Exp. IV.

CM1014
Acid-Base
Fall 10
Titration 1

A titration is a process used to determine the volume of a solution needed to react with a given
amount of another substance. In this experiment, you will first standardize (determine the
concentration of) the NaOH solution which will be used throughout the experiment. The standard
which will be used is a solid, monoprotic acid: potassium hydrogen phthalate (KHP). Once the
NaOH has been standardized, you will use it to determine the unknown concentration of a HCl
solution.

The formula for KHP is KHC8H4O4. It is a solid at normal lab conditions, can be highly purified,
does not easily oxidize, and has a high MW, permitting good precision when weighing convenient
sample sizes. It is therefore a useful primary standard which can make solutions of very well-
characterized concentrations. KHP is a monoprotic acid, reacting 1:1 with NaOH:

KHC8H4O4(aq) + NaOH(aq) 

 KNaC8H4O4(aq)+ H2O(l)

Sample calculation of a standardization run: A student is given a starting solution of NaOH to

standardize, known to be approximately 0.1 M. It took 19.98 ml of the approximately 0.1 M NaOH
solution to reach the equivalence point with a solution of KHP which was made up with 0.4168 g
KHP. What is the concentration of the NaOH, to 4 s.f.?

0.4168 g/(204.2 g/mol) = 2.041 x 10-3 moles KHP

2.041 x 10-3 moles KHP x [1 mol NaOH/1 mol KHP] = 2.041 x 10-3 moles NaOH
2.041 x 10-3 moles NaOH/ 0.01998 L = 0.1022 M NaOH

Once the concentration of the NaOH titrant is well-characterized, it is used to titrate samples of
acids of unknown concentration. In this experiment, the unknown acids are HCl solutions.

Hydrogen ions from the HCl react with hydroxide ions from the NaOH in a one-to-one ratio to
produce water in the overall reaction:
HCl(aq) + NaOH(aq) 
 H2O(l) + NaCl(aq)

Sample calculation of a run to determine the concentration of an HCl solution:

A 10.00 ml sample of the HCl solution is titrated, using the standardized 0.1022 M NaOH solution.
It took 20.04 ml of the NaOH to reach the equivalence point. What is the concentration of the HCl,
to 4 s.f.?

0.1022 M NaOH x 0.02004 L = 2.008 x 10-3 moles NaOH

2.008 x 10-3 moles NaOH x [1 mol HCl/1 mol NaOH] = 2.008 x 10-3 moles HCl
2.008 x 10-3 moles HCl/ 0.01000 L = 0.2008 M HCl
The equivalence point will be determined by analysis of a titration curve, and compared to the value
obtained by the color change of phenolphthalein, a commonly used indicator. Both work well if
used correctly. A common error of beginning students using indicators, though, is “overshooting”
the equivalence point, and hence calculating erroneously
high values.

When an acid solution is titrated with a basic solution, the

pH pH of the acidic solution is initially low. As base is added,
the change in pH is quite gradual until close to the
equivalence point, when equimolar amounts of acid and base
have been mixed. Near the equivalence point, the pH
increases very rapidly, as shown in Fig. 1. The change in pH
Volume NaOH (mL) then becomes more gradual again, before leveling off with
Exp. IV. CM1014
equivalence Fallfinding
point can be extracted, then, by 10 2 of the
the volume corresponding to the peak
first derivative of the pH vs. volume graph, or the zero point of the second derivative graph.

In this experiment, you will use a computer to monitor pH as you titrate. The point of inflection in
the pH curve will then be used to determine the equivalence point, and that determination will be
compared to the value obtained from the color change of a common acid-base indicator,
phenolphthalein. The volume of NaOH titrant used at the equivalence point will be used to both
standardize the NaOH solution (Part 1), and to determine the molarity of the HCl sample (Part 2).

Fig. 1

Reading a buret:
http://www.chem.tamu.edu/class/fyp/mathrev/mr-sigfg.html
Buret Read at the bottom of the meniscus.

The smallest division in this buret is

0.1 mL. Therefore, our reading error
is 0.01 mL. A good volume reading
is 20.38 0.01 mL. An equally
precise answer would be 20.39 mL
or 20.37 mL.

How many significant figures does

our answer have? 4! The "2", "0",
and "3" we definitely know and the
"8" we had to estimate.
Look below for pictures of a buret. Note that
the numbers get bigger as you go down the
buret. This is different from the beaker or the
graduated cylinder, because the liquid leaves Fig. 2 Reading a buret
the buret at the bottom.

The rings on the buret aid in reading the meniscus without parallax error. In the picture, note that
the ring in the back of the buret can be seen, looking up a the 5 ml mark and down at the 7 ml mark.

Using either a white card with

a black bar on it or a plain
white card (moving up from
Parallax error underneath) behind the buret
will help highlight the bottom
of the meniscus
mlab/techniques/buret.html

Fig. 3 Fig. 4
Exp. IV. asCM1014
Work Fall 10 the KHP and set up the buret while the other
partners. Let one partner dissolve 3
connects the computer, LabPro interface, ph probe, and checks the calibration. The LoggerPro
software, example, and template should already have been downloaded from MyPoly CM1014
main site, under the LABS button. Make sure you have download ed and are familiar with the
following :

EXAMPLE: Exp 4 pH vs. ml File: Sample_data_for_Acid_Base_lab.cmbl

Example of how to derive inflection point from pH curve via first and/or second derivative

TEMPLATE: Exp. 4 data input template, titration curve File: Exp_4.cmbl

Template to use in the lab, for inputting experimental data.

Partner A

1a. Obtain a 50-mL buret. Use a buret clamp (or two utility clamps) to attach the buret to the ring
stand with a waste beaker beneath, as shown in Fig. 6. Rinse the buret two times with a few mL
of the ~0.1 M NaOH solution, draining the rinse into the waste beaker. Fill the buret a little
above the 0.00-mL level of the buret with ~0.1 M NaOH solution. Drain a small amount of
NaOH solution so it fills the buret tip (NO BUBBLES!) and leaves the NaOH at the 0.00-mL
level of the buret.

2a. Weigh approximately 0.4 g of KHP in a tared beaker on the analytical balance, carefully
recording the mass to 4 s.f. Add about 50 ml of distilled water to dissolve the KHP.

3a. Place the beaker on a magnetic stirrer and add a stirring bar. Carefully and slowly start the stir
bar moving, and let all the KHP dissolve.

Partner B

1b. Connect the computer interface as demonstrated by your instructor. Prepare the computer for
data collection by opening the file from the MyPoly site, Exp_4.cmbl. The vertical axis has pH
scaled from 0 to 14 pH units. The horizontal axis has volume scaled from 0 to 25 mL. Check to
see that the Meter window shows pH value, indicating the probe and interface is communicating
with the computer.

2b. Check the calibration of the pH probe by reading the pH of the available standard solutions:
Red = pH 4 Yellow = pH 7 Blue =pH 10
Between readings, rinse the pH probe with a wash bottle over a waste beaker. Rinse the pH
probe any time it is transferred to a new solution, to prevent cross-contamination. GENTLY
wipe the outside with a Kimwipe, and wick away rinse water around the VERY DELICATE
bulb, as shown in the Fig. 5. Do not let the probe dry out. A quick and dirty technique is to
keep the probe in an Erlenmeyer flask filled with water when not in immediate use.

Fig. 5 a & b Rinsing and drying the probe

Exp.3b.
IV.Calibration
CM1014– use only if necessary
Fall 10 4

If your system reads more than 0.1 pH units off the standard solutions, calibrate by following
the LoggerPro menu:

Experiment>Calibrate>box opens, choose Sensor Settings>Calibrate Now.

Use the pH 4 then the pH 10 standard, since that encompasses the widest range.

Submerge the tip of a clean probe in the pH 4 standard. You will see a voltage reading in the
gray box. When it stabilizes, click KEEP, and enter pH = 4.00.

Rinse and daub dry the probe as shown in Fig. 6, and repeat the procedure with the pH 10
standard. Again, when the voltage stabilizes, click KEEP, and enter pH = 10.00.

Close the calibration.

Fig. 6 Experimental set-up

All together now - both partners

4. Use a utility clamp to suspend the pH Sensor on a ring stand as shown in Figure 6. Position the
pH probe in the KHP solution and adjust its position so that it is not struck by the stirring bar.
BE EXTREMELY CAREFUL OF THE GLASS TIP OF THE pH PROBE!
5. Move the buret so that it looks like Figure 6, with the buret set to dispense NaOH into the acid
solution.
CAUTION: Sodium hydroxide solution is caustic. Avoid spilling it on your skin or clothing.
6. Add 2-3 drops of phenolphthalein indicator. Click Collect and monitor pH for 5-10 seconds.
Once the displayed pH reading has stabilized, click Keep . In the edit box, type “0” (for 0 mL
added). Press the ENTER key to store the first data pair for this experiment.
7. You are now ready to begin the titration. This process goes faster if one person manipulates and
reads the buret while another person operates the computer and enters volumes.
NOTE: The suggested pH increments below are just that - rough values, suggestions. See
 Exp. IV.
in theCM1014
titration, you will add a lot toFall
get 10 5
the red ball to move. As you get near the equivalence
point, very little NaOH is needed move the red ball a lot. If that happens, STOP. Take the
reading, and proceed more slowly.

Fig. 7 Sample titration curve

The display is controlled several ways. Right click on the graph and select Graph Options. Under
the Graph Options tab, selecting Point Protectors will show the data points, and Connect Points will
draw a line through the points. Left double clicking on a data point opens the Manual Column
Options box. The Options tab in this box lets one set the size and color of the “Point Protectors”.
The default settings are the small red balls, with no lines, as shown.

a. Add an increment of NaOH titrant (enough to raise the pH about 0.15 units, or to move the
new red ball above the previous reading’s postion). When the pH stabilizes, again click
Keep
. In the edit box, type the current buret reading, to the nearest 0.01 mL. Press ENTER.
You have now saved the second data pair for the experiment.
b. Continue adding NaOH solution in increments that raise the pH by about 0.15 units and enter
the buret reading after each increment.
c. When a pH value of approximately 4.5 is reached, change to a one-drop increment. Enter a
new buret reading after each increment. At one point, adding a drop of NaOH will cause the
solution to change color from clear to pink. Write this buret volume on the data sheet in the
box labeled “Volume of NaOH at color change (clear  pink)”
d. After a pH value of approximately10 is reached, again add larger increments that raise the pH
by about 0.15 pH units, and enter the buret level after each increment.
e. Continue adding NaOH solution until the pH value remains constant.
8. When you have finished collecting data, click Stop . Dispose of the beaker contents as directed
by your teacher.
9. Save a copy of the Table window to your computer, and place a copy in Assignments on
MyPoly, labeled with your name(s) and experiment name or number. (For example:
Smith_Jones_Titration_Table1)

11. Save a copy of the Graph window to your computer, and place a copy in Assignments on
MyPoly, labeled with your name(s) and experiment name or number. (For example:
Smith_Jones_Titration_Graph1).
 Exp.InIV. CM1014 calculations, you will
the subsequent Fall
use10the average of the molarities just determined
6 in Part
1 as the accepted value for the concentration of NaOH in Part 2.

PART 2 Determining the concentration of a HCl sample

Using the same setup, the procedure in Part 1 will be repeated, but the sample for each run will
be 10.00 ml of the HCl solution of unknown concentration instead of the KHP solution.

1. Obtain your unknown HCl sample. Record the sample number on the data sheet.

2. Using a volumetric pipet, pipet 10.00 ml of the sample into the beaker. Add about 50 ml of
distilled water, and 2-3 drops of phenolphthalein indicator. Repeat the procedure of Part 1,
titrating and recording pH and volume data using the Vernier interface and pH sensor. As
before, write the volume observed when the solution changes from clear to pink, to the 0.01 ml.
Do two runs, saving your table and graph and depositing copies in Assignments each time.

PROCESSING THE DATA

1. On the graph for each run, left click on the label of the pH axis. From the pop-up menu, choose
First derivative. Enter Control-E. A pop-up box and sliding cursor will appear on the graph.
Move this to highlight the peak value, and record the volume shown in the box for this
maximum value. This is the equivalence point. Do this for each run, recording the volume of
NaOH at the equivalence point in the appropriate box on the data sheet.

.2. Following the illustrative calculations on page one, fill in the data sheet. Show a sample
calculation for Run 1 for Part 1 and for Run 1 for Part 2 in the areas provided.
Exp.
DATA IV. TABLES
CM1014 Fall 10 7

PART 1 STANDARDIZATION OF NaOH

Run 1 Run 2
Mass of KHP, grams

Moles of KHP
(MW=204.2 g/mol)
Volume of NaOH at
equivalence point, from graph
Molarity of NaOH

Average Molarity of NaOH, USE THIS VALUE IN

from graph data PART 2 CALCULATIONS

Volume of NaOH at color

change (clear -> pink)
Molarity of NaOH, based on
color change
Average Molarity of NaOH,
based on color change
Sample calculations, RUN 1
Moles KHP:

Molarity of NaOH, based on graph data:

Exp.
PART IV. 2 CM1014 FallHCl
DETERMINATION OF 10 CONCENTRATION 8

Run 1 Run 2
Concentration of NaOH,
from Part 1
Volume of HCl sample
(better be 10.00 ml!)
Volume of NaOH at
equivalence point, from graph
Molarity of HCl, calculated
from graph data
Average Molarity of HCl,
from graph data
Volume of NaOH at color
change (clear -> pink)
Molarity of HCl, based on
color change
Average Molarity of HCl,
based on color change
Sample calculations, RUN 1
Molarity of HCl, calculated from graph data
Exp. IV. CM1014
PRELAB Fall 10 9
Name____________________________________________Date_______________________

FOR FULL CREDIT, SHOW ALL WORK

1. A student is given a starting solution of NaOH to standardize. It took 20.36 ml of the NaOH
solution to reach the equivalence point with a solution of KHP which was made up with 0.3998 g
KHP. What is the concentration of the NaOH, to 4 s.f.?

2. A different student used different solutions than those used in Question 1. He titrated a 10.00
ml sample of his HCl solution, using a standardized 0.1011 M NaOH solution. It took 30.32 ml of
the NaOH to reach the equivalence point. What is the concentration of the HCl unknown, to 4 s.f.?
Exp. IV. CM1014
POSTLAB Fall 10 10

1. List your data results:

Part 1
Average Molarity of NaOH, from graph data _____________________
Average Molarity of NaOH, based on color change _____________________
Part 2
Average Molarity of HCl, from graph data _____________________
Average Molarity of HCl, based on color change _____________________
a. How well do the results from the two techniques agree?

b. Do the results from the color change data (using the phenolphthalein indicator) tend to be higher,
lower, or randomly fluctuate with respect to the results based on graph data? What can you deduce
about your titration technique, based on this comparison?