Qualitative Analysis

Qualitative analysis is what.

Quantitative analysis is how much.

What is it ?
How much is there?
How pure is it?
What are the impurities?

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Qualitative Analysis
•This experiment is part of a classical analysis scheme developed
by chemists of past generations to identify unknowns.

•In commercial practice the qual-scheme, as it is affectionately

known, has largely been surpassed by automated analytic
instrumentation
•To write the net-ionic equations for each given chemical
reactions;

•Proper techniques on how to handle semi-micro

experiments;

•Writing a flow chart (or schematic diagram) for procedures,

not just merely following the instructions like a “cook-book”
style;
 Principles of Qualitative Analysis

1. Separations:
These are procedures that separate groups of ions from other
groups, or individual ions in a mixture of ions.

 Separations are followed by confirmatory tests to identify the

separated ion.

2. Confirmatory Tests:
These are tests that determine conclusively that a certain
ion is present.

Interfering ions are removed before a confirmatory test is

done.
Techniques in Qualitative Analysis

1. Labelling
2. Documentation
3. Waste and washing of pipettes
4. Mixing of solution
5. Checking of pH
6. Centrifugation
7. Washing of precipitates
8. Heating of solution
9. Reducing of volumes
10.Avoiding cross-contamination
Techniques in Qualitative Analysis
1. Labelling
Techniques in Qualitative Analysis
2. Documentation
3. Washing of pippettes
-wash with distilled deionized water

Chemical waste bin

Techniques in Qualitative Analysis

4. Mixing of solution
- every time a reagent is added the solution needs to mixed

- Mix the solutions at the top and bottom of the test tube

- Stirring rod that is flattened at the bottom can be used

- GENTLE shaking of the test tube can be an option

 Techniques in Qualitative Analysis

5.Checking of pH
• To check the pH of a solution, put a piece of
litmus paper or pH paper on a
clean glass plate or watch glass.

• Dip the stirring rod into the solution in the

test tube, and touch the stirring rod to the
paper.

• Do NOT dip the test paper into the test tube.

This may cause some of the indicator dye to
dissolve in the solution, and the indicator
colour may confuse
subsequent tests.
Techniques in Qualitative Analysis
6.Centrifugation

• Centrifuge solutions so that the solid is packed at the bottom of the

test tube. Don’t forget to counterbalance the test tubes in the
centrifuge with similar test tubes holding equivalent volumes of liquid.
• Let the centrifuge spin for about 30 seconds. Usually the supernatant
liquid (the liquid above the precipitate) can be poured off of the
precipitate.
• Sometimes precipitates tend to float on the surface of the solution. If
this is the case, use a Beral-type pipet to draw off the supernatant
liquid. It is better to leave a little liquid over the precipitate than to
transfer some of the precipitate.
Techniques in Qualitative Analysis

7. Washing of precipitates
• It is almost always necessary to wash precipitates to free them
from ions that might cause confusion in later steps.

• To do this, add 1 or 2 mL of water to the precipitate, stir, centrifuge,

and discard the wash water.

• Sometimes the directions will require a specific reagent in the wash

water.
Techniques in Qualitative Analysis

8. Heating of solution

Water bath method Direct method

Techniques in Qualitative Analysis

9.Reducing of volumes

Direct heating Using water bath

Techniques in Qualitative Analysis

10. Avoiding cross-contamination

•Do not use tap water. Rather, use distilled water or deionized
water.

•Glassware must be clean prior to use. It's not essential that it be

dried.

•Don't put a reagent dropper tip into the mouth of a test tube.
Dispense reagent from above the test tube lip to avoid
contamination.

•Mix solutions by flicking the test tube. Never cover the test tube
with a finger and shake the tube. Avoid exposing yourself to the
sample.
Steps of Qualitative Analysis

1. If the sample is presented as a solid (salt), it's important to note the

shape and color of any crystals.

2. Reagents are used to separate cations into groups of related

elements.

3. Ions in a group are separated from each other. After each separation
stage, a test is performed to confirm certain ions truly were removed.
The test is not performed on the original sample!

4. Separations rely on different characteristics of ions. These may

involve redox reactions to change oxidation state, differential
solubility in an acid, base, or water, or precipitating certain ions.
Qualitative Analysis for cations
•In reality....
• Based on difference of solubility product
Qualitative Analysis for cations
Common Qualitative Analysis Reagents

Reagent Effects
+
6M HCl Increases [H ]
-
Increases [Cl ]
-
Decreases [OH ]
Dissolves insoluble carbonates, chromates, hydroxides, some sulfates
Destroys hydroxo and NH3 complexes
Precipitates insoluble chlorides
+
6M HNO 3 Increases [H ]
-
Decreases [OH ]
Dissolves insoluble carbonates, chromates, and hydroxides
Dissolves insoluble sulfides by oxidizing sulfide ion
Destroys hydroxo and ammonia complexes
Good oxidizing agent when hot
-
6 M NaOH Increases [OH ]
+
Decreases [H ]
Forms hydroxo complexes
Precipitates insoluble hydroxides
6M NH3 Increases [NH3 ]
-
Increases [OH ]
+
Decreases [H ]
Precipitates insoluble hydroxides
Forms NH 3 complexes
+
Forms a basic buffer with NH4
Qualitative Analysis for cations
In our experiment...
•Analysis of cations:

Pertinent equations Observable results (as

color of ppt)
Ag+ (aq) + Cl- (aq)  AgCl (s) white

Fe3+ (aq) + 3OH- (aq)  Fe(OH)3 (s) brown-gelatinous

Cu2+ (aq) + 2OH- (aq)  Cu(OH)2 (s) Yellowish-green
Zn2+ (aq) + 4OH- (aq)  Zn(OH)42+ Formation of complex ion
(aq) (soluble)
In our experiment...
•Confirmatory test:
Cations Confirmatory Net ionic equation Observable
reagents results
Ag+ NH3, followed by AgCl (s) + NH3(aq)  Ag(NH3)+ (complex ion) The ppt
HCl Ag(NH3)+ + HCl (until acidic)  AgCl (s) dissolves in the
base, then
followed by
presence of
white ppt.
Upon addition
of the acid
Fe3+ KSCN Fe3+ (aq) + SCN- (aq)  FeSCN2+ (aq) Deep red color
solution
NH3 Cu2+ (aq) + 4NH3 (aq)  Cu(NH3)42+(aq) Deep blue color
Cu2+ complex
K4[Fe(CN)6] 2Cu2+ (aq) + Fe(CN)64- (aq)  Cu2[Fe(CN)6] (s) Reddish-brown
ppt.
Zn2+ K4[Fe(CN)6] 3Zn2+ (aq) + 2Fe(CN)63- (aq)  Zn3 [Fe(CN)6]2 (s) Blue-green ppt.
(light-green
ppt.)
In our experiment...
•Analysis of anions:
Anions Confirmatory Net ionic equation Observable
reagents results
Cl- AgNO3 Ag+ (aq) + Cl- (aq)  AgCl(s) White ppt.
AgCl (s) + NH3 (aq)  Ag(NH3)2+ (aq) + Cl- (aq)
Ag(NH3)2+ (aq) + HNO3 (aq)  AgCl (s) + NO3-
CO32- Ba(OH)2 Ba2+ (aq) + CO32- (aq)  BaCO3 White ppt in the
BaCO3 (s) + HNO3 (aq) + Δ (heat) CO2 (g) solution in the
presence of
Ba(OH)2
Addition of HNO3
on the ppt. An
effervescent
reaction.
BaCl2 Ba2+ (aq) + SO42- (aq)  BaSO4 (s) Milky-white ppt.
SO42-
NO3- Aluminium Redox-reactions (basic medium): Red-litmus paper
powder 3NO3- (aq) + 8Al(s) + 5OH- (aq) + 18H2O 3NH3 (g) + change to blue,
8Al(OH)4- (aq) pungent smell
 Cations that were used in Group of Cations (based on Fresenius scheme)
this experiment
Ag+ 1: chloride group (precipitating agent is HCl)
Cu2+ 2A: sulphide group (precipitating agent is H2S in
alkaline medium)
Fe3+ 3B: Iron sub-group (precipitating agent is hydroxide)
Zn2+ 3A: Aluminum sub-group (soluble to hydroxide)

Anions that were used in this Group of Cations (based on Dobbins and Ljung
experiment scheme)
Cl- 4: insoluble to silver salts in an acidic solution
CO32- 1: insoluble to calcium salts in basic solution
SO42- 2: insoluble to barium salts in basic solution
NO3- 5: all soluble to barium, calcium and silver salts.
 Precipitation Reactions
Precipitate – insoluble solid that separates from solution
precipitate

Pb(NO3)2 (aq) + 2NaI (aq) PbI2 (s) + 2NaNO3 (aq)

molecular equation

Pb2+ + 2NO3- + 2Na+ + 2I- PbI2 (s) + 2Na+ + 2NO3-

ionic equation

Pb2+ + 2I- PbI2 (s)

PbI2
net ionic equation
Na+ and NO3- are spectator ions
4.2
 Precipitation of Lead Iodide
Pb2+ + 2I- PbI2 (s)

PbI2

4.2
Solubility is the maximum amount of solute that will dissolve in a
given quantity of solvent at a specific temperature.

4.2
 Writing Net Ionic Equations
1. Write the balanced molecular equation.
2. Write the ionic equation showing the strong electrolytes completely
dissociated into cations and anions.
3. Cancel the spectator ions on both sides of the ionic equation
4. Check that charges and number of atoms are balanced in the net ionic
equation

Write the net ionic equation for the reaction of silver

nitrate with sodium chloride.

AgNO3 (aq) + NaCl (aq) AgCl (s) + NaNO3 (aq)

Ag+ + NO3- + Na+ + Cl- AgCl (s) + Na+ + NO3-

Ag+ + Cl- AgCl (s) 4.2

 Sample on Ionic reactions

1. Barium chloride + sodium sulphate

2. Silver nitrate + sodium carbonate
3. Zinc nitrate + sodium hydroxide
4. ferric chloride + sodium hydroxide
5. copper (II) nitrate + sodium iodide
 FLAME TESTS

- To explore the line spectra of a variety of elements by heating

them in a Bunsen burner flame

- The data gathered from the flame colors created by the elements
will be used to identify some elements present in unknown
solutions
 FLAME TESTS
- Electrons in atoms, ions and molecules are restricted to specific
energy levels

- An electron “excited” by some outside energy (flame or

electricity) moves from its present energy level to a higher
energy level

- A photon of light is produced as the electron falls back to its

ground state

- The light given off is of a specific color since it has a specific

wavelength or frequency of light associated with it
FLAME TESTS
 FLAME TESTS

- A glass prism can be used to identify the

various “lines” produced by the photons

- The various photons bend differently as light

passes through a prism depending upon their
wavelength (or frequency)

- The smaller the wavelength the greater the

bending or diffraction and vice versa
Results
Application