9/20/23, 7:34 PM Titration curves & equivalence point (article) | Khan Academy
Acid-base titration
curves
Google Classroom
Before we start discussing about titration and titration curves, we should
quickly refresh the concept of a weak/strong acid and weak/strong base.
A strong acid dissociates (or ionizes) completely in aqueous solution to
form hydronium ions (H3 O+ )
A weak acid does not dissociate completely in aqueous solution to form
hydronium ions (H3 O+ )
A strong base dissociates completely in aqueous solution to form hydroxide
ions (OH- )
A weak base does not dissociate completely in aqueous solution to form
hydroxide ions (OH- )
Examples of weak/strong acids and bases
Type Examples
Strong hydrochloric acid (HCl), sulfuric acid (H2 SO4 ), nitric acid
Acids (HNO3 )
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9/20/23, 7:34 PM Titration curves & equivalence point (article) | Khan Academy
Type Examples
Weak acetic acid (CH3 COOH), hydrofluoric acid (HF), oxalic acid
Acids (COOH)2
Strong sodium hydroxide (NaOH), potassium hydroxide (KOH),
Bases lithium hydroxide (LiOH)
Weak ammonium hydroxide (NH4 OH), ammonia (NH3 )
Bases
Weak acids and weak bases always exist as conjugate acid-base pairs in
an aqueous solution as represented below
Here, HA is the acid and A- is termed as the conjugate base of HA
In the above reaction, A- is a base and HA is the conjugate acid of A-
Rule of thumb is: Weak acids have strong conjugate bases, while weak
bases have strong conjugate acids. As shown in the above two reactions, if
HA is a weak acid, then its conjugate base A- will be a strong base.
Similarly, if A- is a weak base, then its conjugate acid HA will be a strong
acid.
How do we define ‘titration’?
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9/20/23, 7:34 PM Titration curves & equivalence point (article) | Khan Academy
Titration is a technique to determine the concentration of an unknown
solution. As illustrated in the titration setup above, a solution of known
concentration (titrant) is used to determine the concentration of an unknown
solution (titrand or analyte).
Typically, the titrant (the solution of known concentration) is added through
a burette to a known volume of the analyte (the solution of unknown
concentration) until the reaction is complete. Knowing the volume of titrant
added allows us to determine the concentration of the unknown analyte.
Often, an indicator is used to signal the end of the reaction, the endpoint.
Titrant and analyte is a pair of acid and base. Acid-base titrations are
monitored by the change of pH as titration progresses.
Let us be clear about some terminologies before we get into the discussion
of titration curves.
Titrant: solution of a known concentration, which is added to another
solution whose concentration has to be determined.
Titrand or analyte: the solution whose concentration has to be
determined.
Equivalence point: point in titration at which the amount of titrant
added is just enough to completely neutralize the analyte solution. At
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9/20/23, 7:34 PM Titration curves & equivalence point (article) | Khan Academy
the equivalence point in an acid-base titration, moles of base = moles
of acid and the solution only contains salt and water.
Acid-base titrations are monitored by the change of pH as titration
progresses
Indicator: For the purposes of this tutorial, it’s good enough to know that an
indicator is a weak acid or base that is added to the analyte solution, and it
changes color when the equivalence point is reached i.e. the point at which
the amount of titrant added is just enough to completely neutralize the
analyte solution. The point at which the indicator changes color is called the
endpoint. So the addition of an indicator to the analyte solution helps us to
visually spot the equivalence point in an acid-base titration.
Endpoint: refers to the point at which the indicator changes color in an acid-
base titration.
What is a titration curve?
A titration curve is the plot of the pH of the analyte solution versus the
volume of the titrant added as the titration progresses.
Let’s attempt to draw some titration curves now.
1) Titration of a strong acid with a strong base
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9/20/23, 7:34 PM Titration curves & equivalence point (article) | Khan Academy
Suppose our analyte is hydrochloric acid HCl (strong acid) and the titrant is
sodium hydroxide NaOH (strong base). If we start plotting the pH of the
analyte against the volume of NaOH that we are adding from the burette,
we will get a titration curve as shown below.
Point 1: No NaOH added yet, so the pH of the analyte is low (it
predominantly contains H3 O+ from dissociation of HCl).
As NaOH is added dropwise, H3 O+ slowly starts getting consumed by OH
-
produced by dissociation of NaOH. Analyte is still acidic due to
predominance of H3 O+ ions.
Point 2: This is the pH recorded at a time point just before complete
neutralization takes place.
Point 3: This is the equivalence point (halfway up the steep curve). At this
point, moles of NaOH added = moles of HCl in the analyte. At this point, H3
O+ ions are completely neutralized by OH- ions. The solution only has salt
(NaCl) and water and therefore the pH is neutral i.e. pH = 7.
Point 4: Addition of NaOH continues, pH starts becoming basic because
HCl has been completely neutralized and now excess of OH- ions are
present in the solution (from dissociation of NaOH).
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9/20/23, 7:34 PM Titration curves & equivalence point (article) | Khan Academy
2) Titration of a weak acid with a strong base
Let’s assume our analyte is acetic acid CH3 COOH (weak acid) and the
titrant is sodium hydroxide NaOH (strong base). If we start plotting the pH
of the analyte against the volume of NaOH that we are adding from the
burette, we will get a titration curve as shown below.
Point 1: No NaOH added yet, so the pH of the analyte is low (it
predominantly contains H3 O+ from dissociation of CH3 COOH). But acetic
acid is a weak acid, so the starting pH is higher than what we noticed in
case 1 where we had a strong acid (HCl).
As NaOH is added dropwise, H3 O+ slowly starts getting consumed by OH
-
(produced by dissociation of NaOH). But analyte is still acidic due to
predominance of H3 O+ ions.
Point 2: This is the pH recorded at a time point just before complete
neutralization takes place.
Point 3: This is the equivalence point (halfway up the steep curve). At this
point, moles of NaOH added = moles of CH3 COOH in the analyte. The H3 O
+
ions are completely neutralized by OH- ions. The solution contains only
CH3 COONa salt and H2 O.
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9/20/23, 7:34 PM Titration curves & equivalence point (article) | Khan Academy
Let me pause here for a second - can you spot a difference here as
compared to case 1 (strong acid versus strong base titration)??? In the
case of a weak acid versus a strong base, the pH is not neutral at the
equivalence point. The solution is basic (pH ~ 9) at the equivalence point.
Let’s reason this out.
As you can see from the above equation, at the equivalence point the
solution contains CH3 COONa salt. This dissociates into acetate ions CH3
COO- and sodium ions Na+ . As you will recall from the discussion of strong/
weak acids in the beginning of this tutorial, CH3 COO- is the conjugate base
of the weak acid CH3 COOH. So, CH3 COO- is relatively a strong base
(weak acid CH3 COOH has a strong conjugate base), and will thus react
with H2 O to produce hydroxide ions (OH- ) thus increasing the pH to ~ 9 at
the equivalence point.
Point 4: Beyond the equivalence point (when sodium hydroxide is in
excess) the curve is identical to HCl-NaOH titration curve (1) as shown
below.
3) Titration of a strong acid with a weak base
Suppose our analyte is hydrochloric acid HCl (strong acid) and the titrant is
ammonia NH3 (weak base). If we start plotting the pH of the analyte against
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9/20/23, 7:34 PM Titration curves & equivalence point (article) | Khan Academy
the volume of NH3 that we are adding from the burette, we will get a
titration curve as shown below.
Point 1: No NH3 added yet, so the pH of the analyte is low (it predominantly
contains H3 O+ from dissociation of HCl).
As NH3 is added dropwise, H3 O+ slowly starts getting consumed by NH3 .
Analyte is still acidic due to predominance of H3 O+ ions.
Point 2: This is the pH recorded at a time point just before complete
neutralization takes place.
Point 3: This is the equivalence point (halfway up the steep curve). At this
point, moles of NH3 added = moles of HCl in the analyte. The H3 O+ ions are
completely neutralized by NH3 . But again do you spot a difference here???
In the case of a weak base versus a strong acid, the pH is not neutral at the
equivalence point. The solution is in fact acidic (pH ~ 5.5) at the
equivalence point. Let’s rationalize this.
At the equivalence point, the solution only has ammonium ions NH4 + and
chloride ions Cl- . But again if you recall, the ammonium ion NH4 + is the
conjugate acid of the weak base NH3 . So NH4 + is a relatively strong acid
(weak base NH3 has a strong conjugate acid), and thus NH4 + will react with
H2 O to produce hydronium ions making the solution acidic.
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9/20/23, 7:34 PM Titration curves & equivalence point (article) | Khan Academy
Point 4: After the equivalence point, NH3 addition continues and is in
excess, so the pH increases. NH3 is a weak base so the pH is above 7, but
is lower than what we saw with a strong base NaOH (case 1).
4) Titration of a weak base with a weak acid
Suppose our analyte is NH3 (weak base) and the titrant is acetic acid CH3
COOH (weak acid). If we start plotting the pH of the analyte against the
volume of acetic acid that we are adding from the burette, we will get a
titration curve as shown below.
If you notice there isn’t any steep bit in this plot. There is just what we call a
‘point of inflexion’ at the equivalence point. Lack of any steep change in pH
throughout the titration renders titration of a weak base versus a weak acid
difficult, and not much information can be extracted from such a curve.
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