Exploring Analytic Chemistry

Unit 5 – Volumetric Analysis

This unit presents the general directions for volumetric works which
includes standard solution preparations, dilution of stock solution to a lower
concentration solution and titration analysis. Students are required to have
hands on performance activities and calculations of results generated to
develop their laboratory skills and mathematical competencies.

Learning Outcomes

At the end of this unit, you will be able to:

● Develop laboratory skills in preparations of standard and stock solutions;

● Perform volumetric analysis
● Develop mathematical competency in calculating results

Pretest

Direction: Encircle the letter of the correct answer.

1. What is the molar mass of barium perchlorate, Ba(ClO4)2?

a. 189.90 g/mol b. 336.20 g/mol c. 272.24 g/mol d. 304.24 g/mol

2. A sample of copper weighing 6.93 g contains how many moles of copper atoms?
a. 0.109 mol b. 0.0645 mol c. 0.917 mol d. 1.09 mol

3. What results would you expect from a litmus test of a solution of Ba(OH)2?
a. red litmus paper will turn blue b. blue litmus paper will turn red c. there will
be no change with either red or blue litmus paper d. both red and blue litmus
paper will change color

6. A sample of tungsten occupies a volume of 5.38 cm3 . What is the mass, in grams, of
this sample of tungsten? (for tungsten, density = 19.35 g/cm3 )
a. 104 g c. 3.60 g e. 5.38 g b. 0.278 g d. 19.4 g f. 28.9 g

7. A compound has a molecular formula of C12H24O6. What is this compound's

empirical formula?
a. CHO c. C2H4O e. C4H8O2 b. C6H12O3 d. C12H24O6 f. CH2O

8. A non-metallic element X forms a compound with potassium that has the formula K2X.
Which one of the following elements could be X?
a. selenium b. antimony c. silicon d. neon
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9. What is the mass, in grams, of potassium in 12.5 g of K2Cr2O7 (molar mass = 294.40
g/mol)? a. 1.66 g b. 78.2 g c. 8.80 g d. 3.32 g

10. A solution is said to contain 28% phosphoric acid by mass. What does this mean?
a. 1 mL of this solution contains 28 g of phosphoric acid
b. 1 L of this solution has a mass of 28 g
c. 100 g of this solution contains 28 g of phosphoric acid
d. 1 L of this solution contains 28 mL of phosphoric acid

Content

Preparing Standard Solution (http://chem320.cs.uwindsor.ca/Notes_files/320_l01_1.pdf)

One of the most important pieces of laboratory glassware for preparing solutions is the
volumetric flask. Typically, a solid (or liquid) reagent or standard is quantitatively
transferred into the flask, followed by dilution to the mark on its narrow neck.

1. Add reagent, swirl and invert several times.

2. Dilute such that the meniscus rests just above the 500 mL marker

3. Make sure that the flask is very clean, as water droplets can stick to the upper neck,
making the dilution less accurate.

Figure 5.2. Volumetric flask with

lower meniscus above 500mL
line mark.

Figure 5.1. Volumetric Flask,

500mL
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Dilution

Once you make a solution in a volumetric flask, you may be required to produce
solutions of lower concentrations (i.e., diluting the sample).

A simple formula for conducting dilutions is:

Mconc × Vconc = Mdil × Vdil

In other words, to make up a specific volume of a diluted solution (Vdil) with a known
concentration (Mdil) from a solution with a known concentration (Mconc), we would need
a precise volume of the initial concentrated solution (Vconc.)

Note that both sides of this equation give units of moles!

Example:

The HCl (conc) that is used in the lab is typically 12.1 M. What volume of HCl (conc)
would one need to make a 0.100 M solution by diluting to 1.000 L?

(12.1 M) × (x L) = (0.100 M) × (1.000 L) x = 0.00826 L = 8.26 mL

Gravimetric Analysis

Gravimetric analysis is a chemical analysis based upon the accurate weighing (massing)
of a final product. This final product may be the pure substance for which we are
conducting the analysis, or may be another pure substance which contains the
element/compound that we are analyzing for.

Example:

How much iron is there in an iron supplement tablet?

1. Tablets containing FeC4H2O4 (iron (ii) fumarate) are ground and mixed with 150 mL
of 0.100 M HCl to dissolve the Fe2+. The solution is the filtered to remove bits of
particulate matter from the tablet.
2. The Fe2+ is oxidized to Fe3+ using an excess (XS) of H2O2.
3. The Fe3+ is reacted with NH4OH to produce a hydrous iron (III) oxide
(FeOOH·xH2O), which is then heated at 900 oC to produce solid iron oxide (Fe2O3).

Titrations & Volumetric Analysis

Volumetric analysis is a chemical analysis based on accurate measurement of a

volume of reagent that reacts with the analyte. Most often, this is accomplished via
titration, where the reagent solution (the titrant) is added to the analyte.

The titrant is usually delivered via a buret, and one monitors the difference between the
initial and final volume markings.
Exploring Analytic Chemistry

The equivalence point is reached when the amount of titrant added is exactly equal to
the amount of analyte in the receiving flask. This point is actually a theoretical point - in
fact, we never reach this, but rather hit the end point; the closer the end point is to the
theoretical equivalence point, the better the result!

Figure 5.3. Titration set up

Finding the end point

The end point is usually indicated by a change in physical property of the solution, which
may include:
1. a colour change (by eye or spectrophotometric - this may arise from the substances
themselves, or the presence of a reactive indicator
2. a change in current or voltage (potentiometric)
3. precipitation or dissolution of a substance In the case above, the first trace of purple
colour (i.e., excess MnO4- ) signifies the end point.

Figure 5.4. Change in color signifying end point of titration.

 Exploring Analytic Chemistry

All titrations strive for accuracy, and the titrants are almost always made up of very pure
substances (i.e., 99.9% or higher - known as analytical grade reagents). If the pure
reagent is dissolved in a known volume to produce a solution of known concentration,
this is called the primary standard.

In cases where primary standards are not available (e.g., titrations involving
concentrated HCl), the titrant is prepared with an approximately known concentration,
and then used to titrate against a pure analyte or primary standard in order to
determine the precise concentration. This is known as standardization, and this type
of titrant is called a standard solution.

Learning Activities
An acid-base titration is a neutralization reaction that is performed in the lab in order
to determine an unknown concentration (Molarity) of acid or base. As long as the
concentration of one of the solutions is known, the concentration of the other reaction
can be obtained through titration. In a titration reaction, the moles of acid equal the
moles of base at the equivalence point.

Once the equivalence point is reached the concentration of the unknown solution can be
determined because:
MaVa = MbVb
Where:
Ma = molarity of acid
Va = molarity of base
Mb = molarity of base
Vb = volume of base

When you carry out a simple acid-base titration, an indicator is used to indicate when the
acid and base have mixed in exactly the right proportion to neutralize each other.

When the indicator changes color the end point of the titration has been reached. In an
ideal world, the color change would happen when the two solutions are mixed in equal
proportions. This is not always the case, but when it is, this point is known as the
equivalence point. For strong acid/strong base reactions, the equivalence point occurs at
pH =7.

VOLUMETRIC ANALYSIS
 Volumetric Analysis is a method of analysis based on titration.
 Titration is a procedure for determining the amount of a particular substance A
by adding a carefully measured volume of a solution with a known concentration
of B until the reaction is complete.

The following are figures illustrating steps in titration activity retrieved from
https://chemistry.tcd.ie/assets/pdf/Preliminary%20Course/Titration%20Demonstration.pdf:
Exploring Analytic Chemistry

Figure 5.5. Making a standard solution.

Exploring Analytic Chemistry

Figure 5.6. Peparing a standard solution using volumetric flask.

Figure 5.7. Transferring liquid using a pipette.

Figure 5.8. Rinsing burette with the solution before use.

Exploring Analytic Chemistry

Figure 5.9. Adding indicator to the primary standard solution.

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Figure 5.10. Illustration on how to get the reading using a white cardboard.
Exploring Analytic Chemistry

Figure 5.11. Sample calculation on titration.

Exploring Analytic Chemistry

Figure 5.12. Sample calcutation in computing concentration in terms of molarity.

Another example:

Perform Laboratory Activity on Preparing Standard and Dilute Solutions

Introduction

Solutions are in an important part of chemistry. But how are accurate

concentrations of solutions prepared? In this laboratory activity, a copper (II)
sulfate solution will first be prepared, then diluted to prepare several other
solutions with different concentrations.

Concepts

Concentration Dilution Absorbance Molarity

Background

The amount of solute that is dissolved in a given quantity of solvent is called the
concentration of the solution. A dilute solution contains only a small amount of
solute in a given amount of solution, while a concentrated solution contains a
large amount of solute in a given amount of solution. Molarity is the unit most
commonly used to describe the concentration of a solution. The molarity, M, of a
Exploring Analytic Chemistry

solution is defined as the number of moles of solute in one liter of solution

(Equation 1).

Molarity= amount of solute in moles

Volume of solution in liters Equation 1

Combined with the molar mass of a solute, Equation 1, used to calculate the
number of grams of solute needed to prepare a given volume of a solution with a
specific concentration. For example, consider the preparation of 500.0mL of a
0.80M solution of sodium chloride:

Grams of NaCl= 500.0mL x 1L x 0.80moles NaCl x 58.5 g NaCl = 23 g

NaCl

1000mL 1L NaCl 1mole NaCl

The calculations show that 23g of sodium chloride are required to prepare
500.0mL of 0.80M NaCl solution.

Once the calculations have been done to determine how much solute is needed
to prepare a solution, precise analytical techniques must be followed to ensure
accuracy in making the solution. Part A, in the Procedure section, describes in
detail the proper analytical procedure for preparing a solution.

One very important aspect of analytical technique involves choosing the right
type of glassware. Volumetric glassware is glassware that has been calibrated
(and marked) to hold a specific volume. The most common form of volumetric
glassware used for preparing solutions is the volumetric flask (figure 1), which
has a long, narrow neck with a single, hairline marking on it. For a 100-mL
volumetric flask, the mark on the neck indicated that when filled to the mark, the
flask will contain precisely 100.0 mL at room temperature.

Diluting Solutions

Experiments often require a solution that is more dilute than what is on hand in
the stockroom. In this case, a more concentrated stock solution must be diluted
to obtain the desired concentration. To carry out a dilution, the following
equation is used: Molarity concentrated soln X volume concentrated soln= Molarity dilute soln X
volume dilute soln

In this equation, Molarityconcentrated soln is the concentration of the stock solution,

volumeconcentrated soln is the volume of the stock solution required to prepare the
dilute solution, Molaritydilute soln is the concentration of the desired dilute solution,
and volumedilute soln is the volume of the dilute solution needed. The dilution
Exploring Analytic Chemistry

equation is commonly written as shown in Equation 2. The subscripts 1 and 2

refer to the concentrated solution and the dilute solution, respectively.

M1V1=M2V2 Equation 2

For example, assume that the 0.80M sodium chloride solution prepared in the
example above is in the stockroom, but for another experiment, 100mL of a
0.20M sodium chloride solution is needed. In performing a dilution calculation,
M1, M2, and V2 are generally known and Equation 2 is rearranged to solve for the
unknown V1. Substituting the known values for this example into Equation 2
allows us to solve for the volume of the concentrated solution required to prepare
the dilute solution.

V1=M2V2 V1=0.20M * 100mL = V1=25mL

M1 0.80M

Proper analytical technique for preparing the diluted solution requires that the
initial and final volumes (V1 and V2) must be accurately measured using a
graduated cylinder or, preferably, a pipet and a volumetric flask.

Concentration and Absorbance

Molarity and dilution calculations show us how to prepare solutions of known

concentration. Another important problem chemists encounter in the lab is how
to determine the concentration of an unknown solution. If the solution is colored,
the concentration of an unknown solution can be determined by measuring the
intensity of the color. A special sensor or instrument called a colorimeter is used
to measure the absorbance of visible light that gives the solution its color.
Generally, the more intense the color of the solution, the greater the absorbance
of light will be. In using colorimetry, it is important to remember that the color of
light transmitted by the solution (the color we see) is complimentary to the color
of light absorbed by the solution (the color we measure). Since the color of light
depends on its wavelength, the wavelength of light absorbed by a colored
substance in solution is complementary to the wavelength of light transmitted by
the substance. Copper (II) sulfate solutions, for example, are blue. The
absorbance of copper (II) sulfate solutions is measured at 635nm, corresponding
to red light.
Exploring Analytic Chemistry

Experiment Overview

The purpose of this experiment is to prepare a series of blue copper (II) sulfate
solutions of known concentration using the molarity and dilution equations. The
relationship between the concentration of a solution and its absorbance will be
investigated. The accuracy of the solution preparation and dilution procedures
will then be determined.

Pre-Lab Questions

1. Calculate the number of grams of copper (II) sulfate pentahydrate, CuSO 4 •

5H2O, required to prepare 100.0mL of a 0.150M copper (II) sulfate solution.

2. Calculate the number of milliliters of 0.150M copper (II) sulfate solution that
must be diluted to prepare 10.0mL of a 0.0750M copper (II) sulfate solution.

3. Calculate the number of milliliters of 0.150M copper (II) sulfate solution that
must be diluted to prepare 10.0mL of a 0.0230M copper (II) sulfate solution.

Materials

Copper (II) sulfate pentahydrate, Spatula

CuSO4 • 5H2O, 3g Test tube rack

Balance, centigram precision Test tubes, 5

Beral-type pipet Tissues of lens paper

Colorimeter or spectrophotometer Volumetric flask, 100-mL

Cuvets, 5 Wash bottle

Graduated cylinder, 10-mL Wax pencil or labeling tape

Weighing dish
Exploring Analytic Chemistry

Safety Precautions

Copper (II) sulfate is moderately toxic by ingestion and inhalation and is a skin
and respiratory irritant. Avoid contact with eyes and skin. Wear chemical splash
goggles, chemical resistant gloves, and a chemical- resistant apron. Wash hands
thoroughly with soap and water before leaving the laboratory.

Procedure: Part A. Preparing the Stock Solution

1. Review the calculations from Pre-Lab Question #1 for the number of grams of
copper (II) sulfate pentahydrate, CuSO 4 • 5H2O, required to prepare 100.0 mL
of a 0.150 M solution. Check them with your instructor. Once your
calculations have been approved, weigh out the required amount of copper
sulfate on a balance in a clean, dry weighing dish.
2. Transfer the solid to a 100-mL volumetric flask.
3. Use a wash bottle filled with distilled or deionized water to rinse any
remaining solid from the weighing dish into the flask.
4. Add more distilled or deionized water to the volumetric flask until the liquid
level is almost to the 100-mL mark. Fill to the mark with a pipet or wash bottle
drop-by-drop so that no water splashes up on the sides of the flask. Fill until
the bottom of the meniscus is EXACTLY at the 100.0-mL mark.
5. Carefully add a stir bar to the solution in the flask. Place the flask in the
center of the stirrer/hotplate to mix the solution.
6. Stir the solution to give a homogenous solution.

Part B. Preparing Diluted Solutions

7. Place five clean and dry test tubes in a test tube rack and label them #1-5.
Label one pipet “CuSO4” and use it to transfer the stock solution only.
8. Using a 10mL graduated cylinder, measure and pour 10mL of the 0.150M
stock solution into test tube #1. Record the necessary data for this solution in
the data table.
9. Using a clean Beral-type pipet, fill the 10-mL graduated cylinder exactly to the
3.80-mL mark with the stock solution. Try not to get any drops of solution on
the sides of the cylinder. Make sure that the bottom of the meniscus sits
exactly at the 3.80-mL mark.
10. Carefully fill the graduated cylinder to the 10.0-mL mark with distilled or
deionized water. Do not overfill!
11. Mix the solution in the graduated cylinder by repeatedly filling and emptying
the test tube with the solution three times. The agitation caused by filling and
emptying the test tube will mix the solution.
12. Transfer the mixed solution to test tube #2 and record the necessary data for
this solution in the data table.
13. Rinse the graduated cylinder with water and dry it with a paper towel.
Exploring Analytic Chemistry

14. Repeat steps 9-11 using 2.40mL stock solution.

15. Transfer the mixed solution to test tube #3 and record the necessary data for
this solution in the data table.
16. Rinse the graduated cylinder with water and dry it with a paper towel.
17. Before proceeding, review your calculations for preparation of 10.0mL of a
0.075M and a 0.023M cupric sulfate solution (Pre-Lab Questions #2 and #3).
Check with your instructor before proceeding.
18. Using your calculations and the analytical technique described in steps 9-13,
prepare 10.0mL of a 0.075M cupric sulfate solution by diluting the stock
solution. Transfer this solution to test tube #4 and record the necessary data
in the data table.
19. Using your calculations and the analytical technique described in steps 9-13,
prepare 10.0mL of a 0.023M cupric sulfate solution by diluting the stock
solution. Transfer this solution to test tube #5 and record the necessary data
in the data table.
20. Compare the color of the stock solution and each of the dilutions in test tubes
#1-5. Rank them in terms of color from deepest blue to lightest blue. Record
these observations in the data table.

Data Table
Test Tube 1 2 3 4 5

Volume of Stock Solution

(V1)
10.0mL

Concentration of Stock
Solution (M1)
0.150M 0.150M 0.150M 0.150M 0.150M

Final Volume of Diluted

Solution (V2)
10.0mL 10.0mL 10.0mL 10.0mL 10.0mL

Concentration of Diluted
Solution (M2)
0.150M

Color Comparison

(Rank Solutions from

lightest blue=1, deepest
Exploring Analytic Chemistry

blue = 5)

Post-Lab Questions

1. Calculate the concentrations of the diluted solutions in test tubes #2 and 3

using Equation 2 from the Background section.

2. Complete the data table for test tubes #1, 4, and 5. Note: See the Pre-Lab
Questions for the calculated values for solutions #4 and 5.

3. Compare the concentration of each solution to the color ranking. What is the
relationship between the concentration of a solution and its color intensity?

Assessment:

Problems adapted from the following links:

- https://www.mcvts.net/cms/lib07/NJ01911694/Centricity/Domain/540/H
W%20-%20Concentrations%20of%20solutions%20Answers.pdf
- http://www.cabrillo.edu/~aromero/CHEM_30A/30A_Practice_Problems
/Practice%20Problems%20(Chapter%208)%20Solutions%20-
%20KEY.pdf)

Complete the following problems on a separate sheet of paper. Use significant

figures. Note: The density of water is 1 g/mL.

1. What is the molarity of a solution that contains 10.0 grams of Silver Nitrate
that has been dissolved in 750 mL of water?

2. You want to create a 0.25 M Potassium Chloride solution. You mass 5.00
grams of Potassium Chloride. How much water is needed?

3. What is the molality of a solution that contains 48 grams of sodium

chloride and 250 mL of water?
Exploring Analytic Chemistry

4. How many mL of hydrogen peroxide are needed to make a 8.5% solution

by volume of hydrogen peroxide if you want to make 450 mL of solution?

5. What is the mole fraction of the solute in the solution from problem 1?

6. What is the molality of a solution that contains 13.4 grams of calcium

chloride dissolved in 655 mL of water?

7. How many grams of NaNO3 are required to make 500.0 mL of a 3.50 M

solution of NaNO3?

8. If 68.75 mL of 12.00 M HCl solution is diluted to 1000.0 mL, then what is

the new concentration (in molarity)?

9. In order to make 250.0 mL of 1.25 M NaF solution, what volume of an 8.00

M NaF stock solution should be diluted to 250.0 mL?

10. 25.00 g of potassium chloride (KCl) is dissolved in enough water to make

250.0 mL of a solution with a density of 1.14 g/mL. What is the
concentration of the solution in % (m/m), % (m/V), and molarity?