Chemistry 201

Qualitative Analysis

Introduction
General comments: It is always a good idea to use as few chemicals as possible; it makes sense
both from consideration of lab safety and chemical waste disposal. Therefore, keep in mind that each of
the chemical tests that are discussed below can be done with a few drops of solution. Remember that
when using such small amounts, it is extremely important that the equipment that you use is very clean. If
the equipment is “dirty,” the solutions will become contaminated, and it is possible that you will identify
the contaminant rather than the unknown. To avoid cross contamination, make sure to recap reagent
bottles with the original caps and to clean your droppers very well if they are to be reused.

Color of solution: The color of a solution can provide a clue to its chemical Ion Solution
contents. Of the ions commonly encountered in this course, aqueous solutions Color
of transition metal cations will often be colored since the valence d-electron
energy levels of transition metal complexes can often absorb light in the visible Li+,K+, Na+, Colorless
region of the spectrum. This absorption of visible light causes the solutions to Ba2+, Ca2+,
appear colored (see Figs. 23.5 and 23.6 in Silberberg). In contrast, cations of NH4+
alkali (group 1A), alkaline earth (group 2A) metals and ammonium ions are
colorless since the electrons of these ions do not absorb light in the visible region Fe3+ Yellow
of the spectrum. A table of the colors of a selection of cations in aqueous 2+
solutions is given in the margin note area. The color of a solution is a simple type Ni Green
of absorption spectroscopy. Cu2+ Blue

Flame test: The flame test is used in qualitative analysis to identify ions such
Ion Flame Color
as sodium, barium, potassium, calcium and others. In this test, the sample is
Li+ Red
vaporized in a flame and the flame becomes brightly colored as a result of light Na+ Yellow
emitted from atoms and ions in excited energy states. In many cases, the color of K+ Violet
the observed flame can be correlated to the chemical identity of the cations and Ca2+ Dark Red
anions in the solution (see Fig. B7.1, in Silberberg). A table of several such Cu2+ Green
correlations is given in the margin note area. The flame test is a simple type of Cl- Faint Green
emission spectroscopy. Ba2+ Green

The flame test is fast and easy but requires some practice to reliably produce and see the colors (some ions
will be more intensely colored than others). To carry out a flame test, you will use a clean inert wire and a
clean watch-glass with a few drops of the aqueous solution. Clean a piece of nichrome wire (or paper clip)
by first heating the wire in a hot Bunsen burner flame until it glows red hot. Dip the wire into a nitric acid
(or hydrochloric acid) solution (see safety note in margin area), heat again, and then rinse with distilled
water. Repeat these steps until the wire burns without color. To test an unknown, place some unknown
solution onto a watch glass and hold it next to the air inlet at the bottom of your Bunsen burner. Heat the
wire in the flame and then plunge the hot wire into the solution in the watch glass. This will vaporize the
solution, allowing it to be carried with the air into the flame producing a colored flame. If you have any
questions regarding the test, ask your professor to demonstrate.

Solubility: Many qualitative analysis schemes have been proposed that rely on the selective
precipitation of specific cations and anions based on their solubilities. When two solutions are mixed, a
compound formed from a cation in one solution and an anion in the second solution will precipitate if its
concentration is higher than its solubility (see Section 4.4 of Silberberg). Therefore, the solubility test can
be conducted by mixing a few drops from two different solutions and noting whether a precipitate forms.
(The formation of a solid precipitate will be evident due to the increased turbidity of the mixture).

For qualitative analysis, often only general trends in solubility need to be known. These trends can be
summarized by a set of relatively simple rules, often referred to as “the solubility rules” and are given
below. Also see table 4.1 of Silberberg.
(Solubility is defined as greater than 0.01 mol/L at 25° C)

ANION + CATION COMPOUND

THAT IS:
Any + Alkali metal ions, or NH4+ Soluble
NO3-, ClO4- + Any Soluble
Cl-, Br-, I- + Any, except Ag+, Pb2+, Hg22+, Soluble
Cu+
SO42- + Any, except Sr2+, Ba2, Pb2+. Soluble
OH– ,S2- + Any, except alkali metal ions, Insoluble
NH4+, Sr2+. , Ca2+ , Ba2+
PO43-, CO32-, SO32- + Any, except alkali metal ions, Insoluble
NH4+

Acidity: The pH test is used to determine the acidity of aqueous solutions. By placing a drop of a
solution on pH indicator paper, the pH can roughly be determined. The color of the indicator paper after
it is wetted with the test solution is correlated to pH (see text box in margin note area).

For qualitative analysis, it is useful to divide the pH scale into at least three categories: strongly acidic
(pH<3), neutral (pH~7), and strongly basic (pH>10). Sometime the two additional categories, weakly
acidic (3<pH<6) and weakly basic (8<pH<10), are also used.

When a substance dissolves in water and causes an increase in the concentration of protons (H+), the
substance is considered to be an acid. For classification purposes, we will define solutions with pH < 3
as strongly acidic. Examples of strong acids that you may encounter this semester
include: HCl, H2SO4, HNO3 or H3PO4. For the type of pH
paper you will use:
Aqueous solutions of some metal ions also test acidic. The acidity is due to • Red
Acidic
complexes that form between the metal ions and water. For instance, a 0.25 M • Orange
Neutral
aqueous solution of Fe3+ will test strongly acidic. This is due to the following • Blue
Basic
equilibrium,

Fe3+(aq) + 6H2O(aq) ← 3+ ← + 2+
→ [Fe(H2O)6] (aq) → H (aq) + [Fe(H2O)5OH] (aq)
Other metal ions (such as Pb2+, Cu2+, Al3+ and Zn2+) will test only weakly acidic (3<pH<6).

When a substance dissolves in water and causes an increase in the concentration of hydroxide ions (OH- ),
the substance is considered to be a base. For classification purposes, we will define solutions with pH >
11 as strongly basic. Solutions with pH > 11 result from the presence of OH-, NH3, CO32-, or PO43-.

Cations and anions that do not tend to form excess protons (H+) or hydroxide ions (OH-) will test
neutral (pH≈7). Solutions of salts formed by cations of groups 1A and 2A (such as Na+, K+, Ca2+, and
Ba2+) and anions of strong acids (such as Cl–, SO42– SCN-, and NO3–) will be very close to pH≈7.
Remember, the stronger the conjugate acid, the weaker the conjugate base. For example, since
hydrochloric acid is a very strong acid, the conjugate base, Cl–, has virtually no tendency to gain a proton.
Additional information about acid-base chemistry can be found in Silberberg, sections 4.4 and chapter 16.

Gas-Producing Reactions: Some reactions form gaseous products

Safety Note: When a gas is
that can easily be detected by observing bubble formation. For example, expected to be produced,
perhaps you have had the experience of adding vinegar (CH3COOH) to baking make sure to point the
soda (NaHCO3). This is an example of a gas-forming reaction. The resulting reaction test tube away
chemical reaction can written as, from all people, in case the
reaction mixture shoots out
CH3COOH (aq) + NaHCO3 (s) ←
of the tube.
→ CO2 (g) + H2O (l) + CH3COONa (aq)
or alternately the reaction can be written in net ionic form as,

HCO3- (aq) + H+ (aq) ←

→ CO2 (g) + H2O (l)
In addition to being a gas-forming reaction, you should recognize that this reaction is also an example of
acid-base chemistry. Predictably, this type of reactivity can be extended to the base, carbonate (CO32-),
which can react with an acidic solution causing the formation of carbon dioxide bubbles due to the
following reactions,
← ←
CO32- (aq) + 2H+ (aq) → HCO3- (aq) + H+ (aq) → CO2(g) + H2O(l).
Safety Note: If you decide
A smelly example of a gas-producing reaction is an aqueous ammonia (also to smell the odor of a
known as ammonium hydroxide) solution. Ammonia (with its characteristic chemical, minimize your
odor) can be released by the equilibrium between a solution of ammonium exposure to chemicals by
hydroxide (solublized ammonia) and ammonia gas. smelling as small of an
amount as possible. Wave
NH4+ (aq) + OH- (aq) ←
the chemicals towards your
→ NH3 (g) + H2O (l). nose, rather than directly
smelling the container.

Complex ion formation: Many transition metals ions are known to form colored complexes when
bonded with specific molecules or anions in an aqueous solution. Therefore, the color change observed
when an unknown solution is added to a known metal ion containing solution can be applied in
qualitative analysis schemes.

Consider as an example, what happens when aqueous ammonia (also known as ammonium hydroxide) is
added to a solution containing copper (II) cation, which is initially light blue-green. Since ammonium
hydroxide (NH4OH) solutions are basic, when a small amount of aqueous ammonia is added to a Cu2+
solution, a light blue precipitate of Cu(OH)2(s) is formed according to the reaction,

Cu2+(aq) + 2OH–(aq) ←
→ Cu(OH)2(s),
However if you continue to add ammonium hydroxide to the Cu(OH)2(s), a second type of reaction take
place. A complex ion reaction produce a deep blue solution of the soluble copper complex
[Cu(NH3)4]+2(aq),

Cu(OH)2(s) + 4 NH4+(aq) ← +2 +
→ [Cu(NH3)4] (aq) + 2H (aq) + H2O(l) ,
The complex ion, [Cu(NH3)4]+2, can also be formed directly by the addition of excess ammonia to an
aqueous solution of Cu+2(aq). Similarly, aqueous Ni2+ ions (green) can bind ammonia to form a purple
complex of [Ni(NH3)6]+2.

Another colorful example of complex ion formation is the ferric thiocyanate complex. When a yellow,
iron(III) solution is mixed with a colorless thiocyanate (SCN–) solution the blood red ferric thiocyanate
complex is formed.

Fe3+(aq) + SCN–(aq) ← 2+
→ [FeSCN] (aq), or more accurately,
Fe3+(aq) + 5H2O(l) + SCN–(aq) ← 2+
→ [Fe(H2O)5 SCN] (aq).
Case Study Activity
A. The Challenge:
Welcome. You are now a member of a special investigation team. Because of
your academic strength and problem-solving skills, you and your team have been Preparation
selected to help us clean up the laboratories. It seems that last semester’s • Review basic chemical
chemistry class wasn’t very careful. When we were cleaning up the labs earlier reactions.
• Read this lab
this month, we found five bottles of unlabeled chemical waste. To dispose of
• Review Silberberg
these bottles, the chemicals in each bottle will have to be identified. (It would be Chapters 1-4.
both illegal and unethical to dispose of unknown chemicals by putting them
down the drain or in a trash container.)

Since we know the types of experiments that were carried out the previous semester, we know that the
bottles contain the following chemicals: barium nitrate [Ba(NO3)2], nickel(II) chloride [NiCl2], ammonium
hydroxide (NH4OH), sodium carbonate (Na2CO3), and sulfuric acid (H2SO4). Further, it seems fairly
unlikely that a single bottle would contain a mixture of the possible chemical components.

It is now your responsibility to identify the contents of these bottles. The only tools you have available are
the chemical unknowns themselves, pH paper, a Bunsen burner, disposable pipets, paper clips, empty
beakers, glass stirring rods, a bottle of rinse water, and your knowledge of chemistry.

B. Preparing for the challenge:

One important skill that you will need to develop this semester is the ability to collect and organize
scientific information. Since you will often be asked to do this as you go along, it will be to your
advantage to plan ahead. This preparation should be done in your laboratory notebook. Your laboratory
notebook is your permanent record of your entire laboratory experience, from the preparation stage to the
end of the laboratory experiment. Everything you do for case study and laboratory should be recorded
in your laboratory notebook in ink. Copies of your case study and laboratory work will always be
collected at the end of the period and your pre-laboratory exercises will always be collected at the start of
each laboratory session; all items will be graded.

Even before case study, you should begin to evaluate the problem that you will face. For example, for
the case study at hands, you should skim Chapters 1-4 of you textbook (Silberberg) and read the
introduction of this experiment in order to be familiar with the relevant chemical information that you will
use to solve the chemical challenge.

By the end of this evaluation phase of the problem, you should be able to succinctly state the problem and
to be aware of the types of chemical knowledge that you will need to bring to bear. Don’t be surprised if
you are called on in case study and asked to verbally highlight some of the background chemistry needed
to solve the problem. It would be useful for you to organize your thoughts by providing summaries of the
possible chemical compounds and the types of chemical tests that will be used.

As the second step of problem solving, you will want to start to examine specific observations and begin
to correlate these observations to chemical ideas in order to define an experimental strategy. Most of the
time you will need to wait until case study to begin this step, so be ready to think on your feet. In case
study, when we make observations as a group, you will need to record those observations in some kind of
organized format.

Chemical Component Chemical Tests

1. Barium nitrate [Ba(NO3)2], 1. Color of solution
2. Nickel chloride [NiCl2] 2. Color of flame
3. Ammonium hydroxide (NH4OH), 3. Acid-Base reactivity
4. Sodium carbonate, Na2CO3 4. Precipitation reactions
5. Sulfuric acid, 5. Complex ion reactions
(H2SO4) 6. Gas producing reactions

For example, when you get to case study and examine the unknowns, you might use a table similar to the
one below to summarize your initial observations.

Bottle label Observation

Unknown 1 Approximately 25 mL of a clear, colorless, odorless liquid.

Unknown 2 Approximately 25 mL of a clear, yellow, odorless liquid.

So do you think you are ready? …. Here is one last thing to think about. In the case of qualitative analysis,
it is often useful to outline the problem using flow charts. These charts are useful both in communicating
the procedure that was followed, as well as the logic that was used in carrying out the analysis. As a quick
example, consider the problem of identifying three cups; one of Coke®, one of Sprite®, and one of water.
The flow diagrams for such a problem might look like the following:

Expectations/Plan Experimental Results

Note that each vertical line represents a test, and that each distinct result is grouped in its own box. In this
way, the application of successive tests can be expected to separate the unknowns according to their
characteristic properties. By correlating the properties of the unknowns to the properties of known
samples, the identities can be realized.

C. The Case Study Session

In case study, we will be working together to identify five bottles of unknowns. As we work through this
problem, you will want to record the experimental strategy used (e.g. in a flow diagram), any observations
that you make (e.g. in summary tables), and any conclusions that you are able to draw (e.g. in summary
statements). Although you will need to present this information in your own style, the instructor will be
acting as your guide throughout the activity. If at any point you have a question, be sure to ask!

During the case study you will want to make sure to take notes. In particular, the things that we will be
looking for in scoring the work that you turn in include:

1. Your name and section number.

2. A list of the tests that you would like to run first during the investigation.

3. A flow chart of your expected results.

4. A flow chart of the observed results.

5. A table summarizing the conclusions.

IV. Pre-Laboratory Activity
1. Safety is very important in the chemistry lab. It is a good laboratory practice to always be
familiar with the hazards of the chemicals that you will be handling. Therefore, please read
the pertinent information on all of the chemicals that are used in the experiment by looking
up the Material Safety Data Sheet (MSDS) for each chemical before you arrive to lab. This
can be done quickly and efficiently by going to http://ccc.blackboard.com and logging
into the course Blackboard. The experiment link will present a summary of table of chemical
safety information and will facilitate accessing the MSDS information for the chemicals used
in this experiment. Please record the names of all the chemicals that have a health hazard
rating of 3 or above.

2. Suppose you are given three bottles, labeled S1, S2, & S3,
each contains an aqueous solution. You are told that the
possible solutions are: Nickel (II) sulfate, sodium S1, S2, & S3
carbonate, ammonium hydroxide (6. M), potassium Color
thiocyanate, and pure water. Only one type of solution is green colorless
present in each bottle and the concentration is 0.5 M unless S2 S1 & S3
otherwise noted. Several tests are run, and the results are pH test
summarized in the flow chart displayed on the right. Based
on these results, assign the contents of the bottles and write a Basic
brief justification for each assignment. S1 & S3
Add S2 to each
S2+S3→
precipitate S2+S1→ purple
S3 S1 solution

3. To prepare for laboratory:

A. Prepare a table to summarize your initial expectations for the pH and color test. For
each of the eight unknowns solutions that you will identify in lab, identify the pH
category (acidic, neutral, or basic) and the color that you expect to find.
B. Although in your laboratory section you will be free to choose the order of the
chemical tests that you carry out, for this pre-lab suppose that you planned to run the
pH test first and the color test second. Create a flow chart that presents your
expected results for the eight unknowns that you summarized in the question (3A)
above.
C. Finally, write a balanced, net ionic reaction for the reaction of aqueous solutions iron
(III) nitrate (also called ferric nitrate) and sodium phosphate. (Hint: remember to
include the physical state: s, l, g, or aq.)
 Lab Chemicals
Sulfuric acid, barium nitrate,
sodium bicarbonate,
potassium thiocyanate,
V. Laboratory Activity sodium hydroxide, ferric
A. Introduction- Fictitious Scenario nitrate, ammonium
The Chem-Police, a division has just discovered eight bottles containing hydroxide, copper nitrate.
solutions of potentially hazardous chemicals in Truman’s Parking Garage. Solutions will be delivered as
Your job to identify the chemicals and have the site cleaned up and ready aqueous unknowns in
to go before the employees start showing up in the morning. numbered dropper bottles.
A concentrated acid solution
The bottles are found to be labeled with a numerical code, and the math will also be available for
department code breakers are working on the code, but a chemical solution cleaning flame test wires.
to this problem seems more direct. As part of the challenge, the group
suggests that each bottle contains only one of the eight solutions listed
below. Attached to each bottle there
H2SO4(1M) Formed with cation of acid fame, if precipitates anion
is one poorly written poem which
and element 56 to blame.
obviously written by a chemist gone
mad. Ba(NO3)2 March 17th has a color they say, that is the same as this
chemical’s flame test display.
The concentrations are all 0.25 M
unless specified otherwise. It is the NaHCO3 Not as basic as you might think, but adding an acid
task of your team to identify the (10%) might help establish a link.
contents of each bottle. This job
must be completed in the field since KSCN A bloody mess you might see if you put this together
the bottles cannot be transported with iron (III).
from their original location until you
identify their contents. In the field, NaOH BASICally you will find, this one’s easy if you use your
you will only have pH paper, a mind.
Bunsen burner, paper clips wire (and
concentrated acid solution for Fe(NO3)3 Roses are red and violets are blue, red with litmus and
cleaning the wire), test tubes, thiocyanate too.
droppers and spot plates. No other
chemicals are available. NH4OH (6 M) Very emotional and complex, with copper quite blue,
too strong to hold close, causes many to say “PEW!”
( aqueous NH3)

Cu(NO3)2 Color is the key and is easy to see.

B. Your Laboratory Challenge

Part 1 Group Unknowns (Teams of 2-3):
A set of the eight possible unknowns, labeled with identification numbers, will be
Safety Note: In
available at your lab bench. Your lab team will determine the identity of each of the
this lab be careful
unknowns and will report the results as a group.
of strong acids,
Each member of the team should be prepared. As part the pre-lab preparation, each strong ammonia
member should have evaluated the problem so that he/she is familiar with the odor. Be sure you
background information and the experimental objectives. Therefore, the first task to know how to
safely handle each
chemical.
be accomplished by the group is to explore the problem: brainstorm to formulate an experimental
strategy, perhaps carry out a few quick experiments, and distribute the work so that everyone knows
what to do. It is important for each team member to make a definable contribution to the overall
project.

While you execute your plan, using the chemical methods described in Section II- Chemical
Foundations, it is important that you record your results. You should have already read ahead to the
section on Communicating Your Results and know that you will be required to present your work in a
flow diagram. Therefore, you will probably want to make this diagram as you collect your data.
Remember to compare notes and run checks as needed. Every member of the team is responsible for
knowing what the team did, what results were obtained, and what conclusions were drawn from those
results.

Once you are confident of the group’s conclusions, summarize the group’s results and report the
results to your teaching assistant. After the group’s results have been reported, each member of the
team will be given an individual unknown to identify.

Part 2 Individual Unknown (Individually):

When you obtain your individual unknown, you should immediately record the
unknown number in your laboratory notebook. Since there are NO refills on Safety Note:
individual unknowns, you should also make sure that you have at least 2 mL of Do not put chemicals
unknown solution (the vial should be more than half full). down the drain.
Collect your waste at
All of the work in this second part of the experiment should be done as an your laboratory bench
individual. Do not discuss your strategy or results with other members of your and dispose of waste
laboratory section. Teaching assistants can deduct points for inappropriate in the labeled chemical
discussion during this second part of the laboratory challenge. However, you can waste collection
use any of the previously identified solutions and any notes that were taken during bottles located in the
the first part of the experiment. fume hood in lab.

Waste: Dispose of your waste in labeled chemical waste bottle located in the fume
hood or according to the specific instructions of the professor.
C. Communicating Your Results
Group results can be worked on as a group and a single copy turned in for a grade (make sure to
include the names of all group members). It is extremely important that every member of the
group should agree with what is submitted. Every member must have his/her own record of the
data and results recorded in his/her own notebook. The group report should include:

1. A flow chart illustrating the experimental strategy and experimental results. This diagram can
be supplemented by other observations. All observations should be presented in an
organized way.

2. A table summarizing the group’s results. This summary should include the serial numbers of
the unknowns and a brief written statement for each unknown explaining how an
unambiguous conclusion was reached. The reasoning should be based on the tests run and
should have a chemical basis for the result (not only process of elimination). For example:
sample A12345 was determined to be Nickel Sulfate because Ni2+ ion is the only ion amongst the given
chemical set that would be expected to show a green color in aqueous solution and A12345 was green.

Working as an individual, report the following in your laboratory report.

3. Select four reactions that were carried out during the laboratory period (either during the
group work or while working on the individual unknown); one reaction should be selected in
each of the following four categories: (a) acid base reactions, (b) complex ion reactions, (c) gas
forming reactions and (d) precipitation reactions. For each reaction write a balanced chemical
reaction including physical states [solid (s), liquid (l), gas (g) or aqueous solution (aq)]. Net
ionic reaction equations are preferred, but not required. For example, the reaction of
nickel(II) chloride and ammonium hydroxide seen in case study could be written in either of
the following ways:
NiCl2 (aq) + 6 NH4OH (aq)  [Ni(NH3)6]Cl2 (aq) + 6 H2O (l) or
Ni2+ (aq) + 6 NH4+ (aq)  [Ni(NH3)6] 2+ (aq) + 6 H+ (aq).
4. Attach a flow chart showing the procedure you worked out to determine your individual
unknown and write a summary statement briefly explaining how you deduced the identity of
your individual unknown.

Note: It will save time if you work on the report items while you are doing the experiment rather
than waiting until the end of the period.
 Group Unknown Identity Report Form
Group member Names: _________________________, _________________________,

_________________________.

Initial Results: Based on our experimental results we have assigned the following identities to our unknown samples
and are submitting the results to be graded.

Chemical Name Unknown Number Chemical Name Unknown Number

Ammonium Hydroxide Potassium Thiocyanate
Barium Nitrate Sodium Bicarbonate
Copper(II) Nitrate Sodium Hydroxide
Iron(III) Nitrate Sulfuric Acid

NUMBER CORRECT: ________

Final Flow Chart of Experimental Procedure Used:
Individual Unknown Number:

↓ Tests:____________
Chemical Name Written justification for assignment (Tests Ran)
Ammonium Hydroxide

#_______________

Barium Nitrate

#_______________

Copper(II) Nitrate

#_______________

Iron(III) Nitrate

#_______________

Potassium Thiocyanate

#_______________

Sodium Bicarbonate

#_______________

Sodium Hydroxide

#_______________

Sulfuric Acid

#_______________
References
1. University of Iowa, Chemistry 004:011 Lab Manual, 2002

2. http://www.wiredchemist.com/chemistry/instructional/chem_lab_qualitative.html

3. Virtual CrezLab, http://www.crescent.edu.sg/crezlab/Webpages/PrelimExam4.htm

4. http://www.gk12.ilstu.edu/chemistry/PowerPoint202006/LABS%20&%20Activities/
Qualitative%20Analysis/Introduction%20to%20Qualitative%20Analysis.doc

5. http://www.dartmouth.edu/~chemlab/chem3-5/qual_an/full_text/intro.html