In the 1st half of this chapter we will focus on the

equilibria that exist in aqueous solutions

containing:
weak acids
Chapter 16: polyprotic acids
weak bases
Acid-Base Equilibria salts
use equilibrium tables to determine:
equilibrium composition of solutions
pH
% ionization
Ka or Kb

In the 2nd half of the chapter, our focus will shift to
understanding solutions in which there is some
combination of acidic and basic species:
buffer solutions
titration experiments
We will need to consider that neutralization
reactions can/will occur, as well as the equilibria that
exist.
use multiple steps:
determine the pH of solutions after
neutralization reactions are complete
construct and interpret titration curves
Steps for solving weak acid equilibrium problems:
1. Identify all major species in solution.
2. Identify all potential H+ transfer reactions that
could contribute to the [H3O+]total in the soln.
3. By considering K values, determine the dominant
source of H3O+ in the solution.
4. Set up the equilibrium calculation based on
equilibrium identified in step 3.
5. Solve!
x = [H3O ]
+
solve for pH, % ionization, or Ka
 example:
Determine the pH of 0.10 M HCN (aq). For HCN,
Ka = 4.9 x 1010.
1. Identify all major species in solution.
this is an aqueous solution of a weak acid, so the
major species are: HCN & H2O
2. Identify all potential H+ transfer reactions that could
contribute to the [H3O+]total in the soln.
there are 2 possible sources of H3O+ in this soln:
HCN (aq) + H2O (aq) CN (aq) + H3O+ (aq); Ka = 4.9 x 1010
2 H2O (l) H3O+ (aq) + OH (aq); KW = 1 x 1014
example:
Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 1010.
3. By considering K values, determine the dominant source
of H3O+ in the solution.
there are 2 possible sources of H3O+ in this soln:
HCN (aq) + H2O (aq) CN (aq) + H3O+ (aq); Ka = 4.9 x 1010
2 H2O (l) H3O+ (aq) + OH (aq); KW = 1 x 1014
Ka > KW, so the acid ionization of HCN will be the
dominant source of H3O+ in his solution.
OR
[H3O+]total = [H3O+]HCN-ionization + [H3O+]H2O-ionization
but we will assume that [H3O+]H2O-ionization is negligibly small
so [H3O+]total [H3O+]HCN-ionization

example: example:
Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 1010. Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 1010.
5. Solve! x = [H3O+]
4. Set up the equilibrium calculation based on
equilibrium identified in step 3. [H3O+][CN] x2
Ka = ; 4.9 x 1010 =
[HCN] 0.10 x
HCN (aq) + H2O (l) CN (aq) + H3O+ (aq)
use a simplifying approximation
initial [ ] 0.10 M --- 0 0 Because Ka is very small, the reaction does not
proceed very far forward (toward products) before
[] x --- +x +x reaching equilibrium.

equil [ ] (0.10x)M --- xM xM We will assume that x in the denominator will be

negligibly small relative to [HCN]0.
[H3O+][CN] x2 OR
Ka = ; 4.9 x 1010 =
[HCN] 0.10 x 0.10 x 0.10
example: example:
Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 1010. Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 1010.

solution: check the validity of the approximation:

x2
4.9 x 1010 = x2
x x 100 < 5%, the approximation is valid
0.10 x 0.10 if
[HA]0
x = 7.0 x 106

so at equilibrium: for our example:

[H3O+] = [CN] = 7.0 x 106 M 7.0 x 106 x 100 = 0.007%

[HCN] = 0.10 M 0.10
the approximation is valid: 0.10 x 0.10
pH = log (7.0 x 106) = 5.15

example: Percent Ionization

Determine the pH and % ionization of 0.0100 M
CH3COOH (aq). For acetic acid, Ka = 1.8 x 105.
What percentage of a weak acid originally present
is in its ionized form at equilibrium?
[HA]ionized
percent ionization = x 100
[HA]0
percent ionization is another way that we can
assess the acidity of a solution and strength of an
acid
greater % ionization ! higher [ion]
higher [ion] ! higher [H3O+]
higher [H3O+] ! lower pH ! more acidic solution
 Some Comparisons
Percent Ionization and Acid Concentration compare 2 solutions of different concentration of acetic
acid (HC2H3O2, Ka = 1.8 x 105)
for a given acid, HA, % ionization will increase
as [HA] decreases compare 2 solutions of different concentration of
hydrocyanic acid (HCN, Ka = 4.9 x 1010)
dilution effect - changing concentrations of compare acetic acid and hydrocyanic acid solutions of the
species in solution results in Q < K same concentration
reaction proceed forward to re-establish 0.010 M 0.025 M 0.025 M 0.10 M
equilibrium HC2H3O2 HC2H3O2 HCN HCN

new equilibrium [H3O+] and [A] are higher [H3O+], M 4.2 x 104 6.7 x 104 3.5 x 106 7.0 x 106
relative to new [HA]0
pH 3.38 3.17 5.46 5.15
% ionization is greater
%
4.2% 2.7% 0.014% 0.0070%
ionization

Be careful when comparing solutions and making qualitative Determination of Ka from Experimental Data:
statements about them. Given [HA]0 and pH
You can compare 2 different acids at the same concentration: example:
acid with larger Ka is the stronger acid The pH of 0.250 M HF (aq) is 2.036. Determine the
acid solution with larger Ka will have: Ka for HF.
higher [H3O+]
lower pH
higher % dissociation
You can compare the same acid at 2 different concentrations:
Ka is the same, so acid strength is the same
solution with higher concentration will have:
higher [H3O+]
lower pH
lower % dissocation
 Determination of Ka from Experimental Data: Polyprotic Acids
Given [HA]0 and % Ionization
acid with more than one acidic proton
example:
A 0.340 M solution of HNO2 (aq) is 3.65% dissociated polyprotic acids dissociate in a step-wise manner
at equilibrium. Determine Ka for nitrous acid, and the each step corresponds to the dissociation
pH of the solution. of one H+
each step has a unique Ka value

Polyprotic Acids example:

consider oxalic acid, H2C2O4: Consider a 0.040 M solution of carbonic acid.
1st dissociation step: Determine the pH of this solution as well as the
H2C2O4 (aq) + H2O (l) HC2O4 (aq) + H3O+ (aq); Ka1 = 5.9 x 102
equilibrium concentrations of: [H2CO3], [HCO3],
[H3O+], [CO32], and [OH].
2nd dissociation step:
HC2O4 (aq) + H2O (l) C2O42 (aq) + H3O+ (aq); Ka2 = 6.4 x 105
For H2CO3, Ka1 = 4.3 x 107 and Ka2 = 5.6 x 1011.

Ka1 > Ka2 this is always true for polyprotic acids
the acids become weaker with each successive
dissociation step
H2C2O4 is a stronger acid than HC2O4
Why?
1st ionization equation:
H2CO3 (aq) + H2O (l) HCO3 (aq) + H3O+ (aq)
2nd ionization equation:
HCO3 (aq) + H2O (l) CO32 (aq) + H3O+ (aq)
solution: solution:
because Ka1 > Ka2 & Ka1 >> Kw, the primary source to determine [CO3 ] we will have to consider the
2

of H3O+ in the solution will be the 1st ionization 2nd ionization step:
step for H2CO3:
HCO3 (aq) + H2O (l) CO32 (aq) + H3O+ (aq)
H2CO3 (aq) + H2O (l) HCO3 (aq) + H3O+ (aq)
initial [ ] 1.3 x 104 M --- 0 1.3 x 104 M
initial [ ] 0.040 M --- 0 0
[] x --- +x +x
[] x --- +x +x
equil [ ] (1.3 x 104 x)M --- xM (1.3 x 104 + x)M
equil [ ] (0.040x)M --- xM xM
use Ka1; solve for x: x = 1.3 x 104 use Ka2; solve for x: x = 5.6 x 1011
so: [H2CO3] 0.040 M so: [CO32] = 5.6 x 1011 M
[HCO3] = [H3O+] = 1.3 x 104 M
[OH]? [OH] = KW/[H3O+] = 7.7 x 1011 M
pH = 3.89

example:
Steps for solving weak base equilibrium problems:
Calculate pH and % dissociation of 0.40 M NH3 (aq).
1. Identify all major species in solution. For NH3, Kb = 1.8 x 105.
2. Identify all potential H+ transfer reactions that
could contribute to the [OH-]total in the soln. NH3 (aq) + H2O (l) NH4+ (aq) + OH (aq)

3. By considering K values, determine the dominant initial [ ] 0.40 M --- 0 0

source of OH- in the solution.
[] x --- +x +x
4. Set up the equilibrium calculation based on
equilibrium identified in step 3. equil [ ] (0.40x)M --- xM xM
5. Solve!
x = [OH-]

solve for pH, % ionization, or Kb

 Some Comparisons
compare 2 solutions of different concentration of ammonia Be careful when comparing solutions and making qualitative
(NH3, Kb = 1.8 x 105) statements about them.

compare 2 solutions of different concentration of pyridine You can compare 2 different bases at the same concentration:
(C5H5N, Kb = 1.4 x 109) base with larger Kb is the stronger base
base solution with larger Kb will have:
compare ammonia and pyridine solutions of the same higher [OH]
concentration higher pH
0.40 M 0.80 M higher % dissociation
0.15 M NH3 0.40 M NH3
C5H5N C5H5N
You can compare the same base at 2 different concentrations:
[OH], M 0.0016 0.0027 2.4 x 105 3.3 x 105 Kb is the same, so base strength is the same
solution with higher concentration will have:
pH 11.20 11.43 9.38 9.52 higher [OH]
% higher pH
1.1% 0.68% 0.0060% 0.0041%
ionization lower % dissocation

Relationship Between Ka & Kb for Conjugate Acid/Base Pair

example:
consider the conjugate acid/base pair of NH3 & NH4+
Codeine (C18H21NO3) is a naturally occurring amine.
NH3 (aq) + H2O (l) NH4+ (aq) + OH (aq)
The pH of a 0.012 M solution of codeine is
[NH4+][OH]
determined to be 10.14. Kb =
[NH3]
Determine the base ionization constant for codeine,
and the % ionization of the solution. NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq)
[NH3][H3O+]
Ka =
[NH4+]
[NH3][H3O+] [NH4+][OH]
so: Ka x Kb = x
[NH4+] [NH3]
Ka x Kb = [H3O+][OH]
Ka x Kb = KW
 Salt Solutions and pH Considerations
salt - an ionic compound
soluble salts dissolve in water to produce solutions
that may be acidic, basic, or neutral
consider the cation and anion separately
assess the potential acidic or basic nature of each
recall the inverse nature between strengths in a
conjugate acid/base pair:
the stronger an acid or base, the weaker its
conjugate
the weaker an acid or base, the stronger its
conjugate
a closer look at a weak acid/conjugate base pair: HA & A-
HA (aq) + H2O (l) ! A (aq) + H3O+ (aq)
the stronger the acid (HA), the weaker its conjugate base (A-):
strong monoprotic acids produce conjugate bases that are not
effective bases in solution - they are neutral anions
neutral anions are: Cl, Br, I, NO3 , ClO4 neutral cations are: Li+, Na+, K+, Rb+, Cs+, Ca2+, Sr2+, Ba2+
the weaker the acid (HA), the stronger its conjugate base (A-):
weak acids produce conjugate bases that can function as bases
in solution - they are basic anions
base ionization equilibrium for A-:
A- (aq) + H2O (l) ! HA (aq) + OH- (aq); Kb
examples of basic anions include:
F-, CO32-, ClO2-, SO32-, PO43-, NO2-, BrO4-
Steps for solving salt solution pH problems:
1. Identify all major species in solution.
2. Identify all potential H+ transfer reactions that
could contribute to the [H3O+]total OR [OH-]total
in the soln.
3. By considering K values, determine the dominant
source of H3O+ OR OH- in the solution.
4. Set up the equilibrium calculation based on
equilibrium identified in step 3.
5. Solve!
-- x = [H3O+] OR [OH-]
-- solve for pH
a closer look at a weak base/conjugate acid pair: B & BH+
B (aq) + H2O (l) ! BH+ (aq) + OH- (aq)
the stronger the base (B), the weaker its cation:
strong bases produce cations that are not effective acids in
solution - they are neutral cations
the weaker the base (B), the stronger its conjugate acid (BH+):
weak bases produce conjugate acids that can function as acids
in solution - they are acidic cations
acid ionization equilibrium for BH+:
BH+ (aq) + H2O (l) ! B (aq) + H3O+ (aq); Ka
examples of acidic cations include:
NH4+, CH3NH3+, C2H5NH3+, C5H5NH+, C6H5NH3+
 salts that produce neutral solutions:
recall the relationship between Ka and Kb for a
conjugate acid/base pair: pH = 7.00 at 25oC
Ka x Kb = Kw
neutral cation with a neutral anion
OR
pKa + pKb = pKw examples: KNO3, NaCl, Ca(ClO4)2, SrBr2, CsI

and: at 25oC, pKw = -log(1 x 10-14) = 14.00

so: pKa + pKb = 14.00

salts that produce acidic solutions: type 3: hydrated metal cation of high positive charge-
pH < 7.00 at 25oC density with neutral anion

type 1: acidic cation with neutral anion recall:

examples: NH4Cl, CH3NH3NO3, C5H5NHBr

example problem: calculate the pH of 0.10 M NH4Cl (aq)
NH4+ (aq) + H2O (l) ! NH3 (aq) + H3O+ (aq); hydrated metal ion can behave as a Bronsted-Lowry acid:
Ka = Kw/Kb for NH3 = 5.6 x 10-10
type 2: neutral cation with anion from a polyprotic acid [Al(H2O)6]3+(aq) + H2O(l) ! Al[(H2O)5(OH)]2+(aq) + H3O+(aq)

examples: KHSO4, NaHCO3, Ca(HC2O4)2 examples: MgCl2, AlBr3, Zn(NO3)2, Cr(NO3)3

example problem: calculate the pH of .20 M Ca(HC2O4)2 (aq) example problem: calculate the pH of 0.097 M AlCl3 (aq);
HC2O4- (aq) + H2O (l) ! C2O42- (aq) + H3O+ (aq); for [Al(H2O)6]3+, Ka = 1.4 x 10-5
Ka = Ka2 for H2C2O4 = 5.1 x 10-5
 salts that produce basic solutions:
pH > 7.00 at 25oC
neutral cation with basic anion
examples: KF, CaSO4, Na2CO3, K3PO4, Na2C2O4, NaNO2
example problem: calculate the pH of 0.20 M NaNO2 (aq)
NO2- (aq) + H2O (l) ! HNO2 (aq) + OH- (aq);
Kb = Kw/Ka for HNO2 = 2.2 x 10-11
The Common Ion Effect
What happens to the pH of a weak acid (HA) or
weak base (B) solution when a salt containing its
conjugate is added?
resulting solution contains a conjugate acid
base pair
calculate and compare [H3O+] or [OH-],
pH, % ionization

demonstration of LeChateliers Principle

example:
for comparison:
0.10 mol HC2H3O2 and 0.10 mol NaC2H3O2 are
combined in a solution with a total volume of 1.0 L. 0.10 M HC2H3O2 (aq)
0.10 M HC2H3O2 (aq) +
Determine the [H3O+], pH, and % ionization in this 0.10 M NaC2H3O2 (aq)
solution. For HC2H3O2, Ka = 1.8 x 105.
[H3O+] 1.3 x 10 -3 M 1.8 x 10-5 M
the equilibrium that controls the pH of this soln:

HC2H3O2(aq) + H2O (l) C2H3O2 (aq) + H3O+(aq) pH 2.89 4.74

initial [ ] 0.10 M --- 0.10 M 0

% ionization 1.3% 0.018%
[] x --- +x +x

equil [ ] (0.10x)M --- (0.10+x)M xM

for comparison:
Buffer Solutions
0.15 M NH3 (aq)
0.15 M NH3 (aq) + common ion solutions
0.45 M NH4Cl (aq)
solns that contain a conjugate acid/base pair
[OH] 1.6 x 103 M 6.0 x 10-6 M HA & A- or B & BH+

solution resists change in pH when small amounts

pH 11.20 8.78
of strong acid (H+) or strong base (OH-) are added

% ionization 1.1% 0.0040%

How does the pH change after the addition of 0.010 mol HCl to
Consider, again, 0.10 M HC2H3O2 & 0.10 M NaC2H3O2 1.00 L of a solution composed of 0.10 M HC2H3O2 & 0.10 M
common ion solution; starting pH = 4.74. NaC2H3O2 (initial pH = 4.74).
How does the pH change after the addition of 0.010 mol
HCl to 1.00 L of this solution? 1st: addition of strong acid (H+) results in a neutralization
reaction (note: Cl- is a spectator ion; this is the net
1st: addition of strong acid (H+) results in a neutralization ionic equation):
reaction (note: Cl- is a spectator ion; this is the net the added strong acid (H+) will react with the base
ionic equation): (C2H3O2-) in the buffer solution
C2H3O2- (aq) + H+ (aq) " HC2H3O2 (aq)
C2H3O2 (aq) + H+ (aq) HC2H3O2 (aq)
2nd: after the strong acid is consumed, equilibrium is
established that determines the pH of the solution: before rxn 0.10 mol 0.010 mol 0.10 mol
HC2H3O2 (aq) ! C2H3O2- (aq) + H+ (aq) 0.010 mol 0.010 mol +0.010 mol
resulting solution pH = 4.66; pH = -.08 after rxn 0.090 mol 0 0.11 mol
How does the pH change after the addition of 0.010 mol HCl
to 1.00 L of a solution composed of 0.10 M HC2H3O2 & 0.10 M the result of the neutralization reaction:
NaC2H3O2 (initial pH = 4.74).
C2H3O2 (aq) + H+ (aq) HC2H3O2 (aq)
2nd: after the strong acid is consumed, equilibrium is
established that determines the pH of the solution:
C2H3O2 is consumed HC2H3O2 is formed
HC2H3O2 (aq) + H2O (l) ! C2H3O2- (aq) + H3O+ (aq) [C2H3O2] decreases [HC2H3O2] increases
initial [HC2H3O2] and [C2H3O2] in equilibrium problem
determined by consideration of what is in solution after strong acid, H+, is the limiting reactant
the neutralization reaction is complete H+ is completely consumed
HC2H3O2 (aq) + H2O (l) C2H3O2 (aq) + H3O+ (aq)
pH of solution decreases slightly
initial [ ] 0.11 M --- 0.090 M 0 solution becomes slightly more acidic
[] x --- +x +x
equil [ ] (0.11x)M --- (0.090+x)M xM

How does the pH change after the addition of 0.010 mol NaOH
Consider, again, 0.10 M HC2H3O2 & 0.10 M NaC2H3O2 to 1.00 L of a solution composed of 0.10 M HC2H3O2 & 0.10 M
common ion solution; pH = 4.74. NaC2H3O2 (initial pH = 4.74).
How does the pH change after the addition of 0.010 mol
NaOH to 1.00 L of this solution? 1st: addition of strong base (OH) results in a neutralization
reaction (note: Na+ is a spectator ion; this is the net
1st: addition of strong base (OH-) results in a neutralization ionic equation):
reaction (note: Na+ is a spectator ion; this is the net the added strong base (OH) will react with the acid
ionic equation): (HC2H3O2) in the buffer solution
HC2H3O2 (aq) + OH- (aq) " C2H3O2- (aq) + H2O (l)
HC2H3O2 (aq) + OH (aq) C2H3O2 (aq) + H2O (l)
2nd: after the strong base is consumed, equilibrium is
established that determines the pH of the solution: before rxn 0.10 mol 0.010 mol 0.10 mol ---

HC2H3O2 (aq) ! C2H3O2- (aq) + H+ (aq) 0.010 mol 0.010 mol +0.010 mol ---
resulting solution pH = 4.82; pH = +.08 after rxn 0.090 mol 0 0.11 mol ---
How does the pH change after the addition of 0.010 mol NaOH
to 1.00 L of a solution composed of 0.10 M HC2H3O2 & 0.10 M the result of the neutralization reaction:
NaC2H3O2 (initial pH = 4.74).
HC2H3O2 (aq) + OH (aq) C2H3O2 (aq) + H2O (l)
2nd: after the strong base is consumed, equilibrium is
established that determines the pH of the solution:
HC2H3O2 is consumed C2H3O2 is formed
HC2H3O2 (aq) + H2O (l) ! C2H3O2- (aq) + H3 O+ (aq) [HC2H3O2] decreases [C2H3O2] increases
initial [HC2H3O2] and [C2H3O2] in equilibrium problem
determined by consideration of what is in solution after strong base, OH, is the limiting reactant
the neutralization reaction is complete OH is completely consumed
HC2H3O2 (aq) + H2O (l) C2H3O2 (aq) + H3O+ (aq)
pH of solution increases slightly
initial [ ] 0.090 M --- 0.11 M 0 solution becomes slightly more basic
[] x --- +x +x
equil [ ] (0.090x)M --- (0.11+x)M xM

Change of pH of a Buffer Solution With H+ or OH Added How Does a Buffer Work?

pH is controlled by [H+]
in an HA/A buffer solution:
HA (aq) H+ (aq) + A (aq)

[H+][A] [HA]
Ka = OR [H+] = Ka
[HA] [A]

to keep [H+] (and therefore pH) relatively constant,

[HA]/[A] must also remain relatively constant

in buffer solution with HA & A:
addition of H+
neutralization:
H+ + A HA
[HA] increases slightly
[A] decreases slightly
[HA]/[A] increases
[H+] increases
pH decreases
Buffer Capacity
compare 2 HF + NaF buffer solutions:
0.25 M HF & 0.50 M NaF
[HF]/[F] = 0.50
pH = 3.76
after addn of 0.002 mol
H+ to 100 mL solution
[HF]/[F] = 0.56
pH = 3.71
pH = 0.05
better buffer capacity
[HA] Buffer Capacity and Buffer Failure
[H+] = Ka
[A] buffer capacity is the amount of strong acid or
strong base that can be added to a buffer solution
addition of OH before it fails
neutralization:
OH + HA A + H2O a buffer fails when enough strong acid or strong
base is added to cause a pH > 1 unit
[HA] decreases slightly
[A] increases slightly pH of buffer solution depends on the [HA]/[A]
[HA]/[A] decreases
ratio
[H+] decreases capacity of a buffer solution depends on magnitude
pH increases of [HA] and [A]
Henderson-Hasselbalch Equation
[HA]
[H+] = Ka
[A]
0.050 M HF & 0.10 M NaF take log of both sides of equation
[HF]/[F] = 0.50 [A]
pH = pKa + log
pH = 3.76 [HA]
OR
after addn of 0.002 mol [base]
H+ to 100 mL solution pH = pKa + log
[acid]
[HF]/[F] = 0.88
buffer solutions work best when [base]/[acid] is
pH = 3.51
close to 1
pH = 0.25
when [base] = [acid]:
[base]/[acid] = 1 pH = pKa
example:
Consider the following acids and their pKa values:
H2PO4 pKa = 7.21 HF pKa = 3.14
NH4 + pKa = 9.25 HC7H5O2 pKa = 4.19
What would be the best acid/conjugate base to
prepare a buffer solution with pH = 7.00?
What would be the best acid/conjugate base to
prepare a buffer solution with pH = 9.00?
Since buffer solutions work best when [base]/[acid]
is close to 1, the best acid to pick for a buffer is
one with pKa close to the desired pH.
ideally: pKa of acid = soln pH + 1
Acid-Base Titrations: A Quick Review
titration is an analytical technique in which one
reactant is added to another in a very controlled way
stop when the reaction is just complete
at this point there is no limiting reactant, and no
excess reactants
reactants are completely converted to products
stoichiometrically correct mol ratio of reactants
this point is called the:
stoichiometric point
equivalence point
end point
usually some visible indication that you are at the
stoichiometric point (use of indicators)
example:
What is the pH of a buffer solution prepared by
mixing 100 mL of 0.104 M NaF with 200 mL of
0.275 M HF? For HF, pKa = 3.14.
example:
What concentration of NaC7H5O2 is required to
prepare a buffer solution with pH = 4.10 with 0.249
M HC7H5O2 (aq)? For HC7H5O2, pKa = 4.19.
Acid-Base Titrations
we will look in detail at the following titrations:
strong acid + strong base
weak acid + strong base
strong acid + weak base
for each we will:
calculate the pH at points before, at, and
beyond the stoichiometric point
discuss characteristics of each type of
titration
create and interpret titration curves
end with a discussion of acid-base indicators
 Strong Acid + Strong Base Titrations Strong Acid + Strong Base Titrations
basic strategy: example:
1. write the net ionic equation for the neutralization 40.0 mL of 0.110 M HCl (aq) is titrated with
reaction that will occur 0.095 M NaOH (aq).
2. using V and M, calculate mol of each reactant Determine the following:
present initial pH of the solution
3. set up a reaction table; identify the limiting and pH after the addition of 30.0 mL of NaOH
excess reactant pH at the stoichiometric point
4. determine [H+] or [OH] after neutralization pH after the addition of 60.0 mL NaOH
reaction is complete
remember to use the total solution volume!
5. calculate pH of solution

example:
example:
40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M 40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq).
NaOH (aq).
neutralization reaction (Na+ and Cl spectator ions):
H+ (aq) + OH (aq) H2O (l) Determine the initial pH; pH of the solution before
adding any NaOH (aq).
calculate mol H+ (aq):
another way to say this . . .
mol H+ = (0.0400 L)(0.110 mol/L)
What is the pH of 0.110 M HCl (aq)?
= 0.00440 mol H+
[H+] = 0.110 M
calculate volume NaOH (aq) required to reach the
pH = log (0.110) = 0.96
stoichiometric point:
0.00440 mol H+ x 1
mol OH x
1 L soln = 0.0463 L
1 mol H + .095 mol OH
or 46.3 mL
 example: example:

40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq). 40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq).

Determine the pH after the addition of 30.0 mL Determine [excess reactant] after neutralization
NaOH (aq). reaction is complete:
mol OH added = (0.0300 L)(0.095 mol/L) mol H+ after rxn
[H+] =
= 0.0029 mol OH total soln volume
set up a reaction table to identify limiting and excess reactant:
0.0015 mol H+
[H+] =
(0.0400 + 0.0300) L
H+ (aq) + OH (aq) H2O (l)
before rxn: 0.00440 mol 0.0029 mol ---
change: 0 .0029 mol 0.0029 mol --- [H+] = 0.021 M
after rxn: 0.0015 mol 0 --- pH = 1.68

example: example:
40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq). 40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq).
Determine the pH at the stoichiometric point.
Determine the pH after the addition of 60.0 mL
46.3 mL NaOH (aq) added to reach stoichiometric pt NaOH (aq).
at stoichiometric point: mol OH added = (0.0600 L)(0.095 mol/L)
mol OH added = mol H+ present = 0.00440 mol = 0.0057 mol OH
set up reaction table: set up a reaction table to identify limiting and excess reactant:
H+ (aq) + OH (aq) H2O (l)
H+ (aq) + OH (aq) H2O (l)
before rxn: 0.00440 mol 0.0044 mol ---
before rxn: 0.00440 mol 0.0057 mol ---
change: 0 .0044 mol 0.0044 mol ---
change: 0 .0044 mol 0.0044 mol ---
after rxn: 0 0 ---
after rxn: 0 0.0013 mol ---
after reaction the solution is neutral; pH = 7.00
example:
40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq).
Some Titration Data/Titration Curves
Determine [excess reactant] after neutralization Strong Acid/Strong Base Titrations:
Consider the titration of 40.0 mL of 0.110 M HCl (aq) with 0.095 M NaOH (aq).
reaction is complete: mL NaOH added total soln vol. [H3O+] after rxn pH
before 0 40 0.110 M 0.96
stoichiometric 5 45 0.087 M 1.07
mol OH
[OH] = point: 10 50 0.070 M 1.15

total soln volume

30 70 0.021 M 1.68
45 85 0.012 M 1.92
46 86 3.5 x 10 4 M
!
3.46
at stoich. point: 46.3 86.3 1.0 x 10 7 M
! 7.00

0.0013 mol
[OH] = beyond 47 87
[OH] after rxn
0.00115 M 11.06
(0.0400 + 0.0600) L
Some Titration Data/Titration Curves
stoichiometric
point:
50
60
90
100
0.0044 M
0.013 M
11.64
12.11
Strong Acid/Strong Base Titrations:
Consider the titration of 40.0 mL of 0.110 M HCl (aq) with 0.095 M NaOH (aq). 70 110 0.020 M 12.31
mL NaOH added total soln vol. [H3O+] after rxn pH 80 120 0.027 M 12.43
before 0 40 0.110 M 0.96
stoichiometric 5 45 0.087 M 1.07
point:
[OH] = 0.013 M
10
30
50
70
0.070 M
0.021 M
1.15
1.68
45 85 0.012 M 1.92

pOH = 1.89; pH = 12.11

46 86 3.5 x 10 4 M 3.46
!

at stoich. point: 46.3 86.3 1.0 x 10 7 M

!
7.00

[OH ] after rxn
beyond 47 87 0.00115 M 11.06
stoichiometric 50 90 0.0044 M 11.64 Titration of 40.0 mL of 0.110 M HCl (aq) with 0.095 M NaOH (aq)
point: 60 100 0.013 M 12.11
70 110 0.020 M 12.31 14
80 120 0.027 M 12.43

12
Titration Curve for Strong Acid + Strong Base Weak Acid + Strong Base Titrations
Titration of 40.0 mL of 0.110 M HCl (aq) with 0.095 M NaOH (aq)
14
strategy: 10

1. write the net ionic equation for the neutralization

pH
12
8

10
reaction that will occur
strong base is completely ionized
6
pH

stoichiometric pt weak acid is only partially ionized

6 4

4 2. using V and M, calculate mol of each reactant

present
2

0
3. set up a reaction table; identify the limiting and
0
0 20 40 60 80
notes: 0 20 40 60 80

excess reactant
volume NaOH added, mL volume NaOH added, mL

start at low (acidic) pH

pH < 7 before stoichiometric point (OH limiting reactant)
pH = 7 at stoichiometric point (neutral solution)
pH > 7 beyond stoichiometric point (H+ limiting reactant)
end at high (basic) pH
 Weak Acid + Strong Base Titrations Weak Acid + Strong Base Titrations
4. identify the species present when the neutralization example:
reaction is complete, and determine which of them are 30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with
key to determining the pH of the solution 0.100 M NaOH (aq).
before the stoichiometric point, the neutralization
Determine the following:
reaction results in a HA/A buffer solution
initial pH of the solution
at the stoichiometric point, the base ionization of A
will determine the pH pH after the addition of 20.0 mL of NaOH
pH at the stoichiometric point
beyond the stoichiometric point excess OH
determines the pH pH after the addition of 50.0 mL NaOH
5. using post-neutralization concentrations of species, set up
the appropriate calculation and determine pH of solution

example: example:
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH. 30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.

neutralization reaction (Na+ spectator ion):

Determine the initial pH; pH of the solution before
HC2H3O2 (aq) + OH (aq) C2H3O2 (aq) + H2O (l)
adding any NaOH (aq).
calculate mol HC2H3O2 (aq):
another way to say this . . .
mol HC2H3O2 = (0.0300 L)(0.125 mol/L) What is the pH of 0.125 M HC2H3O2 (aq)?
= 0.00375 mol HC2H3O2
weak acid calculation; Ka for HC2H3O2 = 1.8 x 105
calculate volume NaOH (aq) required to reach the
stoichiometric point: x = [H+] = 0.0015 M
1 mol OH
.003750 mol HC2H3O2 x 1 L soln = 0.0375 L
x
pH = log (0.0015) = 2.82
1 mol HC2H3O2 .100 mol OH
or 37.5 mL
example: example:
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH. 30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.

Determine the pH after the addition of 20.0 mL

Determine [HC2H3O2] and [C2H3O2] after
NaOH (aq).
neutralization reaction is complete:
mol OH added = (0.0200 L)(0.100 mol/L)
.00175 mol
[HC2H3O2] = .00200 mol
[C2H3O2] =
= 0.00200 mol OH (.0300 + .0200)L (.0300 + .0200)L
set up a reaction table to identify limiting and excess reactant:
[HC2H3O2] = 0.0350 M [C2H3O2] = 0.0400 M
HC2H3O2 + OH C2H3O2 + H2O this is a buffer solution
before rxn: .00375 mol .00200 mol 0 ---
determine [H+] and pH by using an equilibrium
change: .00200 mol .00200 mol +.00200 mol --- table
after rxn: .00175 mol 0 .00200 mol --- OR
the Henderson-Hasselbalch equation

example: example:
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH. 30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
using an equilibrium table (Ka = 1.8 x 105): Determine the pH at the stoichiometric point.
HC2H3O2 C2H3O2 + H+
37.5 mL NaOH (aq) added to reach stoichiometric pt
initial [ ]: .0350 M .0400 M 0
at stoichiometric point:
change [ ]: x +x +x
mol OH added = mol HC2H3O2 present = 0.00375 mol
equil [ ]: (.0350 x) M (.0400 + x) M xM
set up reaction table:
x= [H+] = 1.6 x 105 M; pH = 4.80
HC2H3O2 + OH C2H3O2 + H2O

using Henderson-Hasselbalch (pKa = 4.74): before rxn: .00375 mol .00375 mol 0 ---
change: .00375 mol .00375 mol +.00375 mol ---
.0400
pH = 4.74 + log
.0350 after rxn: 0 0 .00375 mol ---
pH = 4.80
 example:
example:
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
the equilibrium table and calculation:
after the neutralization reaction, HC2H3O2 and OH C2H3O2 + H2O HC2H3O2 + OH
are completely consumed initial [ ]: .0556 M --- 0 0
base ionization of C2H3O2 controls the pH of soln:

[ ]: x --- +x +x
C2H3O2 (aq) + H2O (l) HC2H3O2 (aq) + OH (aq) equil [ ]: (.0556 x)M --- xM xM
Kb = KW(Ka for HC2H3O2) = 5.6 x 1010 x2
Kb = 5.6 x 1010 =
.0556 x
determine [C2H3O2] after neutralization reaction:
solve for x: x = [OH] = 5.6 x 106 M
.00375 mol pOH = 5.25
[C2H3O2] = = 0.0556 M
.0675 L pH = 8.75
for a weak acid titrated with a strong base, the pH > 7 at
the stoichiometric point

example: example:
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH. 30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
determine [excess reactant] after neutralization
Determine the pH after the addition of 50.0 mL reaction is complete:
NaOH (aq).
mol OH
mol OH added = (0.0500 L)(0.100 mol/L) [OH] =
total soln volume
= 0.00500 mol OH
set up a reaction table to identify limiting and excess reactant: 0.00125 mol
[OH] =
(0.0300 + 0.0500) L
HC2H3O2 + OH C2H3O2 + H2O
before rxn: .00375 mol .00500 mol 0 --- [OH] = 0.0156 M
change: .00375 mol .00375 mol +.00375 mol --- pOH = 1.81; pH = 12.19
after rxn: 0 .00125 mol .00375 mol ---
 point: 60 90 0.025 M 12.40
75 105 0.0357 M 12.55

Titration Curve for Weak Acid + Strong Base

Titration of 0.125 M HCH O (aq) with 0.100 M NaOH (aq)
2 3 2
14

Weak Acid/Strong Base Titrations:

12
Consider the titration of 30.0 mL of 0.125 M HC2H3O2 (aq) with 0.100 M NaOH (aq).
mL NaOH added total soln vol. [H3O+] after rxn pH
before 0 30 1.5 x 10 3 M
! 2.82 10
stoichiometric 5 35 1.2 x 10 4 M
! 3.93
stoichiometric pt

pH
point: 10 40 5.0 x 10 5 M
! 4.30
20 50 1.6 x 10 5 M
! 4.80 8

30 60 4.6 x 10 5 M
! 5.34
35 65 1.3 x 10 6 M
! 5.89
37 67 2.5 x 10 7 M
! 6.61 6

[OH] after rxn buffer zone

at stoich. point: 37.5 67.5 5.6 x 10 6 M
! 8.75
4
beyond 40 70 0.0036 M 11.56
stoichiometric 50 80 0.0156 M 12.19
point: 60 90 0.025 M 12.40
2
75 105 0.0357 M 12.55
notes: 0 10 20 30 40
volume NaOH added, mL
50 60 70 80

start at low (acidic) pH

pH < 7 before stoichiometric point (OH limiting reactant)
pH > 7 at stoichiometric point (basic solution)
pH > 7 beyond stoichiometric point (H+ limiting reactant)
Titration of 0.125 M HCH O (aq) with 0.100 M NaOH (aq)
2 3 2
end at high (basic) pH
14

example:
example:
12

30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.

30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
10
an important point in a weak acid + strong base Determine the pH after the addition of 18.75 mL
pH

titration is the half-way point NaOH (aq).

8

half-way to the stoichiometric point mol OH added = (0.01875 L)(0.100 mol/L)

vol required = !(vol to reach stoich.pt.)
6 = 0.001875 mol OH
set up a reaction table to identify limiting and excess reactant:
for this titration:
4

vol required = !(37.5 mL) HC2H3O2 + OH C2H3O2 + H2O

half-way to the stoichiometric point is after
2
0 10 20 30 40 50 60 70 80
before rxn: .00375 mol .001875 mol 0 ---
the addition of 18.75 mL NaOH volume NaOH added, mL
change: .001875 mol .001875 mol +.001875 mol ---
after rxn: .001875 mol 0 .001875 mol ---
example: Strong Acid + Weak Base Titrations
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
strategy:
determine [HC2H3O2] and [C2H3O2] after
neutralization reaction is complete: 1. write the net ionic equation for the neutralization
.001875 mol .001875 mol reaction that will occur
[HC2H3O2] = [C2H3O2] = strong acid is completely ionized
.04875 L .04875 L
weak base is only partially ionized
[HC2H3O2] = 0.0385 M [C2H3O2] = 0.0385 M
2. using V and M, calculate mol of each reactant
this is a buffer solution with [acid] = [base]
present
using Henderson-Hasselbalch (pKa = 4.74):
.0385 3. set up a reaction table; identify the limiting and
pH = 4.74 + log
.0385 excess reactant
pH = pKa = 4.74
at the half-way point in a weak + strong titration, the
pH of the solution equals the pKa of the acid

Strong Acid + Weak Base Titrations
4. identify the species present when the neutralization
reaction is complete, and determine which of them are
key to determining the pH of the solution
before the stoichiometric point, the neutralization
reaction results in a B/BH+ buffer solution
at the stoichiometric point, the acid ionization of
BH+ will determine the pH
beyond the stoichiometric point excess H+
determines the pH
5. using post-neutralization concentrations of species, set up
the appropriate calculation and determine pH of solution
Strong Acid + Weak Base Titrations
example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with
0.750 M HNO3 (aq).
Determine the following:
initial pH of the solution
pH after the addition of 10.0 mL of HNO3
pH at the stoichiometric point
pH after the addition of 50.0 mL HNO3
example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.
neutralization reaction (NO3 spectator ion): Determine the initial pH; pH of the solution before
CH3NH2 (aq) + H+ (aq) CH3NH3+ (aq) adding any CH3NH2 (aq).
calculate mol CH3NH2 (aq): another way to say this . . .
mol CH3NH2 = (0.0200 L)(1.20 mol/L) What is the pH of 1.20 M CH3NH2 (aq)?
= 0.0240 mol CH3NH2 weak base calculation; Kb for CH3NH2 = 3.7 x 104
calculate volume HNO3 (aq) required to reach the x = [OH] = 0.021 M
stoichiometric point:
pOH = log (0.021) = 1.68
1 mol H+ x
0.0240 mol CH3NH2 x 1 L soln = 0.0320 L
1 mol CH3NH2 .750 mol H+
or 32.0 mL pH = 12.32

example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.

Determine the pH after the addition of 10.0 mL determine [CH3NH2] and [CH3NH3+] after
HNO3 (aq). neutralization reaction is complete:
mol H+ added = (0.0100 L)(0.750 mol/L) .0165 mol
[CH3NH2] = .00750 mol
[CH3NH3+] =
= 0.00750 mol H+ (.0200 + .0100)L (.0200 + .0100)L

[CH3NH2] = 0.550 M [CH3NH3+] = 0.250 M

set up a reaction table to identify limiting and excess reactant:

CH3NH2 + H+ CH3NH3+ this is a buffer solution

before rxn: .0240 mol .00750 mol 0
determine [OH] and pH by using an equilibrium
change: .00750 mol .00750 mol +.00750 mol table
after rxn: .0165 mol 0 .00750 mol OR
the Henderson-Hasselbalch equation
example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.
using an equilibrium table (Kb = 3.7 x 104): Determine the pH at the stoichiometric point.
CH3NH2 + H2O CH3NH3+ + OH
initial [ ]: .550 M --- .250 M 0
32.0 mL HNO3 (aq) added to reach stoichiometric pt
at stoichiometric point:
[ ]: x --- +x +x
mol H+ added = mol CH3NH2 present = 0.0240 mol
equil [ ]: (.550 x)M --- (.250+x) M xM
set up reaction table:
x = [OH] = 8.1 x 104 M; pOH = 3.89
pH = 10.91 CH3NH2 + H+ CH3NH3+
using Henderson-Hasselbalch (pKa of CH3NH3+= 10.57): before rxn: .0240 mol .0240 mol 0
change: .0240 mol .0240 mol +.0240 mol
.550
pH = 10.57 + log
.250 after rxn: 0 0 .0240 mol
pH = 10.91

example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.
the equilibrium table and calculation:
after the neutralization reaction, CH3NH2 and H+
CH3NH3+ CH3NH2 + H+
are completely consumed
initial [ ]: 0.462 M 0 0
acid ionization of CH3NH3+ controls the pH of soln:
[ ]: x +x +x
CH3NH3+ (aq) CH3NH2 (aq) + H+ (aq)
equil [ ]: (0.462 x) M xM xM
Ka = KW(Kb for CH3NH2) = 2.7 x 1011 x2
Ka = 2.7 x 1011 =
determine [CH3NH3+] after neutralization reaction: .462 x
.0240 mol solve for x: x = [H ] = 3.5 x 106 M
+

[CH3NH3 +] = = 0.462 M pH = 5.46

.0520 L
for a weak base titrated with a strong acid, the pH < 7 at
the stoichiometric point
example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.

Determine the pH after the addition of 50.0 mL HNO3 (aq). determine [excess reactant] after neutralization
reaction is complete:
mol H+ added = (0.0500 L)(0.750 mol/L)
= 0.0375 mol H+ mol H+
[H+] =
total soln volume
set up a reaction table to identify limiting and excess reactant:
0.0135 mol
CH3NH2 + H+ CH3NH3+ [H+] =
(0.0200 + 0.0500) L
before rxn: .0240 mol .0375 mol 0
change: .0240 mol .0240 mol +.0240 mol
[H+] = 0.193 M
after rxn: 0 .0135 mol .0240 mol
pH = 0.741

example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.
Determine the pH after the addn of 16.0 mL HNO3 (aq). determine [CH3NH2] & [CH3NH3+] after neutralization
reaction is complete:
mol H+ added = (0.0160 L)(0.750 mol/L)
.0120 mol .0120 mol
= 0.0120 mol H+ [CH3NH2] =
.0360 L
[C2H3O2] =
.0360 L

set up a reaction table to identify limiting and excess reactant: [HC2H3O2] = 0.330 M [C2H3O2] = 0.330 M

CH3NH2 + H+ CH3NH3+
this is a buffer solution with [acid] = [base]
before rxn: .0240 mol .0120 mol 0 using Henderson-Hasselbalch (pKa = 10.57):
.330
pH = 10.57 + log
change: .0120 mol .0120 mol +.0120 mol
.330
after rxn: .0120 mol 0 .0120 mol pH = pKa = 10.57
at the half-way point in a weak + strong titration, the
pH of the solution equals the pKa of the acid
 50 70 0.193 M 0.714
60 80 0.263 M 0.580

Titration Curve for Strong Acid + Weak Base

Titration of 20.0 mL of 1.20 M CH
NH (aq) with 0.75 M HNO (aq)
3 2 3
14

Weak Base/Strong Acid Titrations:

12
Consider the titration of 20.0 mL of 1.20 M CH3NH2 (aq) with 0.75 M HNO3 (aq).
mL HNO3 added total soln vol. [OH] after rxn pH buffer zone
before 0 20 0.021 M 12.32 10
stoichiometric 5 25 0.0020 M 11.30
point: 10 30 8.1 x 10 4 M
!
10.91
8
16 36 3.7 x 10 4 M
!
10.57

pH
20 40 2.2 x 10 4 M
!
10.35
25 45 1.0 x 10 4 M 10.01
stoichiometric pt
!
6
30 50 2.5 x 10 5 M
!
9.40
[H3O+] after rxn
4
at stoich. point: 32 52 3.5 x 10 6 M
!
5.46
beyond 35 55 0.042 M 1.38
stoichiometric 40 60 0.100 M 1.00 2

point: 45 65 0.151 M 0.821

50 70 0.193 M 0.714
0
60 80 0.263 M 0.580
notes: 0 10 20 30 40 50 60 70

start at high (basic) pH

volume nitric acid added, mL

pH > 7 before stoichiometric point (H+ limiting reactant)

pH < 7 at stoichiometric point (acidic solution)
pH < 7 beyond stoichiometric point (OH limiting reactant)
Titration of 20.0 mL of 1.20 M CH
NH (aq) with 0.75 M HNO (aq)
3 2 3
end at low (acidic) pH
14

12
Acid-Base Indicators Acid-Base Indicators
an indicator is used to indicate the stoichiometric
point in a titration - typically by change in color
10 a few examples of indicators:

you want to choose an indicator that will change

8
pH

color very close to the stoichiometric point in your

titration
6

results in minimal experimental error

4
phenolphthalein bromocresol green methyl red
pH of indicator color change should be close acid form: acid form: acid form:
2
(+1) to pH at stoichiometric point colorless yellow orange
base form: base form: base form:
acid-base indicators tend to be large organic
0
0 10 20 30 40 50 60 70 pink blue yellow
molecules that are weak acids: volume nitric acid added, mL
pH range of pH range of pH range of
HIn (aq) + H2O (l) In (aq) + H3 O+ (aq) color change: color change: color change:
acid form base form 8 10 3.8 5.3 4.2 6.2
 Acid-Base Indicators Acid-Base Indicators
the color of an indicator solution depends on the 2 extremes:
pH (and [H3O+]) and the relative amounts of HIn in acidic solution
and In present low pH high [H3O+]
HIn (aq) + H2O (l) In (aq) + H3O+ (aq) equilibrium position far to the left
acid form base form
[HIn] high [In] low
[In][H3O+] [HIn] indicator is in its acid form and color
KIn = ; [H3O+] = KIn
[HIn] [In]
in basic solution
high pH low [H3O+]
pH affects the equilibrium position, and therefore equilibrium position far to the right
the ratio of acid form : base form of indicator in
soln [HIn] low [In] high
indicator is in its base form and color
 Choosing an Indicator for a Titration Strong Acid + Strong Base Titration:
pH at stoichiometric point = 7
In general, an indicator will change color at a
solution pH = pKIn + 1.

You should choose an indicator with pKIn value that

is close to the pH of the solution at the
stoichiometric point of your titration.

Weak Acid + Strong Base Titration: Strong Acid + Weak Base Titration:
pH at stoichiometric point > 7 pH at stoichiometric point < 7
 Final Thoughts on Acid-Base Titrations
Final Thoughts on Acid-Base Titrations
if H3O+ or OH is present after the neutralization reaction,
go straight to pH calculation
neutralization reactions happen 1st
fast at any point in a strong acid + strong base titration
beyond the stoichiometric point in weak + strong titration
go to completion
if HA & A or B & BH+ are present after the neutralization
set up reaction table (with mol of species) for the reaction:
neutralization reaction buffer solution use equilibrium calculation or
Henderson-Hasselbalch equation
assess what is in solution when the neutralization before the stoichiometric point in weak + strong titration
reaction is complete
if A or BH+ are present after the neutralization reaction:
calculate post-neutralization [ ] of important species equilibrium calculation based on ionization:
[ ] = mol total soln volume A (aq) + H2O (l) HA (aq) + OH (aq)
BH+ (aq) B (aq) + H+ (aq)
at the stoichiometric point in weak + strong titration

Final Thoughts on Acid-Base Titrations

pH titration curves:
know the characteristic profiles for the 3 categories of
titrations
know the important points on the curve:
stoichiometric point
half-way point
buffer zone

calculations for titrations:

volume of acid or base reqd to reach stoichiometric pt
initial pH of solution
pH before, at, beyond & half-way to the stoichiometric pt