Chem 221

Acid Base Reactions I

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 Objectives
 Define neutralization reaction.
 Undergo calculations involving acid-
base mixtures.
 Define titration and pH curves.
 Construct titration curves of strong acids
with strong bases.
 Define a buffer solution.
 Apply Handerson Equation.
 Construct titration curves of weak acids
with strong bases.
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 Acid-base reactions
 An acid-base reaction is often called neutralization
reaction. When just enough base is added to react
exactly with the acid in a solution, we say the acid
has been neutralized.
 In this section, we will discuss the changes that
occur in pH during an acid base titration.

 The progress of an acid-base titration is often

monitored by plotting the pH of the solution
being analyzed as a function of the amount of
titrant added.

 Such a plot is called a pH curve or a titration

curve.
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 Strong Acid- Strong Base titrations

 The net ionic reaction for a strong acid-

strong base titration is
 H+(aq) + OH-(aq) H2O(l)

 To compute [H+] at a given point in the titration,

we must determine the amount of H+ that remains
at that point and divide by the total volume of
solution.

 Since titrations usually involve small

quantities (burettes are graduated in milliliters)
we are going to use the mmoles = volume (in
ml) X molarity.
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 CASE STUDY: Consider the titration of 50.0 ml of 0.2M HCl
with 0.1M NaOH. We will calculate the pH of the solution at
selected points during the course of the titration, where
specific volumes of 0.1M NaOH have been added.
 A. No NaOH has been added.
 Since HCl is a strong acid,
 [H+] = 0.2 M and
pH = -log [H+]=-log [H+]= 0.669

 B. 10.0 ml of 0.1M NaOH has been added.

H+ + OH- H2O
 Before reaction 50.0x0.2 10x0.1
= 10.0 mmol =1.0 mmol
 After reaction 10.0-1.0 1.0-1.0
=9.0 mmol =0
 After reaction,
 [H+] = mmol of H+ left/ volume of solution ml
= 9.0/ (50.0+10.0) = 0.15 M
 pH = - log (0.15) = 0.82 5
 (cont.)
 C. 20 ml (total) of 0.1 M NaOH has been added.
H+ + OH- H2O
 Before reaction 50.0x0.2 20x0.1
= 10.0 mmol =2.0 mmol
 After reaction 10.0-2.0 2.0-2.0
=8.0 mmol =0
 After reaction,
 [H+] = mmol of H+ left/ volume of solution ml
= 8.0/ (50.0+20.0) = 0.11 M
 pH = - log (0.11) = 0.942

 D. 50.0 ml (total) of 0.1M NaOH has been added.

 Proceeding exactly as for point B and C, the pH is found
to be 1.301

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 (cont.)
 E. 100.0 ml (total) of 0.1M NaOH has been added.
 At this point the amount of NaOH that has been added is
100ml x 0.1M = 10.0 mmol.
 The original amount of HCl was 50.0 ml x 0.2M = 10.0
mmol.

 Enough OH- has been added to react exactly with

the H+ from the HCl.

 This is the stoichiometric point or equivalence

point, of the titration.

 At that point, the major species are Na+, Cl- and H2O,
and the solution is neutral. (The pH is 7.0)

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 (cont.)
 F. 150 ml (total) of 0.1m NaOH has been added
H+ + OH- H2O
 Before reaction 50.0x0.2 150x0.1
= 10.0 mmol =15.0 mmol
 After reaction 10.0-10.0 15.0-10.0
= 0 mmol = 5.0(excess OH- added)
 After reaction,
 [OH-]= mmol of OH- excess/volume of solution
ml = 5.0/ (50.0+150.0) = 0.025 M
 [H+] = 1.0x10-14/2.5x10-2 = 4.0x10-13M pH = 12.40

 G. 200.0 ml (total) of 0.1 M NaOH has been added

 Proceeding as for point F, the pH is found to be 12.60

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 (cont.)
 The results of the previous steps are
summarized by the pH curve shown in
fig.

 Note that the pH changes very gradually

until the titration is close to the equivalence
point, where a dramatic change occurs.

 This behavior is due to the fact that early in

the titration, there is relatively a large
amount of H+ in the solution, and the
addition of a given amount of OH- thus
produces a small change in pH.

 However, near the equivalence point [H+]

is relatively small and the addition of a small
amount of OH- produces a large change. 9
 Titrations of weak acids with strong
bases
 For strong acids and strong bases titrations,
as they are completely dissociated, the
calculations to obtain the pH curves for
titrations are quite straightforward.

 When the acid being titrated is a weak acid,

there is a major difference: to calculate [H+]
after a certain amount of strong base has
been added, we must deal with the
weak acid dissociation equilibrium.
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 Acid Strength (cont.)
 HA(aq) + H2O H3O+(aq) + A-(aq)
 conjugate base

 A weak acid is one for which the equilibrium

lies far to the left. A weak acid dissociates
only to a very small extent.

 A weak acid has a strong conjugate base.

(i.e. will have basic properties)

 Examples: phosphoric acid (H3PO4), acetic

acid (CH3COOH), benzoic acid (C6H5COOH).11
Examples

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 Calculating pH of weak acid solutions
 For weak acid, as they are not 100%
ionized in water, the previous steps to
calculate the pH can’t be valid but we should
take in account the dissociation constant Ka
which is much more complicated.

 Weak acids dissociates partially (<1%)

while strong acids dissociates completely.

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 Example
Calculate the pH of 1.00M solution of HF (Ka = 7.2x10-4).
 HF H+ + F-
As HF is a weak acid let us consider that the amount dissociated
from it equal x, thus [H+] and [F-] = x and that of [HF]
decreased by x
but this last decrease can be approximated as it is less
than 1% of the original concentration, thus
 K = [H+][F-]  7.2x10-4 = (x)(x)
[HF] 1.00
X2 = (7.2x10-4)(1.00)
X = 2.7x10-2 (x= is the actual amount of H+ present in solution)
pH = -log(2.7x10-2) = 1.57 ,
That is pH= -log K [acid] (Relation commonly USED)
a 14
 Acid- base properties of salts

 Salt simply is another name for ionic

compound. When a salt dissolves in water,
we assume that it breaks up to its ions.

 We can have one of the following cases:

 Salts that produce neutral solutions.

 Salts that produce basic solutions.
 Salts that produce acidic solutions.
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The acid –base properties of salts

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 Acid base properties of salts (cont.)

 If the value of Ka for acetic acid is (1.8x10-5).

 How can we calculate the Kb value for the
acetate ion?

 The answer lies in the relationship among

Ka, Kb and Kw.
 Note that when the expression for Ka for acetic
acid is multiplied by the expression for Kb for the
acetate ion, the result is Kw:
[H ][C2H3O2 ] [HC2H3O2 ][OH ]
Ka x Kb  x  [H ][OH ]  K w
[HC2H3O2 ] [C2H3O2 ]

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 Acid base properties of salts (cont.)

 For any weak acid and its conjugate base,

Ka X Kb = Kw

 For the acetate ion,

 Kb = Kw/ Ka (for HC2H3O2)
= 1.0x10-14 / 1.8x10-5 = 5.6x10-10

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 Example:
Calculate the pH of a 0.30 M NaF solution.
The Ka value for HF is 7.2x10-4.
 Kb = Kw / Ka = 1.0x10-14/7.2x10-4 = 1.4x10-11

pOH = -log K b [base] = 5.69

pH = 14.00 -5.69 = 8.31

As expected,
The solution is basic.

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 Example:
Calculate the pH of a 0.01 M NH4Cl
solution. The Kb value for NH3 is 1.8x10-5.

 Recalling that Ka X Kb = Kw
 Ka= 1.0x10-14/1.8x10-5 = 5.6x10-10

 pH = -log K a [acid] = 5.31

As expected, The solution is Acidic

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 Solutions of acids or bases containing
common ion
 Suppose that we have a solution containing the
weak acid hydrofluoric acid (HF , Ka = 7.2x10-4) and
its salt sodium fluoride (NaF).
 Recall that when a salt dissolves in water, it breaks
up completely into its ions, (it is strong electrolyte).
NaF(s) Na+(aq) + F-(aq)
 Since hydrofluoric acid is a weak acid it will only
slightly dissociate.
 The common ion in this solution is F- since it is
produced by both hydrofluoric acid and sodium
fluoride.
 What effect does the presence of the
dissolved sodium fluoride have on the
dissociation equilibrium of hydrofluoric acid?
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 Solutions of acids or bases containing
common ion (cont.)
 The dissociation equilibrium for HF can be represented as:
 HF(aq) H+(aq) + F-(aq)
While in the presence of F- ions from the NaF, according to
Le Chatelier’s principle, the extent of dissociation of HF
will be less in the presence of dissolved NaF:
HF(aq) H+(aq) + F-(aq)

 The shift in equilibrium position that occurs, leads to a less

acidic solution than in case of HF alone.
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 Solutions of acids or bases containing
common ion (cont.)

 This common ion effect is very important in

solutions of polyprotic acids.

 The production of protons by the first dissociation

step greatly inhibits the succeeding
dissociation steps.

 That is why the hydrogen ion source will be only

the first dissociation step.

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 Example
If the equilibrium concentration of H+ in a 1.0M HF solution is
2.7x10-2M and the percent dissociation of HF is 2.7%. Calculate
[H+] and the percent dissociation of HF in a solution containing
1.0M HF (Ka = 7.2x10-4) and 1.0M NaF.
The acid dissociation equilibrium that controls [H+] in this
solution.
 HF(aq) H+(aq) + F-(Aq)
Ka = [H+][F-] / [HF] = 7.2x10-4
Notice that: the [F-] = 1.0M plus (x) which is resulting
from the dissociation of HF
[H ][F ] (x)(1.0  x) (x)(1.0)
 

K  7.2x10  4
 
(1.0  x)
a
[HF] (1.0)
x= [H+] = 7.2X10-4 M, Notice that, x is much small compared to
the original concentration.
pH =- log 7.2X10-4 = 3.14 24
 Example (cont.)
The percent dissociation (defined as the amount of protons
produced divided by the original acid concentration) in this
solution is:

[H  ] 7.2x10 4 M
x 100  x 100  0.072%
[HF]0 1.0M

Compare these values for [H+] and percent dissociation of HF with those for a
1.0M HF solution, where [H+] =2.7x10-2 M and the percent dissociation is
2.7%.

The large difference shows clearly that the presence of the F- ions
from the dissolved NaF greatly inhibits the dissociation of HF.

The position of the acid dissociation equilibrium has been shifted to

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the left by the presence of F- ions from NaF.
 Titrations of weak acids with strong
bases
 Calculating the pH curve for a weak acid –
strong base titration involves a two step
procedure:
 1. A stoichiometry problem, the reaction of
hydroxide ion with the weak acid is assumed to run to
completion and the concentrations of the acid
remaining and the conjugate base formed are
determined.
 2. An equilibrium problem, the position of the
weak acid equilibrium is determined and the pH is
calculated.
 It is essential to do these steps separately.
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 Example
Consider the titration of 50.0 ml of 0.1M acetic acid
(HC2H3O2, Ka = 1.8x10-5) with 0.1 M NaOH. As before
we will calculate the pH at various points
representing volumes of added NaOH.

 Before doing anything we have to calculate

the volume of NaOH required for complete
neutralization, (MV)acetic = (MV)NaOH
 (50x0.1)acetic = (0.1V)NaOH  VNaOH= 50 ml
 A. No NaOH has been added.
 This is a typical weak acid calculation and the
pH = 2.87
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 Example (cont.)
 B. 10.0 ml of 0.10 M NaOH has been added

 The stoichiometry problem

 Now the solution is a mixture of a weak acid

and its salt i.e. BUFFER 28
 Buffered solutions
 The most important application of acid- base
solutions containing a common ion is for
buffering.

 A buffered solution is one that resists a change

in its pH when either hydroxide ions or
protons are added.

 A buffered solution may contain a weak acid

and its salt (e.g. HF and NaF) or a weak base
and its salt (e.g. NH3 and NH4Cl). By choosing
the appropriate components, a solution can be
buffered at virtually any pH.
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 Henderson-Hasselbalch equation
 For the following acid dissociation reaction,
 HA H+ + A - [H ][A  ]
Ka 
[HA]
K a [HA]
 [H ] 
[A  ]
[HA]
 log[H ]  logKa  log
[A  ]
[HA]
pH  pK a  log
[A  ]
[A  ]
pH  pK a  log
[HA]
[base]
pH  pKa  log
[acid]
 This log form of the expression for Ka is called Henderson-
Hasselbalch equation and is useful for calculating the pH of solutions
when the ratio of [A-]/[HA] is known. 30
 (example cont.)
 The equilibrium problem
 The pH will be determined by the position of the acetic
acid dissociation equilibrium:

 We follow the usual steps to complete equilibrium

calculations:

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 (example cont.)
 Applying Hasselbalch-Handrerson
equation
 pH = pKa + log [base]/[acid]

5 1.0/60.0
 log1.8x10  log
4.0/60.0

 pH = 4.14

 The same value we got from the previous steps.

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 (example cont.)
 C. 25.0 ml (total) of 0.1 M NaOH has been
added
 The procedure is similar to point B. the stoichiometry will be:

 After the reaction,

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 (example cont.)
 This is a special point in the titration because it is
halfway to the equivalence point.
 The original solution, 50.0 ml of 0.1 M HC2H3O2
contained 5.0 mmol HC2H3O2 and this requires 5.0
mmol NaOH for equivalence.
 After 25.0 ml NaOH is added, half the original
HC2H3O2 is converted to C2H3O2-. At this point,
their concentration will be equal then

 Then, at the half way point in titration

 [H+] = Ka and pH = pKa
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 (example cont.)
 D. 50.0 ml (total) of 0.1 m NaOH has been added
 This is the equivalence point of the titration, 5.0 mmol OH- has been
added, which will react with the 5.0 mmol of HC2H3O2 originally present.

 Note that the solution contains C2H3O2-, which is a base.

 Remember that a base wants to react with water to combine

with a proton , thus the reaction will be:

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 (example cont.)

 Therefore,

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 (example cont.)
 This is an important result: the pH at the
equivalence point of a weak acid with a strong base
is always greater than 7.

 This is because the anion of the acid that

remains at the equivalence point is a base, In
contrast to the case of strong acid- strong base
titration, the pH is 7 because the anion remaining
in this case is not an effective base.

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 (example cont.)
 E. 60.0 ml (total) of 0.1 M NaOH has been added.
 At this point excess OH- has been added. The stoichiometry
will be

 After the reaction is complete,

 There are two bases in this solution C2H3O2-, OH-.
However, C2H3O2-,is a weak base compared with OH- .
Therefore the amount of OH- produced by C2H3O2- with
H2O will be small compared with the excess OH-.
 The pH can be calculated as:

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39
 References
 D. A. Skoog, D.A. West, F.J. Holler, S.R.
Crouch, Analytical Chemistry, an
introduction, 7th Edition, ISBN 0-03-
020293-0.
 https://www.khanacademy.org/scien
ce/chemistry/acid-base-
equilibrium/titrations/v/titration-
curves-and-acid-base

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