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EXPERIMENT 3: Ionization of Acids and Bases, pH, Buffers and Acid-Base
Indicators Part 2: Titration Curves and Indicators
Goal: In this experiment you will gain experience in the calibration and use pH meters/
electrodes in acid-base titrations. You will also compare end point and equivalence point of an
acid-base titration.
Objectives: On completion of this lab you should be able to:
Calibrate a pH electrode/meter with standard buffers.
Use calibrated electrode to measure the pH of various aqueous solutions.
Calculate acid and base dissociation constants.
Construct and interpret an acid base titration curve.
Compare equivalence- and end-points
Theory
In acid-base titrations the pH of the solution in the titration flask depends on the concentrations
of the acidic and basic species in the solution which in turn depend on the magnitude of the
equilibrium constant for the equilibrium that exists between them. If the titrand (the species in
the flask) is an acid (base) the initial pH will be less (more) than 7. Before any titrant (the
species being added from the burette) has been added if the acid (base) is a strong acid (base)
then the concentration of the protons (hydroxide ions) will be equal to the concentration of the
acid (base). If however the acid (base) is a weak acid (base) then the initial pH will depend on
the acid (base) concentration and the pKa (pKb; pK = –logK) of the acid (base).
HA(aq) + H2O(l) ⇌ A–(aq) + H3O+(aq) and Ka = [A–][H3O+]/[HA]
or BOH(aq) ⇌ B+(aq) + OH–(aq) and Kb = [B+][OH–]/[BOH]
The pH in the titration flask will change with each addition of titrant. By monitoring the pH in
the titration flask with a pH electrode and plotting the pH against titrant volume the equivalence
point in the titration can be determined and therefore the concentration of the titrand calculated if
the concentration of the titrant is known (the titrant is normally a standard solution). The pH at
the equivalence point can inform you as to which dye indicators could be used to identify the
end point (the point when the indicator changes colour). If the correct indicator is used then the
end point will be a good estimate of the equivalence point. Dye indicators are usually weak
acids which are one colour when predominantly in their acid form and a different colour when
predominantly in their conjugate base form. Since they are weak acids their pKas can be
expressed as for HA above: when [A–] >> [HA] the conjugate base colour will be apparent,
when [HA] >> [A–] the weak acid colour will predominate; the colour of the indicator depends
on the pH and will change as the pH changes through the pKa value.
For weak acids (bases) at half the equivalence volume half of the acid (base) titrand has reacted
to form its conjugate base (acid) and therefore the pH (pOH) of the solution is equal to the pKa
(pKb) of the acid (base): in the equations above [A–] = [HA] or [B+] = [BOH] and therefore Ka =
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[H3O+] or Kb = [OH–].
At any point in the titration the pH of the solution in the titration flask can be calculated if the
relevant pKa (pKb) and the concentrations of the acid (base) and conjugate base (acid) are
known. Alternatively if the pH is measured and the concentrations are known then the Ka (Kb)
can be calculated. The concentrations are either know from the concentration of the standard
acid (base) used or calculated from the determined equivalence volume. Therefore by
monitoring the pH of a solution during an acid-base titration not only can the concentration of
the titrand be determined but also the pKa (pKb) of the weak acid (base). Additionally if the pKa
(pKb) are known then the pH can be calculated at each point during the titration and the
calculated values compared to the measured values to give an indication of how accurately the
electrode is measuring the pH.
In this experiment you will measure the pH of a solution at varying stages of a titration and then
determine the equivalence points and the pKas and/or pKbs of your acids and/or bases. You will
also compare the equivalence point to the end-point obtained by two indicators.
Safety Notes
During this experiment you will be working with a weak acid and strong base. You must wear
eye protection at all times. In the event that any reagent used in this investigation comes in
contact with your skin or eyes, wash the affected area immediately with lots of water. Notify
your instructor.
Method
A demonstrator must be present while you calibrate your electrode.
Users’ manuals for the electrode and meter accompany your instrument. Be very careful with
your electrode. The pH sensing membrane (see electrode users’ manual) is made of very thin
glass and is very fragile; always use such an electrode with an electrode guard in place.
Record all observations directly onto your worksheet.
By following the instructions in the electrode and meter manuals calibrate your electrode with
the supplied buffers and then measure and record the pHs of the buffers.
Pipette 25.00 cm3 of titrand X (Table 1) into the reaction beaker (100 cm3) and fill the burette
with titrant Y. Thoroughly rinse your pH electrode with distilled water and gently shake the
electrode dry. Place the tip of the dry electrode into the titrand. Check to see that the glass bulb
and the porous frit are fully immersed. Record the pH and the burette reading (to two decimal
places) and then add approximately 1 cm3 (record the actual burette readings) of the titrant,
mix/stir the solution in the beaker well and measure and record the pH. Continue with the
titration until you have added at least 5 cm3 of titrand more than that required to reach the final
equivalence point, measuring the pH of the solution in the beaker after each added
approximately 1 cm3 of titrant. No titrand should require more than 20 cm3 of titrant to complete
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the titration as defined.
Plot the pH (y axis) against titrant volume (x axis) and identify the regions of the curve which
exhibit the largest changes in pH per unit titrant volume (ΔpH/ΔV; points of inflection).
Repeat the titration as above but this time ONLY over these region(s) having the large changes
in pH (approximately ±1.5 cm3 around the points of inflection) and adding the titrant from the
burette in approximately 0.1 cm3 aliquots (record all burette readings precisely).
After completing the second titration, measure and record the pHs of the calibration buffers.
Rinse your electrode thoroughly with distilled water and place it into the storage buffer.
Repeat the titration using the appropriate indicators, according to the combinations of X and Y
given in Table 1 (in duplicate per indicator, and using a 125 mL conical flask in place of the 100
cm3 beaker). Note, at third titration maybe needed to obtain concordant values.
NOTE: Groups are allowed to share the first plot. Record the names of group members on this
plot. EACH group member is required to do the ΔpH/ΔV vs. V plot (use excel or some
spreadsheet software to aid with the calculations).
Table 1.
Titrand X (in Beaker or Indicators
Titrant Y (in Burette)
conical flask)
Methyl Orange and
1 NH4OH (~ 0.050 mol dm-3) HCl (~ 0.1 mol dm-3)
Screened Methyl Orange
Phenolpthalein and thymol
2 NH4Cl (~ 0.050 mol dm-3) NaOH (~ 0.1 mol dm-3)
blue
Phenolpthalein and thymol
3 CH3COOH (~ 0.050 mol dm-3) NaOH (~ 0.1 mol dm-3)
blue
Methyl Orange and
4 CH3COONa (~ 0.050 mol dm-3) HCl (~ 0.1 mol dm-3)
Screened Methyl Orange
Apparatus per group:
Access to a pH electrode and meter and associated manuals. One 100 cm3 beaker, two 125 mL
conical flasks, one stirring rod, one wash bottle, one 50 cm3 burette, one funnel to fit the burette,
a titration stand and a burette holder, a white tile.
Chemicals per group:
200 cm3 of each titrant and titrand (Table 1) to be used.
Chemicals and apparatus per pH electrode and meter:
100 cm3 of standard pH buffers 4, 7 and 10.
Three 25 cm3 beakers.
One 250 cm3 beaker.
Three 125 mL conical flasks
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UNIVERSITY OF THE WEST INDIES Total = /77
DEPARTMENT OF CHEMISTRY
WORKSHEET
Name: _____________________ Lab. Day/Time:______________
ID#: _____________________ Date: ____/____/______
Group members: _______________________________________________________
_________________________________________________________
Expt. 3: Construction of Titration Curves and indicators
TITRATION OF A WEAK ACID (BASE) WITH A STRONG BASE (ACID)
(Solution pair # _____ )
Solution in beaker: ________________________
Solution in burette: ________________________
Volume of reagent in beaker: __________ cm3
pHs of calibration buffers measured after initial electrode calibration:
Buffer, pH 4: _____ Buffer, pH 7: _____ Buffer, pH 10: _____
(3)
TITRATION DATA
(a) First Titration (b) Second Titration (extend table)
Burette Volume pH Burette Volume ΔV pH ΔpH ΔpH/
reading / titrant / reading / titrant / ΔV
cm3 cm3 cm3 cm3
0.00 0.00 - - -
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(10 × 2)
pHs of calibration buffers measured after second titration:
Buffer 4: Buffer 7: Buffer 10:
(3)
Indicator 1: _________________________ Indicator 2: _________________________
Solution in conical flask: ________________________
Solution in burette: ________________________
Volume of reagent in conical flask: __________ cm3
Table 2: Burette readings
Indicator 1 Indicator 2
Titration # 1 2 3 1 2 3
Final volume/cm3
Initial volume/cm3
Volume used/cm3
(9)
DATA INTERPRETATION
(i) Plot the data from the first pH titration (ensure all group members are added) (5)
(ii) On this graph of your pH titration, add the pH and volume data for the second titration,
then identify the equivalence point volume (region of maximum change in pH with unit
volume of titrant; i.e. maximum slope). (5)
3
Ve = __________ cm
(iii) From your second titration data plot ΔpH/ΔV against titrant volume and identify
the equivalence point volume (the volume corresponding to the maximum
ΔpH/ΔV).
Ve = __________cm3
(5)
(iv) In one sentence explain why the equivalence point volume is more precisely determined
using the ΔpH/ΔV against titrant volume graph.
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(3)
(v) List the equivalence volumes determined from:
pH titration: ________________________________
Indicator 1: _________________________________
Indicator 2: _________________________________
(3)
(vi) Briefly comment on the relationship between the pKa values (see appendix) of the
indicators and the pH of the equivalence point.
(5)
(vii) Calculate the concentration of your weak acid (or base) from your equivalence volumes,
assuming that the concentration of the titrant is as given in Table 1. (Show one sample
calculation)
pH-titration: ____________ Indicator 1: ____________ Indicator 2: ____________
(6)
(viii) Determine the relative error in the concentrations of the two indicators using the equation
below (and assuming the pH-titration provides the expected value):
= percent (relative) error
= actual value observed
= expected value
Indicator 1: __________________ Indicator 2: ____________________ (2)
(ix) State with reason, which of the two indicators used in your titration is more appropriate to
quantify the concentration of the titrant.
(2)
(x) On the plot of the first pH titration data, identify the point(s) of half neutralization.
(2)
(xi) From part (x) determine the pKa(s) (or pKb(s)) of your weak acid (or base).
(3)
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(xii) Compare your experimentally determined pK values with those given in the laboratory
manual (see appendix) and in one sentence rationalize why they may be different.
(3)
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