Preparation of [NiII(NH3)6]Cl2 and its analysis

by complexometric titration and

spectrophotometry
 Synthesis of Hexamminenickel(Il) chloride

1. Transfer 10 mL solution of [NiII(OH2)6]Cl2 (contains 6 g of NiCl2) in a 250

mL beaker.
2. Take 15 mL solution of aqueous ammonia in a measuring cylinder.
3. Add the ammonia solution drop wise to the solution of nickel chloride
with constant stirring till the colour of the solution has changed from
pale green to intense violet.
4. Allow the solution to stand at room temperature for 5 minutes, cover
with watch glass. Then cool it in an ice bath for about 15 minutes.
5. Filter the solution and wash the crystals with 3-5 mL ammonia solution.
6. Dry the crystals using filter paper.
7. Report the weight and yield of the dried complex.
calculate the
%yield
 Spectrochemical Series
An arrangement of ligands according to their increasing ability to split the d-
orbitals is termed as the spectrochemical series. This splitting is quantified
using the crystal field splitting parameter (Δ). The parameter is determined
experimentally.
Weak Field I-  Br- S2- SCN- Cl- NO3- F-  C2O42- H2O NCS- CH3CN 
NH3 en  bipy phen NO2- PPh3 CN- CO Strong Field

d orbital splitting for an octahedral geometry

The splitting parameter ∆o can be related to the color of a complex

 Spectrochemical Series
1.0
en > NH3 > H2O
0.8
Absorbance

0.6

0.4

0.2

0.0
300 400 500 600 700
Wavelength (nm)
λmax in cm-1
[Ni(OH2)6]2+ [Ni(NH3)6]2+ [Ni(en)3]2+
Band 1 25300 28200 29000
Band 2 13800 17500 18650
Beer-Lambert Law for quantitative analysis

 I1  A = − log(T )
T =  
 Io 

A=ɛCl
A = absorbance
ɛ = molar absorptivity (L/mole/cm)
l = cell pathlength (cm)
C = concentration of analyte (mol/L)

5 cm
Increasing conc. 0.5 cm 1 cm

5
Estimation Ni complex by spectrophotometry
Several solutions (of NiCl2) of known
concentration and one solution of Find the
unknown concentration will be conc of
provided to you.
unknown
1. Measure the absorbance of all the sample
solutions at 395 nm using a UV-
Visible spectrophotometer.
2. Plot absorbance versus mg/mL of
nickel. Determine the concentration
of nickel present in the unknown
solution in g/L.
S. Conc. of Conc. of Abs. at
No. Solution Solution 395 nm
(M) (mg/mL)
1 0.01 0.585
2 0.04 2.34
3 0.05 2.925
4 Unknown Unknown
An overlay of UV/Vis absorption spectra of Nickel
solutions with concentrations: 0.01 M, 0.04 M, 0.05
5 0.06 3.51 M, 0.06 M and an unknown solution
 Complexometric titration with EDTA

Ni2+ + EDTA4- [Ni(EDTA)]2-

Ni

Indicator used is Murexide

Color change for Ni:

Yellow-green to violet

[Link]
 Complexometric titration with EDTA
1. Take 80 mL of 0.05 M EDTA solution in a 250/500 ml plastic beaker and
fill it in a clean burette up to the mark.
2. Weigh accurately 1.15 g of [Ni(NH3)6]Cl2 complex and transfer this to a
100 mL volumetric flask. Now add 50 mL of 1 N H2SO4 to dissolve it and
makeup the solution to the mark with distilled water.
3. Pipette out 10 mL of the complex solution in a 250 mL conical flask and
dilute it with 15 mL of distilled water.
4. Add 2-3 drops of murexide indicator and 5 mL NH4Cl solution (0.5 M) to
the conical flask. Now add ammonia solution (7-10 drops) to maintain a
pH 7 (light green color of the solution).
5. Titrate it with EDTA solution till the endpoint is near, add 3 ml of
ammonia solution and continue the titration till the endpoint (bluish
violet color appears).
6. Repeat the titration and get concordant values.
7. Calculate the amount of Ni present in the complex.
 Estimation of Nickel(ll) by EDTA
Concentration of EDTA solution = 0.05 M
S. No. Volume of EDTA used from the burette (X)
1 10.0 mL
2 10.1 mL
3 10.1 mL
1 mole Ni reacts with 1 mole of EDTA to form of the Ni-EDTA complex.

Moles of Ni = Moles of EDTA

(Molarity x Volume) of Ni = (Molarity x Volume) of EDTA

Molarity of Ni x 10 mL = 0.05 M x Volume of EDTA (Burette Reading)

Suppose Burette Reading is X mL (use concordant value)
Molarity of Ni = (0.05 x X)/10 = Y M
Thus, the solution contains Y moles/Liter of Nickel Find X, Y and Z
Grams/Liter of Ni = Y x 58.69 (Atomic Weight of Ni) = Z g/L

Hence, in 100 mL of solution Z g of Ni is present.

We started with 1.15 g of [Ni(NH3)6]Cl2 , thus Z g of Ni is present
per gram of [Ni(NH3)6]Cl2
 The lab report
1. Synthesis of Hexamminenickel(Il) chloride

Experimental yield is 3.41 g, report the %yield in the lab report

S. Conc. of Conc. of Abs. at
2. Estimation Ni complex No. Solution Solution 395 nm
by spectrophotometry (M) (mg/mL)
Plot the absorbance at 395 1 0.01 0.585
nm vs. concentration of Ni 2 0.04 2.34

solution (normal paper 3 0.05 2.925

is also fine) 4 Unknown Unknown

5 0.06 3.51

3. Estimation of nickel(ll) by EDTA

Find X, Y and Z in the previous slide and report the
calculations in the lab record
 Conclusions
➢ [NiII(NH3)6]Cl2 was synthesized from [NiII(H2O)6]Cl2

➢ The synthesized complex was then used to estimate the amount of Nickel
present
Ni2+ + EDTA4- [Ni(EDTA)]2-
➢ Concentration of a given solution was determined using solutions of known
concentration with the help of UV/Vis absorption spectroscopy
1.0
en > NH3 > H2O
0.8
Absorbance

0.6

0.4

0.2

0.0
300 400 500 600 700
Wavelength (nm)
 Estimation of Iodine in Iodized Common Salt
• Iodine is an essential element for life and one of the heaviest elements required by living
organisms. However, around 1/3 of the world’s population lives in areas of iodine deficiency.

• The practice of adding iodine to salt is a

safe, easy and effective way of
overcoming iodine deficiency in our
diet. Globally two chemical forms of
iodine are used for iodization; Iodates
(IO3-) and Iodides (I-).
• The iodides degrade more readily in
presence of impurities, exposure to
sunlight, moisture and exposure to
heat, whereas the iodates remain
stable under extremes of weather and
handling. USA uses potassium iodide
(77 mg/Kg) while Germany and India
use potassium iodate (25-20 mg/Kg)
for iodine fortification.
[Link], [Link]
 Theoretical Background
The direct iodometric titration method called as iodimetry, refers to titrations with a
standard solution of iodine.

The indirect iodometric titration method, termed iodometry, deals with the titration
of iodine liberated in chemical reactions.

Experiment involves three steps:

➢ Determining whether iodate or iodide anion is present in the given salt sample

➢ Standardising a solution of sodium thiosulphate

➢ Estimating the amount of iodine in given by performing an iodometric titration

using the standardized sodium thiosulphate solution

Iodate anion

IO3-
 Theoretical Background
Estimation of Iodine
2 Na2S2O3 + I2 Na2S4O6 + 2 NaI

Test for Iodate: Iodate in presence of free hydrogen ion, oxidizes added iodide to
give free iodine; which turns starch blue

IO3- + 5 I- + 6 H+ 3 I2 + 3 H2O

Test for Iodide

Iodide is oxidized to free iodine with an acidic solution of sodium nitrite. The free
iodine turns starch blue

2 NaNO2 + H2SO4 2HNO2 + Na2SO4

2 HNO2 + 2 I- I2 + 2 NO + H2O

Starch used as an
indicator for
titrations with iodine
 Theoretical Background
Indicator : Starch

Starch-iodine complex has a strong colour; blue-purple-brown-grey-black.

Starch binds very strongly to iodine (binds to the I3- ion in solution).

We add starch when the iodine concentration is a little less because the starch-
iodide complex has less solubility and can stop iodine from reacting completely with
thiosulphate.

Some of the iodine may bind to copper in solution

To make sure that all iodine reacts with sodium thiosulphate, we add KSCN.
KSCN binds to copper thereby releasing iodine and making it available to react.

Solution containing
Solution containing Iodine
Starch-Iodine complex
 Experimental Protocol
Test for iodate solution: Moisten a pinch of salt with 2-3 drops of the given solution (mixture of
starch (A), KI (D) and (HCl) E). If iodate is present the salt will turn blue/grey and the color will be
retained for several minutes before turning brown.

Test for iodide solution: Moisten a pinch of salt with 2-3 drops of the given solution (mixture of
starch (A), NaNO2 (B) and H2SO4 (C)). If iodide is present the salt will turn blue and remain blue for
several minutes before fading.

Determination of Iodate Content (if test A is positive)

1. Weigh X g of the given salt sample and transfer into a 250 mL conical flask and dissolve it in 50
mL water.
2. Add 1 mL 2 N H2SO4 (use dropper, do not pipette by mouth), then add 5 mL of 10% KI solution
using a measuring cylinder. The solution will turn yellow. Wrap the mouth of conical flask with a
piece of filter paper and keep it in cupboard for 10 minutes.
3. Take 60-80 mL solution of (approx.) 0.005 M Na2S2O3 in a 250/500 mL plastic beaker and use for
titration. Rinse burette and fill it in and adjust zero level.
4. Remove flask from cupboard and titrate with Na2S2O3 solution until the solution turns pale yellow.
Now add approx. 10 drops of starch indicator. The solution will turn dark purple. Continue titrating
until the solution becomes colorless.
5. Record the volume of titrant (Na2S2O3 solution) used and calculate the amount of iodine present
in part per million (ppm).
 Theoretical Background
Standard Solution: A solution for which the concentration is known accurately.
The process of determining the exact concentration of a solution is termed as
standardization.
In a titration, it is critical to know the exact concentration of the titrant (the solution in
the burette which will be added to the unknown) in order to determine the
concentration of solutions being tested.

Standardization of Sodium Thiosulfate

Sodium thiosulphate is titrated against a standard solution of copper sulphate.

2 Cu2+ + 4 I- Cu2I2 + I2
I2 + 2 S2O32- S4O62- + 2 I-
Net Reaction: 2 Cu2+ + 2 I- + 2 S2O32- Cu2I2 + S4O62-
 Experimental Protocol
Standardization of Sodium Thiosulfate

1. Pipette out 10 mL copper sulfate of concentration 0.005 M in a conical

flask and add 5 mL of 5% KI solution. The solution will turn yellow in color.

2. Titrate with Na2S2O3 solution until the solution turns pale yellow. Add 7-8
drops starch indicator solution at this stage.

3. Continue the titration until the purple color fades, then add 5-6 drops of
KSCN solution and titrate again. The end point gives a colorless solution.

CAUTION: To ensure that you have obtained the true end point, stir the flask
for 20 seconds and then wait for 20 seconds to make sure that the purple
color does not reappear.

4. Repeat the titration to get concordant readings. Calculate the molarity of

the given sodium thiosulfate solution.
 Observations and Calculations
Standardization of Sodium Thiosulfate

S. No. Volume of sodium thiosulphate used

from the burette
1 9.4 mL
2 9.5 mL
3 9.5 mL

Given concentration of copper sulphate = 0.005 M

Equivalents of Copper = Equivalents of Thiosulphate

(Normality x Volume) of Copper = (Normality x Volume) of Thiosulphate

0.005 x 10 mL = Normality of Thiosulphate x Volume of Thiosulphate (Burette Reading)

Suppose Burette Reading is 9.5 mL

Normality of Thiosulphate = (0.005 x 10)/9.5
Normality of Thiosulphate = 0.0053 M
 Observations and Calculations
Estimation of Iodine
S. No. Volume of sodium thiosulphate used
from the burette
1 2.4 mL
2 2.5 mL
3 2.5 mL

IO3- + 6S2O32- + 6H+ 3S4O62- + I- + 3H2O

Consider the above reaction of iodate ions present in salt sample reacting with sodium thiosulphate

6 x M1V1 Iodate = M2V2 Thiosulphate

6 x M1 x 50 = 0.0053 x Burette Reading

Value obtained by standardizing sodium thiosulphate against a standard copper solution

Suppose Burette Reading is 2.5 mL

6 x M1 x 50 = 0.0053 x 2.5
Molarity of Iodate solution = 4.4 exp -6
 Observations and Calculations
Thus, the solution contains 4.4 exp -6 moles of Iodine per Liter of solution
The solution contains 4.4 exp -6 x 126.90 grams Iodine per Liter of solution
Atomic Weight of Iodine = 126.90 g

Solution contains 5.6 exp -3 grams Iodine per Liter of solution

= 5.6 mg of Iodine per Liter of solution

Concentration in ppm

To report in ppm

Suppose we started with 10 g of salt,

10 g salt was dissolved in 50 mL of water

In 50 ml of solution;

(5.6 mg x 50)/ 1000 = 0.28 mg of Iodine

Thus, 0.28 mg of Iodine in 10 g of salt

ppm means parts per million; which is mg per Kg

(0.28/10) x 1000 = 28 ppm of Iodine was present in our salt sample

 Results
➢ Iodate anions were identified in the given salt sample

➢ Concentration of iodate ions and iodine was determined by performing an iodometric titration

➢ Concentration of Iodine in given salt sample = 28 ppm

 Cyanotype Blue Printing
Cyanotype is a photographic printing process that produces a cyan-blue print.
Engineers used the process well into the 20th century as a simple and low-cost
process to produce copies of drawings, referred to as blueprints.
 Cyano Type Blue Printing
It was invented by Sir John Herschel in 1842.

The process of blue printing was eminently suited to its

traditional role in reproducing technical drawings, its
most common use in engineering and architecture until
the advent of modern photocopiers.

Sir John Herschel

1792-1871
 Principle of Blue Printing
There are two distinct reactions involved. Ferric (Fe3+) ions in some complexes
such as ammonium ferric citrate and ammonium ferric oxalate are reduced by light
to ferrous (Fe2+) ions.

The ferrous ions are then reacted with potassium ferricyanide to form an insoluble
blue compound; Turnbull’s Blue.

Turnbull’s Blue is very much like Prussian Blue, the only structural difference being
that the position of ferrous and ferric ions are reversed in the cyanide lattice.

It should be noted that, once Turnbull’s blue forms, it immediately converts to

Prussian Blue – Fe4[Fe(CN)6]3.15 H2O
 Prussian Blue

The [Fe(CN)6]4- anion in Prussian blue is octahedral. The right-hand drawing shows
its unit cell, which has a cubic lattice structure.

The name Prussian blue originated in

the 18th century, when the compound
was used to dye the uniform coats for
the Prussian army.
 Prussian Blue
Prussian blue is a pigment that is used to color paints, inks, textiles, and other
commercial products.

But during the past decade, Prussian blue found a high-tech use: Its ability to transfer
electrons efficiently makes it an ideal substance for use in sodium-ion battery
electrodes.

Battery producer Natron Energy (Santa Clara, CA) recently concluded a deal with
Lonza Group (Basel, Switzerland) to supply 700–1000 t/year of Prussian blue for the
Natron BlueTray 4000 battery system to be used for data-center and
telecommunications applications.

[Link]
[Link]
 Experimental Protocol
1. Immerse pieces of bond paper one by one in the sensitizing solution and keep them
immersed for 4-5 minutes.

2. Remove the wet pieces of paper and place them between sheets of filter paper. This should
be done as quickly as possible and in a partially closed locker. Dry it for 10-15 minutes.

3. After the paper has dried, place an opaque object on top of the sensitizing paper, compress
it between sheets of glass and expose to sunlight for 4-6 minutes.

4. Make 3-4 exposures, varying the time of exposure to optimize the best condition.

5. After the exposure, dip the paper into 0.1 M ferric cyanide. It is important that the paper is
immersed all at once, otherwise lines will appear on the blue field of the paper.

6. Remove the paper and dip it in 0.3 M potassium dichromate solution for one minute.
Afterwards, wash the paper first with 0.1 M HCl and then tap water and dry.
 Reactions Involved
2 (NH4)3FeIII(C2O4)3 2 CO2 + 2 FeII(C2O4) + 3 (NH4)2(C2O4) (UV Light)

FeII(C2O4) + K3FeIII(CN)6 KFeIII[FeII(CN)6] + K2(C2O4)

8 KFeIII[FeII(CN)6] 2 FeIII4[FeII(CN)6]3 + 2 K4FeII(CN)6

In our experiment, diammonium phosphate is added to the sensitizing solution
to decrease its sensitivity so that the experiment may be performed in diffused
light, rather than a dark room. Potassium dichromate helps to improve the
contrast of the image.