COMPUTERIZED QUALITATIVE ANALYSIS
INSTRUCTOR RESOURCES
A MicroLAB Experiment by Dale A. Hammond, PhD,
Brigham Young University Hawaii
LEARNING OBJECTIVES
The objectives of this experiment are to . . .
! use the formation of precipitates and complex ions and an understanding of relative stability sequences,
(i.e., transforming one compound or complex into a more stable compound or complex) to separate the
cations and anions from each other into major groupings.
! separate the individual ions of a group from each other in order that each separate ion can then be
caused to undergo a reaction specific for that ion which conclusively identifies it from all other ions in
a “confirmation test”
! understand the origin of and the importance of colors, complex ions, precipitates and stability sequences
in the Qualitative Analysis schema.
! understand and be able to use the logical thought processes involved in developing a qualitative analysis
schema.
PROCEDURE OVERVIEW
! carry out a series of ?characterizing experiments” involving the seven cations (sodium is tested for
separately) which will be summarized in a “reaction grid” of the reaction of each of the cations with
each of the test ion solutions.
! carry out the same processes on the four anions.
! complete the provided tables as you carry out the characterizing experiments,
! keep a careful laboratory notebook in the given format and provide the net ionic equation in the
conclusions section for each reaction.
! use the complex ion, precipitation tables and stability sequences to devise one or more comprehensive
separation schema for the eight cations and four anions.
! Use the separation schema to analyze the following unknowns, listed with increasing difficulty and
awarded increasing points for completion (They might be allowed to repeat each type until it is totally
correct.):
! one cation
! two cations
! one compound (a cation and anion)
! two compounds
! any number of ions
15
COMPUTERIZED QUALITATIVE ANALYSIS
Tips and Traps
1. This is a totally new experience for students at this level. You may wish to hand out the short
introduction that follows to ensure that they understand the terms, operations and logic involved in
qualitative analysis. This could be used as a preliminary introduction to the laboratory to give them a
brief experience before tackling the computerized version, or, it could be used as a classroom
demonstration.
INTRODUCTORY INORGANIC QUALITATIVE ANALYSIS
by Dale A. Hammond, PhD
Introduction
Inorganic Qualitative Analysis is the science of separation of cations and anions from each other for the
purpose of determining the composition of the sample, i.e., determining exactly which cations and anions
are present in each particular sample. Generally there is a complex scheme of reactions involving the
formation of precipitates and complex ions, designed to take an unknown containing any possible cations
and anions, and separating the ions first into major subgroups, of which there are usually five, then smaller
subgroups within each major subgroup, and finally isolating each individual ion that was present in the
solution and confirming that ion by a specific reaction which only that ion undergoes at that stage of the
separation.
This experiment will introduce you to the
physical and chemical aspects of qualitative
analysis such as forming precipitates
(substances of low solubility which form a
solid phase in the solution), centrifuging
(spinning the sample rapidly in a machine to
cause the precipitate to settle to the bottom of
the test tube), the centrifugate (the solution
above the settled precipitate), decanting
(separating the solution from the precipitate),
the decantate (the liquid separated from the
precipitate) washing the precipitate, and
determining a proper scheme for the separation
of the ions involved.
This process is illustrated in the accompanying
diagram using the Silver Subgroup as an
example. This subgroup contains silver,
mercury and lead, and is separated from all
other inorganic cations by precipitation with 1
M HCl. This subgroup is the least complex of
the various inorganic qualitative analysis
subgroups.
Figure 1: Separation scheme for the Silver Group
After separation of the three ions from all other
ions by the addition of the HCl, each ion must be further separated and isolated for a confirming test. In this
case, the PbCl2 has much higher solubility in hot water than the other two ions. The mixture of chlorides is
16
poured onto a filter paper and the filtrate (the liquid passing through the filter) allowed to drain and would
normally be saved to be examined for the presence of addition ions. Very hot, deionized water is then poured
over the precipitate in the filter to dissolve the PbCl2 , and the filtrate collected in a separate test tube.
Potassium Chromate (K2 CrO4 ) is added to the hot filtrate to test for the presence of the lead. A bright yellow
precipitate is a confirming test for the presence of the Pb2+ ion in the unknown.
Silver chloride (AgCl) is soluble in 6 M NH3 , so 5 ml of 6 M NH3 is then poured over the precipitate in the
filter, and the filtrate collected. 6 M HCl is then added to the filtrate dropwise, and the formation of a white
precipitate is the confirming test for the presence of silver ion in the unknown.
Finally, the Hg2 2+ ion is unstable in the 6 M NH3 , and disproportionates (i.e., undergoes auto-oxidation-
reduction) to form metallic mercury, which in finally subdivided form is black, and insoluble HgNH2 Cl,
termed mercury amine chloride, which is white. This leaves a gray to black precipitate in the filter paper,
which is confirming for Hg2 2+.
The ions we will be using as our exploration experiment will be silver (Ag+ ), barium (Ba2+ ) and iron (Fe3+ ).
The main purpose of this experiment is to help you learn the techniques and logical thinking involved in this
type of chemistry in order to apply it to the computer exercise that follows, which will be a little more
complex.
Characterizing experiments:
This exercise will require you to carry out a series of ?characterizing experiments” which are best
summarized in a “reaction grid” of the reaction of each of the cations with each of the test ion solutions. In
order to help you understand this better, we will discuss the simple reaction grid below involving the three
cations (Ag+ , Ba2+ , and Fe3+ ) and the three test solutions (Cl-, SO4 2-, and OH-) you will work with in the
laboratory, as given in Table 1a:
Table 1a
Cations / Test solns Cl- SO4 2- OH-
Ag+
Ba2+
Fe3+
All solution concentrations of the cations and test solutions are 0.10 M. You will need nine (9) 3 inch test
tubes, one for each of the reactions. Make sure you label all test tubes clearly at the time you prepare
them! You will first test the silver ion with each of the test solutions. You will next carry out the tests with
the barium ion, then the ferric ion. Make sure you set up a table in your lab notes like Table 1a, and
record whether a precipitate forms, its color, and any other changes you observe in your results for each of
the nine experiments you carry out. If no reaction occurs, just put down NR. Set up all nine labeled test
tubes in your test tube rack, and carry out each of the nine reactions, one after another. Save the test tubes
with the precipitates and discard the solutions in the test tubes with no precipitate into the appropriately
labeled waste container in the middle hood. All washings can be discarded in a labeled beaker and
discarded in the sink at the end of the experiment.
Centrifuge each of the precipitates, wash each with 2 ml of deionized water, mix well with a small stirring
rod, then centrifuge, decant and discard the centrifugate. Again add 3 ml of deionized water, mix well with
a small stirring rod, and divide the volume into two clean, clearly labeled test tubes.
17
Recentrifuge each of the samples, decant and again discard the centrifugate. To one portion of each of the
precipitate samples, add dropwise with stirring 6 M NH3 , noting any changes after the addition of each drop.
If the precipitate changes, make note of any changes that occurred and how many drops it required in your
lab notes. To those samples that dissolved, add dropwise with stirring 6 M HCl, again noting in your lab
notes if any changes occurred and how many drops it required to cause that change.
To the second portion of each of the precipitate samples, add dropwise 0.1 M KSCN (potassium thiocyanate),
noting in your lab notes if any changes occurred and how many drops it required to cause that change.
You should now have a table 2 that looks something like this.
Cations / Test solns 6 M NH3 6 M HCl 0.1 M KSCN
Ag+ ppt
Ba2+ ppt
Fe3+ ppt
The task is now to translate this information into an analysis scheme which will analyze an unknown solution
for the presence of any or all of the three cations with the three test solutions. To accomplish this, we must
carefully analyze the data in the two tables. Keep in mind, that an unknown solution for this group could
contain one, two or all three of the ions in it, you don’t know which! It is your task to devise a scheme which
will allow separation and unequivicable identification (a con firming reaction) of each ion in the presence
of any or all of the other ions.
Following are a few hints to assist in this. First, examine carefully how each test solution reacted with each
cation. Was there a cation that reacted with all three of the test solutions? Was there a test solution that did
not form a precipitate with any of the cation solutions? In reactions of the cations with the test solutions in
which no precipitate formed, was there any color change? Which test solution was the most unique in
reacting with a given test solution?
If so, it might seem reasonable to start our analysis by testing a portion of the unknown with that test
solution. If a precipitate forms, then we know that we must have that cation ion present, because that is the
only ion which formed the white precipitate with that test solution.
This mixture would then be centrifuged to separate out the precipitate and the centrifugate is then decanted,
and the separated liquid (termed the decantate) is saved for further testing for the other two cations. We will
call this solution decantate1. Based on the reactions in table 2, you now need to devise a confirming
reaction for the cation that has just been separated out by this precipitation. Does this cation react with the
6 M NH3 , 6 M HCl or 0.1 M KSCN? If so, can this be a confirming reaction for that cation? Once you have
determined the confirming reaction, be sure to include it in your flow chart for this analysis scheme, similar
to Figure 1.
We now must decide which of the two test solutions to use next. Knowing that one of the cations has already
been removed, is there a cation that only reacted with one of the remaining test solutions? If so, addition of
that test solution to decantate1 would give a precipitate if that cation were present. If such a precipitate were
obtained, then we would again centrifuge and decant, producing decantate2. Again, consider what can be
used as a confirming reaction for this cation. Does this cation react with the 6 M NH3, 6 M HCl or 0.1 M
KSCN? If so, can this be a confirming reaction for that cation? Again, be sure to add this to your flow chart.
If no precipitate formed upon addition of that test solution, then it would be reasonable to assume that cation
was not present.
18
Finally, we add the last test solution to decantate2. If a precipitate forms, then that indicates the presence
of the last cation in the unknown. Again, consider what can be used as a confirming reaction for this cation.
Does this cation react with the 6 M NH3 , 6 M HCl or 0.1 M KSCN? If so, can this be a confirming reaction
for that cation? Again, be sure to add this to your flow chart. If no precipitate forms, then that confirms
the absence of the last cation in the unknown.
This information should now have been constructed into a Flow chart similar to Figure 1. This provides
a logical, systematic approach to solving any unknown containing any or all of those three ions.
The experiments carried out here, and the logical thinking required to construct the flow chart for this
analysis, is characteristic of the experiments and thinking involved in constructing any analysis scheme and
is preparation for you for the next exercise, which will be a computer qualitative analysis for seven cations
and four anions. This is a challenging activity, dig into it and enjoy it. It will stretch your mind, and make
you a better thinker.
DOING THE UNKNOWN
You will now be given an unknown containing one, two or all three of the cations discussed here. Use the
flow chart you have developed here to analyze your unknown, then report to your instructor which ion or
ions, i.e., Ag+ and/or Ba2+ and/or Fe3+ , present in your unknown. Be sure to record the unknown number
in your lab notes when you receive it, and report this unknown number with your results. GOOD
LUCK ! ! !
2.
19
COMPUTERIZED QUALITATIVE ANALYSIS
Tips and Traps
3. If the previous information and lab activity is not used, it would be very helpful to guide them through
a basic set of reactions on the overhead or chalk board as displayed in the accompanying set of grids.
The task is to determine a qualitative separation scheme involving Ag+ , Ba2+ and Fe3+ ions, using only
the test solutions NaCl, Na2 SO4 and NaOH in a series of nine characterizing reactions. When the
reagents are added one at a time either as a demonstration or as an overhead or chalk board exercise,
the students are able to visualize the characterizing reactions and are then, with prompting, able to come
up with the scheme in Figure 10. The exact same process is what will take place on the computer as
the students work through the characterizing reactions as outlined on the accompanying two grids, the
Reaction Grid and the Precipitate and Complex ion worksheet.
20
COMPUTERIZED QUALITATIVE ANALYSIS
Tips and Traps (continued)
4. The separation scheme for the seven cations and four anions is quite a bit more complicated than the
simple three cations discussed above. The students will need significant assistance in ferreting out the
schema charts. It has been very helpful to have an advanced student available during and outside of lab
time to assist the students to think through the schema.
5. There is a particular problem of the zinc with ammonia and excess hydroxide. At decantate 1,6, one
can add either excess hydroxide, or ammonia to undergo the next separation. Adding excess hydroxide
precipitates magnesium and nickel ions, leaving chromium and zinc in solution as complex ions.
Adding ammonia precipitates magnesium and chromium, leaving nickel and zinc in solution as complex
ions. Thus, zinc is a complex ion in solution either way. The problem comes in that in the next step
or two, depending which route was taken, it is necessary to add an excess of hydroxide, which converts
the zinc amine complex ion into the tetrahydroxozincate complex ion. Most of the students, (and
sometimes the faculty) forget that the only way to get to the confirming step of precipitating the zinc
as Zn(OH)2 , is to heat the solution to drive off the ammonia, leaving the Zn(OH)4 2! complex ion.
Addition of HCl to neutralize the excess hydroxide, then addition of NaOH precipitates the zinc as the
white Zn(OH)2 for the confirming test.
6. Following herewith are the completed Reaction Grid, Precipitation / Complex Ion Worksheet, and
two versions of the overall schema, differing by the addition of excess NaOH or ammonia to the 1,6
Decantate. These should be carefully studied by all who will be assisting in the lab to ensure complete
understanding of each reaction on each of the grids or schema.
7. The WINQUAL program can be obtained from their web site at www.chem.wwu.edu/qual
where you can download a trial version and order site licences. Communication with the
authors of the program is via [email protected] and one of them will respond.
21
22
23
24
25
26
27
28
29
30
