Cations

Cations
Cations are the positive part of any salt The cations cannot be tested directly as anions Therefore, we classified cations according to the solubility of their salt in H2O i.e we found that the chlorides of Pb2+ , Ag+ , Hg22+ are insoluble in water, so we put them in one group and say that The group reagent is cold dil HCl Also we found that the sulphides of Pb2+, Hg2+, Bi3+, Cu2+, Cd2+are insoluble in water, so we put them in one group and say that The group reagent is H2S
2

Classification of cations
Group I (Silver group) Group reagent Dilute HCl Ions Ag+, Pb++, Hg2++ Distinguishing features Ppt as Chlorides

II (Acid sulphide gp)

HCl + H2S

Hg++, Pb++, Bi+++, Cu++, Cd++, Sn++, As+++, Sb+++, Sn++++ Al+++, Cr+++, Fe+++
Ni++, CO++, Mn++, Zn++

Ppt as Sulphides in acid medium

III (Iron group)

IV (Alkaline sulphide gp)

NH4OH + NH4Cl
NH4OH + NH4Cl +H2S

PPt as Hydroxides
Ppt as Sulphides in alkaline medium

V (Alkaline earth group)

VI (Alkali metal group)

NH4OH + NH4Cl + (NH4)2CO3

No group reagent

Ba++, Sr++, Ca++

Ppt as Carbonates.

Mg++, Na+, K+, NH4+

Ions not pptd in previous groups.

( Pb2+ , Ag+ , Hg22+ )

Group I

Group I ( Pb2+ , Ag+ , Hg22+ )

The chloride salt of these metals have low solubility so they are ppt as Cl- and called HCl group Group reagent : cold dil HCl slight excess with stirring

Procedure for separation :1 ml mix + 1 ml cold dil HCl

Residue Group I

centrifuge
Centrifigate Rest of groups

Pb Cl2 white ppt of lead chloride Ag Cl white ppt of silver chloride Hg2Cl2 silky white ppt of mercurus chloride

Ques.1 : Why cold HCl ? Ans: Because Pb Cl2 is soluble on hot so escape to group II
5

N.B. Pb Cl2 have the highest Ksp, therefore it is the last to ppt. Pb Cl2 Ksp = 1.6 x 10-6 Ag Cl Ksp = 1.0 x 10-10 Hg2 Cl2 Ksp = 1.0 x 10-18 Therefore the order of ppt Hg2+2 then Ag+ then Pb+2 Ques.2 : Why dil. HCl ? Ans: Because Pb Cl2 tends to form soluble complex and escape to group II in conc. HCl (i.e PbCl2 is soluble in excess Cl-) Pb+2 + ClPbCl2 PbCl2 + Cl[PbCl3]- + Cl[PbCl4]2Soluble complex

Ques.3 : Why slight excess with stirring ? Ans : We add slight excess HCl to ensure complete pptn. By the common ion effect. (Strong acid) HCl H+ + Cl- (strongly ionize) (1) (ppt ) AgCl Ag+ + Cl- (partially ionize)(2) common ion effect

By common ion effect reaction 2 moves to the left preventing the dissolution of Ag Cl With stirring because Pb Cl2 tends to form supersaturated soln. i.e. go to soln. therefore we have to break this supersaturation by stirring.

Procedure for separation Residue (group I) + 2 ml hot water centrifuge

Residue AgCl, Hg2Cl2
+ dil NH3 centrifuge Residue Hg
Hg2Cl2 + NH3 Hg(NH2)Cl + Hg0 white black

centrifugate (1) PbCl2

centrifugate (2) Ag
AgCl + NH3 Ag(NH3)2Cl

It is called disproportionation reaction because (Hg22+) tends to form (Hg0) mercury and (Hg2+) mercuric.
8

Confirmation of lead(Pb2+):1- By cooling centrifugate(1) white ppt of lead chloride 2- Centrifugate(1)+ KI yellow ppt of Pb I2 (soluble in excess KI) PbI2 + excess I[PbI4]2soluble complex

3- Centrifugate + acetic acid + K2CrO4 (pot.chromate) yellow ppt of lead chromate

PbCl2 + K2CrO4 PbCrO4 + 2 KCl Ques.: yellow ppt Why acidification with acetic acid and not strong mineral acid ? Ans : Because in strong acid 2CrO42- +2 H+ Cr2O72- + H2O
i.e. dichromate is formed and form soluble lead dichromate Pb Cr2O7

In presence of alkalinity the yellow ppt turns red 2 PbCrO4 + H2O Pb2CrO5 + H2CrO4
red ppt (basic lead chromate)
9

In presence of high alkalinity the ppt will dissolve because Pb is amphoteric PbCrO4 + 2 OHPb(OH)2 + CrO42white ppt Pb(OH)2 + OH[HPbO2]- + H2O soluble plumbite ion N.B. Amphoteric metals (i.e. soluble in both acid and alkaline medium) Pb2+ , Sn2+,4+, As3+,5+, Sb3+,5+, Al3+,Cr3+, Zn2+ gp I gp IIb gp III gp IV
4- centrifugate + H2SO4 PbCl2 + H2SO4 white ppt of lead sulphate PbSO4
10

Confirmation of silver (Ag+):

1- acidify centrifugate(2) with dil HNO3 of silver chloride soluble in dil. NH3. [Ag(NH3)2]Cl + 2 HNO3 AgCl + NH4NO3
white ppt

white ppt

Silver amine complex have high Kstab,so it ionizes to give a quantity of Ag insufficient to exceed Ksp of Ag Cl (10-10) therefore AgCl is soluble in dil NH3.

The addition of acid increase the dissociation of silver amine complex to give more silver which exceeds Ksp of AgCl and a white ppt of AgCl is formed. [Ag(NH3)2]+ Ag++ 2 NH3 NH3 + H+ NH4+
push the reaction forward forming more Ag+

The addition of H+ convert NH3 to NH4+ so increase the dissociation of the silver amine complex.

11

2- Centrifugate 2 + KI [Ag(NH3)2]Cl

yellow ppt of silver iodide

Ag+ + KI AgI (insoluble in NH3 but soluble in KCN) Ag amine complex ionizes to give Ag+ which exceeds Ksp of AgI (10-16)(ver low Ksp) so AgI ppt N.B. KCN dissolves all Ag salts except Ag2S which have low Ksp (10-50) Ag+ + 2CN[Ag(CN)2]Ag cyanide complex (very stable)

Ag cyanide complex has very high Kstab, so it yields a small amount of Ag+ insufficient to exceed Ksp of AgI
12

Confirmation of mercurus (Hg22+):

The ppt (Hg0 + Hg (NH2)Cl) is dissolved in aqua regia [HNO3 1: 3 HCl] then heat to evaporate excess aqua regia.
Hg(NH2)Cl + HNO3 + HCl Hg0 + HNO3 + HCl HgCl2 + NO + N2 + H2O HgCl2 + NO + H2O

i.e. the ppt is transformed to soluble mercuric chloride. 1- Add stannous chloride Hg2Cl2 + SnCl4 white Hg2Cl2 + excess SnCl2 2 Hg0 + SnCl4 black 2- Add KI scarlet red ppt of mercuric iodide soluble in excess KI. Hg+2 + KI HgI2 + 2K+ HgI2 + excess I[HgI4]-2 + 2K+ 13 soluble Nesselar reagent 2 HgCl2 + SnCl2

Group IIA,B

14

IIA IIB

Group IIA,B Pb2+, Hg2+, Bi3+, Cu2+, Cd2+ As3+,5+, Sb3+,5+, Sn2+,4+

It is called the Acid Sulphide group Group reagent : dil HCl + H2S Both group II and group IV have their sulphides insoluble in water. But group IV have higher Ksp (needs high S-2 to ppt) So to ppt gp II only we use dil HCl with H2S (strong acid) HCl H+ + Cl- (completely ionize) ( weak acid) H2S 2H+ + S-2 (partialy ionize)
common ion effect

By common ion effect the ionization of H2S is decreased therefore decrease sulphide ion concentration which become sufficient to ppt group II (have low Ksp easily exceeded) but insufficient to ppt group IV.
15

Ques.1: Why not use conc HCl to ensure that group IV will not interfere? Ans: Because if we use conc HCl the concentration of S2- ion will decrease dramatically that it becomes insufficient to ppt some cations of group II which has slightly high Ksp eg: Cd, Pb, Sn. Therefore we have to adjust acidity. The suitable acidity was found to be 0.2 - 0.3 N HCl (0.25N). We use crystal violet (external indicator) to adjust acidity. blue add HCl i.e low acidity gp IV will ppt with gp II 0.25 N HCl bluish green
add H2O

green or yellow i.e high acidity gp II will incompletely ppt

16

Procedure for separation:1- On the filterate from group I , adjust acidity to 0.25 N HCl using C.V. + excess H2S centrifuge
Residue gpII Pb S black ppt Hg S black ppt Cu S black ppt Bi2S3 brown ppt Cd S canary yellow ppt As2S5, As2S3 yellow ppt Sb2S5, Sb2S3 orange ppt SnS2, SnS yellow ppt Centrifugate Test for complete pptn Add excess H2S,centrifuge
Residue added to gp II Centrifugate Rest of gps

17

Group IIA Copper Subgroup Pb2+, Hg2+, Bi3+, Cu2+, Cd2+

Procedure for separation :Residue of group IIA + dil HNO3 + dil H2SO4 (for Pb)
Residue HgS, PbSO4 PbS+HNO3+H+
Pb2++H2SO4

centrifuge

Pb2++NO+S+H2O soluble PbSO4 (white ppt)

Centrifugate Bi+3, Cu+2, Cd+2 CuS+HNO3+H+ Cu2++NO+S+H2O Bi2S3+HNO3+H+ Bi3++NO+S+H2O CdS+HNO3+H+ Cd2++NO+S+H2O

Residue (Pb and Hg) + saturated ammonium acetate

Residue Hg Confirm as in gp I

centrifuge
Centrifugate Pb Confirm as in gp I

18

Centrifugate ( Bi, Cu, Cd) + conc NH4OH

centrifuge
Residue
Bi3+
Bi3++NH4OH Bi(OH)3 + NH4+ White ppt

Centrifugate
Cu2+, Cd2+
Cu2++NH4OH [Cu(NH3)4]2++H2O soluble Cu amine complex (blue) Cd2++NH4OH [Cd(NH3)4]2++H2O soluble Cd amine complex (colorless)

19

Confirmation of Bismuth (Bi+3) :1- Bismuth hydroxide (white ppt) + alkali stannite ( SnCl2 + excess NaOH) black ppt of metallic bismuth. SnCl2 + NaOH Sn(OH)2 + NaCl white ppt NaHSnO2 alkali stannite 2Bi0+ 3 [HSnO3]- + 3 H2O Black ppt

Sn(OH)2 + excess NaOH 2 Bi(OH)3 + 3 [HSnO2]-

20

Confirmation of copper (Cu2+) and cadmium (Cd2+) :On the centrifugate from conc NH3 [ Cu amine complex (blue col.) and Cd amine complex (colorless)] Cu can be tested in presence of Cd but the opposite is not true because Cu gives all tests of Cd. Therefore we have to separate them

Cyanide procedure :Divide the solution into two unequal portions :

The smaller portion :- Test for Cu2+

1- Acidify with acetic acid + potassium ferrocyanide Cu2++ [Fe(CN)6]4Cu2[Fe(CN)6] reddish brown ppt N.B. Acetic acid is used to decompose Cu amine complex [Cu(NH3)4]2+ + CH3COOH Cu(CH3COO)2 + NH3 2- Soln + KI white ppt of cuprous iodide in brown soln of iodine 2Cu2+ + 4 ICu2I2 + I2 white ppt brown soln
21

3-

Soln + KCNS Cu2+ + CNS-

black ppt Cu(SCN)2

The larger portion :- Test for Cd2+

First we should mask Cu by adding KCN till blue color disappear (Cu(NH3)4]2+ + 2 CNCu(CN)2(greenish yellow ppt) + 4 NH3 2 Cu(CN)2 Cu2(CN)2(white ppt) + (CN)2(cyanogen) Cu2(CN)2 + 4 CN2 [Cu(CN)3]2- cuprocyanide complex (very stable) [Cd(NH)3)4]2+ + 2CNCd(CN)2(buff ppt) + 4 NH3 Cd(CN)2 + 2 CN(Cd(CN)4]2-Cadmicyanide complex(unstable) Then add H2S canary yellow ppt of Cd S is formed. Since Cd cyanide complex is unstable. Therefore it yields sufficient Cd+2 to react with H2S and exceed Ksp of CdS [Cd(CN)4]2- + H2S CdS + HCN + CNN.B. If Cu is absent in the centrifugate from conc. NH4OH (no blue color) Therefore you can test for Cd directly by adding H2S canary yellow ppt. 22

Group III

23

Group III Fe3+, Al3+, Cr3+

It is called Ammonium hydroxide group as they are ppt as hydroxide Group reagent : NH4Cl + NH4OH Procedure for separation :1- We have to boil the filtrate from group II to expel H2S .Gr. Ans.: Because group III ppt in alkaline medium and group IV ppt as sulphide in alkaline medium so if H2S is not expelled group IV will ppt with group III 2- Test for iron Drops of the filtrate + conc HNO3 cool + NH4SCN blood red color , therefore iron is present If iron is present, add 2 drops of conc. HNO3 to the filtrate to oxidise Fe2+ to Fe3+
24

Ques.1. Why do we oxidize Fe2+ to Fe3+ ? Ans. : Because H2S used in pptn of group II is a reducing agent which reduces Fe+3 (if present) to Fe+2 and Fe(OH)2 has high Ksp so not ppt in conditions such that of group III but Fe(OH)3 has a lower Ksp which can ppt with group III and iron does not escape 3-Soln + conc HNO3 cool + NH4Cl + NH4OH centrifuge cool,

Residue Centrifugate Gp III + Mn3+ (from gp IV) other gps Fe3+ + OHFe(OH)3 Ferric hydroxide (reddish brown ppt) Al3+ + OHAl(OH)3 Aluminium hydroxide (white gelatinous ppt) Cr3+ + OHCr(OH)3 Chromium hydroxide (greyish green ppt) Mn3+ + OHMn(OH)3 Manganic hydroxide ( brown ppt)

25

Ques.2. Why do we add NH4Cl ? Ans.:

1- Group IV and Mg from group VI ppt as OH- but it has higher Ksp i.e needs excess OH- ions, therefore by adding NH4Cl the ionization of NH4OH decrease due to common ion effect so it gives OH- ions sufficient to ppt group III but insufficient to ppt group IV Salt (completely ionize) NH4Cl NH4+ + ClWeak base (partially ionize) NH4OH NH4+ + OHcommon ion effect 2- NH4Cl is an electrolyte which aids in coagulation of the gelatinous ppt of group III 3- It reduces OH- ion conc so prevent solubility of amphoteric cations Al3++ OHAl(OH)3 + excess OHAlO2- soluble aluminate Cr3++ OHCr(OH)3 + excess OHCrO2- soluble chromite 4- NH4Cl forms soluble complex with group IV cations.
26

Ques.3. Why do we boil after NH4Cl ? Ans.: 1- To coagulate the ppt 2- To break Cr Amine complex [Cr(NH3)6] (OH)3 Cr(OH)3 + 6NH3
soluble Cr amine complex

3- To expel O2 and prevent oxidation of manganus (Mn2+) which has higer Ksp i.e. [not ppt as OH- ] to manganic (Mn3+) which has low Ksp and can be ppt as Mn(OH)3 so it escapes from group IV to group III

27

Separation of group III :ppt of group III + NaOH + H2O2

Residue Fe3+, Mn3+(from gp IV)

centrifuge
Centrifugate AlO2-, CrO42-

It depends on the amphoteric character of Al3+ and Cr3+ so dissolve in NaOH, they dissolve as stable AlO2- and unstable chromite CrO2- which is oxidised by H2O2 to the stable chromate CrO42- (has yellow color) Al(OH)3 + OHAlO2- + 2H2O Cr(OH)3 + OHCrO2- + 2H2O
unstable chromite

CrO2- + H2O2

CrO42- + 4 H2O
stable yellow chromate
28

Separation of ferric and manganic-: Residue + HNO3 + H2O2 dissolve, divide to 2 portions
Fe(OH)3 + 3HNO3 MnO(OH)2 + 3HNO3 + H2O2 O2 Fe(NO3)3 + 3H2O Mn(NO3)3 + 3H2O +

First portion

Test for iron :blood red color [Fe(SCN)]2+

1- soln + NH4SCN Fe3+ + SCN-

2- soln + potassium ferrocyanide

Fe3+ + K4[Fe(CN)6]

prussian blue ppt K Fe [Fe(CN)6]

29

Second portion Test for manganus :1-With red lead Pb3O4 soln + dil HNO3 + H2O2 + PbO2 pink color
Pb3O4 + Mn2+ + H+

till no O2 bubbles

MnO4- + Pb2+ + H2O pink color

H2O2 must be completely removed because it reduces MnO4so bleach color formed
MnO4- + H2O2 + H+ Mn2+ + O2 + H2O colorless

N.B H2O2 is oxidising agent but with MnO4-, it is reducing agent because it has lower oxidation potential [ MnO4- has the highest oxidation potential]
30

Separation of aluminium and chromium :Divide the soln. containing AlO2- and CrO4- to 2 portions: First portion Test For CrO42- :1- With pb acetate yellow ppt of lead chromate Pb(CH3COO)2 + (CrO4)2PbCrO4

2- Perchromic acid test soln + dil H2SO4 + ether + 1 drop H2O2 blue color in ether layer +H2O2 CrO42- + 2H+ Cr2O72- + H2O
dichromate

[CrO8]3perchromate

31

Second portion Test for AlO2- :1- Soln + NH4Cl solid cool white gelatinous ppt

Al(OH)3 + OHwhite ppt

AlO2- + H2O

NH4Cl reduces OH- concentration and reverse the reaction i.e move backward and ppt Al(OH)3
NH4+ + OHNH4OH NH3 + H2O

32

Group IV

33

Group IV Mn2+, Zn2+, Co2+, Ni2+

This group is called Ammonium sulphide group Group reagent is : NH4Cl + NH4OH + H2S It is ppt as sulphide in alkaline medium H2S (weak base, partially ionize) NH4OH
(weak acid, partially ionize)

2H+ + S2OH- + NH4+

H2O
Due to formation of water which is weakly ionized. The ionization of H2S is pushed forward and increase S-2 ion conc so ppt group IV as sulphide (has higer Ksp)

34

Procedure for separation-: 1- Centrifugate from group III + NH4Cl + NH4OH + H2S centrifuge
Residue Centrifugate gp IV rest of groups MnS buff ppt Manganous sulphide ZnS white ppt Zinc sulphide CoS black ppt Cobalt sulphide NiS black ppt Nickel sulphide

Ques.1. Why do we add NH4Cl ?

Ans. : 1- By common ion effect it decreases OH- conc so prevent pptn of group IV as hydroxide Salt (completely ionize) NH4Cl NH4+ + ClWeak base (partially ionize) NH4OH NH4+ + OHcommon ion effect 2- NH4Cl is an electrolyte to coagulate the colloidal ppt of group IV eg ZnS, MnS so it become easily filtered
35

Ques.2. Why do we boil after add NH4Cl ?

Ans.:
1- To decompose Ni amine complex and ppt NiS Ni(NH3)6S NiS soluble Ni amine complex black ppt 2- By boiling CoS and NiS undergo condensation and change in physical characters so become insoluble in very dil HCl 3- To coagulate the ppt N.B. If iron is not completely oxidised in group III it will ppt as FeS (black ppt) in group IV
36

Separation of group IV-:

ppt of group IV + very dil HCl centrifuge

Residue Centrifugate NiS , CoS Zn2+, Mn2+ black ppt It depends on the amphoteric character of Zn, therefore soluble in dil HCl and NaOH

Centrifugate

+ NaOH + Br2 water

centrifuge

Residue Centrifugate MnO2 ZnO22black ppt Zn2+ + OHZn(OH)2 zinc hydroxide Zn(OH)2 + OH- (excess) ZnO22- soluble zincate While Mn(OH)2 is oxidized by hypobromite to MnO2 which is black ppt OH- + Br2 OBr- + Br- + H2O 37 Mn2+ + Br2 + OHMnO2 + 2Br- + 2H2O

N.B.
The centrifugate must be heated to expel H2S because if H2S is still present, so on adding NaOH, ZnS will ppt as it is ppt as sulphide in alkaline medium

Confirmation of zinc-:
1- By adding excess H2S
sulphide ZnO22- + S2- + H+ Zn S + OHwhite ppt of zinc

2- Add acetic acid + pot. ferrocyanide

Zn2+ + [Fe(CN)6]4Zn2[Fe(CN)6] Zinc ferrocyanide

sky blue ppt

Confirmation of Manganus :As under group III

38

Confirmation of cobalt and nickel-:

ppt is dissolved in aqua regia [ HNO3 1 : 3 HCl ] 3CoS + 2HNO3 + 6HCl 3CoCl2 + 2NO + 3S + 4H2O 3NiS + 2HNO3 + 6HCl 3NiCl2 + 2NO + 3S + 4H2O

Divide the soln to 2 portions : First portion Test for Co2+ :1-soln + NH4Cl + NH4OH + pot ferricyanide

red ppt Co2+ + [Fe(CN)6]3Co3[Fe(CN)6]2 red ppt cobaltus ferricyanide insol in NH3 N.B. Nickelous ferricyanide is yellow and soluble in NH3 (that is why we add NH4OH) 2- Vogel test soln + dil H2SO4 + SnCl2 + ether + NH4SCN blue color in etherial layer Co2+ + SCN[Co(SCN)4]2- blue color N.B. H2SO4 contains traces of Fe+3 which interfere with the test by giving blood red color with SCNTherefore we add reducing agent eg SnCl2 to reduce Fe+3 to Fe+2 or we add F- or PO4- to make complex with Fe+3
39

Second portion Test for Ni2+ :1- Dimethyl glyoxime test

Soln + NH4Cl + NH4OH + D.M.G.
CH3 CH3 C C NOH NOH Ni
2+

red color
CH3 CH3 C C red ppt NO NOH Ni2+
2

2 H+

2- Test with KCN

soln + KCN + NaOH + Br2 water black ppt of NiO2 OH- + Br2 OBr- + Br- + H2O OBrNi2+ + 2CNNi(CN)2 (excess CN-) [(Ni(CN4)]2NiO2 . unstable Ni cyanide complex Cobalt will not interfere Co2++ 2CNCo(CN)2 (excess CN-) [Co(CN)6]4- atm. O2 [Co(CN)6]3stable cobalticyanide complex Cobalticyanide complex does not interfere as it is an oxidising agent which does not react with OBr40

Group V

41

Group V Ba2+, Sr2+, Ca2+

It is called Alkaline earth group or Ammonium carbonate group Group reagent : NH4Cl + NH4OH + (NH4)2CO3 The cations ppt as carbonate in alkaline medium The three cations belong to the same group in the periodic table, therefore have similar characters and their separation is somewhat difficult

Procedure for separation :Centrifugate from group IV is evaporated nearly to dryness + NH4Cl + NH4OH + (NH4)2 CO3 soln to 60oC wait, centrifuge Residue Gp V BaCO3 white ppt SrCO3 white ppt CaCO3 white ppt Centrifugate gp VI

42

Ques.1. Why we evaporate the centrifugate from group IV till nearly dryness ?
Ans. : To expel H2S, to prevent oxidation of S2- to SO42- and prevent pptn of Ba2+ and Sr2+ as SO42- [ CaSO4 has higher Ksp so need more SO42- ion conc. to ppt]

Ques.2. We must add a moderate amount of NH4+ ?

Ans. : Because excess NH4+ will decrease carbonate ion concentration. NH4+ + CO32NH3 + HCO3N.B. The soln must be a little basic. If acidic the carbonate will change to HCO3which are soluble CO3- + H+ HCO3-

Ques.3. Why we use NH4Cl ?

Ans. : 1- By common ion effect it decreases OH- ion conc. and CO32- ion conc. so prevent pptn of Mg as Mg(OH)2 or as MgCO3 2- To coagulate the ppt
43

Ques.4. Why we use NH4OH ?

Ans 1- It converts NH4HCO3 to (NH4)2 CO3 NH4HCO3 + NH3 (NH4)2CO3 2- Converts ammonium carbamate into carbonate NH4CO2NH2 + H2O (NH4)2CO3

3- To make the medium faintly alkaline to prevent HCO3- formation as all

M(HCO3)2 are soluble N.B. Ammonium carbonate is prepared from equimolar concentration of ammonium bicarbonate NH4(HCO3)2 and ammonium carbamate NH4CO2NH2

Ques.5. Why we heat to 60oc and not boil ?

Ans. : 1- To convert HCO3- to CO32M(HCO3)2 MCO3 + CO2 + H2O 2- Warming aid in the formation of more crystalline ppt 3- Warming aid in the conversion of carbamate to carbonate Excess heat cause loss of NH3 so convert CO32- to bicarbonate by pushing 44 the reaction forward

Separation of group V-:

ppt + acetic acid BaCO3 + 2 CH3COOH SrCO3 + 2 CH3COOH CaCO3 + 2 CH3COOH The ppt will dissolve as acetate Ba(CH3COO)2 + CO2 + H2O Sr(CH3COO)2 + CO2 + H2O Ca(CH3COO)2 + CO2 + H2O

Test for Barium-:

1-2 drops of the soln + K2CrO4 (pot. chromate) If yellow ppt, therefore Ba is present If Ba is present add K2CrO4 soln till soln acquire orange tint, centrifuge
Residue BaCrO4 Yellow ppt Centrifugate Sr2+, Ca2+ reppt [NH4OH + NH4Cl + (NH4)2CO3 to 60oc Centrifuge Residue SrCO3, CaCO3 white ppt Centrifugate reject
45

Test for Ba2+ :1-Flame test

ppt of BaCrO4 + HCl soluble BaCl2 (volatile in flame ) and gives apple green color If Ba is absent reject the portion used for test and the remainder of the soln is used to test for strontium and calcium

N.B.
If we add excess K2CrO4, SrCO4 and Ca CrO4 will also ppt as the chromate of this group are insoluble. But Ksp of BaCrO4 < SrCO4 < CaCrO4. So we add amount of K2CrO4 sufficient to ppt barium but not strontium and calcium We use also acetic acid to convert part of K2CrO4 to K2Cr2O7 so decrease CrO42- conc

Ques: Why we do not use HCl or HNO3 instead of acetic acid ? Ans.:
Because they are strong acids which convert all CrO42- to Cr2O72- and no ppt is formed
46

Identification of Strontium and Calcium :Residue dissolve in acetic acid Soln + (NH4)2SO4 Residue Sr2+ Sr(CH3COO)2 + (NH4)2SO4 to dissolve centrifuge Centrifugate Ca2+

SrSO4 + 2CH3COONH4 white ppt The test depends on that Ca form double salt with ammonium sulphate which is soluble Ca2+ + (NH4)2SO4 (NH4)2Ca(SO4)2 double salt formation N.B. If we used dil H2SO4 instead of (NH4)2SO4, both Sr and Ca will ppt as SO4

47

Test for Calcium-:

1- Soln + NH4OH + ammonium oxalate white ppt of calcium oxalate C2O4(NH4)2 + Ca2+ C2O4Ca + 2NH4Cl white ppt

2- Soln + NH4Cl + pot. ferrocyanide

Ca2+ + NH4+ + K+ + [Fe(CN)6]4-

pale yellow ppt

CaNH4K[Fe(CN)6] triple ferrocyanide

Flame test-: For Sr2+

SrSO4 is heated in the reducing zone of the flame SrCl2 volatile in flame with crimson red color Sr S + HCl

For Ca2+
Ca C2O4 + HCl Ca Cl2 volatile in flame with brick red color.
48

Group VI

49

Group VI Mg2+, Na+, K+, NH4+

This group is called Alkali metal group It is also called the Soluble group because it has no group reagent (all Na, K and NH4 salts are soluble) Removal of traces of alkaline earth group :Centrifugate of group V + ammonium oxalate [to ppt any Ca2+] + ammonium sulphate [to ppt any Ba2+ or Sr2+] centrifuge
Residue rejected Centrifugate gp VI

Divide the centrifugate into two unequal portions :

50

The smaller portion : Test for Mg2+ :1- soln + conc HCl + Na2HPO4 render alkaline by excess NH4OH white gel ppt
Mg2+ NH4+ + PO43Mg2+ + OH-(excess NH4OH)

MgNH4PO4 white ppt

Mg(OH)2 white ppt

51

The larger potion : Test for Na+ and K+ :N.B. Before we test for K+ we must remove NH4+. Gr. Ans. : Because NH4+ gives all tests for K+ Removal of NH4+ :Larger portion + conc. HNO3 evaporate to dryness, Residue is dissolved in water and divided to 2 portions This treatment also remove Mg+2 as MgO NH4+ + HNO3 NH4NO3 NH4NO3 N2O + NH3
52

Test for Sodium-: 1- By pot. dihydrogen antimonate or pot. pyroantimonate

Soln + KH2SbO4 or KH2Sb2O7 white ppt KH2SbO4 + Na+ NaH2SbO4 + K+ K2H2Sb2O7 + 2Na+ Na2H2Sb2O7 + 2K+
2- By magnesium uranyl acetate yellow ppt

Na++ HMg(UO2)3(CH3COO)9NaMg(UO2)3(CH3COO)9+ H+

3- Flame test :- golden yellow color

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Test for Potassium-:

1- By sodium cobaltinitrite
Na3[Co(NO2)6] + 3K+

yellow ppt
K3[Co(NO2)6] + 3 Na+

2- Flame test

violet color in flame

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Test for Ammonium :It must be tested on the original solid because we add NH4Cl and NH4OH during the course of analysis 1- Solid + Na OH NH3 odour NH4+ + Na OH NH3 + H2O

Other tests for NH4+ :2- Turns red litmus paper blue 3- With Nesselar reagent
NH3 + 2[HgI4]2- + 3OH

brown ppt
NHg2I. H2O + 7I- + 2H2O

brown ppt
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The smaller portion : Test for Mg2+ :1- soln + conc HCl + Na2HPO4 by excess NH4OH Mg2+ NH4+ + PO43Mg2+ + OH-(excess NH4OH) render alkaline white gel ppt MgNH4PO4 white ppt Mg(OH)2 white ppt

2- Test with Magneson reagent (blue lake test)

Mg(OH)2 + HCl soluble MgCl2 + Magneson I reagent (pnitro benzene azo resorcinol) a blue dye + NaOH Mg(OH)2 The ppt adsorb the blue dye
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