CHAPTER 18 : CHEMICAL ANALYSIS v In chemical analysis, we want to find out the identity of a unknown substance just like a detective

wants to find out who is the criminal. v Chemist use different methods to help us find out the identity of chemicals through various tests. v In this chapter, we are going to learn one important method called qualitative analysis Qualitative analysis In qualitative analysis, we are interested to find out the identity of one or more unknown substances after carrying out some basic tests on them. v Observation of appearance colour and texture of substance v Heating heating the solid or liquid and use chemical test for the gases evolved. v Testing for cations use chemical test to identify the positive ion (cation) present in an ionic compound. v Testing for Anions use chemical test to identify the negative ion (anion) present in an ionic compound.

Identification of Ionic Compounds

Testing for the presence of ions: Assuming you are given a beaker of colourless solution which you suspect to be sodium chloride, we have to test for the presence of Na+ cation and Cl- anion to conclude that this solution is indeed sodium chloride. Hence we need to identify the two ions present by using specific reagents. Na+ Cl- (aq)

Test A for cations

Test B for anions

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Testing for cations: v To test for the cations (positive ions) present in a salt solution, we use two types of chemicals/reagents _______________________ ______________________________________________________ v When we add the two chemical into a solution, we are always looking out for precipitates (ppt). Both chemical provide hydroxide (OH-) ions to combine with the positive cation. Example: Solution A Ca2+ + sodium hydroxide OHWhite precipitate Ca(OH)2

v Hence we will observe a white precipitate appearing in the solution after the addition of sodium hydroxide. v We then add an excess of sodium hydroxide to see whether this precipitate dissolves to correctly conclude the presence of this particular ion. v As a confirmation test, we will add aqueous ammonia and see whether we obtain the correct results for Ca2+. Annex I given shows a list of cations and their results with both sodium hydroxide and aqueous ammonia Important: Some cations produce hydroxides which are coloured. This can be used to correctly identify these types of ions Example: Cu2+ (aq) + OH- (aq) Cu(OH)2 (s) Blue precipitate

From NaOH / NH4OH

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Exercise 1. Read the following observations. Refer to annex I to conclude the cations that are present. Test 1 Observation On adding sodium hydroxide, a redbrown ppt is formed. The ppt does not dissolve in excess sodium hydroxide 2 On adding sodium hydroxide, a white ppt is formed. The ppt dissolves in excess sodium hydroxide 3 On adding sodium hydroxide, a green ppt is formed. The ppt does not dissolve in excess sodium hydroxide. 4 On adding sodium hydroxide, a blue ppt is formed. The ppt does not dissolve in excess sodium hydroxide 5 On adding sodium hydroxide, no ppt is observed. On warming the solution, ammonia gas is produced (a) Look at your conclusions. Do you think sodium hydroxide alone gives a conclusive result for the cations? Why? _____________________________________________________________ _____________________________________________________________ _____________________________________________________________ ___ (b) If your answer is No in (a), what do you think we can do to overcome this problem? _____________________________________________________________ _____________________________________________________________ Page 3 Conclusion Chemical formula of precipitate

_____________________________________________________________ ___ ______________________________________________________________ 2. What would you expect to see if dilute sodium hydroxide was added to a solution of the following until there is no further change? (a) iron (II) sulfate : ______________________________________________ ______________________________________________ (b) zinc nitrate : ________________________________________________ ________________________________________________ 3. A bottle contains a colourless solution. This was believed to be a solution containing Zn2+. How would you test this solution and what are the results you would obtain to conclude that Zn2+ is present? _____________________________________________________________ _____________________________________________________________ _____________________________________________________________ ___ _____________________________________________________________ _____________________________________________________________ _____________________________________________________________ ___

Testing for anions and gases v The test for anions (negative ions) are more diverse that the test for cations. There five types of anions that you have to learn. They are nitrate NO3 carbonate CO32 sulfate SO42 chloride Cl iodide Iv Each of these anions have their own confirmation test. Annex II shows the various test for the anions and their results. Page 4

v Some of these confirmation test involves testing for gases. Hence you also have to learn the confirmation tests for the various gases. v This can be found in Annex III. v In a normal qualitative test for an unknown compound, these three tests are often used in conjunction with each other.

Exercise 1. Some test were carried out on salt X and Y. The results are given in the following table. Salts X Test (a) sodium hydroxide was added to the solution until no further change is observed. (b) dilute nitric acid was added to a solution of the salt. Silver nitrate was then added. Y (a) dilute nitric acid was added to a solution of the salt. Barium nitrate was then added. (b) sodium hydroxide was added to the solution until no change was observed. (c) aqueous ammonia was added to the solution until no A green ppt was obtained. It did not dissolve in excess sodium hydroxide Page 5 A green ppt was obtained. It did not dissolve in excess sodium hydroxide A white ppt was obtained Observations No ppt is observed. On warming the solution, a gas produced turned moist red litmus blue. A white ppt was obtained conclusion

change was observed. From your conclusion, identify the salts (i) salt X is ______________________________________________________ (ii) salt Y is ______________________________________________________

2. The diagram below shows some reactions of a salt S. yellow precipitate acidified Pb(NO3)2(aq) Salt S a little aq NaOH White precipitate excess aq NaOH Precipitate dissolves

excess dilute H2SO4 Solution Q

(a) In salt S, the anion is ___________________ The anion can be concluded when _____________________________ _________________________________________________________ (b) The cation is ______________________ The cation can be concluded when _____________________________ _________________________________________________________ (c) Precipitate P is ________________________________________ (d) Write a chemical equation for the conversion of P to Q. _________________________________________________________ _ Additional information Besides testing for cations, anions and gases, there are also some ways which we can guess the identity of compounds. v Colour of common substances. Page 6

Colour Black Grey Blue Green Orange Yellow

In solid form C, CuO, MnO2 Most metals eg, Al, Mg, Zn Hydrated copper(II) salts CuCO3, hydrated CuCl2, hydrated iron(II) salts K2Cr2O7 (potassium dichromate) Iron (III) salts, K2CrO4

In aqueous solution Cu2+ ion Fe2+ ion Cr2O72- (dichromate) ions Fe3+, Cr2O42-, dilute Br2/I2

v Changes upon heating Heating of solids may sometimes help us to deduce the presence of some ions Upon heating What the result may mean Carbon dioxide (CO2) gas produced Oxygen(O2) gas produced Ammonia (NH3) gas produced Solid changes from green to black Solid changes to yellow when hot and back to original colour when cold Annex I Tests for cations Cation Aluminum (Al3+) Ammonium (NH4 ) Calcium (Ca2+) Copper (Cu2+) Iron(II) (Fe2+) Iron (III) (Fe3+)
+

Carbonate (CO32-) is present Substance may be a metal oxide or metal nitrate Ammonium (NH4+)salt is present Green CuCO3 changes to black CuO Solid contains Zn2+

Effect of aqueous sodium hydroxide White ppt, soluble in excess No ppt, ammonia gas produced White ppt, insoluble in excess Light blue ppt, insoluble in excess Green ppt, insoluble in excess Red-brown ppt, insoluble in

Effect of aqueous ammonia / ammonium hydroxide White ppt, insoluble in excess No test No ppt or very slight white ppt Light blue ppt, soluble in excess to produce a dark blue solution Green ppt, insoluble in excess Red-brown ppt, insoluble in excess Page 7

excess Zinc (Zn2+) Lead(II) (Pb )

2+

White ppt, soluble in excess White ppt, soluble in excess

White ppt, soluble in excess White ppt, insoluble in excess

* Al3+ and Pb2+ can be differentiated by the insolubility of lead(II) chloride.

Annex II Tests for anions Anion Chlroide (Cl-) Iodide (I-) Nitrate (NO3-) Tests Add nitric acid dropwise followed by aqueous silver nitrate (AgNO3) Add nitric acid dropwise followed by aqueous lead(II) nitrate Add sodium hydroxide then add Warm Carbonate (CO32-) Add dilute HCl, H2SO4 or HNO3 Results A white ppt of silver chloride (AgCl) is formed A yellow ppt of lead(II) iodide (PbI2)is formed Ammonia gas is produced (b) forms white fumes with concentrated HCl Effervescence is seen Carbon dioxide gas produced, gives a white ppt in limewater Sulfate (SO42-) Add Barium nitrate (Ba(NO3)2) A white ppt of barium sulfate (BaSO4) is formed Annex II Tests for gases Gas Ammonia (NH3) Carbon dioxide (CO2) Chlorine (Cl2) Nature of gas Alkaline Acidic Acidic Test for gas and results Turns moist red litmus paper blue Forms a white ppt in water Turns blue litmus paper red, then bleaches it Page 8

aluminium foil or aluminium powder. (a) turns moist red litmus blue

Hydrogen (H2) Oxygen (O2) Sulfur dioxide (SO2)

Neutral Neutral Acidic

Extinguishes a lighted splint with a pop sound Rekindles a glowing splint (a) Turns acidified potassium dichromate (VI) solution from orange to green (b) Turns potassium manganate (VII) solution from purple to colourless

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