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Group 3 Zinc-aluminum group Solution containing ions 2+ 2+ 3+ 2+ 3+ 3+ of remaining groups Zn , Fe , Fe , Ni , Cr , Al These ions precipitate from an alkaline + Na2CO3 solution of H2S. Some tend to form sulfides, Solution contains ions some the hydroxides. Further discrimination of Group 5 is possible, because FeS, Cr(OH)3 and (Na+, K+, and NH4+) Al(OH)3 will redissolve if the precipitate is layered with 10-2M acid, but NiS and ZnS will not.
Filtration
Rationale (1): ZnS, NiS, FeS as sulfides, i.e. borderline acids bind to a very soft base, when the pH is adjusted so as to weaken the M(OH2)nm+ hydrated cation. Rationale (2): Fe(OH)3, Cr(OH)3, Al(OH)3 precipitate because these are hard acids reacting with the hard base OH-. As acidic cations, they will tend to precipitate when the pH is equal to the pKa. These are all hard cations, and therefore prefer the hard base OH.
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Group 4 Alkaline earths Ca2+, Sr2+, Ba2+ Precipitate from basic solution on the addition of CO32- in the form of sodium carbonate. The carbonates are the insoluble products formed. Rationale: These are weakly acidic (Bronsted definition) cations. The carbonates are insoluble because of the favorable lattice energy when the weakly basic carbonate ion reacts with these cations, since the cation and anion are both doubly charged and similar in size.
Group 5 Alkali elements Na+, K+ and NH4+ These have soluble hydroxides and carbonates. They do not precipitate from the qualitative analysis scheme. Rationale: Lattice energy for carbonates is unfavorable, since the cations are small, and bear a 1+ charge. The hydroxides are soluble because the cations are nonbasic, while hydroxide is strongly basic.
Non-metals Be Mg Ca Sr Ba Ra
G R O U P 4
B
Group 3
C Si Ge Sn
Group
N P As Sb
2
O S Se
F Cl Br
Al Cr Mo W Mn Tc Re Fe Ru Os Co Rh Ir Ni Pd Pt Cu
d
Sc Y
LaLu AcLr
Ti Zr Hf
V Nb Ta
Zn Cd Hg
Ga In Tl
Ag Au
Te
Po
Pb
Bi
Group 1
Group 2 Group 3
La Ac
Ce Th
Pr Pa
Nd U
Pm Np
Sm Pu
Eu Am
Gd Cm
Tb Bk
Dy Cf
Ho Es
Er Fm
Tm Md
Yb No
Lu Lr
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2.
2.
3.
4.
5.
6.
7.
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8.
Centrifuging solutions that contain a solid and a liquid is a substitute for filtering the solid to separate it from the liquid portion. When centrifuging, it is critical that the centrifuge be balanced so the tubes will not break. To do this, place a test tube in one slot and another tube with the same volume of liquid (usually water, multiple samples or another persons sample) diametrically opposite the slot. Coarse precipitates may require only a few seconds of centrifugation while finely divided precipitates may take a few or many minutes. It would be wise to mark your tube before centrifuging in case another persons sample is the same. The solid remaining in the bottom, after centrifugation, is the precipitate and the solution above the solid is the supernatant or the centrifugate. In this lab we will call it the supernatant. To remove the supernatant from the solid, it can simply be poured off if the solid is very compacted. If the supernatant is required for further tests then it should be removed to a new (labeled) tube otherwise it can be discarded into the waste beaker. Note: It is better to save solutions until you are positive they are not needed. If the precipitate is only loosely compacted at the bottom of the test tube, then use a Pasteur pipette to draw off the majority of the liquid portion.
9.
Decanting a solution is a technique of separating a solid from a liquid. Think about a mixture of sand and water. To separate the sand from the water, you would allow the sand to settle to the bottom of the container and then carefully (so as not to disturb the settled sand) you would pour off the liquid and leave the sand behind. Decanting a liquid from a precipitate is done in the same manner. Precipitation is most often done to remove select ions. It is desirable therefore to make sure that all ions are removed from the solution or that precipitation is complete. To test for completeness of precipitation, simply add a drop or two of the precipitating reagent to the clear supernatant (after centrifugation and separation of the liquid from the solid). If more precipitate forms then there are still ions in solution. Centrifuge and combine the precipitates and test the supernatant for completeness of precipitation until no more precipitate forms. Often when an ion precipitates out of solution, it may carry other contaminating ions with it. It is important that precipitates be washed free of any contaminating ions as these may interfere with subsequent testing. To do this, add 0.5 to 1 mL of distilled water to the precipitate. Suspend the precipitate by vigorous shaking or stirring with a stirring rod to wash it, centrifuge and decant the liquid from the solid. The instructions should tell you whether washing is required and how much. Solutions in small test tubes need to be heated in a hot (not boiling) water bath. This allows for even, gentle heating and it is also a safer way to heat solutions in test tubes. To do this place the tube in a hot water bath, without a cork in the top, and with the mouth pointing away from you (towards the back of the hood). Allow the tube to heat for five minutes to ensure complete and even heating. The presence of a precipitate means the solution must be mixed intermittently to prevent the solid from settling and bumping out.
10.
11.
12.
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13.
When the volume of a solution needs to be concentrated, or reduced, then evaporation is required. Transfer the liquid to a small beaker or an evaporating dish on a hot plate. Using a pair of tongs to hold the container, gently move the container back and forth to mix the liquid and prevent it from burning. Remove it from the heat when the desired volume has been obtained or when there are still a few drops left. The last drops will disappear very quickly so be careful not to overheat the solution. To get correct results in qualitative analysis, good organizational skills and techniques are essential to preventing cross contamination. Be sure to clean out and rinse glassware and to wipe stirring rods off between solutions. Cross contamination is one of the most common causes for false observations leading to incorrect conclusions.
14.
Note: If you do not get a positive result for a cation from your separation scheme, then you do
not have that cation. DO NOT continue to test for anything that gives a negative result. Move on as you do not have that cation. Testing for negative results is a waste of time. You will not have every cation from every group.
Be sure to keep good records of what you have done and what you have observed. Your chemistry laboratory booklet should be titled & dated. Any observations and entries (right hand page only) into the booklet or report sheets must be organized and properly titled. It is a good idea to come well prepared so that you do not waste precious time reading and looking for things.
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I II
Ag , Pb , Hg22+ Cu , Bi , Hg , Cd , Sn , Sn , Sb
2+ 2+ 4+ 3+ 2+ 3+ 2+
III
Al , Cr , Co
2+ 2+
3+
3+
2+ 2+
Fe , Mn , Ni , Zn IV V Ba , Ca , Mg Na , K , NH4
+ + + 2+ 2+ 2+
2+
0.1M H2S, pH of 9
In general, concentrations of reagents and pH are adjusted such that only one group is affected by the precipitating agent. Once a select group is precipitated out of solution, it is removed by first centrifuging the mixture to get all the precipitate out and then collecting the supernatant (potentially containing other groups) by a process called decanting. In a mixed solution, the supernatant can be further tested for other groups by selective precipitation and the remaining precipitate can be tested for Group members by further selective precipitation and confirmatory chemical tests.
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2+
Procedure:
Note: Because you will be collecting solutions and saving them in various tubes, you should not trust yourself to remember which is which. Be sure to clearly label your tubes. Do not discard any solutions or precipitates until you are sure you do not need them any longer. 1. Each person will receive approximately ~6 mL of unknown sample. Record this unknown number - there is little your instructor can do for you if this number is lost. There are 2 types of unknowns, group unknowns and mixture unknowns. The mixture is the only unknown sample that may contain cations from all groups and must be treated accordingly. To 3 mL of unknown solution (save the rest in case you have to repeat something) add 0.5 mL of 6M HCl. Stir well. The presence of a precipitate indicates the presence of one or more Group I cations. When working with the mixture unknown and no precipitate forms, there were no Group I cations present in the solution and you can proceed with testing for Group II cations. Note: The 6M HCl is in excess and as a result the solution becomes slightly acidic. 3+ This prevents the precipitation of BiOCl if Bi from Group II is present in the mixture unknown solution. 2. Centrifuge the solution in a balanced centrifuge and decant the supernatant into a separate tube. Test for completeness of precipitation by adding 1 drop of 6M HCl to the decanted supernatant. If precipitation is complete, store the liquid until testing for Group II can be performed. Label the tube i.e.: further group testing. This is relevant only if working with the mixture unknown. If precipitation is not complete, add a further 1 mL of 6M HCl and repeat the centrifugation process. Combine the precipitates and keep the supernatant for further Group II testing. The precipitate containing one or more of the chlorides of Group I cations can now be analyzed.
3.
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4.
To the precipitate, add approximately 5 mL of distilled water. Heat the contents in a boiling waterbath for 5 minutes with stirring. Centrifuge any remaining precipitate in a balanced centrifuge. Decant the supernatant to a different test tube leaving behind the precipitate. Save the precipitate for further testing of Ag+ and Hg22+. Lead(II), Pb2+, is the only cation of Group I that is soluble in hot water. Therefore the supernatant must be tested for the presence of Pb2+.
5.
Note: If Pb2+ was present in your sample, then wash any remaining precipitate with ~2mL hot
water again to remove all traces of PbCl2 as it may interfere with further tests. 6.
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Note: If Pb2+ was present in your sample it may interfere with further tests.
Therefore to ensure the precipitate from step 4 is free of traces of PbCl2, the remaining precipitate is washed with ~2mL hot water and isolated from the wash by filtration through Whatman paper. The wash is discarded. A clean test tube is positioned to + collect the filtrate which may contain Ag(NH3)2 when the precipitate is treated with 20 drops of freshly prepared 6M NH4OH. If all the precipitate dissolves, then only AgCl was present. If the precipitate becomes black or grey, due to the formation of Hg and 2+ Hg(NH2)Cl then Hg2 was present in the unknown.
Results:
Be sure to include your unknown number and the positive cations present in your unknown. Submit the Group I cation(s) identified in your unknown on the report sheet provided.
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2Bi Cu Cd Sn
+ 3H2S Bi2S3 (brown) + 6H + H2S CuS (black) + 2H + H2S CdS (yellow) + 2H+ + H2S SnS (brown) + 2H
+ +
2+
2+
2+
and Sn
4+
The precipitation procedure will result in a mixture of a number of sulfides. It is necessary to separate and identify the components of the sulfide mixture. If Sn is present, or thought to be present, it is first necessary to treat the solution with a little 2+ 4+ H2O2 in order to oxidize Sn to Sn before the Group II sulfides are precipitated by H2S. Once the Group II cations are precipitated, SnS2 can be removed from the bulk by dissolving it in ammonium sulfide (NH4)2S as it is the only Group II sulfide that is soluble in ammonium sulfide. The SnS2 can be reprecipitated from the SnS3 complex ions by the careful addition of acetic acid which readily dissolves in excess HCl. The formation of this yellow precipitate and subsequent solution in excess acid can be taken as evidence that tin maybe present. The confirmation of tin can be obtained by reducing Sn4+ to Sn2+ with iron filings and adding HgCl2 solution which reacts with Sn2+ to give Sn4+, Hg2Cl2(white) and Hg (black). Sn
2+ 2-
+ H2O2 + 2H Sn4+
+