Experiment 5 Determination of Composition of a Complex by Job’s Method

EXPERIMENT 5
DETERMINATION OF COMPOSITION
OF A COMPLEX BY JOB’S METHOD

Structure
5.1 Introduction Principle

Expected Learning Outcomes Requirements

5.2 Experiment 5: Determination Procedure

of the composition of the
Observations & Calculations
Fe3+-salicylic acid complex in
solution by Job’s method. Result

5.1 INTRODUCTION
In the previous experiment, you performed spectrophotometric titration and
determined the concentration of the KMnO4 in the given coloured solution of
KMnO4. In this experiment, you will determine the composition of the Fe3+-
salicylic acid complex in solution by Job’s method using a spectrophotometer.

Expected Learning Outcomes

After studying this unit you should be able to:

 understand Job’s method, and

 determine the composition of the Fe3+-salicylic acid complex in solution
by Job’s method using a spectrophotometer.

5.2 EXPERIMENT 5: DETERMINATION OF THE

COMPOSITION OF THE Fe3+-SALICYLIC ACID
COMPLEX IN SOLUTION BY JOB’S METHOD
In the previous experiment, you used the spectrophotometer for determining
the concentration of the KMnO4 in the given coloured solution of KMnO4. In
this experiment, you will determine the composition of the Fe3+-salicylic acid
complex in solution by Job’s method using a spectrophotometer. 97
BCHCL-138 Chemistry Lab IV

5.2.1 Principle
You have already studied about the details of Coordination chemistry in the
Mole fraction is the Units 4 and 5 of the course BCHCT 137. A few ligands are polydentate (such
ratio of the number of as EDTA). The formula of a metal ion/ligand complex in the solid state can be
moles of one determined by direct analysis of the stoichiometric amounts of each element
component in a that make up the complex. Once in solution however, determination of the
mixture to the total complex formula is not quite as direct. But, Job first developed a technique
number of moles of
which used a method of continuous variation and helps us to find the formula
all substances in that
mixture. The symbol
for the complex in solution. In this method, several solutions are prepared in
for mole fraction is x. which the concentrations is kept constant. Using these solutions, the light
E.g. , in a mixture of absorption of the solution is measured and plotted versus the mole fraction of
metal M, and ligand the ligand. The experiment employs a UV- visible spectrophotometer about
L, the mole fraction of which you have been introduced in the previous experiment.
component L (xL)
would be calculated In this experiment, the composition of the Fe3+-salicylic acid complex in
according to the solution by Job’s method is determined. The reaction of Fe3+ with salicylate ion
following formula. to form a violet colored complex is as follows.
moles(L)
xL  xFe3   y C6H4 (OH)COOH Complex
moles(M)  moles(L)

The complex is formed by the anion of salicylic acid which complexes with
ferric ion, and thus the stability constant of the complex varies with pH. The
experiment is carried out at pH 2.6 at which the phenolic group of acid is
undissociated and the carboxylic acid partly so. This pH range is achieved by
using Fe3+ solution and salicylic acid in 0.002 M HCl.

The optical absorbance of the complex ‘A’ is given by the Beer-Lambert law
(given in the previous experiment),

I
A  log 0  cl
It ….(5.1)

where It and I0 are the incident and transmitted light intensities,  is the
extinction coefficient of the complex and l is the path length.

The empirical formula of the complex may be found using Job’s method. When
amount at equimolar solutions of the reactants are mixed in varying
proportions, the maximum amount at equilibrium is formed when the two
reactants are present in the same mole ratio as required for the complex
formation. Equimolar solutions are made up and mixed in volume ratios 1:9,
2:8,…, 9:1. The total reaction concentration is therefore the same in each
case. The maximum absorbance of each solution is plotted against the mole
fraction of one of the components to give a Job’s plot. The maximum of this
curve then indicates the empirical formula of the complex. In present case we
expect the maximum to occur for the 5:5 mixture, confirming the 1:1 formula
Fe3+ (salt).

First you you have to determine the wavelength of maximum absorption ( max )
using any set of the complex solution. The use of blank solution (0.0025 M

98
Experiment 5 Determination of Composition of a Complex by Job’s Method

HCl) compensates for reflection losses at the air glass and glass solution
interface so that only absorption due to the sample is measured.

5.2.2 Requirements

Apparatus Chemical

Spectrophotometer with 1 salicylic acid

cuvettes

standard flasks (100 ml) 1 sulphuric acid (H2SO4)

volumetric flasks (100 ml) 1 ferrous ammonium sulphate

hexahydrate
[Fe(NH4)2(SO4) 2.6H2O][Mohr’s salt]

graduated pipette (10 ml) 1

weighing bottle 1

5.2.3 Procedure
 Firstly, prepare 0.001 M salicylic acid solution in 0.002 M HCl and
0.001 M Fe3+ ions as ferric chloride in 0.002 M HCl. Then make the
following solutions using different sets as in Table 5.1.

Table 5.1

3+
Fe ions 9 8 7 6 5 4 3 2 1
3
(cm )

Salicylic 1 2 3 4 5 6 7 8 9
3
acid (cm )

 Determine max using any of the above solution say 5:5 Fe3+: salicylic acid.
 Record the readings of absorbance of the solution in the range of 400-700
nm and record the readings in Observation Table I.
 Draw the spectrum by plotting absorbance as a function of the wavelength
in the graph as in Fig. 5.1.
 Then, select the wavelength which gives the maximum absorbance, i.e.
max .
 At max record the absorbance of each solution as in Observation Table II.
 Plot the graph between the absorbance against volume of Fe3+ ions
solution in a mixture from Observation Table II as in Fig. 5.2.
 Mark the maximum point in the curve which corresponds to the
composition of the complex. In this case, it is found it is found to be 1:1
molar ratio for Fe3+ ions and salicylic acid.
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BCHCL-138 Chemistry Lab IV

5.2.4 Observation and Calculations

Observation Table I
Determination of max of Fe3+ -salicylic complex
Wavelength Absorbance Wavelength Absorbance Wavelength Absorbance
(nm) (nm) (nm)
400 500 600
410 510 610
420 520 620
430 530 630
440 540 640
450 550 650
460 560 660
470 570 670
480 580 680
490 590 690
700

3+
Fig. 5.1: Graph between wavelength and absorbance for the of Fe ions solution
in a mixture

From graph max  .........nm.

Observation Table II: Determination of composition of the complex

3+ 3
Fe ions (cm ) Salicylic acid Absorbance
3
(cm )
9 1
8 2
7 3
6 4
5 5
4 6
3 7
2 8
1 9

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Experiment 5 Determination of Composition of a Complex by Job’s Method

Fig. 5.2: Graph between absorbance and volume of Fe3+ ions solution in a
mixture.

Maximum point in the curve=………composition of complex

5.2.5 Result
Result: The composition of Fe3+ -salicylic acid complex in solution by Job’s
method is found to be ………….

101
BCHCL-138 Chemistry Lab IV

APPENDIX (BCHCL 138)

o
Table 1.4: Solubility Product Constants at 25 C

Name of Solid Formula Ksp

33
Aluminium hydroxide Al(OH)3 1.9 x 10

 20
Aluminium phosphate AlPO4 1.3 x 10

 93
Antimony sulphide Sb2S3 2.0 x 10

9
Barium carbonate BaCO3 8.1 x 10

3
Barium hydroxide Ba(OH)2 5.0 x 10

10
Barium sulphate BaSO4 1.1 x 10

72
Bismuth sulphide Bi2S3 2.0 x 10

29
Cadmium sulphide CdS 4.0 x 10

9
Calcium carbonate CaCO3 4.8 x 10

6
Calcium hydroxide Ca(OH)2 7.9 x 10
* 21
Cobalt sulphide (α) CoS(α) 6.0 x 10

36
Copper (II) sulphide CuS 8.7 x 10

15
Iron (II) hydroxide Fe(OH)2 8.0 x 10

38
Iron (III) hydroxide Fe(OH)3 6.3 x 10

18
Iron (II) sulphide FeS 5.0 x 10

88
Iron (III) sulphide Fe2S3 1.0 x 10

5
Lead chloride PbCl2 1.6 x 10

28
Lead sulphide PbS 8.0 x 10

5
Magnesium carbonate MgCO3 4.0 x 10

11
Magnesium hydroxide Mg(OH)2 1.5 x 10

13
Manganese (II) hydroxide Mn(OH)2 2.0 x 10

15
Manganese(II) sulphide MnS 5.0 x 10

18
Mercury(I) chloride Hg2Cl2 1.1 x 10

 53
Mercury(II) sulphide Hgs 3.0 x 10

 15
Nickel hydroxide Ni(OH)2 2.0 x 10
* 21
Nickel sulphide (α) NiS(α) 3.0 x 10
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Experiment 5 Determination of Composition of a Complex by Job’s Method

 13
Silver bromide AgBr 5.0 x 10

 10
Silver chloride AgCl 1.8 x 10

 16
Silver iodide AgI 1.5 x 10

50
Silver sulphide Ag2S 7.0 x 10

10
Strontium carbonate SrCO3 9.4 x 10

4
Strontium hydroxide Sr(OH)2 3.2 x 10

15
Strontium sulphate SrSO4 2.8 x 10

29
Tin(II) sulphide SnS 8.0 x 10

17
Zinc hydroxide Zn(OH)2 4.5 x 10

21
Zinc sulphide ZnS 1.1 x 10

* When freshly precipitated from basic solution, the more soluble alpha (α) forms of CoS and NiS are
formed.

Table 1.5: Formation Constants of Some Complex Ions

Complex ion Equilbrium reaction Kf

[AgCl 2 ]  Ag   2Cl  ⇌ [AgCl 2 ]  1.1 10 5

[Ag(NH3 ) 2 ]  Ag   2NH 3 ⇌ [Ag(NH3 )2 ]  1.6  10 7

[Ag(CN ) 2 ]  Ag   2CN - ⇌ [Ag(CN ) 2 ]  5.6  10 18

[Ag(S2O3 )2 ] 3 Ag   2S 2 O 32  ⇌ [Ag(S2O3 )2 ] 3 1.7  1013

[Cu(NH3 ) 4 ] 2 Cu 2 + 4NH3 ⇌ [Cu(NH3 ) 4 ] 2 1.1 10 13

[Cu(NH)3 ] 2 Cu 2 + 3CN  ⇌ [Cu(NH)3 ] 2 2.0  10 27

[CdCl 4 ] 2  Cd 2 + 4Cl  ⇌ [CdCl 4 ] 2 6.3  10 2

[Cd(CN) 4 ] 2  Cd 2 + 4CN  ⇌ [Cd(CN) 4 ] 2  7.1 10 18

[Co(NH3 ) 6 ] 2 Co 2  + 6NH3 ⇌ [Co(NH3 ) 6 ] 2 1.3  10 5

[Ni(NH3 ) 6 ] 2 Ni2 + 6NH3 ⇌ [Ni(NH3 )6 ] 2 5.5  10 18

[Zn(NH3 ) 4 ] 2 Zn 2 + 4NH3 ⇌ [Zn(NH3 ) 4 ] 2 2.9  10 9

[Fe(CN)6 ] 4 Fe 2 + 6CN  ⇌ [Fe(CN)6 ] 4 1.0  10 37

[Fe(CN)6 ] 3 Fe 3 + 6CN  ⇌ [Fe(CN)6 ] 3 1.0  10 42

[HgCl) 4 ] 2  Hg2 + 4Cl  ⇌ [HgCl) 4 ] 2 1.2  1015

[PbCl) 4 ] 2  Pb 2 + 4Cl  ⇌ [PbCl) 4 ] 2 40

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BCHCL-138 Chemistry Lab IV

Table 1.6: Solubility Product Constants and Molar Solubilities of Sulphides of

Group II and IV at 25 C

Sulphide Group II Molar Sulphide Group IV Molar

Ksp solubility Ksp solubility
-11
Sb2S3 2.0  10 -93 1.1 20 -19 M ZnS 1.1 10 -21 3.3 x 10
M
-21 -11
Bi2S3 2.0  10 -72 1.8  10 -15 M NiS 3.0 x 10 5.5 x 10
M

-11
HgS 3.0  10 -53 5.5  10 -27 M CoS 6.0  10 -21 7.8 x 10
M

-15 -8
CuS 8.7  10 -36 3.0  10 -18 M MnS 5.0 x 10 7.1 x 10
M

-15
CdS 4.0  10 -29 6.3 x 10 M

SnS 8.0  10 -29 8.9  10 -15 M

-28
PbS 8.0 x 10 2.8  10 -14 M

Table 1.7: Variation of the S2 ion concentration in a saturated solution of

H2S with the pH of the solution

2- -3
pH [S ] mol dm
1 1.3  10 -19
3 1.3  10 -15
5 1.3  10 -11
7 1.3  10 -7
10 0.13

Table 1.8: Solubility Product Constants of the Hydroxides of Cations of

Group III, IV, V and VI at 25 C

2- -3
pH [S ] mol dm
Fe(OH)3 6.3  10 -38
Al(OH)3 1.9  10-33
Cr(OH)3 7.0  10 -31
Zn(OH)2 4.5  10 -7
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Experiment 5 Determination of Composition of a Complex by Job’s Method

Co(OH)2 2.0  10 -16

Ni(OH)2 2.0  10 -15
Mn(OH)2 2.0  10 -13
Mg(OH)2 1.5  10 -11
Ca(OH)2 7.9  10 -6
Sr(OH)2 3.2  10 -4
Ba(OH)2 5.0  10 -3

Table 1.9: Solubility Products and Molar Solubilities of Group V

Carbonates and MgCO3

2- -3
Compound [S ] mol dm Molar Solubility
MgCO3 4.0  10 -5 6.6  10 -3 M

BaCO3 8.1 10 -9 9.0  10 -5 M

CaCO3 4.8  10 -9 6.9  10 -3 M

SrCO3 9.4  10 -9 3.1 10 -3 M

Table 1.10: Separation of Cations into Analytical Groups

Analytical Group reagent Ion Product

group
I 0.2 M HCl Pb (II) PbCl2 (white)

II 0.3 M HCl,
+H2S Pb(II) PbS (deep
brown)
Bi(III) Bi2S3 (black)
Cu(II) CuS (black)
Cd(II) CdS (yellow)
Sb(III) Sb2S3 (orange)
Sb(V) Sb2S5 (orange)
Sn(IV) SnS2 (yellow
brown)
III NH4OH/NH4Cl Fe(III) Fe(OH)3 (reddish
brown)
Al(III) Al(OH)3 (white)
Cr(III) Cr(OH)3 (green blue)
IV H2S/ NH4OH/ NH4Cl Co(II) CoS (black)
Ni(II) NiS (black)
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BCHCL-138 Chemistry Lab IV

Mn(II) MnS (pink)

Zn(II) ZnS (white)
V (NH4)2CO3/NH4Cl/NaOH4 Ba(II) BaCO3 (white)
Sr(II) SrCO3 (white)
Ca(II) CaCO3 (white)

Zero None NH4 ,K  ,

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Experiment 5 Determination of Composition of a Complex by Job’s Method

Scheme 1.1: Separation of Cations into Analytical Groups

Take original solution in a test tube. Add dilute HCl dropwise and with stirring. If a precipitate
forms, allow it to settle. Add more acid and check if precipitation is complete. Filter.

Precipitate : Filtrate:
(Group I) Add 3% H2O2 and warm in a water bath. Add enough dilute HCI to make the solution acidic.
PbCl2. Warm the solution and pass H2S. Allow the precipitate to settle and filter. Dilute the filtrate
with distilled water (check wife only a small portion and dilute 100 times, if no precipitate
forms, there is no need to pass H2S) and pass H2s through the warm solution until
precipitation is complete. Filter.

Precipitate: Filtrate:
(Group II) Acidify with dil. HCl and boil of H2S. Heat to near dryness. Add 5-10 drops
3
Sulphidesof of concentrated HNO3 and heat. Add 1 cm distilled water and remove
Pb(ll), Bi(lll), any sulphur that separates by filtration or centrifugation. Add NH4Cl and
Cu(ll), Cd(ii), make the solution basic by addition of dilute NH4OH dropwise. Add a few
Sb(lll), Sb(V) & drops of NH4 OH in excess. Heat in a boiling water bath for 1-2 minutes.
Sn(IV). Follow Filter.
Scheme 1.2-1.4 Precipitate: Filtrate:
3
For analysis of (Group III) Add 1 cm of dilute NH4OH and pass H2S. Warm on a
individual Fe(OH)3, water bath and allow to stand for 2-3 minutes. Filter.
cations. Al(OH)3,
Cr(OH)3. Precipitate: Filtrate:
Follow (Group IV) Acidify with dilute HCl and boil off H2S. Add
Scheme 1.5 CoS, NiS, 5-10 drops of concentrated HNO3 and heat
3
for analysis ZnS, MnS. to dryness. Cool and add 1cm distilled
of individual Follow water. Add NH4Cl and ammonia (6 M) till
cations. Scheme 1.6 the solution is basic. Add (NH4)2CO, stir
for anlaysis well and filter.
of individual
cations. Precipitate: Filtrate: (Group V)
BaCO3, SrCO3, and + 
K , NH 4 . Refer to
CaCO3 Follow
Scheme 1.7 for Sections 1.12.8 for
analysis of analysis of these
individual cations cations.

Scheme 1.2: Precipitation and Separation of the Cations of Group II into Group IIA and
Group IIB

The filtrate from Group I may contain cations belonging to Group II to V. Acidify with dil. HCl
3
(0.3 M). Add 1 cm 3% H2O2 and saturate with H2S. Dilute the filtrate and pass H2S again to
ensure complete precipitation of Group II cations. Heat in boiling water bath for 5 minutes to
coagulate the sulphides. Filter. The precipitate may consist of PbS, Bi2S3, CuS, CdS, Sb2S3,
Sb2S5, SnS2. Wash the precipitate with water. Treat the washed precipitate with minimum
volume of yellow ammonium sulphide. Heat in a boiling water bath for 2-3 minutes and filter.

Precipitate: Filtrate:
May contain PbS, Bi2S3, CuS, CdS. Group IIA 3 2
May contain thioanions, SbS 4 , SnS . Add
present. Follow Scheme 1.3. 3
dilute HCl till just acidic ad warm gently. A
yellow or orange precipitate, which may
contain Sb2S3, Sb2S5, and SnS2, indicates the
presence of Group IIB. Follow Scheme 1.4.

Scheme 1.3: Separation and Identification of Group IIA Cations

The precipitate may contain PbS, Bi2S3, CuS, CdS. Wash the precipitate with water. May
2+ 3+ 2+ 2+
contain Pb , Bi , Cu , Cd . Add a few drops of conc. H2SO4 and evaporate until a dense
white cloud of SO3 is produced showing that HNO3 has decomposed. Cool and dilute with
water. Filter. Dilute and divide into three parts.

107
BCHCL-138 Chemistry Lab IV

Filtrate:
Precipitate: 3+ 2+ 2+
May contain Bi , Cu , Cd . Add NH4OH dropwise till in slight excess. Filter.
White (PbSO4). Dissolve the
precipitate in hot ammonium Precipitate: Filtrate:
acetate containing acetic and White (Bi(OH)3). Divide the 2 
precipitate into three parts. Blue ([Cu(NH ) ] ), colourless
divide into two parts. 3 4
i) Add K2CrO4 – a yellow i) Add freshly prepared sodium
precipitate of PbCrO4. stannite solution – a black deposit ([Cd(NH ) ]
2 
), Divide into three parts.
ii) Add KI-a yellow precipitate of of Bi. 3 4
Pbl2, soluble in hot water. Golden ii) Dissolve the precipitate in dilute i) Add acetic acid and K4[Fe(CN)6] solution
spangles on cooling. HCl and drop into water – a white – a reddish brown precipitate of
Pb(ll) confirmed precipitate of BiOCl. Cu2[Fe(CN)6].
iii) Dissolve the precipitate in acetic Cu(ll) present.
acid and add KI solution – a black ii) Add Na2S2O4(s). Heat in a water bath for
precipitate of Bil3 dissolves in 1-2 minutes till all the blue colour of copper
excess of Kl producing orange is gone. Observe and filter.
colour. (a) brown red precipitate, Cu(ll) present.
Bi(lll) confirmed (b) pass H2S through the filtrate – a yellow
precipitate. Cd(ll) present.
iii) Acidify with dilute HCl and pass H2S.
Filter.

Precipitate: Filtrate:
Black(CuS) May
Cu(ll) confirmed contain
Cd(ll).
Dilute and
pass H2S-
a yellow
precipitate.
Cd(ll)
confirmed

Scheme 1.4: Separation and Identification of Group IIB Cations

The precipitate may contain containSb2S3, Sb2S5 and SnS2. Wash with hot water, boil
with concentrated HCl.

 2
Colourless, may contain [SbCl 4 ] and [SbCl 6 ] . Divide into two parts.

i) Add NH4OH, oxalic acid and pass H2S an orange precipitate confirms Sb(lll).

ii) Add Fe/Al wire. Filter and add a few drops of HgCl2-a white precipitate turning gray
confirms Sn(IV).

Scheme 1.5 : Analysis of Group III Cations

The precipitate may contain Fe(OH)3, Cr(OH)3, Al(OH)3. Wash it well with a little
3 3
ammonia solution (6 M). Treat the precipitate with 3 cm NaOH solution and 1cm 3%
H2O2. Stir well and allow the reaction to proceed till evolution of O2 ceases. Boil for 2
minutes in a water bath. Extract the residue with a little distillated water and filter.

Precipitate: Filtrate:

May contain Fe(OH)3 (brown). 

May contain [Al(OH) (H O) ] (colourless) and
4 2 2
3 2
Dissolve in 0.5-1.0 cm dilute HNO3. CrO 4 (yellow). The solution, if yellow indicates the

Warm in a water bath and divide the presence of Cr(lll). Divide the solution into four parts and

108
Experiment 5 Determination of Composition of a Complex by Job’s Method

solution into two parts. perform tests for Al(lll) and Cr(lll).

i) To first part, add 2-3 drops of

KSCN solution-a blood red colour.

ii) To second part, add one drop of Tests for Al (lll) Tests for Cr (lll)

K4[Fe(CN)6] solution-a Prussian blue

i) Add NH4Cl (s)and boil-a i)Acidify with acetic acid
precipitate
gelatinous white and add
Fe(III) confirmed precipitate of Al(OH)3 BaCl2/Pb(CH3COO)2
reappears. solution-a yellow
precipitate of
ii) Acidify with dilute HCl.
BaCrO4/PbCrO4.
Add aluminon reagent ( or
blue litmus solution). Add ii) Acidify with HCl, add
dilute NH4OH (6 M) from amyl alcohol (or ether) and
3
the side of the test tube-a 1-2 cm H2O2 (3%) and
red/(blue) floating lake shake-blue colour in non-
due to adsorption of dye aqueous layer.
on Al(OH)3.
Cr (lll) confirmed
Al (lll) confirmed

Scheme 1.6: Analysis of Group IV Cations

The precipitate may contain CoS, NiS, ZnS, MnS. Wash the precipitate with H2S
containing 1% NH4Cl. Treat the precipitate with dilute HCl. Stir for a minute and filter.

Precipitate: Filtrate:

May contain NiS, CoS. Dissolve the precipitate May contain MnCl2 and ZnCl2. Boil to expel
3 3
in aqua regia, followed by heating to near H2S. Add 1 cm H2O2(3%), 1 cm NaOH
3
dryness. Extract with 2 cm water and make solution and warm in water bath for 2 minutes.
basic by addition of dilute NH4OH solution (6 Dilute with distilled water and filter.
M). Divide the solution into four parts and
perform tests for Co(ll) and Ni(ll).

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BCHCL-138 Chemistry Lab IV

Test for Cobalt (ll) Test for Nickel (ll) Precipitates: Filtrate:

i) Add acetic acid iv) Add 1% aclcoholic MnO2.xH2O (brown). 2

[Zn(OH) 4 ]
and KNO2(s). Wait solution of dimethyl Dissolve the
for 1-2 minutes-a glyoxime-scarlet red precipitate in dilute (colourless). Divide
golden yellow precipitate. nitric acid and add 1 into two parts.
3
precipitate. cm H2O2 (3%).
Ni(ll) confirmed i) Pass H2S through
Warm in a water
ii) Acidify with the solution-a dirty
bath for 2 minutes.
concentrated HCl (if white precipitate
Cool and add
HCl is added in NaBiO3 (s) or ii) Acidify with acetic
great excess, the PbO2(s). Stir and acid and add
solution may turn allow the solid to K4[Fe(CN)6] solution-a
blue due to the settle-purple/pink grayish white
formation of colour in aqueous
2- precipitate soluble in
[CoCl4] ) till just layer. NaOH solution.
acidic. Add 0.5 g
NaF(s). Stir and Mn(ll) confirmed Zn(ll) confirmed
add NH4SCN (s)
and amyl alcohol.
Shake. Blue-green
colour in amyl
alcohol layer.

iii) Add 1-nitro-2-

naphthol reagent
solution-an orange
red precipitate
extractable in
CCl4/CHCl3,
unaffected by
addition of HCl (12
M).

Co(ll) confirmed

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Experiment 5 Determination of Composition of a Complex by Job’s Method

Scheme 1.7: Analysis of Group V Cations

The precipitate may contain BaCO3, SrCO3, CaCO3. Dissolve it in minimum volume (1
3 3
cm ) of dilute acetic acid. Add K2CrO4 solution and 0.5 to 1 cm ammonium acetate.
(Excess K2CrO4 will cause SrCrO4 to precipitate). Stir and filter.

Precipitate: Filtrate:
3 2+ 2+ 3
BaCrO4(yellow). Dissolve in 0.5 cm Sr (aq), Ca (aq), Concentrate the solution to 1 cm
of concentrated HCl. and add saturated solution of (NH4)2SO4. Heat in a
i) Perform flame test-green or yellow boiling water bath with stirring. Cool and filter.
green flame
ii) Dilute with water and place one
drop on a strip of Whatman filter Precipitate Filtrate
paper No. 1 and add sodium 2+
rhodizonate reagent-red to brown SrSO4 (white). Wash the Ca (aq). Make basic with
spot. precipitate with water NH4OH and add
Ba(II) confirmed containing (NH4)2 SO4. (NH4)2C2O4 solution. Stir
3
Dissolve it in 0.5 cm of vigorously for 1 minute-a
concentrated HCl. white precipitate of
3
Dissolve it in 0.5 cm of CaC2O4.
3
concentrated HCl. Dissolve it in 0.5 cm HCl
i) Perform flame test- (12 M) and perform flame
crimson red colour test-brick red colour is
ii) Dilute with water and imparted to the flame.
add NH4OH. Boil to expel Ca (ll) confirmed
NH3. Place a drop of
nautral solution on a strip
of filter paper. Add sodium
rhodizonate reagent-red
brown spot, disappears on
addition of dilute HCl.
Sr (ll) confirmed

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