Acid-Base Equilibria and Application

1/20/2015
Acid-Base Equilibria and

Neutralization Methods
Acid-Base Equilibria
and
Neutralization Methods
Review units of concentration (calculations)

Acid Base theory
Relative strength of acids and bases
Chemical equilibrium
Electrolyte effects on chemical equilibria
Distribution of acid base as a function of pH
Systematic method of equilibrium calculation
PBE, MBE, CBE
Calculation of pH
Buffer solutions
Acid base titrations/Applications
REVIEW: Units of Concentration

concentrat ion
amount of solute
amount of solution
Molarity
(M)
- also called Equilibrium,

or Species Molarity
M=
moles solute
liters of solution
Analytical and Equilibrium Concentrations

Equilibrium Molarity, [X] = concentration of a given
dissolved form of the substance
Analytical Molarity, Cx = sum of all species of the
substance in solution
Formality (F) or Analytical molarity

F=
Example:
What is the concentration (M and F) of a
solution prepared by dissolving exactly 1
mol of acetic acid in 1 liter of solution?
(The acid is 0.42% ionized)
moles solute
liter of solution
Normality (N)
N
# of equivalents of solute
liter of solution
Molality (m) - defined as the number of

moles of a substance per kilogram of solvent
(not solution)
m=
moles of solute
kg of solvent
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Parts per thousand:
TRY THIS!
Calculate the N, m and F of 5.700g H 2SO4 in
1L solution (H2SO4=98.08 g/mole)
Show relationship between N and M.

Percent concentration (or parts per hundred)
Weight percent (w/w):

C(w/w) = weight solute x 100%
weight solution
Cppt = weight of substance x 1000

weight of solution
Parts per million (ppm) or parts per billion (ppb)
Cppm = weight of substance
weight of solution
x 106
Cppb = weight of substance

weight of solution
x 109

Density and Specific Gravity
A. Density = mass/volume
B. Specific Gravity = Density of substance
Density of water
Volume percent (v/v):

C(v/v) = volume solute x 100%
volume solution
Indicate
the unit!!!
Weight/Volume percent (w/v):

C(w/v) = weight solute(g) x 100%
volume solution(mL)
Sample Calculations:
a.Calculate the molar concentration
and molality of commercially available
concentrated acids and bases below:
Reagent
CH3COOH
NH3
HCl
HF
HNO3
HClO4
H3PO4
H2SO4
%w/w
Specific gravity
99.7
29.0
37.2
49.5
70.5
71
86
96.5
1.05
0.90
1.19
1.15
1.42
1.67
1.71
1.84
PREPARATION OF SOLUTION
Describe the preparation of the following
solution
a. 2.00 L of 0.150 M HClO4 from a 12.0 M
HClO4
b. 2.00 L of 0.150 M HClO4 from a
concentrated solution that has a specific
gravity of 1.66%
c. 100 mL of 0.1500 M of Na2SO4 from
Na2SO4 crystals.
d. 250.0 ml of 100.0 ppm of Na from Na2SO4
crystals.
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ACID BASE THEORY
Bronsted and Lowry
Arrhenius theory - Svante Arrenhius

(1857-1927)
Acids a substance that increases the
concentration of H3O+ when added to water
Bases - a substance that decreases the
concentration of H3O+ when added to H2O
or produces OH-
Acids proton donors

Bases- proton acceptors
The Bronsted and Lowry definition does not
require that H3O+ be formed
Bronsted and Lowry

A BrnstedLowry acid
must have a removable (acidic) proton.
HCl, H2O, H2SO4
Bronsted and Lowry

A BrnstedLowry base
must have a pair of nonbonding electrons.
NH3, H2O
Fundamental ideas from Bronsted and Lowry
Assignment:
Samples of Bronsted and Lowry acid
and base but not Arrhenius
1. Amphiprotic species (or amphoteric)

species that have both acidic and basic properties
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Practice: Determine the conjugate

acid base pair
2. 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.
3. Autoionization
OH-
Lewis Acid-Base Concept

Lewis Acids
electron-pair acceptors.
Atoms with an empty valence orbital can be Lewis
acids.
A compound with no Hs can be a Lewis acid.
Lewis Acid-Base Concept

Lewis Bases
STRENGTH OF ACIDS AND BASES

Strong acid - dissociates more or less
completely when it dissolves in water.
- Their conjugate bases are quite weak.
Weak acid - dissociates only slightly when it

dissolves in water
- Their conjugate bases are weak bases.
electron-pair donors.
Anything that is a BrnstedLowry base is also a Lewis
base.
Substances with negligible acidity do not dissociate

in water.
Their conjugate bases are exceedingly strong.
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In any acid-base reaction, the equilibrium

favors the reaction that moves the proton to
the stronger base.
Acetate is a stronger base

than H2O,
so the equilibrium favors the
backward reaction (K<1).
HCl(aq) + H2O(l) H3O+(aq) + Cl(aq)

acid
base
c. acid
The stronger base wins the

proton.
c. base
H3O+(aq) + C2H3O2(aq)
HC2H3O2(aq) + H2O
Assign:
Explain why HF behave as a
weak acid while HI, HCl, HBr
are all strong acid

Leveling solvent
two or more acids give the same acid strength
one in which all acids are dissociated to the same
degree and have equal acid or base strength
Example:
HCl(aq) + H2O(l) H3O+(aq) + Cl(aq)
HClO4(aq) + H2O(l) H3O+(aq) + HClO4- (aq)

Differentiating solvent
allows relative strength to be measured
a solvent where various acids dissociate to
different degrees and have different strengths.
e.g. Which is a stronger acid HCl or HClO4?

HClO4 + HAc H2Ac+ +
ClO4+
HCl
+ HAc H2Ac +
ClHClO4 dissociate 5000 times greater in Hac than HCl
p- Functions
The negative logarithmn (to the base 10) of
the number
pX = -log X
pH = - log H+
pOH =- log OHpKw = - log Kw
pH - is a measure of the acidity or alkalinity of
a substance
Assign: Show that: pH
pOH = 14
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Significant figure in pH calculations:

The number of digits in the mantissa would be the
number of significant digits in x of log x.
CHEMICAL EQUILIBRIUM
aA +
bB
Or
Keq
The number of significant figure in the x of log x

would be the number of digits in the mantissa.
Example:
Le Chteliers Principle
When a stress is imposed on a system at equilibrium
the system will respond in such a way as to relieve
the stress.
Addition of a reactant
Change in pressure or volume of a gas
Change in temperature
+ dD
C D
A B
"[ ]" means..
The equilibrium, molar concentration of a solute

The partial pressure (in atmospheres) for a gas.
Is assumed to be "1" if the species is..
o
o
o
o
pH = 2.460
[H+] = 0.00347
cC
C
A pure liquid in excess.

A pure solid.
The solvent in a dilute solution.
The solvent, water.
Types of equilibria
1. Dissociation constant of water Kw
2. Ionization constant for acid - Ka
3. Ionization constant for base - Kb
Types of equilibria
1. Dissociation constant of water - Kw
K equil
[ H 3O ][OH ]
K equil [ H 2O ]2 [ H 3O ][OH ]
[ H 2O ]2
K w H 3O OH
At 25C, Kw = 1.0
Practice :
Calculate pH of pure water at 25C and 50C.
10-14
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Ionization constant for acid - Ka
Types of equilibria
The greater the value of Ka, the stronger the acid.
2. Ionization constant for acid - Ka
Ka
[ H 3O ][ Ac ]
[ HAc ]
Ka can be used to distinguish between

strong acids and weak acids.
Types of equilibria
3. Ionization constant for base - Kb
NH3 + H2O
Kb
NH4+
H3O+
[ NH 4 ][ H 3O ]
[ NH 3]
Assignment: Why is it that H2O does not appear in

equilibrium constant expression for aqueous
solutions?
Relationship between Ka and Kb for

conjugate acid - base pair
HAc + H2O
Ac-
Ac- + H2O
Ka
[ H 3O ][ Ac ]
[ HAc ]
HAc
Kb
H3O+
OH[ HAc ][OH ]

[ Ac ]
Show that: Kw= kakb
Practice:
What is the Kb for the equilibrium where
Ka is 6.2 X 10-10
CN- + H2O
HCN +
OH-
Assign:
For a diprotic acid, derive relationship between
each of two acids and their conjugate base
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ELECTROLYTE EFFECTS
aA +
ELECTROLYTE EFFECTS ON
CHEMICAL EQUILIBRIA
bB
cC
Keq '
+ dD
C C D D
AA B B
Ideal Solutions
Equilibrium constants are independent of
the presence and concentration of electrolytes.
Real Solutions
Constants vary based on electrolyte concentration.
This results in deviation from ideal behavior.
Electrolyte Effects
Consider the effect of added NaCl to increase
the size of the Ksp for barium sulfate:
1. At 0 M NaCl, Ksp = 1.1 x 10-10.
2. At 1 x 10-3 M NaCl, Ksp 1.8 x 10-10.
3. At 1 x 10-2 M NaCl, Ksp 2.85 x 10-10.
Electrolyte Effects
Consider the effect of added NaCl to increase the size
of the Ka for acetic acid:
1. At 0 M NaCl, Ka = 1.75 x 10-5.

2. At 1 x 10-2 M NaCl, Ka 2.1 x 10-5.
3. At 1 x 10-1 M NaCl, Ka 2.7 x 10-5.
The electrolyte effect is dependent upon its ionic
strength.
Ionic strength,
Ionic strength,
- a measure of the total concentration of

ions in solution
1
AZ A2 BZ B 2 C Z C 2
2
A, B , C
are the molar concentrations
of each ionic species
and ZA, ZB, ZC .... are the
charges on each species
Sample calculation:
Calculate the ionic strength () of a 0.1 M
NaNO3 solution.
Calculate the ionic strength () of a 0.1 M
Mg(NO3)2 solution.
Calculate the ionic strength () of 0.020 M KBr
plus 0.010 M Na2SO4
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Activity and Activity Coefficients
Ionic strength,
The higher the charge in the ionic atmosphere the
greater the ionic strength of a solution.
The stoichiometry of the electrolyte determines the
ionic strength.
Type of
electrolyte
1:1
1:2 or 2:1
1:3 or 3:1
2:2
Example
Compound
NaCl
MgCl2,Na2SO4
Al(NO3)3
MgSO4
Ionic
strength
C
3C
6C
4C
Activity coefficient, x , is the numerical factor

necessary to convert the molar concentration
of the chemical species to activity.
Where:
[X] = molar concn

of species X
= activity coefficient
Debye-Huckel equation
Dimensionless factor that measure the

deviation of behavior from ideality.
Assumed to be "1" for uncharged molecules.
Calculation of Activity Coefficients
Debye-Huckel Equation
Extended Debye-Huckel equation
Davies equation
log x
0.512 Z X
1 3.3x
The constants 0.51 and 3.3 are applicable to

aqueous solutions at 25 oC
The value of is approximately 0.3 nm for most
singly charged ions; for ions with higher charge,
may be as large as 1.0 nm
when 0.01, then the equation becomes
- permits the calculation of activity coefficients of ion

from their charge and their average size.
0.512 Z X
log x
where
Debye-Huckel equation
- Term used to account for the effects of

electrolytes on chemical equilibria.
aX X X

The activity coefficient
Activity,ax , is the "effective" concentration of a

chemical species.
1 3.3x
Zx = charge of the ion x

= ionic strength
x = effective diameter of the hydrated ion in
nanometers
log x 0.512 Z 2 X
This equation is referred to as the Debye

Huckel Limiting Law (DHLL)
DHLL can be used to calculate/approximate
activity coefficients in solutions of very low
ionic strength.
log x 0.512 Z 2 X
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Sample calculation: Calculate the activity
coefficient for Hg2+ in a solution that has an
ionic strength of 0.085. = 0.5 nm
For the general equilibrium

aA +
bB
Concentration
Equilibrium
Constant
Thermodynamic
Equilibrium
Constant
cC
Since:
dD
[C ]c [ D ]d
Keq '
[ A]a [ B ]b
Keq
aC a D
a A aB
aX X X
Then:
C C D D
A
B
A A B B
C
Keq
Keq
Keq
a A aB
C D C D
A
B
A B A B
C
aC a D
C D
Keq '
A B
DISTRIBUTION OF ACID BASE AS A

FUNCTION OF PH
DISTRIBUTION OF ACID BASE AS

A FUNCTION OF PH
Objective:
To find an expression for the fraction of an
acids and bases () as a function of pH.
An fraction is the ratio of the equilibrium
concentration of one specific form of a solute
divided by the total concentration of all forms
of that solute in an equilibrium mixture.
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FUNCTION OF PH
Monoprotic system
Consider 0.10 M HAc Ka = 1.8 x 10-5
HAc (aq) + H2O
H+ (aq) + Ac (aq)

FUNCTION OF PH
o= the fraction of HAc
1 = the fraction of Aco
MBE: CHAc= [HAc ] + [Ac-]

PBE:
[H+ ] = [OH- ] + [Ac-]
Ka
[ H ][ Ac ]
[ HAc ]

FUNCTION OF PH
Rearranging Ka to get HAc and [ Ac ]
Ka
[ Ac ]
Ka [ HAc ]
[H ]
[ H ][ Ac ]
[ HAc ]
[ HAc ]
Substituting the above equations into o

expression
Ka [ HAc ]
[ HAc ]
[ Ac ]
o
[H ]
[ HAc ] [ Ac ]
[ H ][ Ac ]
Ka
Substituting the above equations into 1

expression
[ Ac ]
[ HAc ] [ Ac ]
[ HAc ]
[ H ][ Ac ]
Ka
[ Ac ]
[ Ac ]
[ HAc ] [ Ac ]
c HA

FUNCTION OF PH

FUNCTION OF PH
[ HAc ]
[ HAc ]
[ HAc ] [ Ac ]
C HA
[ HAc ]
[H ]

c HA
[H ] K a

FUNCTION OF PH
When:
[HAc] = [Ac-]
o 1
Assign: Derive this
Ka = [H+]
pKa = pH
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FUNCTION OF PH
Plot of the fraction of Ac- present in each of

the 2 forms as a function of pH.
CH3COOH (aq)
H+ + CH3COO (aq)
Example: Calculate values:

1. at pH 2.00
2. at pH 4.74
3. at pH 6.50
Distribution Diagram
Practice: 0.20 M HCN Ka = 4.91010
HCN + H2O
CN + H3O+
1. Draw the distribution
diagram
2. Calculate the
concentration at pH 3.5
of HCN and CN3. What species will
predominate at pH 2.5
and pH 12
4. At what pH will
[HCN]=[CN-]
Distribution diagram: Carbonate

system
Ka1=4.45 x 10-7
Ka2=4.45 x 10-11
Distribution Diagram
Derivation of Expressions for

Polyprotic Weak Acids
For H2CO3
fraction of H2CO3
fraction of HCO3-
fraction of CO32-
[ H ]2
[ H ]2 [ H ]K a1 K a1 K a 2
[ H ] K a1
[ H ]2 [ H ]K a1 K a1 K a 2
K a1 K a 2
[ H ] [ H ] K a1 K a1 K a 2
2
General form for the polyprotic acid HnA
Hn
H
A
K a1 H
H n1 A
D
Where D = [H+]n + K1[H+]n-1 + K1K2[H+]n-2 + . + K1K2K3.Kn
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Assignment:
Derive the alpha expressions for all PO4bearing species in a phosphoric acid or
phosphate solution. Draw the distribution
diagram
SYSTEMATIC METHOD OF EQUILIBRIUM

CALCULATION
Four types of algebraic expressions commonly
derived/used in solving multiple equilibria.
Equilibrium constant expressions (Ka, Kb,
Ksp, Kf, etc.).
Mass-balance equations (MBE)
Charge-balance equations (PBE)
Proton Balance equations (PBE)
Mass balance equations (MBE )

Example:
Write a mass balance expressions for the ff:
a)
b)
c)
d)
e)
f)
g)
h)
HA, H2A, H3A

0.50 M CH3COOH
0.50 M HCN
0.50 M H2CO3
NaHCO3
Na2CO3
H3PO4
Satd solution of Ag3PO4
SYSTEMATIC METHOD OF
EQUILIBRIUM CALCULATION

Equations that relate the equilibrium
concentrations of species in a solution to each
other and the formal (analytical)
concentrations of the solutes.
It states that C HA A , that is analytical
concentration of an acid or base is equal to
the sum of concentrations of the protonated
and unprotonated species.
HA

ASSIGN:
Write the MBE for the following solutions:
1)
2)
3)
4)
0.10 F H2SO4
0.20 F Na2S
0.10 F NH4Cl
0.20 F Na2H2Y
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Proton Balance Equation (PBE)

Matches the concentration of species which
have released protons with those which have
consumed.
# protons consumed = # protons released
proton rich = proton poor
Practice:
Write a proton balance expression for the following:
proton rich = proton poor
a)
b)
c)
d)
e)
f)
H 2O
strong acid - HBr
strong base - KOH
weak acid(monoprotic) - HCN
weak base(monobasic) NH3
Salt - KCN

Try this:
Write a proton balance expression for the following:
ASSIGN:
Write PBE for the following acids and bases:
PBE for weak base(monobasic)
1. H2CO3
2. Na2CO3
3. H3PO4
4. Na3PO4
NH3
CH3COONa
PBE for polyprotic acids and bases

H2 S
NaHS
Na2S
Charge Balance Equation (CBE)

Equations that express the electrical neutrality
of a solution by equating the molar
concentrations of the positive and negative
charges.
Charge Balance Equation (CBE)

Example: Write CBE for 0.1 M solution of NaHCO3
Na+(aq) + HCO3-(aq)
(1)
NaHCO3(s)
(2)
HCO3-(aq) + H2O(l)
HCO3-(aq) + H2O(l)
(3)
2H2O(l)
sum (+) charge = sum (-) charge
Neutral species are not included
5. NaH2PO4
6. Na2HPO4
7. Na2H2Y
H3O+(aq) + CO32-(aq)
OH-(aq) + H2CO3(aq)
H3O+(aq) + OH-(aq)
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Steps in solving problems of multiple

equilibria
TRY THIS!
Write the charge balance expression
Write balanced reactions for all equilibria.

Write all equations (PBE, MBE, CBE)
Write out all equilibrium constants and obtain
their values
1) HBr
2) Na2HPO4
3) H3PO4

equilibria
Count the number of unknown species in the
equilibrium system and count the number of
independent algebraic relationships available
in the MBE, CBE, and Keq expressions.
If the number of independent equations > the
number of unknowns, a solution is possible.
If the number of independent equations < the
number of unknowns, you must either find
more equilibria or else a solution is not
possible.

equilibria
Make suitable approximations to simplify the
algebra.
Solve the algebraic equations.
Check the validity of the approximation.
Calculation of pH
Strong acids and bases
Calculate the pH of 0.50 M HX
Write balanced reactions
1. HX
2. H2O
H+
+
H+
X+ OH-

PBE: [H+] = [OH-] + [X-]
MBE: 0.50 M =[HX] + [X-]
CBE: [H+] = [OH-] + [X-]

Write out all equilibrium constants and obtain their
values
Kw = 1.0 x 10-14 = [H+] [OH-]
Count the number of species [H+] [OH-] [X-] [HA]
Count the number of independent algebraic
relationships
PBE, MBE, Kw
solution is possible
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Make suitable approximations to simplify the
algebra
Solve the algebraic equations
Calculate pH
a.) 0.025 M KOH
b.) 0.15 M Ba(OH)2
c.) 1.0 x 10-8 M KOH
d.) 1.0 x 10-6 M HCl
General formula for strong acid would be:
C HX C HX 4Kw
2
This formula is applicable for strong

acid with concentration HX 10 6 M
6
For strong acid with HX 10 M
H X C
Then
HX
Consider a weak acid HA (0.50 M)

Write balanced reactions
1. HA
H+ +
A+
2. H2O
H
+ OH
PBE:
[H+] = [OH-] + [A-]
MBE: CHA = 0.50 M = [HA] + [A-]
CBE: [H+] = [OH-] + [A-]
pH log C HX
Weak acids and bases

Write out all equilibrium constants and obtain their
values
Kw = 1.0 x 10-14 = [H+] [OH-]
Ka
H A

Make suitable approximations to simplify the algebra
Two assumptions to remove the unknown terms:
HA
Count the number of species: [H+] [OH-] [A-] and

[HA]
Count the number of independent algebraic
relationships:
PBE, MBE, Kw
Solvable
1. Most of the H+ come from the dissociation of the

acid and contribution from water is negligible.
PBE: [H+] = [OH-] + [A-]
2. Most of the acid HA remains in the undissociated
form such that [HA] >>[A-]
MBE: CHA = 0.50 M = [HA] + [A-]
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pH Calculations

Substituting this to Ka expression
H A
Ka
HA
H H
Exercise
Calculate the pH of 0.10 M CH3COOH, Ka = 1.8 x 10-5
C HA
C HA
pertinent equilibria
CH3COOH H+ + CH3COOH2O H+ + OH-
KaC HA
H KaC HA
4 species: H+, OH-, CH3COOH, CH3COO-
pH Calculations
pH Calculations
4 independent equations
Since the solution is acidic, we can assume that

[OH-] is very small
PBE
[H+] = [OH-] + [CH3COO-]
[H+] = [OH-] + [CH3COO-]
MBE
0.10 = [CH3COOH] + [CH3COO-]
Ka
PBE
[CH 3COO ][H ]

[CH 3COOH ]
K w [H ][OH ]
pH Calculations
K a 1.8 10 5
2
[H ][H ]
0.10 [H ]
0 [H ] Ka[H ] 0.10 Ka
0.10 - [CH3COO-] = [CH3COOH]

0.10 - [H+] = [CH3COOH]
Exercise
Calculate the pH of 0.10 M CH3COOH, Ka = 1.8 x 10-5
Steps are the same
For the last step, approximations are used to
solve for the unknown
Using the quadratic equation

[H ] 1.33 10 3 M
pH 2.88
0.10 = [CH3COOH] + [CH3COO-]
Method of Successive Approximations
Substituting and simplifying equations
MBE can be rewritten as
K a 1.8 10 5
[H ][H ]
0.10 [H ]
assume that
[H+] is negligible
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[H ]I K a 0.10 (1.8 10 5 )(0.10) 1.34 10 3 M
Substitute the answer to the Ka expression, then

solve for [H+]II
K a 1.8 10 5
K a 1.8 10 5
[H ]III 1.33 10 3 M
[H ]IV 1.33 10 3 M
[H ][H ]
0.10 [H ]
Iterations have
converged
[H ]V 1.33 10 3 M
[H ][H ]
0.10 1.34 10 3
[H ]II 1.33 10 3 M

Exercise
Calculate the pH of 5.0 x 10 -7 M NaOH solution

3 independent equations
PBE
[H+] + [Na+] = [OH-]
NaOH Na+ + OHH2O H+ + OH-
MBE
FNaOH 5.0 10 7 M [Na ]
[H+] may be derived from the Kw expression

3 species:
H+,
OH-,
Na+
[H ]
Kw
[OH ]

Kw
FNaOH [OH ]
[OH ]
Assume water has very small contribution in [OH -]

Kw
FNaOH [OH ]
[OH ]
Kw
FNaOH [OH ]II
[OH ]I
1.0 10 14
5.0 10 7 [OH ]II
5.0 10 7
[OH ]II 5.2 10 7 M
[OH ]I FNaOH 5.0 10 7 M
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pH Calculations
pH of Polyprotic Acids/Bases
Kw
FNaOH [OH ]III
[OH ]II
1.0 10 14
5.0 10 7 [OH ]III
5.2 10 7
[OH ]III 5.19 10 7 M
[OH ] 5.19 10 7 M
IV
7
Iterations
[OH ] 5.19 10 M
[H ] 1.have
93 10 8 M
converged
V
7
pH 7.72
[OH ] 5.19 10 M
H2B - diprotic acids

H2B + H2O H3O+ + HB-
K a1
[H3O ][HB ]
[H 2 B ]
HB- + H2O H3O+ + B2-
K a2
[H3O ][B 2 ]
[HB ]
pH Calculations
pH Calculations
Example
Alanine Hydrochloride is a salt consisting of the
diprotic weak acid H2L+ and Cl-. Calculate the pH of
0.10 M H2L+ solution (Ka1 = 4.487 x 10-3, Ka2 = 1.358 x
10-10).
pH of Polyprotic Acids/Bases
Usually Ka1 Ka2
K a1
Ka1 H3O+ from neutral species

Ka2 H3O+ from a charged species
H2L+
pH Calculations
K b2
K a2
HL
K b1
L-
pH Calculations
H2L+ + H2O HL + H3O+
K a1
[HL ][H3O ]
[H2L ]
HL + H2O L- + H3O+
K a2
[L ][H3O ]
[HL ]
2H2O H3O+ + OH-
K w [H3O ][OH ]
Assume that any solution containing an

appreciable quantity of H2L+ will contain
essentially no L- (Since Ka1 Ka2)
PBE
[H3O+] = [OH-] + [HL]
MBE
CH
2L
[ H 2 L ] [ HL ]
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pH Calculations
pH Calculations
Since H2L+ is a weak acid

PBE
K a1
[H3O+] = [OH-] + [HL]
K a1
MBE
CH
2L
[ H 2 L ] [ HL ]
[ H 2 L ] C H
[ H 2 L ] C H
2L
2L
[ HL ]
Solving the quadratic equation or using MSA

[H3O ] 1.91 10 2 M
pH 1.72
pH Calculations
L-
+ H2O HL +
OH-
K b1
HL + H2O H2L+ + OH2H2O
H3O+
K
1.0 10 14
w
7.364 10 5
K a 2 1.358 10 10
K b2
Kw
1.0 10 14
2.229 10 12
K a1 4.487 10 3
K w [H3O ][OH ]
OH-
pH Calculations
K b1
K b1
[HL ][OH ]
[L ]
[OH ]2
FL [OH ]
Solving the quadratic equation or using MSA

[OH ] 2.677 10 3 M
[H3O ] 3.736 10 12 M
pH 11 .43
[ H 3O ][ H 3O ]
C H L [ H 3O ]
2
[ H 3O ]
Example
Calculate the pH of 0.10 M L- solution (Ka1 = 4.487 x
10-3, Ka2 = 1.358 x 10-10).
[HL ][H3O ]
[H2L ]
pH Calculations
Assume that any solution containing an
appreciable quantity of L- will contain
essentially no H2L+ (Since Kb1 Kb2)
PBE
MBE
[H3O+] + [HL] = [OH-]
FL [L ] [HL ]
[L ] FL [HL ]
Equilibrium constant expression
K b1
[HL ][OH ]
[L ]
pH Calculations
Example
Calculate the pH of 0.10 M HL solution (Ka1 = 4.487 x
10-3, Ka2 = 1.358 x 10-10).
HL + H2O L- + H3O+
K a2
[L ][H3O ]
[HL ]
HL + H2O H2L+ + OH-
K b2
K w [H2L ][OH ]
K a1
[HL ]
2H2O H3O+ + OH-
K w [H3O ][OH ]
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pH Calculations
CBE
[H3O+] + [H2L+] = [OH-] + [L-]
MBE
FHL = [H2L+] + [HL] + [L-]
pH Calculations
Next we solve Kb2 for [H2L+]
K b2
Assume that [H2L+] and [L-] are significantly

lower than [HL]
MBE
[H2L ][OH ] K w
[HL ]
K a1
[H2L ]
K w [HL ]
[OH ]K a 1
[H2L ]
[H3O ]FHL
K a1
FHL = [H2L+] + [HL] + [L-]
pH Calculations
Next we solve Ka2 for [L-]
K a2
Substituting equations into the charge balance

equation
[L ][H3O ]
[HL ]
K [HL ]
[L ] a 2
[ H 3O ]
[L ]
pH Calculations
K a 2 FHL
[ H 3O ]
CBE
[H3O+] + [H2L+] = [OH-] + [L-]
[ H 3O ]
F
1
K w K a 2FHL
[H3O ] 1 HL
K
[
H
a1
3O ]
pH Calculations
[H3O ]2
[ H 3O ]
K a 2 FHL K w
FHL
1
K a1
K a 1K a 2 FHL K a1K w
FHL K a1
[H3O ]
FHL [H3O ]
Kw
K F
a 2 HL
K a1
[H3O ] [H3O ]
pH Calculations
For a solution of 0.10 M HL
[H3O ] (4.487 10 3 )(1.358 10 10 ) 7.807 10 7 M
pH 6.11
K a1K a 2
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pH Calculations
Exercise Calculate pH
1.) 0.10 M H2SO3 solution
(Ka1 = 1.2 x 10-2, Ka2 = 6.6 x 10-8).
2.) 0.10 M H2C2O4 solution
(Ka1 = 5.6 x 10-2, Ka2 = 5.42 x 10-5).
CHEM 32
3.) 0.04 M CH3NH2 solution

(Kb = 4.35 x 10-4)
4.) 0.200 M Na2CO3
Calculations required to establish titration curve

Initial - Solution of only strong acid (solution of
H3O+)
Pre equivalence - Excess moles of strong acid +
limiting moles of strong base (solution of H 3O+)
Equivalence Point - [H3O+] = [OH-]
Post equivalence - Excess moles of strong base
+ limiting moles of strong acid (solution of OH -)
Sample problem:
Derive a curve for the titration of 50.00 mL
0.0500M HCl with 0.1000 M NaOH
1. Initially, before any base is added to the acid
sample, the [H3O+]total = CHA + [H3O+]water.
If the CHA is greater than 10-6 M, the [H3O+]water
can be ignored.
3. At equivalence:
2, Preequivalence - As strong base is added but

prior to equivalence, [H3O+] is consumed
3. At equivalence:
The acid and base have reacted at the
stoichiometric ratio.
[H3O+] = [OH1-]
All the acid is

consumed; only base is
present.
The amount of base is
calculated from the
excess added beyond
equivalence.
Figure 1: Titration curve of a strong base

titrating a strong acid
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4. Beyond equivalence:
All the acid is consumed; only base is
present.
The amount of base is calculated from the
excess added beyond equivalence.
Note that...
If the CAcid > 10-6 M, we have assumed that the
water contribution to the hydronium ion
concentration can be ignored.
If the CAcid < 10-8 M, you can also assume that the
water is primarily responsible for the hydronium
ion concentration, and that the added acid is
insignificant.
Only when the CAcid is between 10-8 - 10-6 M must
the water contribution to the hydronium ion
concentration be considered
Sample problem:
Derive a curve for the titration of 50.00 mL 0.0500M
HCl with 0.1000 M NaOH
SUMMARY:
Region
Major constituents
1. Initial
2. Pre-equivalence
3. At eq pt.
4. After eq pt.
HCl
HCl + NaOH
NaCl
NaCl + NaOH
TITRANT ADDED
0.00 mL
10.00 mL
24.90 mL
25.00 mL
25.10 mL
30.00 ml
40.00 ml
Comments
pH OF RESULTING
SOLUTION
Practice:
Fill up the table for the titration of HBr with
NaOH
SAMPLE: 50.00 mL of a 0.100 M HBr(aq)
solution.
TITRANT: stepwise addition of a 0.200 M
KOH(aq) solution
Calculate the pH during the titration of 50.00 mL

of 0.0500 M NaOH with 0.1000 M HCl after
the addition of the following volumes of
reagent (a). 24.50 mL (b). 25.00 mL (c). 25.50
mL
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Derive a curve for the

titration of 50.00 mL
of 0.1000 M acetic
acid(Ka = 1.75 x 10-5)
with 0.1000 M NaOH
Figure 2: Titration curve of a strong acid
titrating a strong base
Practice:
SAMPLE: 50.00 mL of a 0.100 M HF(aq) solution
TITRANT: 0.200 M KOH(aq) solution
titrant added region classification
0.00 mL
10.00 mL
24.90 mL
25.00 mL
25.10 mL
30.00 ml
40.00 ml
Titration of weak base with a strong acid

Titrant: HCl
Analyte: NH3
pH of resulting solution
Practice:
A 50.00 mL aliquot of 0.0500 M NaCN is
titrated with 0.1000 M HCl. Calculate the
pH after the addition of (a). 0.00 (b).
10.00 (c). 25.00 and (d). 26.00 mL of
acid.
Summary:
Region
Major constituents
1. Initial
NH3
2. Before E.P.
NH3 + NH4Cl
3. At E.P.
NH4Cl
4. After E.P.
NH4Cl + HCl
Comment
Titration curve and effect of

concentration and Ka
As the acid becomes
dilute the EP become
shorter, become less
distinct, the more
limited the choice of
indicator.
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TITRATING POLYFUNCTIONAL
ACIDS AND BASES
Regions:
1. Initial - No titrant added.
2. Titrant added, but before
EP1
3. At EP1
4. After EP1, but before the
EP2
5. At EP2
6. After EP2
ACIDS AND BASES
Sample problem
Consider 20.00mL of 0.100 M H2A, titrated with

0.100 M NaOH.
(Ka1 = 1.00 x 10-4, Ka2 = 1.00 x 10-8)
ACIDS AND BASES
Acid-Base Indicators
Acid-base indicators (pH indicators) are weak organic
acids or weak organic bases that change color as a
function of ionization state.
Try this!
Find the pH of a 50 mL solution of a 0.10 M
H2CO3 after addition of 0, 25, 50, 75, 100, and
150 mL of 0.10 M NaOH. Ka1=4.3x10-7 and ka2
= 4.8x10-11
Act as a second acid or base in the solution being

titrated and must be weaker than the analyte so that
it reacts last with the titrant.
For a typical indicator
In 10
we can see the In- color...
In 10
we can see the HIn color
HIn
H O In
Ka
HIn
H O Ka HIn
In
HIn
In
pH pKa log
HIn
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1/20/2015
Selected pH indicators
Common name
Methyl yellow
Methyl orange
Methyl red
Chlorophenol red
Bromthymol Blue
Cresol Purple
Phenolhpthalein
Thymolphthalein
Ex. Phenolhpthalein (phe)
pKa Indicator Range

3.3
2.9-4.0
4.2
3.1-4.4
5.0
4.2-6.2
6.0
4.8-6.4
7.1
6.0-7.6
8.3
7.4-9.0
9.7
8.0-9.8
9.9
9.3-10.5
acid form
Selecting the Proper indicator
The transition range of the indicator should
overlap the steepest part of the transition
curve.
Indicator range = pKa
Titration curves
for HAc with
NaOH
A: 0.1000 M HAc
with 0.1000 M
NaOH
B: 0.001000 M
HAc with
0.00100 M
NaOH
base form
Titration curves for
HCl with NaOH
A: 50.00 mL 0.0500
M HCl with 0.100
M NaOH
B: 50.00 mL of
0.000500 M HCl
with 0.00100 M
NaOH
Indicator Error
Determinate error
difference between the endpoint and the equivalence
point
pH at which the indicator completes its color change is
not the same as the pH of the EP
Indeterminate error
inability to decide if its end point or not
26
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Sample problem 1: For bromcresol green, the following
general reaction exists.
acidic endpoint basic

bromocresol green yellow green
blue 4.0-5.6
Indicate the reaction that will take place when
acid is added
base is added
What is the pH transition range of the indicator

What species and color will predominate in a solution of
pH 8.0
ph 2.0
Sample problem 2:
Consider the indicator, phenol red which has a
yellow HIn form, a red In- form, and a Ka of 5.0
x 10-8. What is the ratio of HIn/In- .
If a few drops of this indicator are added to a
solution of pH 2.3, what color would the
solution be?
APPLICATIONS OF ACID BASE

TITRATIONS
APPLICATIONS OF ACID BASE

TITRATIONS
Concept of equivalence (review)

Preparation of standard acid solutions
Standardization of acids
Primary standards for acids
Preparation of standard base solutions
Standardization of bases
Applications of neutralization titrations
Elemental analysis
Determination of inorganic substances
Determination of organic functional groups
Describe the preparation of 5.00 L of 0.1000 N

Na2CO3 (105.99 g/mol) from the primarystandard solid, assuming the solution is to be
used for titrations in which the reaction is
Exactly 50.00 mL of an HCI solution required

29.71 mL of 0.03926 N Ba(OH)2 to give an end
point with bromocresol green indicator.
Calculate the normality of the HC!.
CO32- + 2H+ H2O + CO2
27
1/20/2015
Preparation of standard acid solutions
Strong acids are used like HCl, H2SO4, HClO4

HCl widely used for titration of bases
H2SO4 and HClO4 useful for titrations where
chloride ion interferes by forming precipitates
HNO3 are seldom used because of their oxidizing
properties
Na2CO3 available commercially or can be

prepared by heating purified NaHCO3 between
2700C to 3000C for 1 hour
2NaHCO3
Na2CO3
H2O +
CO2
THAM or TRIS - tris-hyhydroxymethyl)aminomethane
(HOCH3)CNH2
Na2CO3
CO32- + H3O+ HCO3- + H2O
pH 8.3
HCO3- + H3O+ H2CO3 + H2O pH 3.8
H2CO3 CO2 + H2O

Effect of CO2 absorption
sodium tetraborate - Na2B4O7
Ex. 27.65 mL of HCl were used to titrate

0.4916 g of Borax. Molarity of HCl is:
Bases (e.g. NaOH ) react rapidly with atmospheric CO2

to produce carbonate
CO2(g) + 2OH CO32- +
H2O
So that this carbonate will also be titrated
CO32- + 2H3O+ H2CO3 + 2H2O
But no error is incurred because it cancels out by the
OH- consumed
28
1/20/2015
Effect of CO2 absorption
e.g. NaOH
But if an indicator in the basic transition range is used
then each CO32 reacted with only one hydronium ion
when the color change is observed
CO32- + 2H3O+ HCO3- +
2H2O
The effective concentration of the base is thus
diminished by absorption of CO2, and a systematic
error (called a carbonate error) results.
Standardization of bases
Primary standards:
Potassium Hydrogen Phthalate,
KHC8H4O4
Benzoic acid
Potassium hydrogen iodate,
KH(IO3)2
Applications of neutralization titrations
Kjeldahl Method for Determining Nitrogen
Elemental analysis
1. Digestion
2. Distillation
3. Titration
Nitrogen
sulfur
Determination of inorganic substances

ammonium salts
nitrates and nitrites
carbonate and carbonate mixtures
Determination of organic functional groups

Determination of salts

Digestion in strong sulfuric acid in the presence
of a catalyst
Sample + H2SO4 (NH4)2SO4(aq) + CO2(g) + SO2(g) + H2O(g)
Conversion of ammonium ions into ammonia

gas, heated and then distilled.

Titration
back titration - the ammonia is captured by a carefully
measured excess of a standardized acid solution in
the receiving flask
Receiver: 2NH3 + 2H2SO4 (NH4)2SO4 + H2SO4

Titration: H2SO4 + 2NaOH Na2SO4 + 2H2O
(NH4)2SO4 + 2NaOH 2NH3 + Na2SO4 + 2H2O
29
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direct titration
Sample problem:
A 0.7121 g sample of wheat flour was analyzed
by the kjeldahl method. The ammonia formed
by addition of concentrated base after
digestion withH2SO4 was distilled into 25.00
mL of 0.04977 M HCl. The excess HCl was then
back-titrated with 3.97 mL of 0.04012 M
NaOH. Calculate the percent protein in the
flour.
DOUBLE INDICATOR
DOUBLE INDICATOR
Titration curves for NaOH
Titration curves for NaHCO3
Titration curves for Na2CO3
30
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Sample problem:
Sample problem:
An impure mixture that may contain NaOH, Na2CO3,

and/or NaHCO3 with other inert matter was analyzed.
0.5000 g of this sample was titrated to the
phenolphthalein endpoint with 0.1042 N NaOH,
requiring 16.33 mL. A second 0.5000 g sample was
titrated to the modified methyl orange endpoint,
requiring 48.15 mL. Determine (a) the component(s)
present from the three listed; and (b) the %
composition of each of the component(s) that are(is)
present.
The alkalinity of natural waters is usually controlled by

OH, CO32, and HCO3, which may be present
singularly or in combination. Titrating a 100.0-mL
sample to a pH of 8.3 requires 18.67 mL of a 0.02812
M solution of HCl. A second 100.0-mL aliquot requires
48.12 mL of the same titrant to reach a pH of 4.5.
Identify the sources of alkalinity and their
oncentrations in parts per million.
Sample problem:
Sample problem:
A 1.200 g sample of mixture containing NaOH

and Na2CO3 was dissolved and titrated with
0.5000 N HCl. With phenolphthalein as
indicator, the solution turns colorless after the
addition of 30.00 mL of the acid. Methyl
orange is then added, and 5.00 mL more of
the acid is required to reach the endpoint.
Wht is the percentage composition of the
sample?
A 1.200 g sample of mixture containing

NaHCO3 and Na2CO3 was dissolved and
titrated with 0.5000 N HCl. With
phenolphthalein as indicator, the solution
turns colorless after the addition of 15.00 mL
of the acid. Methyl orange is then added, and
22.00 mL more of the acid is required to reach
the endpoint. Wht is the percentage
composition of the sample?
Sample problem:
Sample problem:
An impure mixture that may contain NaOH,

Na2CO3, and/or NaHCO3 with other inert matter
was analyzed. 1.000 g of this sample was
dissolved in 30.00 mL dH2O and titrated to the
requiring 16.33 mL. A second 1.000 g g sample
was titrated to the methyl orange endpoint,
requiring 21.17 mL. Determine (a) the
component(s) present from the three listed; and
(b) the % composition of each of the
component(s) that are(is) present.
A 1.200 g sample of mixture containing NaOH

and Na2CO3 was dissolved and titrated with
0.5000 N HCl. With phenolphthalein as
indicator, the solution turns colorless after the
addition of 30.00 mL of the acid. Methyl
orange is then added, and 5.00 mL more of
the acid is required to reach the endpoint.
Wht is the percentage composition of the
sample?
31
1/20/2015
Sample problem:
Sample problem:
A 1.200 g sample of mixture containing

NaHCO3 and Na2CO3 was dissolved and
titrated with 0.5000 N HCl. With
phenolphthalein as indicator, the solution
turns colorless after the addition of 15.00 mL
of the acid. Methyl orange is then added, and
22.00 mL more of the acid is required to reach
the endpoint. Wht is the percentage
composition of the sample?
An impure mixture that may contain NaOH,

Na2CO3, and/or NaHCO3 with other inert matter
was analyzed. 1.000 g of this sample was
dissolved in 30.00 mL dH2O and titrated to the
requiring 16.33 mL. A second 1.000 g g sample
was titrated to the methyl orange endpoint,
requiring 21.17 mL. Determine (a) the
component(s) present from the three listed; and
(b) the % composition of each of the
component(s) that are(is) present.
32

Acid-Base Equilibria and Application

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Acid-Base Equilibria and

Review units of concentration (calculations)

REVIEW: Units of Concentration

REVIEW: Units of Concentration

- also called Equilibrium,

Analytical and Equilibrium Concentrations

Formality (F) or Analytical molarity

REVIEW: Units of Concentration

REVIEW: Units of Concentration

Molality (m) - defined as the number of

REVIEW: Units of Concentration

REVIEW: Units of Concentration

Show relationship between N and M.

REVIEW: Units of Concentration

Weight percent (w/w):

Cppt = weight of substance x 1000

Cppb = weight of substance

REVIEW: Units of Concentration

Volume percent (v/v):

Weight/Volume percent (w/v):

ACID BASE THEORY

Bronsted and Lowry

Arrhenius theory - Svante Arrenhius

Acids proton donors

Bronsted and Lowry

Bronsted and Lowry

Fundamental ideas from Bronsted and Lowry

1. Amphiprotic species (or amphoteric)

Fundamental ideas from Bronsted and Lowry

Practice: Determine the conjugate

2. Conjugate Acids and Bases:

Fundamental ideas from Bronsted and Lowry

Lewis Acid-Base Concept

Lewis Acid-Base Concept

STRENGTH OF ACIDS AND BASES

Weak acid - dissociates only slightly when it

Substances with negligible acidity do not dissociate

STRENGTH OF ACIDS AND BASES

STRENGTH OF ACIDS AND BASES

In any acid-base reaction, the equilibrium

Acetate is a stronger base

HCl(aq) + H2O(l) H3O+(aq) + Cl(aq)

The stronger base wins the

STRENGTH OF ACIDS AND BASES

STRENGTH OF ACIDS AND BASES

STRENGTH OF ACIDS AND BASES

e.g. Which is a stronger acid HCl or HClO4?

Significant figure in pH calculations:

The number of significant figure in the x of log x

"[ ]" means..

The equilibrium, molar concentration of a solute

A pure liquid in excess.

Ionization constant for acid - Ka

The greater the value of Ka, the stronger the acid.

2. Ionization constant for acid - Ka

Ka can be used to distinguish between

Assignment: Why is it that H2O does not appear in

Relationship between Ka and Kb for

OH[ HAc ][OH ]

Show that: Kw= kakb

1. At 0 M NaCl, Ka = 1.75 x 10-5.

- a measure of the total concentration of