 The equilibrium should shift to the left.
 α of acetic acid is decreased.
 The NaAc has Ac- in common with HAc, so the infl
uence is known as the common-ion effect.
libria (Common-Ion
Common ion effect Salt effect

HAc+ H2O H3O++Ac- HAc+ H2O H3O++Ac-
NaAc→Na++ Ac- NaCl→Na++ Cl-
Equilibrium← ， α ↓ Equilibrium→ ， α
↑
The shift in equilibriu The shift in equilib
m caused by the additio rium caused by the a
n of a compound having ddition of a compoun
an ion in common with t d without a common i
he dissolved substance on is called the sal
is called the common-io t effect .
libria (Common-Ion
Calculating the Common-Ion Effect on Acid Ionization
Example The α of HAc in a 0.10M aqueous solution at

25℃ is 0.013. The pH of 0.10M acetic acid is 2.
88. Ka at this temperature is 1.7×10–5. Calculate
the α of HAc in a 0.10M solution at 25℃ to whi
ch sufficient NaAc is added to make it 0.10 M Na
Ac. How is the degree of ionization affected? Wh
at is the pH of this solution at 25℃? Calculate
the change in pH that results when 0.01mol HCl i
s added to 1.00 L of a solution containing 0.10
M HAc and 0.10 M NaAc. Compare the pH change wit
h what would occur if this amount of acid were a
dded to 1 L of pure water.
libria (Common-Ion
Solution (1)Before addition of HCl

HAc+ H2O H3O++Ac-
starting: 0.10 0
0.10
change: -x +x
+x
 0.10  x  x 0.10-
equilibrium:
K a 10 +x 
0.10 xx x
5
0.
 1.7  10 x  1.7 10  mol  L1 
5
0.10  x 0.10

≈0.10
pH  lg[H ]≈  0.10
lg(1.7  10 5 )  4.74
1.7 10 5
α  0.00017
0.10
libria (Common-Ion
(2)After addition of HCl

HAc+ H2O H3O++Ac-
starting: 0.10 0.01 0.1
0
change: +0.01 -0.01 -0.01
F(S): 0.11 0 0
.09
change: -x +x +
x
equilibrium: 0.11-x x 0.09 +x
Ka 
0.09 x
0.11
 
 1.7 105 x  2.2 105 mol  L1
≈0.11
≈0.09  5
pH  lg[H ]  lg(2.2 10 )  4.66 pH  0.08
libria (Common-Ion
1 L of pure water
pH = 7.00
0.010 mol of HCl was added
[H+] = 0.10 mol·L-1 pH = 2.00
pH changes 5.00 units.
If 0.01 mol of hydrochloric acid is added to 1 L of
pure water, the pH changes from 7.0 to 2.0 - a
pH change of 5.0 units. By contrast, the additi
on of this amount of hydrochloric acid to 1 L o
f the solution containing weak acid and its con
jugate base might change the pH by only 0.1 uni
t.
d-Base Equilibria (polyprotic base)
4. Polyprotic Acids
 Step- ionization
 When polyprotic acids ionize, they do so by step
s, releasing one hydrogen ion with each step.
1st stage H2CO3 + H2O H3O++ HCO3- Ka1
2st stage HCO3- + H2O H3O++ CO32- Ka2
 Each succeeding acid is weaker than the one befo
re. For any diprotic acid, Ka2 < Ka1. This is alw
ays true because it is more difficult to remove
a proton from a negatively charged species (HA-)
than from an uncharged molecule (H2A).
4. Polyprotic Acids
 Ionization Constants for Acids (Ka) and Base (Kb)
1st H2CO3 + H2O H3O++ HCO3- Ka1 = 4.3×10-7
2st HCO3- + H2O H3O++ CO32- Ka2 = 5.61×10-11
CO32- + H2O HCO3- + OH- Kb1
HCO3- + H2O H2CO3 + OH- Kb2
H2CO3 ～ HCO3- Ka1 Kb2 =KW
HCO3- ～ CO32- Ka2 Kb1 =KW
3.4
3.4 Solving
Solving Problems
Problems Involving
Involving Aci
Aci
d-Base
d-Base Equilibria
Equilibria (polyprotic
(polyprotic base)
base)
Calculating the concentrations of species in
a solution of a polyprotic acid (Approximatio
n Method)
monoprotic acid[H3O+] polyprotic acid[H3O+]
HA+H2O A-+H3O+ H2A+H2O HA-+H3O+
HA-+ H2O A2-+H3O+
ca/KOa≥500(or
[H 
]  [ A  α<5%):
]  K a ca
Ka1/Ka2 > 102, [H3O+] is due to
3
the first dissociation ONLY .
[HA]≈ ca c[aH/KOa1≥] 500
[HA：

]  [HK2A]≈c
c a
3 a1 a
[A2-] ≈ Ka2
 A2- ion is produced in the second ionization;
its concentration equals Ka2.
2st stage HA- + H2O H 3O + +
A2- Ka2
Starting x x 0
Change -y +y +y
Equilibrium
[H 3O x-y≈x
][A 2 ] x  y x+y ≈x 2y
K a2  
  y  [A ]
[HA ] x
Example 1 H2S is a diprotic acid. What is the pH o
f a 0.10 M solution? What is the concentration of
[H+], [HS-] and [S2-]? （ Ka1=9.1×10-8 ， Ka2=1.
1×10-12 )
Example 2 What is the pH of a 0.10 M Na2CO3 sol
ution? （ H2CO3:Ka1= 4.3×10-7 ， Ka2= 5.61×10-
11 ）
Example 3 How to calculate concentrati

ons of species in a solution of H3PO
4?
Monoprotic Acid Polyprotic Acid
HA H++ A- H2A H+ + HA- Ka1
★ ★ WhenHApolyprotic
-
H+ + Aacids
2-
Ka2ionize,
[H  ][A  ] they do so by steps, releasing on
Ka 
[HA] e hydrogen ion with each step. Fo
★ r any diprotic acid, Ka2 < Ka1.
[H  ]
★ α
c a
★ If: ca /Ka1≥500 and Ka1/Ka2
If:α<5% or ca /Ka≥500 > 10 2
x  [H  ]  [HA  ]  K a1 ca
x  [H  ]  [A  ]  K aCa [H2A]≈ca
[HA]≈ ca pH=-log[H+ ]
★
pH=-log[H+ ]
★ A2- ion is produced in the seco
K a  ca 2
nd ionization; [A2- ]its
= Kaconcentration
2
equals Ka2.
d-Base Equilibria (Amphoteric Subst
ances)
5. The pH of Amphoteric Substances
 Questions Consider NaHCO3,
 Since HCO3- is an amphiprotic substance, will so
lutions of HCO3- be acidic or basic?
 How to determine Ka or Kb for HCO3- ？ What is th
e conjugate acid of HCO3- ion?
 How do you predict the pH of HCO 3- ion?
 Solution
 If Ka > Kb, the solution is acidic.
 If Ka = Kb, the solution is neutral.
 If Ka < Kb, the solution is basic.
ances)
5. The pH of Amphoteric Substances
HCO3- + H2O H3O+ + CO32-
Ka2= 4.8×10-11
HCO3- + H2O OH- + H2CO3
Kb2= Kw / Ka1 = 2.3×10-8
 K a1 ( K a 2 c  K w )
[H ] 
K a1  c
 K a1 K a 2 c
[H ] 
cKa2 ＞ 20Kw ， K a1  c cKa2 ＞ 20Kw, c ＞ 20Ka1
c ＞ 20Ka1 , 
[ H ]  K a1 K a 2 [ H  ]  K a1 K a 2
ances)

cKa2 ＞ 20Kw, c ＞ 20Ka1 [ H ]  K a1 K a 2
 Note that K is the acid-ionization constant w
a2
hen an amphoteric substance acts as a weak ac
id; Ka1 is the its conjugate acid-ionization cons
tant when it acts as a weak base.
Example 1 What is the pH of a 0.1 mol·L-1 NaHC
O3 solution?
（ H2CO3:Ka1= 4.3×10-7 ， Ka2= 5.61×10-11 ）
Example 2 Identify a salt solution is ac
idic or basic. (a)NaH2PO4; (b)Na2HPO4
3.5 Buffers
1. Definition, Composition and Action of Bu
ffer Solutions
 Definition: A buffer is a solution characterized by
the ability to resist changes in pH when limited
amounts of acid or base are added to it.
 Composition : Buffers contain either a weak acid
and its conjugate base or a weak base and its
conjugate acid.
HAc ～ NaAc; NH4Cl ～ NH3
kH2PO k2HPO
4 4
3.5 Buffers
 Question Which of the following soluti
ons are buffer systems? (a) KH2PO4/H3PO4,
(b) NaC1O4/HC1O4, Explain your answer.
 How a Buffer Works
HAc(aq) + H2O(l) H3O+(aq) + Ac-(aq)
large concentration large concentration
(added acid) Ac - + H3O+ HAc + H2O
(added base) HAc + OH- H2O + Ac-
Antiacid component-base (Ac - )
Antibase component- acid (HAc)
3.5 Buffers
2. The pH of a Buffer-Henderson-Hasselbalch
Equation
HB+H2O B-+H3O+
[H3O ][B ]
Ka 
[HB]
 K a [HB] [HB]
[H3O ]  
 log[H ]  logKa  log 
[B - ] [B ]
[B ] [base]
pH  pK a  lg  pKa  lg
[HB] [acid]
3.5 Buffers
 Notice
 Influencing factors: pKa and [HA]/[A-]. Note Ka
for the conjugate acids.
 [HA]≈Ca [A-] ≈Cb
 Another expressions nB
pH  pKa  lg
n HB
 Mixing equal concentrations of HA and A-,
VB 
pH  pKa  lg
 Buffer pairs that find extensive application VHBa
re HAc and Ac-, NH3 and NH4+, H2CO3 and HCO3-, H2P
O4- and HPO42-. Note Ka for the conjugate acids.
3.5 Buffers
 Application
 Calculating the pH of a Buffer
Example 1 Instructions for making up a buffer s
ay to mix 60 mL of 0.100 M NH3 with 40 mL of
0.100 M NH4C1. What is the pH of this buffer
? Kb for NH3 is 1.8 ×10 –5.
Example 2 A 0.10 M solution of aqueous ammonia,
also containing ammonium chloride, has a hy
droxide ion concentration of 5.6 ×10 –10 M.
What is the concentration of the ammonium i
on in the solution?
3.5 Buffers
 Application
 Calculating the pH of a Buffer
Example 3 Ten milliliters of 4.0 M acetic acid is
added to 20 ml of 1.0 M sodium hydroxide. Cal
culate the hydrogen ion concentration of the
resulting solution. Ka for HAc is 1.8 ×10 –5 .
Example 4 Estimate the pH of a solution prepared
by dissolving 0.03 mol of H3PO4 and 0.05 mol o
f K3PO4 in 1 liter of water. (H3PO4: pKa1= 2.16,
pKa2= 7.21, pKa3= 12.67)
3.5 Buffers
 Application
 Calculating the change in pH of a buffer soluti
on on addition of a small amount of strong base
Example 1 Calculate the change in pH that results
when 0.50 mL of 0.200 M NaOH is added to 10.00
mL of a buffer solution containing acetic acid
and potassium acetate, both at a concentration
of 1.00 M.
Conclusion
n(B ) - n(H  )
(added acid) pH  pK a  log
n(HB)  n( H  )
(added base) n(B )  n(OH  )
pH  pK a  log
n(HB)  n(OH  )
3.5 Buffers
3. Buffer Capacity and Buffer Range
 Buffer Range : HB(aq) H+ (aq)+ B-(aq)
[B ] [base]
pH  pK a  lg  pKa  lg
[HB] [acid]
 When the [base]/[acid] ratio is 1, pH = pKa
, the buffer efficiency is largest.
 If the [base]/[acid] ratio is larger than 1
0 or smaller than 0.1, the solution will no
t be particularly effective at keeping the
pH constant.
3.5 Buffers
3. Buffer Capacity and Buffer Range
 If this ratio is between 1:10 and 10:1, t
he solution will be effective at keeping
the pH constant.
 [base]/[acid] =10, pH=pKa + 1
[base]/[acid] =0.1, pH=pKa -1
Buffer
Buffers Range :pKapKa±1
(Acid-Base) Buffer Range
HAc-Ac- pKa = 4.76 3.76 ～ 5.76
NH3 - NH4+ pKa = 9.25 8.25 ～ 10.25
H2CO3 -HCO3- pKa1= 6.37 5.37 ～ 7.37
HCO3- - CO32- pKa2= 10.32 9.32 ～ 11.32
3.5 Buffers
 Buffer Capacity
 Definition: the amount of strong acid or base
needed to change the pH of one liter of buffer
by 1 unit.

d[B] [HA] [A ]
  2.303   c
 d[pH] factors: the
Influencing c totalc buffer concentr
ations c and [HB]/[B-]
ratio→same,β∝c (c (total)= [HB] + [B-])

c (total)→same, [base]/[acid] =1, βmax =0.576c
3.5 Buffers
4. Preparing a Buffer
 Principles
 Most buffers are made from solutions with con
centrations in the range from 0.05 to 0.2 M.
 The pKa value should be as close as possible
to the desired pH .
x
 Methods pH  pKa  lg
 HB + B- V -xx
pH  pKa  lg
 HB(excess) + NaOH→B -
V  2x
 B- (excess) + HCl→ HB V  2x
pH  pKa  lg
x
3.5 Buffers
 Procedure
 The first step in the process is to choose a
suitable weak acid. The H-H equation is real
ly only valid in a pH range near the pKa of t
he weak acid; therefore, we select a weak aci
d with a pKa near the pH range of interest
 Second Step  Calculate the required ratio o
f conjugate base to weak acid from the Hender
son-Hasselbalch Equation
3.5 Buffers
 Calculation
 HB + B-: Mixing equal concentrations of HB a
nd B-, VB 
pH  pKa  lg
VHB
 HB + NaOH→B- How to calculate the volume
for preparing a buffer by mixing a strong ba
se with a weak acid? The total volume of a b
uffer =100ml,V(NaOH)=x.
HB + NaOH→B- + H2O
Starting (100-x)c cx 0
Change -cx -cx +cx x
pH  pKa  lg
Equilibrium (100-2x)c 0 cx 100 - 2x
3.5 Buffers
Example 1 A student wishes to prepare a buffer
solution at pH=8.60.Which of the following
weak acid should she choose and why? HA(Ka=2
.7×10-3), HB(Ka=4.4×10-6), HC(Ka = 2.6× 10-9).
Example 2 What volume of 2.00 M NaOH must be ad
ded to 100.00 m L of 2.50 M HCOOH to prepar
e a buffer with pH = 4.00?
Example 3 How to prepare 30ml a phosphatic buff
er with pH = 7.21 by using 0.1 mol/L NaOH a
nd 0.1 mol/L KH2PO4?
3.5 Buffers
5. Biological meaning
 Question: The pH of human blood remains very ne
arly 7.35. Why?
 Solution: Blood contains H2CO3 and HCO3-, as well
as other conjugate acid-base pairs: H 2PO4- - HPO4
2- and proteins, HPr – Pr. Most of the bufferi
ng of blood is carried out by a carbonic acid-b
icarbonate buffer.
H2CO3 + H2O HCO3 - + H3O+
(added acid) HCO3 - + H3O+ H2CO3 + H2O
 The extra carbon dioxide is released in the lun
gs and exhaled
3.5 Buffers
H2CO3 + H2O HCO3 - + H3O+
(added base) H2CO3 + OH- HCO3 - + H2O
 The extra bicarbonate ion formed is eventu
ally expelled by the kidneys.
 Terms
 If the pH of the blood drops below 7.2, a
potentially fatal condition called acidosi
s results.
 If the pH of the blood increases to over 7
.5, another serious condition known as alk
alosis results.
Summary
Acid If: Ca/Ka≥100,[H  ]  K aCa

[H  ][B ] [H ]
K aK b = K w Ka  α
[HB] Ca
Base If: Cb/Kb≥100,[OH  ]  K bCb
[HB][OH  ] [OH  ]
Kb  α
[B- ] Cb
Buffers (two 1.pH [B ] [base]
pH  pK a  log  pK a  log
[HB] [acid]
forms) 2. Buffer range: pKa±1
3.β: the total buffer concentrat
ions and [B]/[A]

MBBS Chapter 3 and Chapter 4 Electrolyte Solutions and Buffers

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MBBS Chapter 3 and Chapter 4 Electrolyte Solutions and Buffers

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HCl HC

Nonelectrolyte strong 1O4 H2S

 Using acid-base indicators

  K a / ca As ca gets smaller, αmust increas

Common ion effect Salt effect

Example The α of HAc in a 0.10M aqueous solution at

Solution (1)Before addition of HCl

(2)After addition of HCl

Example 3 How to calculate concentrati

ratio→same,β∝c (c (total)= [HB] + [B-])

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