Scheme of Analysis for Unknown 9A/9B

CHM 2046 L

Fair Game Unknowns

Cations: Na+, K+, NH4+, Ca2+, Mg(H2O)62+, Al(H2O)63+, Zn(H2O)62+,
Cu(H2O)2+, Ag(H2O)+
Anions: Cl-, NO3-, SO4-2, HSO4-, OH-, CO3-2, HCO3-, S-2
Insoluble Salts: Ca(OH)2, CaCO3, CaSO4, Mg(OH)2, MgCO3, Ag2O,

AgCl, Ag2S, CuO, CuCO3, CuS, Zn(OH)2, ZnCO3, ZnS

Alums: [Al(OH2)6]2(SO4)36H2O, Na[Al(OH2)6](SO4)26H2O,
K[Al(OH2)6](SO4)26H2O, NH4[Al(OH2)6]2(SO4)26H2O
Hydrated Ions: Na2CO310H2O, Na2SO410H2O, Ca(OH2)6Cl2,
Mg(OH2)6Cl2, Mg(OH2)6(NO3)2, Mg(OH2)6SO4H2O, Al(OH2)6Cl3

Note: Sample 9A is a guaranteed pure salt, unless it is an alum.

Procedure of Analysis for Sample 9A/9B

Describe sample, noting color, shape, and odor.

Test on Original Sample

Flame Test (Remember to clean with 16 M HONO 2 in between each

test)
Orange flame indicates presence of Na+, with K+, Ca2+, and NH4+ as
possibilities.
Purple flame indicates presence of K +, with NH4+ as a possibility. No Na+
is present.
Red flame indicates presence of Ca2+, with K+ as a possibility. No Na+ is
present.
Green flame indicates presence of Cu2+, with other ions as possibilities.
No Na+ is present.
No color indicates presence of NH4+, Al3+, or Mg2+. No Na+, K+, or Ca2+ is
present.
NH4+ Test
Method I
Place portion of sample in test tube and add 1 M NaOH, and then
suspend a piece of red litmus paper over the tube. Remember to add a
drop of deionized water to the paper before hovering over the tube. If
it turns blue, NH4+ is present.
Method II
Place portion of sample in a crucible and heat. If gray fumes and
smoke are emitted, then NH4+ is present.
K+ Test
If NH4+ is present, then place small portion of the same in a crucible
and heat strongly until fumes and smokes are no longer discharged.
Next, dissolve any residue in 1-2 mL of deionized water and place in a
spot plate. Add a drop of 6M HAc and 2-3 drops of sodium cobaltnitrite
(Na3Co(NO2)6). If a yellow precipitate forms, K+ is present.
If NH4+ is not present, dissolve a small portion of the sample in 1-2 mL
of deionized water and place in a spot plate. Add a drop of 6M HAC and
2-3 drops of sodium cobaltnitrite. If a yellow precipitate forms, K + is

present.

CO32-/HCO3- Test
Treat a small portion of the solid unknown with 6 M HCl.
If there is rapid formation of bubbles, then either CO 32- or HCO3- is
present.
Confirm which with pH test.
If there is a weak formation of bubbles, then it is likely a hydroxide salt
(this should be confirmed by the pH test).
Prepare a Solution for Further Testing
Dissolve approximately half of the sample in 10 or so mL of deionized
water for further tests.
If the solution does not readily dissolve in water, heat while stirring to
attempt to dissolve the solute.
If it still does not dissolve, then centrifuge the solid. Save the
supernatant solution in a vial, rinse with water, and centrifuge again.
If the solubility test fails, then it is likely not an alum, but confirm with
aluminum test on supernatant solution.

Tests on (Supernatant) Solution

pH Test
Prepare a solution of the sample in neutral water, and then test the pH
with indicators.
Remember, if the salt is insoluble, this test will be on the supernatant
solution after centrifuging.
The following pHs correspond to presence/absence of ions:

pH: 1-2 implies HOSO3 is present while HO, CO32,and HCO3 are
absent (likely calcium is also absent because of precipitation).
pH: 3-3.5 implies Al(OH2)63+ is present while HO, HOSO3, CO32,
and HCO3 are absent.
pH: 5-6 implies possibly NH4+, Mg(OH2)2+, SO42, or no pH-affecting
ions are present as well as absence of HO, HOSO4, Al(OH2)63+,
CO32, and HCO3.
pH: ~7 implies possibly Cl, NO3, implies absence of HO, HOSO3,
CO32, and HCO3, Al(OH2)63+, NH4+, and Mg(OH2)2+.
pH: 8.5-9.5 implies HCO3 present while HO, Al(OH2)63+, and
HOSO3, CO32- are absent.
pH: 11-12 implies CO32- present while HO-, HCO3-, HOSO3- and NH4+
are absent.

pH: 13-14 implies HO present while HOSO3 and NH4+ are absent
(likely aluminum, calcium, and magnesium are absent by
solubility as well).
Ag+ Test
Add excess Cl- to the solution.
If a precipitate forms, then Ag+ is present.

Zn2+ and Cu2+ Test

Add 6 drops of H2SO4 and 2 mL of TAA to the solution and heat in a hot
water bath. If no precipitate forms, add NaAc and another 2 mL of TAA.
If precipitate still does not form, then Zn2+ or Cu2+ are not present.
If a white precipitate forms, then only Zn 2+ is present.
If a black precipitate forms, Cu2+ is definitely present with Zn2 as a

possibility.
Add H2SO4 to the precipitate, if a smell of rotten eggs liberates, then
Zn2+ is present as well.
Al3+ and Mg2+ Test
Add excess 6 M NH3 to the solution.
If precipitate forms, add excess 2 M NaOH
If precipitate does not dissolve, centrifuge the solution and add excess
1 M NH4Cl to the supernatant liquid.
If no precipitate forms when NH3 is added, neither ion is present.
If the precipitate dissolves when NaOH is added, then only Al 3+ is
present.
If precipitate persists, then Mg2+ is present, but Al3+ is still a possibility.
When the NH4Cl is added, if a precipitate forms, both Mg 2+ and Al3+ are
present.
If no precipitate forms when NH4Cl is added, then only Mg2+ is present.

Cl- Test
Acidify the solution with 6 M HONO2 (remember to stir solution and test
for acidity with blue litmus paper). Once acidified, add a few drops of
0.02 M AgNO3; if a white precipitate forms, then Cl - is present.

SO4-2 Test
Acidify the solution with 6 M HONO2. Once acidified, add a few drops of
Ba(NO3)2; if a white precipitate forms, then SO 4-2 is present; however:
If pH was greater than 2.0, then SO4-2 is present without HSO4-.
If pH was less than or equal to 2, then SO 4-2 cannot be determined.
If a precipitate does not form, then both SO 4-2 and HSO4- are absent.

NO3- Test
Place a single small crystal of Fe(OH2)6(NH4)2(SO4)2 in the hollow of a
spot plate, then cover the crystal with a few drop of the prepared test
solution. Immediately add two drops of 18 M H2SO4 and allow it to flow
freely (do not agitate). If the crystal turns brown, then NO 3- is present.

HSO4- and OH- Test

These have already been tested for using pH. Note, if the unknown is a
mixture, and HSO4- is present, it is not possible to determine whether
or not SO4- was present because it will still be in high concentration;
thus, write HSO4- (SO4-2) is HSO4.

Test on Insoluble Compound

HNO3 Test
Add excess 1 M HNO3 and heat gently.
If it is insoluble, then it is CaSO4, Ag2S, or CuS.
If it is white, then it is CaSO4.
If the precipitate is black, it is either Ag 2S or CuS.
Add 6 M HNO3, heat, and watch for precipitation.
If the precipitate is white, then it is Ag 2S, with no CuS.
If the precipitate is blue, it has CuS; add Cl - to vial to see if Ag+ present;
if precipitate forms upon addition of Cl -, Ag+ is also present.
If it is soluble, and no bubbles form, then OH - is present.
Then proceed to test for Cu2+, Ca2+, Mg2+, Ag+, and Zn2+.

If it is soluble, and bubbles form, then CO 3- is present.

Then proceed to test for Cu2+, Ca2+, Mg2+, Ag+, and Zn2+.

Indicator chart
Indicator

Abbreviation

Useful pH range

color

0.0 (YG)
3.0 (R)
3.8 (Y)

and
corresponding
1.0 (BG)
4.0 (O)
4.6 (G)

Methyl violet
Methyl orange
Bromcresol
green
Bromthymol
blue
Thymol blue
Alizarin Yellow R
Indigo Carmine

HMV/MV
HMO/MO
HBG/BG
HBtB/BtB

6.0 (Y)

7.0 (G)

8.0 (B)

HTB/TB
HAY/AY
HIC/IC

8.0 (Y)
10.0 (Y)
12.0 (B)

9.0 (G)
11.0 (O)
13.0 (G)

10.0 (B)
12.0 (RO)
14.0 (Y)

2.0 (B)
5.0 (Y)
5.4 (B)